Acacia gum: History of the future Christian Sanchez, Michael Nigen, Véronica Mejia Tamayo, Thierry Doco, Pascale Williams, Chloé Amine, Denis Renard
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Christian Sanchez, Michael Nigen, Véronica Mejia Tamayo, Thierry Doco, Pascale Williams, et al.. Acacia gum: History of the future. Food Hydrocolloids, Elsevier, 2018, 78, pp.140-160. 10.1016/j.foodhyd.2017.04.008. hal-01602791
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Distributed under a Creative Commons Attribution - ShareAlike| 4.0 International License Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). content, andalllegaldisclaimersthatapplytothejournalpertain. Please notethatduringtheproductionprocesserrorsmaybediscoveredwhichcouldaffect copyediting, typesetting,andreviewoftheresultingproofbeforeitispublishedinitsfinalform. our customersweareprovidingthisearlyversionofthemanuscript.Themanuscriptwillundergo This isaPDFfileofanuneditedmanuscriptthathasbeenacceptedforpublication.Asserviceto 2017.04.008 D. Renard,Acaciagum:HistoryoftheFuture, Please citethisarticleas:C.Sanchez,M.Nigen,V.MejiaTamayo,T.Doco,P.Williams,Amine, Renard C. Sanchez,M.Nigen,V.MejiaTamayo,T.Doco,P.Williams,Amine,D. Acacia gum:HistoryoftheFuture Accepted Manuscript To appearin: Accepted Date: Revised Date: Received Date: Reference: DOI: PII: Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: Food Hydrocolloids Food 07 April2017 10 March2017 10 January2017 FOOHYD 3856 10.1016/j.foodhyd.2017.04.008 S0268-005X(17)30611-2
Food Hydrocolloids Food (2017),doi:10.1016/j.foodhyd. Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). Graphical abstract Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT
Acacia gum: Acacia gum: HistoryoftheFuture Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). Highlights Future research areas are identified including Interfacial toproperties ofAcaciagumsare related high M major challenges and bottlenecks Hydration, rheological and interfacial propertiesofdiscussed Acacia gum are Molecular reviewed fractionsextensively structures are madeofmolecularAcacia Senegalgumsare three fractions and minorcomponents Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT
w components content Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). 3 2 Montpellier34060 France cedex, 1 D. Renard C. Sanchez UR1268 Biopolymères Interactions Assemblages, INRA, 44300, Nantes, France Nantes, 44300, BiopolymèresInteractionsINRA, UR1268 Assemblages, Viala, 2placePierre F-34060 MontpellierFrance INRA-UM, cedex, UMRSPO, UM-INRA-CIRAD-MontpellierViala, UMRIATE, Supagro,2placeF- Pierre Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 3 1 , M.Nigen 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: : History oftheFuture Acacia gum:History 1 , , V. Mejia Tamayo ACCEPTED MANUSCRIPT
1 1 , , T. Doco 2 , P.Williams 2 , C.Amine 3 and Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). interfaces and emulsions Keywords: Acacia gum; hydration; rheology; aggregation; coacervation; this review. We sincerely hope Glyn, one of the “father of Arabic gum”, will find some positive echo in gum. and decipher between the existence of one or more amino-acid sequences in Acacia senegal liquid chromatography coupled to on line mass spectrometry could unravel the sequence unknown today and future developments based on enzyme/chemical In modifications addition, the and amino-acid sequence contained in this complex polysaccharide are totally properties ofstill Acaciagumare without answertoday. these last past years and fundamental questions arising from the adhesive and stabilizing conformational changes. This area of research seems to have been quite neglected during stabilization at liquid and solid for a interfaces) better understanding of the will interfacial function of be this polysaccharide (adhesion and to ways probe to modified them upon the enzymatic modifications. In our interfacial opinion, the main challenges induced functionality of gums, the physicochemical properties of purified molecular fractions and the fractions, the role of minor components (minerals, polyphenols, lipids) on the structure and mechanism upon exudation, the structure properties of and this conformation polysaccharide concerns of the different Some of detailed the main molecular challenges study in a near of future for a the better understanding of gum the functional maturation bulk and interfacial properties. Biological properties of Acacia gums were not considered. composition to the functional properties with a particular attention toward structure and summarizes the main updated data of this decades. complex After remembering polysaccharide a synthetic from historical perspective, the the present chemical critical review extensively studied by Glyn and his collaborators all around the world during these last five this publication to make a review on On Acacia behalf of the 90 gum, one of the favorite polysaccharides Abstract Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: th birthday of Professor Glyn O. Phillips, it is a great honor for authors of 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT
2 Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). Content list 3. Physico-chemical propertiesof Acaciasenegalgum 2. Chemical composition and structureofsenegalgum Acacia 1. WhatisAcaciagum? GeneralOverview: 6. Literature 5. Conclusions and futureprospects 4. Enzymatic modifications ofAcaciagum Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 3.7. Surfaceproperties:adsorption atsolid-liquid and liquid-liquid interfaces 3.6. Assemblypropertiesof Acacia gum 3.5. Flow and viscoelastic propertiesof Acaciagumdispersions 3.4. Rheological propertiesofgumAcacia 3.3. Hydration propertiesof Acaciagummacromolecules 3.2. Solubility of Acaciagumin alcohol solutions 3.1. Solubility in polar and non polar solvents 2.2. StructureofAcaciasenegalgum 2.1. Chemical composition 1.3. Uses ofAcaciagum 1.2. Historical aspects 1.1. Definition andproduction 3.7.1. Surface properties:adsorption atsolid-liquid interfaces 3.6.2. Coacervation of Acacia gum 3.6.1. Self-association and aggregation propertiesof Acaciagum 2.2.3. Structureof the glycoproteinfraction (GP,fractionor 3 F3) 2.2.2. Structureof the arabinogalactan-protein fraction (AGP, 2orF2) 2.2.1. Structureof the arabinogalactan-peptide fraction (AGp,fraction 1orF1) 3.7.2. Surface properties:adsorption atliquid-liquid interfaces 3.6.2.2. Complex coacervation 3.6.2.1. Simple coacervation 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT
3 Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). and as ingredient in adhesive and bone technologies in South (at least 70 000 Dewettinck, 2003). AG was already years used in the Stone Age as food in ago) Sahara (Chevalier, 1924) AG is the oldest and, apparently, best known of all natural gums (Verbeken, Dierckx, & aspects 1.2. Historical exports. Gumis mainly exportedto Europefrom which it isworldwide. re-exported producer followed by Chad and Nigeria. In 2007 they produced together 90 to 95% of world Database (COMTRADE/DBS)," 2011) but can reach 100 world 000 exports tons. of Sudan AG is were of the about biggest 60 Niger, Nigeria, Chad, Cameroon, Sudan, Eritrea, Somalia, 000 Ethiopia, Kenya and Tanzania. Total tons in 2009 ("Commodity Trade Statistics all along a belt covering arid and semi-arid areas of Mauritania, Senegal, Mali, Burkina Faso, export history. Gum is harvested from Acacia or Acacia Senegal Seyal found in Sahel region Although harvested in Arabia, Egypt and Asia since Antiquity, sub-saharian AG has a long (FAO, 1999).Itincludes both therefore AcaciaSenegal andAcaciaSeyalspecies. branches of A. Senegal (L) Willdenow or close species from Acacia (leguminosae for family)” Food Additives") of FAO/WHO, it is defined like "a dried exudation obtained from beyond the to Pakistan and India (Cecil, 2005). According to the JEFCA ("Joint Expert Committee found in arid regions (areas) of the sub-saharian belt, mechanism from of tree Senegal against to insects East and molds Africa, invasion and and of healing of soluble fibers of wounds. low viscosity (Williams & Phillips, . 2000) The Gum gum production is a protection is from the trunk and branches of Acacia senegal and Acacia Acacia gum (AG, E414), seyal also called trees, gum arabic, is which an edible is dried gummy exudate rich obtained in production and 1.1. Definition bothbetween gums is provided. reported in the following concerns Acacia Acacia seyal gum has attracted much less attention over years. Then most of the information senegal gum. When available, comparison structure, physico-chemical and functional properties of senegal Acacia gum. Unfortunately, A significant number of studies have been done 1. General Overview: isAcaciagum? What on the composition, polydispersity, Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT
4 Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). dissolve slowly. In Transvaal, a plaster made from capsicum fruit, catarrhal affections Cape and irritation gum of the and faces, by strong being held in the mouth and allowed to bites. When blown up the nostrils, it stops severe nosebleed. The gum is also employed in etc. (Caius, et al., 1942). The powdered gum is used in checking topical irritation and to protect in cases of hemorrhage superficial excoriation, ulcers, burns, sore nipples, from leech described AG as an ingredient in poultices or eye compresses. It was also used physician to relieve Abu Zayd Hunayn ibn Ishaq al-Ibadi, writing based in on AG his (Gramatica Ten & Treatises Zanardelli, on 2003). the In the Eye, with ninth dates. century The of famous our queen era, the Cleopatra Arab requested the papyrus written preparation in 1550 B.C.) of already suggested to use curative AG as a contraceptive recipes in association writings (Amy, 1934; Merat & de Lens, 1831). However, the Ebers manuscript (a medicinal The therapeutic use of AG was already mentioned in Pliny, Discoridis and Theophrastus (Cecil, 2005). From Sudanese sources, AG was an article of commerce as early as & Radha, 1942; the Parry, 1918). It was called 12 gum arabic after its place of origin (Pomet, 1735). Sudan has been an article of commerce shipped to Arabian ports and hence to Europe (Caius d'Alembert, 1777). Since the first century of the Christian era, the soluble gum provided by Mazurek, & Quirke, 2009). Ancient Greeks also mentioned bodies, were painted with gum-containing the pigments (Scott, et al., use 2004; Scott, Warmlander, of gum (Diderot & specific type of Egyptian material for cases enclosing or elements placed writing on, in mummified the fifth century B.C., mentions its use in embalming in Egypt. Cardboard (?), and a as an adhering agent to make flaxen wrappings for embalming mummies. Herodotus, inscription refers to it as kami. Furthermore, it was used as a binder in cosmetics and inks It was used as a pigment binder and adhesive in paints for making hieroglyphs, and ancient Nubia and exported north to Egypt for use in the preparation of inks, watercolors and dyes. of ancient Egyptians. Early Egyptian fleets shipped AG as a trade good. It was collected in AG for painting. Its use can be also traced back to the third or fifth millennium B.C., the time applications since the more ancient times. Well before 4000 B.C. Chinese and Japanese used likely than in these arid lands where Acacia grows, human used AG for food and non-food North East Africa (Olszewski, et al., 2010; Rots, Van Peer, & Vermeersch, 2011). It is very (d'Errico & Henshilwood, 2007; Lombard, 2008; Wadley, Hodgskiss, & Grant, 2009) and Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT
5 th century B.C Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). conquest of French West Africa. As the Atlantic slave conflict trade with inland weakened African in states over the the supply early of 19 gum, providing an early spur for British trading colonies in modern the Senegal and Mauritania. France in particular first started a During most of the 19 maintain agarrisonwastoo expansiveand thetradeof thegummovedto thesouth. 1721, 1723 and 1724 campaigns. Arguin was trading of definitely gum was important left for the European for industry, France occupied good Arguin after the in 1728 because created a colonial domain. Successors left the trading post to the Dutch in 1717. Since the years (Raffenel, 1846). In 1685, Frederick William of Brandeburg replaced the French and the Senegal River (Compagnie Française du Sénégal) had been trading for more than fifty settlement at Saint Louis at the mouth of the Senegal River, where the French Company of Arabia. By 1678 the French had textile pattern driven printing, this out gum was considered the superior to Dutch those previously obtained and in exploiting established the AG a trade. Produced permanent by the Acacia trees of Trarza replaced and by the Brakna Dutch of and the Occidental used India Dutch Company, in who were the first to begin 1580, Portugal became the dominant influence along the coast. In 1638, however, they were 19 modern Mauritania), which acquired AG and slaves for Portugal. Between the 14 In 1445, Prince Henry the Navigator set up a trading post on Arguin island (off the coast of Gum". was also developed for a time around Bombay, hence the names "East Indian" or "Indian was controlled by the Turkish Empire, giving rise to the name turkey gum. An export trade two centuries before our era (Flieder & Duchein, 1983). During the same period, AG trade Europe, for instance by painters like Rembrandt. The ink manufacturing was known at least centuries, AG was used in the composition of the metallo-gallic ink, the most used this, ink in illustrators mixed pigment in a gilding binding of letters in illuminated manuscripts, the medium. application of color was the final Between stage. For the 12 By the Middle Age, AG was valued in Europe among scribes and illustrators. Following the to themouth in thrush and sprue(Caius, etal.,1942). vinegar, is applied in acute inflammation of the bone marrow, and a mucilage of Cape gum th centuries, AG was an important trade associated to slave economy (Cultru, 1910). From Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: th century, century, AG was the major export product from the French and ACCEPTED MANUSCRIPT
6 th and the 19 th and the th th
Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). agent. It also activates turbidity or retards sugar crystallization. These properties make it a it is widely used as a stabilizer, emulsifier, flavoring agent, thickener, or AG is unique among surface-finishing the natural gums because of its properties, including high solubility and etal.,1995). Wickens, (Touré, 2008; age, between 15 and 25 years old, its wood is used for both fuel and charcoal production small-scale carpentry or for making agricultural tools. When it passes its to make hedges gum-productive to enclose cattle or protect agricultural farms. The tree can also be used for ropes can be made from the bark fibers of the roots, and the thorny branches are often used The tree has wide usage: the foliage and seed pods make excellent fodder for livestock, Sita, & Nahal,1995). decomposition of dead leaves reinforces anti-erosive roots of trees (Wickens, Seif El important Din, for dune fixation. soil In moisture. Trees are addition, resistant in period trees of drought. participate They act they as naturally to grow. wind They barrier prevent soil and degradation, soil are fix atmospheric nitrogen and fertilization maintain and Acacia senegal/seyal trees are important for the ecology of arid and semi-arid areas where 1.3. UsesofAcaciagum of(Chevalier,1924). 000 tons year AG per independence in 1959-61. In the beginning of the 20 and Niger) and French Equatorial Africa (modern Chad) until from the Sahel areas of French West Africa (modern Senegal, Mauritania, these Mali, Burkina Faso, nations gained their involvement in the interior of West Africa. AG continued to be exported in large quantities expand to the north of the of Senegal 1825 in order River to avoid for Arabs controlling the the gum trade. first The war time, incited Emirate of Trarza the and the French. In the 1820s, French the French heralding launched the Franco-Trarzan War to French direct gum to the British traders at Portendick, eventually resulted in a direct conflict between the doubled in the decade of 1830 alone. Taxes, and a threat to bypass Saint-Louis by sending supplier of world AG by the 18 quantities for its use in industrial fabric production. collected taxes on West trade, especially Africa AG that had the French were become purchasing in the ever-increasing sole century, the Emirate of Trarza and its neighbors in what is today southern Mauritania Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT th century, and its export from the French colony of Saint-Louis
7 th century, Europe consumed about 20 Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). 16% 16% rhamnose, 15-16% glucuronic acid, 1.5-2.6% protein, 0.22-0.39% nitrogen, and 12.5- Idris et al. (1998) reported AG to be comprised of 39-42% galactose, 24-27% arabinose, 12- & Stoddart, 1996; Islam, Phillips, Sljivo, Snowden, & Williams, 1997; Verbeken, et al., 2003). and 4-O-methyl--D-glucuropyranosyl, the last two mostly as end units (D. M. W. Anderson chains contain units of -L-arabinofuranosyl, -L-rhamnopyranosyl, -D-glucuronopyranosyl galactopyranosyl units, joined to the main chain by 1,6-linkages. Both the main and the side galactopyranosyl units. The side chains are salt of composed a polysaccharide of acid (Arabic two acid). or The backbone five is AG composed is 1,3-linked of a complex 1,3-linked polysaccharide, β-D- β-D- either neutral or slightly acidic, found as a mixed calcium 2.1. Chemicalcomposition structureofsenegal and Acacia gum 2. Chemicalcomposition carbon nanotubes& (Bandyopadhyaya,Yerushalmi-Rozen, Nativ-Roth,Regev, 2002). and lotions smoother. New uses begin to emerge such as for instance the stabilization industry of as an adhesive when making face powders and masks and to alsorender creams matchsticks are also made with gum. Touré (2008) adds that AG is finishing and for metal corrosion used inhibition. Moisture -sensitive postage-stamp adhesives and in the cosmetic production of carbonless copy paper, laundry detergents etc. It is used in textile sizing and a coating for papers and a key tech ceramics and as a flocculating agent. It is used as a binder for color pigments in crayons, ingredient in the micro-encapsulating process for photosensitive plates. the The same quality also makes gum useful in sprayed glazes and high- emulsify highly uniform thin liquid films makes it desirable as an ingredient antioxidant in coating gum for bi-chromate prints. It is now used According in to Cecil (2005), gum was lithography, important in the 19 where its ability to The modern industrial era has produced an explosion of pharmaceutical, printing, textile,and cosmeticindustriesal., et 2003). (Verbeken, manufacturing uses for AG. mentioned above, AG has been prevents also color pigment and protein precipitations, used confers body and stabilizes the color. for As ages in brewing (Touré, non-food 2008; Verbeken, et al., 2003; Wickens, et al., industries 1995). In wine production, AG including (including Coca-Cola®), confectionery, emulsions, flavor encapsulations, bakery products and very interesting additive in the food industry, including for the production of beverages Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT
8 th century in early photography as an Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). senegal or seyal gums. Minor components are mainly minerals (~3-5%) including Na, K, Ca, AGP-type macromolecules represent about 94-96% of total compounds found in Acacia family.AGP’s and were precipitated by Yariv’s reagent, which indicated that all four fractions belonged to array of anti-arabinogalactan-protein monoclonal antibodies via anti-carbohydrate epitopes amino acid composition and molecular weight distribution. All four fractions reacted with an which had a similar carbohydrate composition, but differed in (Islam, et al., 1997). Osman their et al. (1993) fractionated AG content by HIC to yield four fractions, of all of protein, hydroxyproline, serine and proline, whereas in GP, aspartic acid was the (2006). The main amino most acids present in the proteinaceous component abundant of AG and AGP were their results were in broad agreement with those of Randall et al. (1989) and Renard et al. Ray et al. (1995) fractionated AG by both HIC and gel permeation chromatography (GPC); conditions,origin,storage age, etc…(Al-Assaf,Andres-Brull,&Phillips, Cirre, 2012). content 24.6%, (Renard, et al., 2006). These different values may change depending on gum g.mol least three glycoprotein populations with molecular weight ranging from 2.510 fraction (1.3% of total gum), referred as glycoproteins (GP, fraction 3 or F3), will consist of at F2), contained 9% protein and had a molecular weight of 1.910 The second fraction (10.4% of total), an arabinogalactan-protein complex (AGP, Fraction 2 or molecular weight of 2.910 arabinogalactan-peptide (AGp, Fraction 1 or F1), had a very low protein content (1.1%) and a example, we showed on one hydrophobic interaction chromatography sample (HIC) (Randall, Phillips, that & Williams, 1989). most As an of AG is a the highly heterogeneous material that gum can be separated (88.3% into three main fractions of by total), an al.,(Al-Assaf,Phillips, et 2003) Verbeken, 1998; &Williams,Islam,etal.,1997). 2005; Morrison, & Wang, 1990; Idris, Williams, & Phillips, 1998; K. A. Karamalla, Siddig, & Osman, harvest (D. M. Anderson, Dea, Karamall.Ka, & Smith, 1968; D. M. W. obtained, Anderson, climatic Douglas, conditions and soil environment, and the with process its submitted origin after (Acacia its senegal or Acacia seyal), the 16.0% age moisture. The chemical composition of and physical chemical the properties of AG can trees vary from which it was Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: -1 . One of the GP had a molecular weight of 2.95 x 10 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: 5 ACCEPTED MANUSCRIPT g.mol
-1 (Renard, Lavenant-Gourgeon, Ralet, & Sanchez, 2006). 9 5 g.mol 6 -1 g.mol and the highest protein -1 . The third minor 5 to 2.610 6
Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). data from literature, it appears that the [] vs M this fraction a slope of 0.49 (Sanchez, et al., 2008). Based on a large number of structural or 0.47 (Idris, et al., 1998). These values are mainly due to the AGp fraction as we found for the log-log plot of [] vs M (Idris, et al., 1998). For instance, the Mark-Houwink-Sakurada exponent , i.e. the slope of radius of gyration R molecules was also deduced from the relationships between the intrinsic viscosity [] or the Anderson & Dea, 1971; Swenson, et al., 1968). The globular or not-extended shape of AG molecules was suggested previously based on the low viscosity of gum solutions (D. M. W. Regarding the structure in solution, globular and close-packed shape of Acacia senegal gum AGp main fraction ofAG(Sanchez,etal.,2008). (Renard, et al., 2006). A maximum persistence length of about 3 nm was estimated for the AG and its fractions gave 223, 1259 and 1605 charges for AGp, AGP and Nakagaki, 1984) with a low charge density (Vandevelde & Fenyo, GP, 1987). Recently, titration of respectively 1984; Swenson, Kaustinen, Kaustinen, & Thompson, 1968; Yomota, AG is a highly branched polyanionic polysaccharide (Fincher, Stone, Okada, & Clarke, 1983; Keentok, Mochida, & senegalgum 2.2. StructureofAcacia Glicksman1909). Malandkar, 1925; &Sand,Leo,Taylor,Lindsey,Reinitzer, 1973; 1945; peroxidases, diastases and pectinases (Billaud, M.P. Lecornu, Yadav, Moreau, & Johnston, Nicolas, & 1996; fractions. AGs also contain traces of lipids (M. P. Hicks, Yadav, Igartuburu, Yan, & Fowler Nothnagel, 2007; 2012) & and enzymes trans such ferulic as acid, ferulic oxidases acid and and 8-5’ non contradiction cyclic with data diferulic from Minzhi acid (2002, 2003). in Renard et AG al. (2006) identified and traces of AGP and not GP on Acacia senegal var. only on five senegal samples (Minzhi, 2003). Other emphasized that tannins can be found in AGs but gums (K.A. Karamalla, 2000) tannins content was reported which both for A. senegal (0.3-0.6%) or A. seyal (0.6-1.2%) gums but is clearly in more or less colored gums, which is especially remarkable with seyal. Acacia Variability in 2003). Small concentrations of tannins, around 0.4% (Mhinzi, 2003), can be Earquhar, found & giving Mcnab, 1983; Debon & Tester, 2001; Kunkel, Seo, Mg, & and Minten, 1997; trace Mhinzi, metals such as Zn, Fe, Pb and Cu ions (D. M. W. Anderson, Bridgeman, Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: g or the ratio value between R 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: w , produced a slope of 0.54 (D. M. W. Anderson & Rahman, 1967) ACCEPTED MANUSCRIPT
10 w relationship is not linear over the entire g and R h and the molecular weight M w , , Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). from raw to spray-dried gums, on the conformations of molecules. Our group analysed the influence of the geographical area of harvest and the post-harvested treatment, especially gums (i.e. the country). This missing information could raise Few studies focused some on the questions structural properties of about Acacia gums the according to the origin of Alzahrani, &Harding,2016). coupled to multi-angle light scattering (SEC MALS) and differential viscometry (Gillis, Adams, sedimentation velocity analytical ultracentrifugation and size exclusion conformation of chromatography A. senegal molecules is also confirmed using prolate hydrodynamic technics ellipsoids, as for A. senegal molecules (Lopez-Torrez, while it et varies from oblate ellipsoids to al., more anisotropic conformations, such as 2015). oblate and The ellipsoidal molecules. The conformation varies from spheres to oblate ellipsoids for A. seyal molecules, increase of molecular weight, with however more anisotropic conformations for A. senegal Williams, Doco, & Sanchez, 2015). For both A. gums, compact the than anisotropy those increases of with Acacia the senegal gum (Al-Assaf, discussing et al., about 2005; Acacia Lopez-Torrez, seyal Nigen, gum structure evidenced is that available these regarding molecules the structure are of more Acacia seyal molecules. However, and/or alternatively the to differences in the few affinity for the studies aqueous solvent. Little information appear more extended. These differences could be due only to g.mol differences in structures Q. Wang, Burchard, Cui, Huang, & Phillips, 2008). AG macromolecules with M Randall, et al., 1989; Renard, et al., 2006; Swenson, et al., 1968; Veis & Eggenberger, 1954; Osman, Menzies, Williams, Phillips, & Baldwin, 1993; 2011; Mahendran, Picton, Williams, Phillips, Bataille, Al-Assaf, & & Baldwin, Muller, 2008; Mukherjee 2000; & Deb, Kateyama, et 1962; al., 2006; Kuan, Bhat, Senan, Williams, & Karim, 2009; Li, et al., 2009; Li, et al., 2010; Idris, et al., 1998; Jurasek, Kosik, & Vandevelde, 1993; Phillips, Y. Fang, et 1993; al., 2007; K. Y. P. Fang, A. Al-Assaf, Phillips, Karamalla, Nishinari, & Williams, et al., Chikamai, 1998; Osman, Menzies, & Banks, 1995; Anderson & Stoddart, 1966; D. Deeble, M. W. Anderson & Weiping, et 1990; Chikamai & Banks, 1993; al., 1990; Duvallet, D. M. Fenyo, W. & Anderson, et al., 1983; D. Aoki, & Sasaki, 2007; M. Al-Assaf, et al., 2005; Al-Assaf, Sakata, McKenna, Aoki, & Phillips, W. 2009; Anderson, Douglas, et al., 1990; D. M M. W. w range, indicating that the conformation is molecular weight dependent (Al-Assaf, Phillips, Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: -1 are thus more spheroidal than macromolecules with M 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT
11 w above 110 w 6 below 110 g.mol -1 that 6
Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). Fourier transform infrared spectroscopy suggested the presence of extended -sheet and - by the low amino-acid composition of the AGp fraction (Renard, secondary et structures al., could be 2006). detected using However, circular dichroism, which could be explained ability to self-assemble and to interact with proteins. At the ‘‘network’’. molecular The level, structure no of specific AGp could explain the low viscosity of AG morphology with a diameter of solutions, 20 nm, a thickness of and less than 2 nm and its a central intricated et al., 2008). Data analysis 6.5 nm, a R and modeling of SANS experiments light scattering, AGp appeared to be revealed a dispersion of two-dimensional structures with a R a disk-like angle neutron scattering (SANS) experiments in charge screening conditions and dynamic The first structural model for AGp was recently proposed (Sanchez, et al., 2008). From small 1orF1) (AGp, fraction fraction 2.2.1. Structureofthearabinogalactan-peptide and glycoproteins (GP)fractions. isolated from HIC, i.e. the arabinogalactan-peptide (AGp), the arabinogalactan-protein (AGP) actual knowledge on the structures of the three molecular fractions fractions remain uncertain of from studies A. on total senegal AG. gum The following section reports on the mesoscopic structures in solutions. The to precise sugar ratio, conformations molecular weight and of charges (Renard, different et al., molecular 2006), but To summarize AG is composed of a also continuum of molecular species differing by their protein by different structure of Acaciaseyalmolecules. treatment (from raw to spray-dried gums). These the Acacia gum specie, but not on the geographical area of harvest or the post harvested dried and raw A. seyal gum. Hence, the conformations of Acacia gum molecules depend on ranging from 0.53 to 0.55 for spray-dried and raw A. senegalgum and 0.43 to 0.44 for spary- A. seyal gums. The hydrodynamic coefficient, analyses concerned 202 spray-dried and 100 raw A. senegal gums, 28 spray-dried and 6 raw Senegal, Eritrea, Mali, Mauritania and Burkina Faso (Figure spray-dried 1, Acacia senegalandseyal gums unpublished harvested in data). several countries These as Sudan, Chad, R h conformation plots (log-log plot of R Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: h of 9.1 nm and an inner dense branched structure (Renard, et al., 2006; Sanchez, 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT
h vs. M 12 w h ) after SEC MALS experiments of raw and , , is constant for each specie with values h values confirm again the more compact g of Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). around 400 amino acids was calculated previously for the AGP fraction (Qi, Fong, & Lamport, one with a M one with a M serine and hydroxyproline residues. Two folded polypeptide chains would be present in AG, g.mol followed by GPC analysis indicated that AG consists of carbohydrate AGP was blocks proposed recently of (Mahendran, et ~4.510 al., 2008). Mild alkaline hydrolysis of the gum From a study on total Acacia gum, a more detailed picture of the wattle-blossom structure of Vandevelde,etal.,1987). al.,Picton,et 2000; al., Idris,et 1998; 1988; have a spheroidal structure, which better supports the wattle-blossom model (Connolly, et indicated previously, most studies strongly suggested that the molecules of the AGP complex carbohydrate blocks (30 sugar residues) attached to hydroxyproline residues. However, as like protein (150 nm al. long) (1991) in the form of a hairy twisted rope. This model would with be comprised of a core rod- a highly Vandevelde, repetitive 1987, 1988; Fincher, et al., 1983). An alternative model was amino-acid suggested by Qi et sequence and g.mol the composed of large carbohydrate blocks with a molecular weight of approximately AGP 210 complex. It was postulated that the high (Renard, et al., 2006). A wattle-blossom model was proposed to describe molecular the structure of the weight fraction of the gum is polyproline II -turns -sheets, structures, and unordered structures, but not-helices At the molecular level, AGP contains various secondary structures, including about 27% of al.,. al.,Vandevelde, et 1987) Renard, et 2006; al., 1998; Picton, et al., 2000; Randall, et al., 2009; Castellani, 1989; Guibert, et al., 2010; Ray, Elmanan, Al-Assaf, Phillips, Bird, & Williams, 2008; Idris, Iacobucci, et & Clark, 1995; between 1 and 410 and about 9% of the total protein concentration. Its M The arabinogalactan-protein fraction from AG represents about 10-15% of total molecules (AGP,fraction2orF2) fraction 2.2.2. Structureofthearabinogalactan-protein bycircularpartly theabsenceofasrevealed dichroism. secondarystructures turn structures but not -helix (Renard, et al., 2006). The absence of -helix could explain Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: -1 -1 , blocks much lower in mass than those previously reported, covalently linked to , these blocks being covalently linked to a polypeptide backbone (Connolly, Fenyo, & w w around 310 of about 510 6 g.mol 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: 4 g.mol ACCEPTED MANUSCRIPT -1 3 (Al-Assaf, et al., 2007; Al-Assaf, et al., 2005; Al-Assaf, et al., g.mol -1
corresponding to about 250 amino acids and the second -1 , corresponding to about 45 amino acids. A number of 13 w is variable but generally comprised 4 5
Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). an aggregated fraction of AGp units stabilized It was by recently suggested that low AGP would be molecular in fact a weight molecular association resulting from proteinaceous diameters of about 1-5nm. These building structural subunits were mainly branched chains and ring-like structures with supramolecular assemblies of smaller structural subunits with dimensions of about 2-10 nm. (Renard, Garnier, Lapp, Schmitt, & Sanchez, 2013). Remarkably, all the particles were porous 10 to 40 nm) or more anisotropic morphologies TEM highlighted the (lengths existence of isolated spheroidal particles (diameters ranging from about from 20 up to about 60 nm) scattering form factor gave a maximum dimension for AGP of 64 nm (Renard, et al., 2012). conformation corresponding to a triaxial ellipsoid while inverse Fourier transform size of the of the carbohydrate branches. SANS polymer with form conformations ranging factor from globular revealed to elongated shape an depending on elongated the Schmitt, & Sanchez, average 2012). AGP would behave in solution as a branched or hyper-branched conformations depending on the molecular weight range considered (Renard, Garnier, Lapp, values are identified in the R g.mol informative insights. AGP in solution has a weight average molecular weight of Regarding 1.8610 the possible morphology of AGP in solution, linked (covalentlypolypeptide ornot)thembyseveral between backbones. HPSEC-MALLS provided some folded protein network and interacting massive sugar blocks or an assembly of sugar blocks structure of macromolecules. One can imagine that AGP is a two-dimensional object with a configuration is questionable and merits much more spatial investigation, configuration as of well AGP. as The the steric fine arrangement Sanchez, of et al., carbohydrate 2008). The model blocks is interesting since in it gives a such clearer view a of the possible carbohydrate blocks may have a thin oblate ellipsoid structure (Mahendran, et al., AGp 2008; fraction, as already demonstrated by Renard et al. (2006). It was then assumed maturation that history. The 45 amino acids peptide is probably associated with sugars in symptomatic the of different assembly states of the AGP fraction, due to different origins and based on different experimental Renard et al. (2006) for the AGP fraction. Such a large discrepancy is difficult to explain solely approaches. Rather we think 1991). These that values are it much lower is than the 2250 probably amino acid residues determined by Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: -1 and a radius of gyration 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT
g of 30 nm (Renard, et al., 2006). In addition, two exponent , [], R
h vs M 14 w relationships highlighting two types of 6
Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). 2.2.3. Structure of the glycoprotein fraction (GP, fraction 3orF3) fraction(GP, 2.2.3. Structureoftheglycoprotein Lavenant-Gourgeon, Lapp,& Nigen, Sanchez,2014). symmetrical distribution of arabinosides and polysaccharide substituents (Figure 2) (Renard, origin of the assembly of AGP Lamport, 1994). It was finally from suggested that a self-similarity driven-process would be at a the consensus glycopeptide building backbone (Goodrum, block Patel, Leykam, & Kieliszewski, 2000; with Kieliszewski, 2001; Kieliszewski & a sequence and the overall symmetry of enzymatic treatment in the accordance with the carbohydrate repetitive and moieties palindromic nature of along peptide the (by SANS) would be in favor of a high flexibility of the polypeptide backbone before and after protein adopted by control and enzyme-cleaved AGPs probed at the molecular and mesoscopic scale AGPs surprisingly predicted similar secondary structures content. The similar conformations from 1.79 × 10 cleavages and papain was found to be the most efficient protease with a decrease of after M enzymatic treatment confirmed the accessibility structure of of AGP molecular enzymes fraction at low toward pHs. The decrease polypeptide in molecular weight of AGP degradation in acidic conditions questioned conditions used, AGP about was found to be degraded only the in alkaline conditions. The absence potential of modification of fractions of senegal Acacia gum. While the AGp fraction kept intact whatever the enzymes and and alkaline proteases in order to probe the conformation and structure of the two main Very recently, AGP and AGp molecular fractions were degraded enzymatically using acidic processing. chemical composition of gum sample and its maturation process, combinations natural between or AGP, induced AGp and by GP. This structural heterogeneity likely depends on population varying in anisotropy, chain density and porosity, and of all possible molecular aggregation (Al-Assaf, et al., 2009). In summary, the so called AGP is in fact a heterogeneous addition, spray-drying was found to increase the molecular molecular reorganization of weight the gum and the appearance of composite AGP architectures. In of AGP due to self- maturation process would promote interactions between AGP, AGp components and GP, found inducing in a the GP fraction of AG (Al-Assaf, et al., 2009). More accurately, Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 6 to 1.68 × 10 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: 5 g mol ACCEPTED MANUSCRIPT −1
. The molecular structure of control and enzyme-treated 15 w
Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). (Renard, et al., 2013). GP monomer, with a rather globular shape and homogeneous long- arabinogalactan (AG) subunits, as suggested by the secondary modules. structures content of These GP ring-like structures In were summary, the certainly GP fraction from due AG would to be an hydroxyproline assembly al., et 2014). 8 to11nmdiameters(Renard,Lepvrier, of (Hyp) ring-like glycoproteins – thick shell and a central hole giving rise to the particles a typical ring-like morphology with a morphology. These spheroidal particles were structurally made of an inhomogeneous outer an inner porous network of interspersed chains was observed in the spheroidal Contrary to what was previously observed particles on AGp and AGP, no outer structure combined to spheroidal shape while slight anisotropy appeared when ring-like structures self-associated. TEM on single isolated ring-like structures. identified by SAXS in agreement with the All dimensions (diameters of 8 to 11 nm) identified by the identified isolated particles morphology, had certainly a attributed to GP oligomers. A conformation 9 probed nm by diameter SAXS particle was was ascribed also R to a thin object with anisotropic oligomers a in GP solution as triaxial suggested by the two exponent ellipsoid values found in the AG isolated from HIC and SEC, which revealed a mixture of spheroidal monomers and more Very recently, Renard et al. (2014) studied the structure of one glycoprotein (GP) fraction of surface properties(Castellani, Gaillard, etal., 2010). well, physical chemical properties of GP fraction are almost unknown, except its very active However, no mesoscopic models have been proposed to date for these glycoproteins. As -turns(38%), (23%) and unordered structures (18%) (Renard, characterized by Lepvrier, the presence et of al., polyproline II 2014). conformation (9%),-helix -sheet (9%), understand the complexity of this minor fraction. Like AGP, the different glycoproteins are continuum of species. It appears obvious that a deeper study of three GP fractions were is purified and needed displayed each to three better molecular populations, with a clear M (Renard, et al., 2006). Using HIC, at least three different fractions were identified in GP with but richer in asparagine and aspartic acid, but also in tyrosine and phenylalanine residues Regarding the amino acid composition, GP fraction is less rich in hydroxyproline and serine The glycoprotein fraction is a minor component of AG (< 2%) but is rich in proteins (25-50%). g W vs. M ranging from 310 Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: w relationship and TEM observations (Renard, Lepvrier, et al., 2014). The GP 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: 5 to 310 ACCEPTED MANUSCRIPT 6 g.mol
-1 (Renard, et al., 2006). Following HIC and SEC, the 16 Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). induce phase separation/precipitation in polysaccharides, and more generally biopolymers have not been studied in great details. However the ability of alcohols (and some salts) to The nature of interactions and mechanism of demixing in AG-ethanol- water ternary system 1958). been reported that prolonged contact with alcohol decreases the solubility of AG (van Beek, Oakley, 1935; Taft, et al., 1931; Thomas & Murray, 1928; Veis, et al., 1954). However, it has purify AG (Mukherjee, et al., 1962; Mukherjee & results Ghosh, clearly depend 1949; on gum Nelson concentration. Alcohol & precipitation has Ander, been long 1972; used to alcohol an opalescent/turbid ("faint”) precipitate is obtained (Waters & Tuttle, 1916). These alcohol (Norman, 1929; Parry, 1918). With 30% alcohol, no precipitate occurs, and with 40% water is of about 50%, with a complete AG precipitation is soluble of in dilute AG alcohol solution macromolecules and precipitates when with the alcohol 60% concentration in solutions ofAcaciaguminalcohol 3.2. Solubility Taftother than(Taft,etal.,1929; &Malm,1931). water actually demonstrated using a great number of solvents that AG is poorly soluble in solvents ammonium oxalate, mercuric chloride and ferric salts (Parry, lead 1918). acetate. The In AG solution addition, also it precipitates using was potassium or sodium silicate, borax, aqueous solution of AG forms a white jelly with basic acetate while it is soluble with neutral in water, the mineral composition of the bulk 37% was can experimentally determined at 25°C induce (Taft & Malm, 1929). the Despite its high solubility precipitation of AG. The to prepare a dispersion of gum at 50% concentration and for instance a gum solubility 2005; Turner, 1832; Verbeken, of et al., 2003; Waters & Tuttle, 1916). However it is not so easy and insoluble in alcohol (Erni, et al., 2007; Ewart & Chapman, 1952; Izydorczyk, Cui, & Wang, and it is said that AG is soluble in cold and hot water up to concentrations of about 50-55% The ability of AG to easily dissolve in water is not new (Diderot, et al., 1777; Pomet, 1735), solvents polar non and inpolar 3.1. Solubility ofsenegal3. Physico-chemical properties Acacia gum related totheself-association mode. compact conformation and bigger oligomers with a more extended conformation closely chain branches, would be able to self-associate giving rise to small oligomers with a rather Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT
17 Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). significantly different from those of bulk water (Hatakeyama & Hatakeyama, 1998). Bound where melting/crystallization temperature and enthalpy of melting/crystallization are not bound water (Chandler, 1941; Gortner, et al., 1934). Free or freezing When water analyzing is interactions of the biopolymers water with water, one can thus distinguish free and and of totherelease bound fromAG macromolecules during water self-association process. concentration, leading to the decrease of water accessibility towards AG macromolecules that some self-association (i.e. aggregation) of AG macromolecules occurred with increasing bound water decreased from 1.2g to 0.6g/g of gum (Newton & Gortner, 1922). It is possible that when AG concentration in studied dispersions increased from 3% to 10%, the amount of which seems to confirm previous results (Gortner & Gortner, 1934). An interesting point was by a cryoscopic method and no hydration of the gum in presence of KCl or KBr was found, equilibrium method (Oakley, 1937). A minimal value of 0.6-0.7 g water/g of gum was found of 0.9g water/g for Ca gum and 1.1g water/g for Na gum was measured using a membrane With 0.18M sucrose, 0.7g water/g of gum was measured. In a subsequent study, a hydration NaCl (0.05M) or KCl (0.07M), which would indicate that ions were preferentially hydrated. 1931). Using vapor pressure measurements, no hydration of the gum was measured with that AG is not hydrated to a great extent as has been claimed by many authors (Grollman, hydration properties. Few papers can be found in literature. In one example, it was shown The observed hydrophilic nature of AG has probably not motivated many studies propertiesofAcacia gummacromolecules 3.3. Hydration on the another offractions thethree could beidentified. physical chemical properties, it is likely that simple ways to obtain AG enriched in AGp, one or AGP and GP. As these three fractions display or characterize in each phase the macromolecular composition, i.e. the relative compositions of are supposed to display different It would be useful to determine phase diagrams of mechanism will bediscussed in thesection «Assemblyproperties of AG». AG-alcohol-water systems and to phase separation of biopolymers experiencing a change in the solvent quality. This demixing & Carless, 1966; van Oss, 1988; Veis, 2011). Simple coacervation is basically a liquid-liquid Simicglavaski, Tansey, & Walton, 1976; Koets, 1944; Mohanty & Bohidar, 2003; Nixon, Khalil, Bohidar, 2008; Bungenberg de Jong, 1949a; Gupta, Reena, dispersions is & not Bohidar, new 2006; and Jamieson, is called simple coacervation (Bamford & Tompa, 1950; H.B. Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT
18 Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). starch (Al-Muhtaseb, McMinn, & Magee, 2004) or chitosan (Rosa, Moraes, & Pinto, 2010), could expect a concomitant decrease of the structural water, as determined for instance for hydrogen bonding is at the basis of polysaccharide hydration (Q. Wang & Cui, 2005), water/g one gum. As an increase in temperature lowers the energy of hydrogen bonding, and as increasing the temperature from 25 to 45°C resulted to an increase of X concerns the effect of temperature on conditions the used, water indicating monolayer a (X preferential interaction 1954) with were water. found An for interesting AG. result The values macromolecules. Values were of low 5.10 but positive, under the A experimental bad affinity for the solvent and attractive interactions between biopolymers while positive solvent, can be calculated from light scattering measurements. Negative A coefficient A the non-freezing water (W (Phillips, Takigami, & Takigami, 1996). The bound water (W the range of values found for other previously mentioned polysaccharides (Takigami, Takigami, & such Phillips, 1995). as The saturation xanthan W and hyaluronan Generally, water (W andwater possibly trappedwithin water macromolecules. water within its matrix (Robertson & Eastwood, 1981). WHC encompasses both adsorbed holding capacity (WHC). The WHC is a measure of the ability of a fiber source to immobilize dealing with the interaction of biopolymers and especially fibers with water is the water- interacting with a biopolymer is then the sum of free and bound water. Another parameter biopolymer structures (Luschermattli & Ruegg, 1982). The 2004). This type of total hydration water has to be considered as an integrating amount part of the native of water (W (Brunauer-Emmet-Teller) or the GAB (Guggenheim-Anderson-de Boer) model method) (Blahovec, following the use of an appropriate model, the most often biopolymer. used The being the monolayer BET is generally calculated from sorption of isotherms a monolayer, (gravimetric possibly multilayers, of water molecules in very close interaction with the properties than free water (Hatakeyama & Hatakeyama, 1998). Non-freezing water is made and freezing bound water that is less closely water gathers associated non-freezing water but that is displays very closely different associated with physical the macromolecules 2 values indicate preferential interactions with the solvent and repulsions between Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 2 (mL.mol.g c or WHC) in AG amounts to about 3-6 g water/g gum, which is a range 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: -2 , , also called B2 or B22), an indirect way to define the affinity for nf ) is within 0.4-0.7 g water/g gum. In addition, the second virial ACCEPTED MANUSCRIPT -5 (Picton, et al., 2000) or 4.2.10
19 b ) is around 1 g water/g gum and -5 mlmolg m ). It was found that m from 0.08 to 0.11 g 2 values indicate a -2 (Veis, et al., c value is in c ) Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). dissolves the gum again (Fremy, 1860). The ability of AG to re-bind water which has been known for a long time (Fremy, 1860). Boiling the gum or adding alkali at cold temperature (Cozic, 2007). The insolubilization of the gum by heating at high degradation temperature also (150 occurs °C) at is temperatures above 100 °C that may affect the gum solubility as heating from 100 to 170 °C results in an increase of the dehydration viscosity of the gum. of However, it is solutions. likely that aggregation Protein of AG macromolecules occurs non-sticky (Moorjani & Narwani, 1948). This in insolubility alsowater, swells up to is a great extent explained but does not dissolve by and the gel the thus formed is complete standing. in AG powder form heated above 100°C, and especially at 170 °C, when immersed dried, the gum swells in water to a jelly-like mass which does not dissolve except on long (vacuum distillation), it becomes practically insoluble (Thomas, et al., 1928). When it is thus It is interesting to note that when AG in solution is dried, either with alcohol or by heating preventing theformation of theideal icestructure. molecular voids which could be occupied by structure (Phillips, et al., water 1996). Thereafter, there would in be large intra-molecular and a inter- variety of metastable chains, which could form intra-molecular hydrogen bonds within the highly cross-linked states, gum (Phillips, et al., 1996). Freezing-bound water is also tightly associated the hydroxyl with (OH) groups carbohydrate associated with the uronic acids, forming the non-freezing water of hydrophilic aminoacids (Renard, et al., 2006). The sugars units would first bind water at The polypeptide component also interacts with water since it contains a significant number carbohydrate component of AG and its highly branched characteristic (Phillips, et al., 1996). extremely favorable environment for binding water, which is probably mainly due to All these the results converge on the same conclusion. The affinity of AG for water provides an etal.,2006)ormyosinCarter (Das&citedal., Das,2002) byVernon-Carteret 2006). trends were demonstrated for microcrystalline cellulose (Cadden, 1988) cited by Vernon- here for AG are somewhat counterintuitive. However, these results are not unique as similar adsorbent. As a result, the amount of adsorbed moisture decreases. The results reported allow the leaving of some adsorbed increasing temperatures water there is an increase of molecules energy of adsorbed water molecules, from which the active centers but also of for soy proteins the (Cassini, Marczak, & Norena, 2006). It is also well known that by Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT
20 Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). Randall, 1990). 1989). Similar results were obtained by other authors Morris, (Amy, 2004), 1934; resulting in Williams, a Phillips, lower viscosity & (Smidsrod & Haug, 1971; Tinland polymer with the same number of residues & linked in the same way (Giannouli, Richardson, & Rinaudo, repulsions and allows the molecules to compact towards viscosity. the Addition volume of of an uncharged a simple conformation as a result electrolyte of long-range electrostatic effects. screens This behavior results these in higher intermolecular electrostatic repulsions electrostatic due to the charges on the macromolecule favor a stretched chain The increase in NaCl concentration induced a decrease in viscosity. For a salt-free solution, was alsopH6.2 measuredbetween and8.5 byRiddell & Davies(1931). the viscosity was almost steady between pH 5 and 9. A steady viscosity of AG dispersions in a reduction of charged groups-induced electrostatic repulsions. It can also be noticed that in less efficient interactions with water or, alternatively, to conformational changes resulting pH larger than 8-10 could be explained by a strong weakening of hydrogen bonds, resulting can also contribute to the lower measured viscosity. The decrease in viscosity observed at (Vanderreijden, Veerman, & Amerongen, 1994). Acid-induced hydrolysis of polysaccharide bearing polysaccharides, and hence, in repulsions decrease. This leads to the a decrease in the hydrodynamic viscosity volume of the carboxyl- of the explained by the fact that, polysaccharide due to neutralization of carboxyl groups solution at low pH, electrostatic pH in the range 5.5-6.3 (Thomas, et al., 1928). This can be clearly observed with arabic acid The where a maximum of viscosity was reached at a lower viscosity at acidic pH can be Hofmeister serie) must have a significant effect on the viscosity (Stephen & Churms, 1995). polyelectrolytes, it is expected that pH, ionic strength and type of ions molecules and (according is affected by temperature to and pressure. Since AG the macromolecules are weak dispersions. Viscosity is also governed by the shape, molecular size and concentration The of molecular interactions of AG with Viscosity the (atshearrate)ofAcaciazero gumdispersions solvent determine in part the viscosity of propertiesofAcaciagum 3.4. Rheological applications (Phillips, etal.,1996). released by increasing the temperature is of great value in confectionary and jellies Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT
21 Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). was suggested that the aggregation of AGP component was at the origin of this behavior (Li, thixotropic flow behavior was also observed (Li, et al., 2009; Sanchez, Renard, et al., 2002). It formation of these hypothetical aggregates (Li, et al., 2009). In addition, time-dependent or behavior (Li, et al., 2009; Mothe, et al., 1999). Hydrogen bonding could partly explain the hypothesized that the presence of AG aggregates Sanchez, Renard, could Robert, Schmitt, explain & Lefebvre, such 2002; Weinbreck & an Wientjes, 2004). unusual It was flow behavior, even at AG concentrations as low as 1-4% (Li, et al., 2009; Mothe & More Rao, 1999; recently, it has been shown that AG dispersions also display Nussinovitch, Williams, 1997; etal., 1990). shear-thinning flow 1966; Dunstan, Chai, Lee, & Boger, 1995; Gomez-Diaz, Navaza, & Quintans-Riveiro, 2008; AG dispersions is observed at high AG concentrations, typically 15-30% and above (Araujo, Avalos, & Ramos-Ramirez, 2012). This depends on gum concentration. Shear-thinning flow of 2005). Some experimental results seem to confirm this behavior (Salazar-Montoya, Jimenez- rate ( , s behavior is newtonian, i.e. the relationship between the shear stress (s, N.m The observed low viscosity of AG dispersions probably can explain the belief that their flow (except when AG powder is thermally treated at high T then rehydrated, as noted above). 2005), AG dispersions display low viscosity even at quite high concentration and do not gel Unlike most polysaccharides, used for their thickening or gelling properties (Wand & Cui, propertiesofgum viscoelastic Acacia dispersions and 3.5. Flow viscositywhere sharplywithincreases concentration. one region where the viscosity gently increases with concentration and the described other by region a single exponential (Figure 3). Such an exponential delimitates two regions, conditions of sample preparation for viscosity of the measurements, geographical practically origin all of AG, data various are over chemical a 0.13-56 wt% concentration range. However, compositions what is important to notice, irrespective and physical chemical relationship between the relative viscosity / the effect of AG concentration, we collected a great number of data from literature and the al., 1990) and decreased with the increase in temperature (Stephen, et al., 1995). Regarding Like for other common biopolymers, viscosity increased with AG concentration (Williams et Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: -1 ) is linear (D. M. W. Anderson, et al., 1967; BeMiller, 2001; Izydorczyk, et al., 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT
22 0 and the AG concentration was exponential -2 ) and the shear Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). newtonian. Sometimes, the measured flow behavior is non-newtonian and even thixotropic applied shear rates are usually above 100 s about 20wt% and shear-thinning above. However, in practical industrial situations where In summary, AG dispersions display newtonian flow behavior at gum concentrations below time of a predominantly elastic interfacialwas structure demonstrated. entire range of selected frequencies (Sanchez, Renard, et al., 2002). The building-up with rheometer therefore showed a typical gel-like behavior with G' mechanical larger spectra than after G" 120 over min the rest of AG samples at 6wt% liquids. gum Surface concentration effects in also the have an impact on measured viscoelastic properties. Dynamic (Sanchez, Renard, et al., 2002). It was then concluded that AG dispersions were structured 0.8, respectively, smaller than the exponents 2 and 1 classically found for viscoelastic liquids and G" as a function of frequency followed a power law behavior with exponents of 1.4 and 2000) or 50wt% (Goycoolea, et al., 1995) AG concentration. Interestingly, the evolution of G' (Sanchez, Renard, et al., 2002). Similar behavior was recorded at 18wt% (Matsumura, et al., throughout a wide frequency range but G' became larger than G" at the highest frequencies or loss modulus (G", N.m spectra obtained at 6wt% AG concentration by oscillatory testing revealed that the viscous Matsumura, Satake, Egami, & Mori, 2000; Sanchez, Renard, et al., 2002). Indeed, mechanical a predominant liquid-like behavior Viscoelastic properties of AG dispersions were also characterized and revealed, as expected, (Goycoolea, Morris, Richardson, & demonstrated with AG dispersions al., (Sanchez,Renard,et 2002). Bell, 1995; between surface and bulk rheological properties may occur. These features properties were of macromolecules during rheological measurements. clearly In this case, an equilibrium rheological properties of diluted biopolymer dispersions can also properties be (Lefebvre, caused by et surface al., 1997; globular Renard, proteins or et protein al., aggregates 1999). Faucheron, & is However, Sanchez, responsible time-dependent 1999). It for is the generally 1997; Matsumoto & supposed Chiba, observed 1990; Renard, that Axelos, Boué, & rheological bulk Lefebvre, 1996; Renard, Robert, aggregation between dispersions (Giordano, Grasso, Teixeira, Wanderlingh, & Wanderlingh, 1992; Lefebvre & Riot, biopolymer concentrations have been previously reported for colloidal et globular al., protein 2011). Time-dependent thickening flow behavior at low shear rates and low Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: -2 ) was higher than the elastic or storage modulus (G', N.m ACCEPTED MANUSCRIPT
23 -1 , flow behavior of AG can be considered as -2 ) Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). al. showed the increase of R scattering and microscopy experiments. Using static light scattering measurements, Wang et aggregation properties were also highlighted over a large concentration range in AG using filters, was attributed to the elution of aggregates (Al-Assaf, et al., 2009). Association and which was removed from SEC chromatograms after filtration of AG solution al., 1998; Mukherjee, et al., on 1949; Ray, et al., 1995; Sanchez, Renard, 0.45 et al., 2002). This peak, µm column, in addition to the peaks corresponding to the three main fractions of AG (Idris, et exclusion chromatography (SEC) that showed an elution peak in the Aggregation void of volume AG of in the aqueous solution was also evidenced growolderupoccurs whenthetotrees about 15years. in several studies using size gyration of AG and the proportion of aggregates in solution. This aggregation mechanism of different ages, from 5 to 15 years old, showed both the increase in the mean radius of and particularly the ageing (Idris, et al., 1998). The characterization of AG harvested on trees Aggregation of AG is apparently a natural mechanism depending on the physiology of trees, aggregationpropertiesofAcacia gum and 3.6.1. Self-association following different mechanismssuch asaggregationorcoacervation(simple or complex). presence or not of other macromolecules as partner of the with assembly, specific AG can functional assemble properties. According to in physical several areas chemical (food, pharmaceutical, conditions medicine, etc.) and to the elaborate AG-based assemblies other biopolymers, such as proteins. Its association and assembly properties are often used functional properties of the assemblies. It is well known that AG can associate with itself or physical chemical properties can influence the such as assembly solvent pathway chemical properties, and physical of chemical course macromolecule-solvent treatments and the and macromolecules macromolecule-macromolecule interactions. Several factors Molecular associations and assembly of biopolymers depend strongly ofgum3.6. Assembly properties Acacia on the extent of orneutronray scattering. are needed to clarify the situation, by using for instance rheology coupled to small angle x- and reversible shear-induced aggregation of AG macromolecules. In this case, further studies at low AG concentrations. This unusual behavior seems to be mainly due to surface effects Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: g ACCEPTED MANUSCRIPT from 20 to 50 nm on filtered AG samples as the concentration
24 Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). HIC. The self-aggregation behavior of GP fraction during its rehydration was attributed to the included in AGp and AGP fractions, in agreement with the delayed elution of this fraction by some macromolecules with a lowest affinity towards aqueous solvent compared to those undissolved material (Renard, et al., 2012; Sanchez, et al., 2008). Hence, GP fraction contains AGp and AGP powders were complete centrifugation in (Ray, et al., aqueous 1995; Renard, solution et al., 2013). without On the contrary, the the rehydration of formation macromolecules of aggregated with the formation of a substantial undissolved material after of all that it was not assemble and aggregate in aqueous solution. The easy study focusing on GP fraction showed first to rehydrate GP powder. main A fractions towards their affinity significant for aqueous solvent and proportion of course their ability of to self- GP 2014; Sanchez, et al., 2008). These studies highlighted some differences between the three isolated macromolecules (Renard, et al., 2012, 2013; Renard, Lavenant-Gourgeon, et isolated al., AG, AGP and GP fractions, also evidenced Recently, the studies self-assembly devoted behavior to of the these characterization of the three dimensional structure of component of thehigh-strengthbythis adhesivesecreted plant (Y. J.al.,Huang, et 2016). climb vertical surfaces was due to AGP recently, it was proved that the capacity of adventitious roots assembled of English ivy helix(Hedera ) to in nanospheres that were the association property key of AG in solution is consistent with the adhesive nature of AGPs. Very Capataz-Tafur, Trejo-Tapia, Rodriguez-Monroy, & Sepulveda-Jimenez, 2011). Hence, the self- assemble and aggregate both in vitro and in recognition cellular vivo mechanism (Showalter, 2001). (Baldwin, It is also McCann, well known & that AGPs can Roberts, self- 1993; AGPs is well established: these macromolecules have specific functions in interaction and macromolecules (Akiyama, Eda, & Kato, 1984). In plant kingdom, the association property of from AG. Indeed, as described above, AG is self-associate could origin from the chemical composed composition of the molecular fractions isolated of arabinogalactan-protein type The apparent contradiction between the high solubility of AG in water and its propensity to of alargerange concentration.over 2006). All these experiments confirm the self-association behavior of AG in aqueous solution and SANS measurements, and observed using cryo-TEM (Dror, Cohen, & Yerushalmi-Rozen, were also evidenced in more concentrated AG solution, ranging from 5 to 300 g·L of AG increased from 0.0413 to 5.21 g·L Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT
-1 , respectively (Q. Wang, et al., 2008). Aggregates 25 -1 , , by SAXS Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). aggregation aggregation with an increase of R the proteinaceous components. Irradiation of AG in the presence of acetylene also enhances aggregates are formed between AGp and GP fractions involving hydrophobic association of pasteurization step included in the process (Al-Assaf, et al., 2009). During heat treatment, solution compare to raw material. Aggregation in spray-dried AG has been attributed to the was also revealed in spray-dried AG samples, displaying a large proportion of aggregates in stored at 110°C during two days under control humidity (Al-Assaf, et al., 2007). Aggregation irradiated. Al Assaf et al. showed that R natural aggregation process of AG. Aggregation behavior is enhanced when AG is heated or drying or irradiation before to be used. These treatments can also influence the extent of the After harvesting, AG can be submitted to several physical treatments such as heating, spray- and in aggregation aqueous solution. fractions could explain the highest sensitivity of GP macromolecules towards self-assembly protein content and the presence of hydrophobic amino-acids in higher proportion in GP phenylalanine than AGp and AGP fractions (Renard, et al., fraction contains 2006). more hydrophobic amino-acids Hence, such as glycine, both valine, isoleucine, leucine, the high fractions is therefore around 1.1%, 9% and 24.6%, respectively (Renard, et al., 2006) and GP protein content and amino-acids composition. The protein content in AGp, could AGP be and GP explained by their differences in Differences between chemical AGp, AGP composition and GP and fractions towards aggregation particularly in aqueous their solution al.suggested by Renardet (2012). Mahendran et al. (2008) and/or hydrophobic interaction between polypeptide backbones as attractive weak forces such as hydrogen bond between saccharidic residues as suggested by and GP macromolecules in aqueous solution could be promoted by several intermolecular 2013), but not with AGp fraction (Sanchez, et al., 2008). The aggregates evidenced with AGP aggregated macromolecules were observed with AGP and GP fractions (Renard, et al., 2012, for TEM experiments could formed aggregates depend clearly impact on the fraction studied. It is likely that the drying of samples observed morphologies. each fraction Self-assembled also revealed or that the self-aggregation Renard, et behavior al., 2006). and Transmission Electron the Microscopy (TEM) morphology experiments performed of on more pronounced hydrophobic nature of the GP macromolecules (Renard, et al., 2013; Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT g from 25 to 67 nm for AG irradiated at 6 kGy (Al-Assaf, et
g increased from 33 to 73 nm when dried AG was 26 Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). mechanism once a critical ethanol macromolecules percentage will has tend been to reached. spontaneously Whatever self-associate containing the according liquid to AG a droplets, coacervation called coacervates, The addition of ethanol to dispersed AG/water dispersion led to the formation in of a new dense phase a continuous al., etal., Mohanty, et 2003). al.,Mauguet, 2002; Ezpeleta, et 1996; phase. AG (bio)-polymer, into a marginal one (H.B. increasing/decreasing temperature, thus turning the Bohidar, aqueous solvent medium, good for the 2008; Bungenberg de Jong, miscible 1949a; non-solvent (ethanol, promoted by the action of salts (sodium sulphate, sodium chloride), the addition of a methanol, water- acetone, physical chemical properties of the solvent. In aqueous solutions, etc…), simple coacervation can be by modifying in the pH solubility of (bio)-polymers or through water involved competition(H.B. Bohidar, 2008; Bungenberg de Jong, 1949a). It occurs as a result of a caused decrease by modifying the Simple coacervation is a liquid-liquid phase separation where coacervation 3.6.2.1. Simple only one (bio)-polymer is about theassemblyof AGaccordingto simple andcomplex coacervationmechanism. simple or complex (Bungenberg de Jong, 1949a). In the following sections, we will discuss number of (bio)-polymers involved in the phase separation, coacervation can be classified as dilute liquid phase remains in equilibrium with the coacervate phase. supernatant (Bamford, et al., Depending 1950; Bungenberg de Jong, 1949a; Menger & Sykes, 1998). The on the dense phase, called the “coacervate” phase, coexisting with a very dilute colloidal phase, the phase separation gives rise to two incompatible and immiscible liquid phases: a (bio)polymer accepted that coacervation corresponds to a dehydration process of (bio)-polymers. (bio)-polymers The solutions under suitable conditions (Bungenberg de Jong, 1949b). It is well Coacervation has generally been defined as a liquid-liquid phase separation gum 3.6.2. CoacervationofAcacia occurring in could beimprovedbyits self-assemblyproperties. properties (Al-Assaf, et al., 2007). Consequently, the natural functional properties Interestingly, aggregating AG through controlled Maillard reaction can improve of its functional AG carbohydrate moieties. al., 2009). In this case, aggregates were formed through C-C covalent bonds between the Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT
27 Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). Schmitt, Sanchez, Thomas, & Hardy, 1999; Weinbreck, de Vries, Schrooyen, & de Kruif, 2003; Popineau, & Boury, 2004; Liu, Low, & Nickerson, 2009; Niu, et al., 2015; Schmitt, et al., 1998; de Jong, 1949a, 1949b; Burgess & Singh, 1993; Dong, et al., 2013; Ducel, Richard, Saulnier, (wheat, pea, soybean and lentil proteins) kingdoms (Aryee & Nickerson, 2012; Bungenberg animal (gelatin, bovine serum albumin, β-lactoglobulin, sodium caseinate, etc) and complex plant coacervates by mixing it with positively charged AG proteins is extracted a from weak polyelectrolyte both negatively charged extensively used was first for evidenced in 1911 by the Tiebackx by mixing Arabic elaboration gum with gelatin (Tiebackx, of 1911). Sanchez, 2000; Schmitt, Sanchez, Desobry-Banon, & Hardy, 1998). Complex coacervation droplets called coacervates (Bungenberg de Jong, 1949b; interact and associate involving Doublier, a liquid-liquid phase separation with Garnier, the formation of liquid Renard, & Complex coacervation is based on the ability of two oppositely charged (bio)-polymers to 3.6.2.2. Complexcoacervation properties. corresponds to a dehydration process due to the modifications of solvent physical chemical coacervation of AG macromolecules by the addition favor the self–association of macromolecules (Mohanty, et al., 2003). Consequently, induced of a non-solvent such as ethanol decreases the dielectric constant and consequently the polarity of the solvent that addition could to the role of ethanol in the disturbance of hydrogen bonds network, ethanol also the polarity of the medium (H. B. Bohidar & Mohanty, for the solubility of 2004; AG macromolecules, by both modifying the Mohanty, hydrogen bond network and et al., 2003). In 1944). When ethanol is added, the quality of the solvent decreases, becoming a poor solvent shifts the energetic balance in favor of the attraction between AG macromolecules (Koets, In this ternary water/ethanol/AG system, ethanol acts as a suitable dehydrating agent which solubility/affinity of AGmoleculesfor water/ethanolsolution decreases. unpublished data). Upon the increase in ethanol percentage and determined AG concentration, by the our group for respectively. The A. binodal senegal curve, delimiting gum the in one-phase and coacervated and water/ethanol diluted two-phases phases that both regions, solution contain concentrated and was diluted AG (Figure molecules, 4, precipitation point (unpublished data). Simple concentration, coacervation the induces coacervation mechanism the occurs for formation ethanol of concentration below the Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT
28 Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). and moisture). The use of microcapsules is also a mean to deliver the encapsulated interest processing (heat, shear, redox potential, etc…) and storage conditions (oxygen, temperature protect sensitive molecules (aroma in compounds, many bioactives, industries (food, drugs, pharmaceutical, enzymes) cosmetics, complex agricultural, coacervation is microencapsulation. against Polysaccharide/protein microcapsules are used etc…) to entrap and biopolymer assemblies. One of the first and the most important industrial applications of interest to value them, by enhancing their Indeed, functional the properties formation of and complex developing coacervates novel between AG and proteins is of industrial numerous protein-polysaccharide mixturesforindustrial issues. with those obtained in bulk. This method should µl find biopolymers droplets, applications binodal curve was for able to the be determined screening with a of good agreement authors proved that by using turbidity measurements based on image analysis within only 2 innovative miniaturized approach based on millifluidic (Amine et al., submitted). In this work diagram of a β-lactoglobulin - AG and mixture large quantities has of been raw material. recently Trying to determined overcome through these phase diagram and major where an binodal curve drawbacks, is determined, is a phase tedious work that requires time 2008). The identification of the specific conditions resulting in a two phase system, named concentration) of biopolymers (polysaccharides and proteins) (Schmitt, et structural and physical chemical properties al., (global charge, charge distribution, flexibility and 1998; Ye, properties of the solvent (pH, ionic strength, nature of interactions, this salts assembly mechanism and is temperature) substantially influenced and by the the physical chemical coacervation mechanism mainly occurs groups of AG by macromolecules and the protonated the amino groups of proteins. involvement As involvement complex of of non-specific weak electrostatic electrostatic interactions between Complex coacervation between de-protonated AG and carboxyl proteins occurs by charge neutralization with the Schmitt Turgeon,Beaulieu,Schmitt, &Turgeon,2011; Sanchez,. 2003) Kizilay, Kayitmazer, & Dubin, 2011; Sanchez, Mekhloufi, et al., 2002; Schmitt, et al., 1998; features of AG-protein complexes and coacervates (de Kruif, Weinbreck, & de Vries, 2004; complex coacervation mechanism describing the physico-chemical, structural and functional Ye, Flanagan, & Singh, 2006). Several review papers well summarized the AG-protein Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT
29 Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). Schmitt et al. reported that the surface activity of -lactoglobulinAG/ complexes formed at oil/water interfaces in a variety of foamed each and biopolymer. Hence, emulsified complex products coacervates can (Dickinson, also 2008). be used to The complex stabilize coacervates formed between AG air/water and proteins gather the or surface properties of the viscoelastic propertiesofphase. thecoacervated highlighted an interrelationship between the biopolymers mass ratio, the charge density and AG/Chitosan complex coacervates (Espinosa-Andrews, et al., 2013). neutralization In of their the work, two biopolymers. they This viscous behavior was similarly The maximum of evidenced viscosity is obtained on for mixing conditions leading to the complete charge and ionic strength are key parameters for the rheological properties of complex coacervates. interactions mainly stabilize complex coacervates, protein/polysaccharide molar ratio, pH that these assemblies displayed a viscous et character (Weinbreck, al., 2004). As electrostatic characterization of the rheological properties of AG/whey protein coacervates evidenced the formation of microstructures as complex individual biopolymer. coacervates It is expected that (Schmitt, the bulk viscosity of et the system is al., improved with 2011). The polysaccharide in associative conditions result in coacervates different behaviors between compare to AG each and The rheological properties of proteins. solutions could also be modified by the The formation of complex rheological properties of AG/polysaccharide mixturessuch asAGand chitosan (Butstraen& Salaün, 2014). protein and ). The preparation of microparticles by complex coacervation was similarly performed on Umeki, Mohri, & Iso, 1991; Palmieri, Martell, Lauri, & Wehrle, 1996; Weinbreck, et al., 2004) 2015; Leclercq, Harlander, & Reineccius, 2009; Lv, Yang, Li, Zhang, et al., & 1984; Hedayati, Jahanshahi, Abbas, & Attar, 2012; 2014; Jain, Thakur, Ghoshal, Omi, Katare, & Shivhare, & Biliaderis, 2014; Ducel, et al., 2004; Eratte, Wang, Dowling, Barrow, & Adhikari, 2014; Gao, flavors, oil, pesticides and flavonoid compounds (Aberkane, et al., 2012; Bosnea, Moschakis, developed and elaborated to encapsulate different molecules such as lemon and Several orange AG/protein (gelatin, whey proteins, gliadins, conditions pea (pH), mechanical globulin) process (chewing) microcapsules or enzymatic action were (Schmitt, et al., 2011). molecules to the specific target with the optimal kinetic by changing the physical chemical Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT
30 Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). 2008; 2008; J. E. Song, et al., 2011) Sahoo, 2010; Kannan, et al., 2012; ; Kattumuri, et al., 2007; Ma, et al., 2012; and Roque & Wilson, flavonoids nanoparticles(Aberkane, et al., 2012)). silver, magnetic or bioceramic nanoparticles (Batalha, Hussain, & Roque, 2010; Gils, Ray, & Rhee, 2011; Kumar, Reddy, & Ramaprabhu, 2008; Najeeb, Lee, Chang, & Kim, 2010) , gold, al., 2002; Dror, Pyckhout-Hintzen, & Cohen, 2005; Edri & 2010; Regev, M. T. Kim, Park, Hui, & carbon nanotubes (Amiri, Shanbedi, Eshghi, Heris, & Baniadam, 2012; Bandyopadhyaya, et Surface properties of Acacia senegal gum can be used to stabilize solid nanoparticles such as interfaces solid-liquid at 3.7.1. Surfaceadsorption properties: or solid particles,especially nanoparticles. studies on foaming properties of AG are rare as compared to studies on stabilization of liquid Beaulieu, & Curti, 2005), emulsions and to stabilize solid nanoparticles. It can be noticed that & Gast, 1997). These properties can be used to form and stabilize foams (Redgwell, Schmitt, these interfaces through steric and electrostatic interactions and hydration forces (Adamson interfacial tension between gas-water, liquid-liquid or solid-liquid interfaces, and to stabilize polysaccharide world. By surface properties, we mean both the ability of AG to Surface decrease properties of AG, and of a number interfaces liquid-liquid and solid-liquid at 3.7. Surfaceadsorption properties: of plant gum exudates, are unique in the efficient tostabilize oil droplets. elasticity. In addition, the authors reported that charged complex coacervates were more The coacervates films were characterized by a long oil/water interfacial relaxation tension than the pure protein (Ducel, time Saulnier, Richard, & Boury, 2005). and a high surface globulin and AG/α-gliadin complexes or coacervates tend to decrease more stabilized strongly by the AG/protein complexes or coacervates. Ducel et the al. adsorption of AG/protein complexes evidenced at the air bubble that interfaces. Emulsions can AG/pea also be (Schmitt & Kolodziejczyk, 2010). Consequently, the stability of the foam can be improved by results were obtained in chilled dairy foams permeability using of the film whey was significantly protein reduced compare to isolate/AG pure -lactoglobulin. Similar complexes -lactoglobulinAG/ complexes were stronger than those of the pure protein and condition the (Schmitt, et al., gas 2005). However, the viscoelastic properties of the film formed by charge neutralization ratio (pH 4.2) was as high as the pure adsorbed protein in the same Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT
31 Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). liquid and liquid-interfaces. surfaces could be very interesting and useful to unravel the role and function of AG at solid- for a similar material. Future prospects in this important area of adhesion properties on solid literature on the testing of AG adhesion or any appropriate standard adhesion method used quartz crystal microbalance exist today. In our knowledge addition, while novel and efficient there techniques such as ellipsometry are coupled or not to no information in surfaces and their the related interfacial properties have never been performed to the best of nanoparticles (Kong, et al., 2014). Surprisingly, studies of the adsorption of AG on 2D solid Roberton, Chandrasekhar, Kannan & Katti, 2007) or to improve antioxydant properties of nanomedicine (Kattumuri, et al., 2007)(Kattumuri, Katti, Bhaskaran, Boote, Casteel, Fent, biocompatible gold nanoparticles concerned the use for of AG as a nontoxic material in diagnostic the production of readily administrable and applications as therapeutic a MRI applications contrast agent 2008, 2010; in for Palma, et cell-labeling al., 2015) . applications. AG coupled Other magnetic nanosystem applications could applications, namely therefore magnetic nanoparticles find (Ali, Ziada, & Blunden, 2009; Banerjee & Chen, above, AG has also been explored high layer thickness after adsorption of AG as on latex particles (Gashua, et al., 2016). As noted coating agent of nanomaterials alternative for model of end-on biomedical or multilayer adsorption was recently proposed to explain the and tails extending away from the surface into solution (M. L. Snowden, et al., approximately 1987). half of An its segments close to the surface in trains and the other half in loops Electronic spin resonance data indicated that AG adsorbed at the solid-liquid interface with was ineffective in the stabilization of the latex dispersions (M. L. Snowden, to be the most effective to be adsorbed et at the interface after only 15 min while AGp fraction al., 1987). emulsions (Randall, Phillips, & Williams, 1988) . The high M 1987). The surface coverage was found to be concentration similar (Gashua, at Williams, liquid-liquid & interfaces Baldwin, in 2016; O/W M. L. Snowden, surface coverage Phillips, of & about 0.5 Williams, – 5 mg/m AG was also used to stabilize latex nanoparticles as a model system of interface with 2009) . a manufacturing (Balantrapu & Goia, 2009; J. K. Song, Choi, & Chin, 2007; D. W. Wang & Zhao, Obviously, the ability of AG to stabilize solid interfaces was at the basis of ink and paint Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT
2 depending on solvent conditions and initial AG 32 w fraction of AG, AGP, was found Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). and we may wonder whether surface properties of AGP were highlighted or heat-induced Phillips, 2012). Here emulsion stability was checked following heating at 60°C for 3 weeks seemingly AGP critical concentration of about 10% (Nishino, Katayama, Sakata, Al-Assaf, & relationship between AGP concentration and emulsion stability was recently shown with a the AGP complex, which mainly provides the surface properties of gum. A fair It non-linear is today widely accepted that it is the protein-rich high-molecular weight fraction of AG, origin of surfacepropertiesofthegum. stability. Here we wish to focus on the composition and structural aspects at the expected pressure, etc.) all influence the structure of physical chemical parameters (pH, ionic strength, type of ions, temperature, homogenization biopolymer-stabilized emulsions and their being exhaustive but shows clearly the abundant literature on the subject. We know that al., 2007; X. Yao, et al., 2016; X. L. Yao, et al., 2013; Zhang & Liu, 2011). The listing is far from al., 1996; Vernon-Carter, Pedroza-Islas, & Beristain, 1998; Xiang, et al., 2015; M. P. Yadav, et 1987; Vasile, Martinez, Pizones Ruiz-Henestrosa, Judis, & Mazzobre, 2016; Vernon-Carter, et Shotton & Wibberley, 1960; M. J. Snowden, Phillips, & Williams, 1988; M. L. Snowden, et al., Reiner, Reineccius, & Peppard, 2010; Seifriz, 1925; Shi, et al., 2017; Shotton & Davis, 1968; Piorkowski & McClements, 2014; Prakash, Joseph, & Mangino, 2008; 1990; Ozturk, Ray, Argin, et Ozilgen, al., 1995; & McClements, 2015; O'Riordan, & O'Sullivan, Padala, 1998; Mirhosseini & Williams, Tan, 2010; Nakamura, & 1986; Nakauma, et Phillips, al., 2009; Garti, 2010; Ma, et al., 2012; Mahfoudhi, et al., 2014; Matsumura, et al., 2000; McNamee, Jin, Cai, Li, Yadav, & Zhang, 2017; Y. D. Kim, Morr, & Schenz, 1996; Klein, Aserin, Svitov, & Khodaiyan, & Hamedi, 2012; X. Huang, Kakuda, & Cui, 2001; Jayme, Dunstan, & Gee, 1999; 2008; Dluzewska & Leszczyñski, 2005; Murray, Stainsby, Gashua, & Anderson, 1988; et Djordjevic, Cercaci, Alamed, al., McClements, & Decker, 2016; Elverson, Gharibzahedi, & Mousavi, Murray, 1989; Dickinson, Galazka, 2016; & Desplanques, Anderson, Renou, Grisel, 1991a, & 1991b; Malhiac, Dickinson, 2012; 2010; Charoen, Dickinson, et al., 1988, 2012; Charoen, 2003; et al., 2011; Dickinson, Chivero, Gohtani, Yoshii, & Reineccius, Nakamura, & Oehlert, 2001; Castel, Rubiolo, & Carrara, 2017; Castellani, McClements, Guibert, 2016; et Briggs al., & Schmidt, 1915; R.A. Buffo & A Reineccius, great 2000; number R. of A. studies Buffo, dealt with emulsification properties of AG (Bai, Huan, Gu, interfaces liquid-liquid at 3.7.2. Surfaceadsorption properties: & Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT
33 Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). preferential adsorption onto oil-water interfaces of Padala, protein-rich et fractions al., occurred, 2009) all . However, (Alftren, Penarrieta, Bergenstahl, a & Nilsson, 2012; Flindt, Al-Assaf, Phillips, & Williams, 2005; careful examination of results reveal 1988). that Similar results while using a the same methodological approach were obtained droplets that protein-rich by fractions adsorb strongly at others the oil-water interface (Randall, et al., (Dickinson, et al., 1988). It was also shown between by the SEC emulsifying on supernatants capacity after and removing the oil initial between the nitrogen rate content of the of gum and its change limiting long-time interfacial of tension and tension with species, time having nitrogen contents in the range (Randall, from et al., 0.1% 1988; Ray, to et al., 7.5%, 1995). It a was then good reported with correlation samples rich of macromolecules play various an important AG role in the emulsifying/stabilizing properties of AGs AG while a lower ratio of 1:10 is common for proteins. It is then not surprising that protein- stabilize oil-in-water emulsions. An oil to emulsifier ratio of about 1:1 is therefore needed for Despite its good surface properties, AG is far from being as efficient as proteins to form and andAGP GP). benefit from what we know on the surface properties of individual molecular fractions (AGp, clarify the effect of gum molecular composition on its surface properties. The discussion will of AGP. A detailed analysis of experimental facts reported in literature can then be useful to 8%, can produce sometimes o/w emulsions with better stability than gums with higher levels reality seems a bit more complex since AG samples containing small amounts of AGP, e.g. reinforcing the current opinion on the role of AGP on gum surface properties. However, the AGP and displays better o/w controlled Maillard reaction (Al-Assaf, et al., 2007). The modified gum contains about 20% of emulsion stabilizing properties than with unmodified higher content gum, in high-molecular weight fractions was samples with developed high proportions of e.g. AGP, above 12%. recently This explains also why modified gum through their products, for instance to make stable oil-in-water (o/w) emulsions, want to obtain gum concentrations of the AGp fraction. One direct consequence is that companies using gum in encompasses the so-called AGP Katayama, and et the al., high 2007). M described We below (Al-Assaf, et remember al., 2007; here Aoki, Al-Assaf, that Katayama, aggregation & of Phillips, “AGP” AGP 2007; at the Aoki, interfaces, molecular in line with fraction the process of both “Super Gum” formation Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT
34 w GP fractions as well as minor Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). mean to convert it into a good emulsifier (Al-Assaf, et al., 2007). Structural stabilization modifications of emulsions, structural modifications of Acacia senegal gum was proposed as a Since the presence of proteins and steric effects are important in the formation 1988). and origin of emulsion stabilization by AG, especially against Electro-steric forces, coalescence probably including (Dickinson, hydration et forces, and al., elastic interfaces are at the solid behavior (Erni, Jerri, Wong, & Parker, 2012; Erni & Parker, 2012; strongly Erni, shear-elastic et and exhibit al., non-linear 2007). interfacial shear rheology indicative of 2D soft Wibberley, 1959; Shotton, et al., 1961; Wibberley, 1962). AG interfaces are jammed, very new (Briggs, et al., 1915; Serrallach, Jones, ability of & AG to form Owen, highly cohesive viscoelastic 1933; interfacial multilayer (gel-like) Shotton, films is not 1955; Shotton Another & very important parameter defining emulsion stability is interfacial rheology. The Djordjevic, et al., 2008; Vernon-Carter, et al., 1998) are unfavorable to emulsion stability. (1999) as both minerals (R. A. Buffo, et al., 2001) and 2008). It low is better to pH say electro-steric stabilization (R. mechanism as suggested A. by Jayme et Buffo, al. et al., 2001; indicates that the primary mechanism is steric stabilization (Dickinson, 2003; Trindade, et al., Ray, et al., 1995) , and (negative) zeta potential, 10-20 mV under beverage emulsion conditions (Jayme, et al., 1999; the pH-independent destabilization mechanism (coalescence), electrostatic contribution to the colloidal stabilization, however the relative low value of the (Shotton & Wibberley, 1961). mechanical Surface properties provided by interfacial charged films rather than to groups a low interfacial tension provide In the fact, the efficiency of AG basis is better related to the for way it adsorbs onto interfaces some and the Randall al. et the polypeptide chain, casting some doubt on the model chain, and no structural data today exist about the spatial position (buried or in periphery) of proposed by Islam et al. and However, numerous hydrophilic hydroxyamino acid residues are present in the polypeptide barrier towards flocculation and coalescence (Islam, et al., protruding 1997; hydrophilic Randall, carbohydrate blocks et attached al., to this 1989). chain provide a strong co-polymers, steric the more hydrophobic protein chain kinetics. In the frame of the wattle-blossom model, anchors it is supposed that, in analogy with block at the interface while the molecular fractions seems to be present at the interfaces with however different adsorption Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT
35 Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). composition of supramolecular structures change too with the incorporation of AGp and low by Maillard reaction. Not only the AGP M et al., 2006). Another concern deals with the nature of supramolecular structures produced lower for oil to emulsifier ratios above 1 but was not different for ratios below 1 (Kateyama, results difficult. For instance, it was shown that initial emulsion droplet size was significantly gum concentration, oil to emulsifier ratio, dispersion pH, etc…), rendering the comparison of never been prepared under the same experimental conditions (homogenizing conditions, regarding initial emulsion droplet size and emulsion stability. In addition, emulsions have is that few studies have been done to definitely conclude on the benefit of matured gums high M Although these results using matured AGs seem conclusive on the interfacial properties of (Castellani, Gaillard, etal., 2010). matured gums are very close to that of the AGP fraction as obtained by HIC chromatography 2010; Castellani, Guibert, et al., 2010). It is interesting to note that higher surface viscoelasticity properties of of interfaces formed from matured gums (Castellani, Al-Assaf, et al., Yao, et al., 2013). The improved stability of produced emulsions could be due partly to the Katayama, et al., 2007; Castellani, Al-Assaf, et al., 2010; Castellani, Guibert, et al., 2010; X. L. which is an important parameter in determining emulsifying capacity as noted above (Aoki, modified gums have the ability to decrease interfacial tension faster than unmodified gums, Castellani, Gaillard, et al., 2010; X. L. Yao, et studies (Aoki, al., Katayama, 2013). et al., In 2007; addition, Castellani, Al-Assaf, it Axelos, was Phillips, shown & Anton, that 2010; was improved with high M this case, the initial size of emulsion droplets was not impacted by M 1991a) or surface rheological properties (Nakamura, 1986) was previously demonstrated. In control gum. The effect of AG molecular weight (M improved interfacial viscoelasticity and emulsion stability as compared to the unmodified Modified gums allow the production of M oil-in-water emulsions with smaller droplets, authors (Al-Assaf, Phillips, Sasaki, & Katayama, 2003). This process resulted in an increase of 60°C under controlled moisture mimicking natural maturation process were induced according through controlled to Maillard reaction incubating the kibbled gum many weeks at w of AG from about 4.2x10 Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: w protein-rich macromolecules, some comments may be of interest. The first remark 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: w ACCEPTED MANUSCRIPT . Similar results using matured gums were obtained in other 5 g.mol
-1 up to about 20x10 w 36 (and their concentration) increases but the w ) on emulsion stability (Dickinson, et al., 5 g.mol -1 (Al-Assaf, et al., 2007). w but emulsion stability Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). Gaillard, et al., 2010; Fauconnier, et al., 2000; Lopez-Franco, et al., 2004). It was clear from measurements and Langmuir-Blodgett films (Castellani, Al-Assaf, et al., studies 2010; focused Castellani, on interfacial properties of fractions as determined by interfacial tension effect of fractions on oil-in-water emulsions characteristics (Ray, et Lopez-Franco, al., et al., 2004; 1995) Ray, et al., 1995). and Among these studies, one three of them studied the (Castellani, Al-Assaf, et al., 2010; Castellani, Gaillard, et al., 2010; Fauconnier, et al., 2000; the remaining studies were classically concerned by HIC fractions, i.e. components. AGp, Unlike one study where four fractions were obtained AGP by SEC (Ray, et al., 1995), and GP scarce studies tried to unravel Owing to the the expected surface properties specific of protein-rich molecular properties fractions of AG, of some individual macromolecular similar component structurefortheAGP (Renard,Lavenant-Gourgeon,etal., 2014). 1988) and AGP conformation remain largely unaffected by proteases, polysaccharide component suggesting (Connolly, et a al., 1987; self- Mahendran, et al., 2008; Randall, et al., change in macromolecular conformation. one may wonder whether In the loss in surface properties is due fact, to a decrease in M both (Elmanan, et al., chemical 2008; Flindt, et al., 2005). As AGP architecture is structure modified after hydrolysis, of the pronase but to a lesser extent, which can be partly due to its more compact conformation note that high M hydrolyzing the gum in the bulk or at an interface did not produce the same results. One can 510 min hydrolysis, interfacial viscoelasticity decreased but remained high. It is possible that However, by hydrolyzing AG while measuring interfacial viscoelasticity showed that, after Assaf, et al., 2007; Connolly, et al., 1987, 1988; Elmanan, et al., 2008; Randall, et al., 1988). in relation with the significant decrease of protein-rich high M therefore form interfacial films less viscoelastic than with native AG (Elmanan, et al., 2008), Acacia senegal gum, hydrolyzed by pronase (a mixture of proteases) for 24h at 37 °C, did emulsification properties was observed (Chikamai, Banks, Anderson, surface & properties Weiping, was to 1996). hydrolyze it with protease-type enzymes. Another In approach to this demonstrate case, the role loss of protein-rich of high M highcompare matured M architecture of supramolecular structures is also modified. In M these conditions, how to w GP fractions (Aoki, Al-Assaf, et al., 2007). Obviously it can be anticipated that the global Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: w macromolecules present in Acacia seyal gum are also hydrolyzed by 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: w macromoleculeswith asmallerAGP fraction of control gum? ACCEPTED MANUSCRIPT
37 w AGP concentration (Aoki, Al- w macromolecules in AG w or to a Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). centers centers (D. M. W. Anderson, 1978). In addition, the -1,3 galactan backbone should form an significant proportions (< 10 mol%) of terminal Rhap groups, which possess suggested hydrophobic that the superior emulsifying power ofconsiderably on gum the polysaccharide Arabic component (Goodrum, may et al., be 2000). Anderson related (1978) to Wang, the & Zhou, 2011). It emulsifying and emulsion has stabilizing properties than Acacia senegalgum been (Qian, Cui, Wang, suggested that macromolecules extracted from AGP Peach exudate and not containing protein surface displayed better properties depend Buffo, et al., 2001). More surprisingly, it was shown recently that high M (0.8%) have been found to give better emulsion stability than Acacia stable senegal emulsions gum and (R. some A. Acacia seyal gum samples with a much lower protein content overall amount. Gums with higher protein content do not also necessarily produce distribution more of the proteinaceous component of the gum which is important, and emulsion stability (Dickinson, not et al., 1991b), confirming the view that it is the just nature and its Gums with similar protein content may exhibit significant differences in emulsifying capacity nitrogen content alone cannot be used to predict performance of AGs for emulsification. fractions, and of the important role of high M Although there is no doubt about the important surface activity of AG protein-rich molecular composition, which mayexplain in parttheobserveddifferences. obtained using the same Acacia senegal gum concentration (10wt%) but different subphase GP fractions, the latter being the less elastic (Fauconnier, et al., 2000). These results were study showed that films from AGp fractions were more elastic than films made from AGP or fractions which formed films with similar elasticity (Lopez-Franco, et experiments. al., One 2004). study Another showed that the whole gum unclear produced more in elastic films than terms of Gaillard, et surface al., 2010; elasticity Fauconnier, et al., as 2000; Lopez-Franco, determined area, GP et fraction was again the more efficient al., and AGp fraction the less efficient 2004). (Castellani, from Results were Langmuir-Blodgett film higher gum concentration should be instructive. In terms of surface pressure and limiting experiments were done at 0.05wt% gum concentration and that about similar 45 mN.m experiments at values at equilibrium of about 23 mN.m these studies that GP fraction was the more efficient to decrease interfacial tension with Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: -1 for AGp (Castellani, Al-Assaf, et al., 2010). It is important to note that 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT
-1 as compared to values of 30 mN.m 38 w fractions in the stabilization of emulsions, w arabinogalactan -1 for AGP and Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). lower than 10%, still display excellent ability to stabilize oil-in-water emulsions or that gums M on their surface properties, e.g. free proteins, peptides, oleoresin, feruclic acids. These low Yadav, et al., 2012). This points out the potential role of minor components present in AGs macromolecules, would improve the surface properties of AG (M. P. Yadav, et al., 2007; M.P. Finally, it is important to mention that trace levels of lipids, probably attached to the “AGP” Ostwald ripening and coalescence(Chanamai,al., et 2002). low polarity and low water-soluble oil (e.g. hexadecane), decane), emulsions are stable to coalescence, but unstable emulsions to Ostwald ripening. Finally, with are stable to both AG (Chanamai, et al., 2002). When a low polarity and high water-soluble oil Ostwald ripening and coalescence when stabilized by a weakly adsorbing is biopolymer such as used (e.g. polarity and high water-soluble oil (e.g. decanol), oil-in-water emulsions are unstable to both solubility of the dispersed phase influence the water destabilization emulsions mechanism. (Chanamai With & a McClements, high 2002). In addition, instance, both hexadecane-in-water polarity emulsions made and with water AG are more stable than decanol-in- fraction when the non polar n-hexadecane is used (Castellani, Gaillard, et may al., explain 2010). why For the hydrophobic GP fraction adsorbs faster at interfaces emulsions, limonene, the main than orange oil component, being the a non polar molecule. AGP This also tensioactive components. This is the basis of the extensive use of AG to stabilize orange oil display a higher interfacial tension with water oil (Dickinson, et al., 1991b; Shotton, et al., 1960). A non polar dispersed phase will therefore and will favor adsorption of the efficiency with which more AG is adsorbed depends at least in part on the nature and polarity of stability against washing of emulsions made with different oils, it was suggested that is the important to determine emulsion formation and stability. Based on the varying degree of The presence of surface active components in AG implies that the nature of dispersed phase substantial impact on theadsorption ofontoAG hydrophobic surfaces. “hydrophilic” carbohydrate blocks attached to the polypeptide chain could therefore have a groups oriented toward the outer surface inside of the of helix comprising a hydrophobic surface the with the bulk of helix the galactan hydroxyl (Goodrum, et amphipathic al., helix, and 2000). recently confirmed The by Kitazawa et al. (Kitazawa, et al., 2013), the w components could explain that some gums with low AGP concentrations, for instance Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT
39 Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). (Chikamai, et al., 1996). Analysis by SEC showed a broadening of the decrease in AGP galactose content was fraction observed in parallel and to a 27% a increase in protein content When using specific enzymes of polysaccharide such a-galactosidase, hydrolysis hasasto beensuggested away improve theirprocessing (Chikamai, etal.,1996). a limited 8% 1988; Renard, Lavenant-Gourgeon, et al., 2014). The decrease of gum viscosity after enzyme values obtained were in the range 12-15 mL.g block of the gum as obtained by protein enzymatic hydrolysis. The limiting intrinsic viscosity obtained with papain (Renard et al., 2014). This can be considered as the nominal building 1.7-2x10 Lavenant-Gourgeon, et al., 2014). The lower M al., 2005; Mahendran, et al., 2008; Osman, et al., 1993; Randall, et al., 1988, 1989; Renard, low M the gum, i.e. both AGP and high M treatment of Acacia senegal gum mostly degraded the protein-rich high M (Connolly, et al., 1987, 1988; Randall, et al., 1988). It was then demonstrated that protease component of the gum and contribute to the elaboration demonstrate of that the most wattle-blossom model of proteins were associated Enzymatic with modifications the of higher molecular AG, weight especially protein hydrolysis, aclassical thegumrecovered distributionstorage, ofmolecular fractions. were used primarily to heterogeneous with part of kibbles containing very and it high appeared that green M gum displayed a peculiar rheological behaviour and was highly origin is known. A recent Ph.D. student has studied these changes during gum maturation fluid and entirely soluble (Reinitzer, 1909). Neither the nature of these enzymes nor their during several months, a change is observed probably due to enzymes, so that gum becomes mucus-like fluid from which a perfect solution separates after a certain time. After storage from the earliest exudation, called “green gum”, is not Modifications entirely of soluble AGs with yielding enzymes a first occurred glairy during its maturation process. The gum ofAcaciagum 4. Enzymatic modifications differences in stability. This subject should muchmoreattention deserve in thefuture. with similar protein content and AGP concentration produce emulsions with significant Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: w GP components (Aoki, Al-Assaf, et al., 2007; Connolly, et al., 1987, 1988; Flindt, et 5 g.mol -1 , depending on the enzymes and conditions used with the lower values 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT w
GP fractions, but did not degrade or marginally AGp and 40 -1 (Chikamai, et al., 1996; Connolly, et al., 1987, w obtained after hydrolysis was in the range w AGP (Cozic, 2007). Upon w component of Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). related to the presence ofrelated tothepresence protein-rich high molecular weightspecies. liquid, liquid-liquid and solid-liquid interfaces. Surface properties viscosity even at quite of high gum concentrations and gums the ability to are adsorb and stabilize gaz- strongly display interesting functional properties such as high affinity polyphenols, for etc...). water, Besides low their newtonian known biological properties, explain Acacia their gum ability biopolymers to interact with different porous kinds ellipsoidal of objects. In entities fact, these (e.g. macromolecules are proteins, kinds of minerals, sponges, which can Acacia senegal gums have generally anisotropic shapes and components such can as minerals, polyphenols be and traces of described lipids. Arabinogalactan-proteins in as highly degree of branching, conformation and physicochemical properties. It also contains minor complexes differing by the amount of protein, type of sugars, sugar to amino-acid contains ratios, a continuum of Acacia senegal gums hyperbranched are composed of arabinogalactan-proteins (AGP) amphiphilic type biopolymers. It charged polysaccharide-protein but also in non-food applications (pharmacy,cosmetics,materials). the last ten years. Gums are mainly used in Food industry (confectionary, drinking industry) times and continue to be widely used today, the World demand having risen by 25% since part of Acacia seyal sales in recent years. Acacia gums are used by humans since prehistoric and studied whereas a growing demand of low cost natural gum can explain the growing uses, Acacia senegal gum and seyal Acacia gum. The first one was in the past the most used natural ingredient of geo-political and economic importance. Two gums are authorized for Acacia gum is a plant exudate mainly produced in sub-sahalian regions of Africa. It futureprospects and 5. Conclusions is a compare toemulsions madewithnative(Dilokpimol AG &Geshi, 2014). modified gum arabic were slightly smaller in droplets incorporated size up and to 1/3 remarkably of more AG total stable weight. Oil-in-water emulsions made isolated from Arabidopsis thaliana and used with AG. It was found that glucuronic acids were by the enzyme- properties (Heidebach, Sass, & de With, 2013). Very recently, a glucuronosyltransferase was reported the use of -galactosidase to produce modified AGs with improved emulsifying narrowing of the AGp fraction, GP fraction being unchanged. Interestingly, a recent patent Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT
41 Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). components which deserve much more attention. Part Nature of and variability concentration in of gum minor components: functional Acacia gums contained 3-6% of minor crosslink molecules AGP byoxidative enzymes. be detrimental as far as solubility is concerned, however this could open the possibility to suspensions can be achieved using high gum concentrations. The presence of polyphenol can interfaces covered by this gum. However, we stabilization of know assemblies appear that difficult. stabilization We do of not know emulsions the structure or solvent of polarity oil-in-water or temperature. We know that assemblies with proteins are possible but molecule compactness and whether such a compactness can unknown be and their functional properties modified badly known. We do not changing know the reasons for the the hydrolysable by enzymes. The structure and conformation of AGP from proteins, Acacia more seyal compact, are more unstable in solution, less charged, less surface active, distribution. less However, Acacia seyal gum is richer in minerals and polyphenols, less rich in amino-acid compositions are mostly known, as studied than Acacia senegal gum. The differences between both gums in terms of sugars and well as the major differences Acacia seyal in gum M represents actually 50-75% of sales. Composition, structure and However, functional properties of Acacia seyal gum: for economic reasons, it has been much less can havesignificant functional consequences,especiallywhen itis richin polyphenols. enzymes has never been reported. Apart from hydrolysis, gum can also be oxidized which may be caused by the action of some glycosidases and/or proteases. The presence of these rheological behaviour. With time, even in the dry state, the M “green gum”. Initial glairy gum is composed by very of high the M most challenging questions is the mechanism leading to the known biopolymer gum composition and from distribution, structure the and functional properties. Probably one and minor components upon storage and processing. The consequences are a drying, change oxidation, in (enzymatic) hydrolysis and interactions between AGP and between AGP Maturation mechanisms of Acacia gums: once exuded, gums evolve with time through sun of views. Someofpoints, themostrelevant in our opinion, aredescribedin thefollowing. important issues and bottlenecks can be identified both on scientific and technological point Based on the literature survey, socio-economic challenges and our own work, some Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT
42 w w of AGP decreases, which is AGP that imparts specific w
Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). chains is unknown, e.g. nature of interactions between sugar chains recent and advances. between The sugar organization of sugar blocks onto the polypeptide SEC or Ion-Exchange Chromatography. The or architecture of fractions remains polypeptides unclear despite Other possibilities are to combine controlled alcohol or salt-induced precipitation and HIC, Hydrophobic Interaction Chromatography (HIC) then Size Exclusion Chromatography (SEC). new structural insights through the use proportions including gum aggregates. Highly purified molecules are then needed to provide of combined approaches, for instance conformations. However, results were using obtained on mixtures containing fractions in various ability to stabilize colloidal suspensions. We know that these fractions display anisotropic that protein-rich high molecular weight fractions have important surface properties and the composition, sugar to amino-acid molar ratio, charge density and hydrophobicity. We know gums are hyperbanched arabinogalactan-proteins with various M Structure of arabinogalactan-proteins (AGP): all biopolymers in Acacia senegal and seyal present butwedo not knowtheirnatureororigin. responsible of the time-dependent maturation of gum. We know that these enzymes are enzymes mentioned in the literature, e.g. oxidases, or from may AGP degradation. be It cannot hydrolase-type be ruled enzymes out that these molecules could be some of concentrations. the These molecules could be free proteins or oligosaccharide-proteins issued presence of highly rich-protein molecules with low M lipids. When we perform SEC-MALLS experiments on gums, UV profiles show invariably the are present, at which concentration and whether they are limited to GPI or other kinds of the presence of lipids impacts the gum surface properties. We need to know whether lipids anchor) linked to high M in oxidation phenomena and modify functional properties of AGP. Traces of lipids (the GPI nature of these polyphenols and their concentration need to be determined; they can result nodules depending on the gum type (Acacia senegal vs Acacia seyal gum) and origin. The stabilization of colloidal suspensions. Polyphenol type molecules are present in colored gum an important role in the hydration, solubility and compactness of important AGP since they are supposed as to impact the charge well density of AGP, which as in turn plays in the major part is composed by minerals (3-5%). The properties concentration must originate and from nature these of minor ions compounds. are Among these components, the Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: w AGP has been reported in Acacia senegal gum. It is obvious that ACCEPTED MANUSCRIPT
43 w (long elution times) at very small w , , size, sugar or amino-acid Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). chaotropic solvent and temperature, then varying interactions the between strength AGP of should hydrogen be bonding, studied fractions. in The relation effect of with solvent the polarity ionic on hydration strength, properties the of the soluble dynamics the part of of F3 fraction as intra- compared to total and gum, F1 or inter-molecular F2 fractions display different solvent affinities. This can be of seen Acacia senegal gum depending on gum as concentration. This suggests that some well molecular through the huge we have noted recently aggregation-disaggregation phenomena involving protein-rich AGP Solution properties: solvent affinity, phase behavior, formation and dynamics of aggregates: fractionssome attention.synergism between deserves on the solvent polarity, their surface properties. In addition, their rheological properties, their the solution properties (phase behavior, assembly) question depending of functional fraction functional properties. Today, we have no idea about their to hydration understand properties, and control gum functional properties was tried (gum concentration, pH, ionic strength, nature of oil, temperature). It is impossible without a precise knowledge of fractions were not highly purified and no systematic investigation of experimental conditions find in the literature some conflicting data on interfacial properties of F1, emulsions made with the two major fractions purified from HIC (HIC-F1 and F2 HIC-F2). One can and F3 but the different AGP fractions that have been rarely studied so far. Only rheological behavior, etc..) but the most important one concerns the functional properties of one paper reports seyal gum. A number of issues remains (solvent affinity, formation of aggregates, unusual senegal gum have been characterized in more or less details. This is not the case for Acacia functional properties (hydration, assembly, rheological and surface properties) of Functional Acacia properties of Acacia gums and their arabinogalactan-proteins (AGP) fractions: the macromolecularfunctional properties. density of AGP should be determined as well, both to better understand the structure and degraded either by chemical or enzymatic treatments or both. Please note that the charge Determine the amino-acid sequences is challenging determine because the linking sugar of blocks sugar have blocks. Theses to sequences be the are unknown molecules for is Acacia gum. directly related (e.g. helix of the 1,3- to galactan backbone). In addition, the global structural organization of the amino-acid sequences of chains and polypeptides, polypeptides steric constraints, that possible secondary structures of sugar blocks Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT
44 Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). strength is a bottleneck that has limited up On the to other now hand, their the industrial stabilization of applications. these Since assemblies against interactions between Acacia senegal gum and changes proteins is not a difficult in task at the lab scale. pH or ionic stabilization, industrial scaling: the formation of nano/microparticles based on electrostatic Nano/microparticles-based on AGP assembly aroma. with other biopolymers: affect emulsion stability formation, and for instance permeability to hydrophobic molecules such multilayers), surface as gum concentration and topology of fractions. These characteristics will the structure of interfaces remains unknown, especially in terms of thickness (monolayers vs electrosteric repulsion mechanisms stabilize emulsions. Depending on process conditions, emulsification process need to be clarified. Solid-like viscoelastic properties of interfaces and quantity of interfaces. The relative contributions of the different fractions during the however it full seems to depend on gum concentration, hydrophobicity of dispersed phase and homogenization energy. The important role of concentration, protein-rich nature fractions of makes oil phase no (hydrophobicity), doubt, protein-rich AGP clear concentration picture and emerged from such studies about the intricate the relationships formation and between stabilization of oil-in-water gum emulsions based on Acacia senegal gum. No structure and mechanical properties of interfaces: a huge number of studies have reported Emulsifying-stabilization properties of Acacia gum: processing conditions, role is theroleofAGP fractions onviscoelastic properties. of AGP, concentrated solutions can be characterized as soft colloidal gels or polymeric gels and what seemingly dominated by the viscous clarify the component. situation. At We high concentrations, do gum solution not display and viscoelastic know may properties be to whether AGP-induced aggregation. highly Performing rheo-SAXS experiments will help and to time dependent flow of diluted senegal Acacia gum is probably due to surface effects Rheological properties: unusual flow behaviour and viscoelastic properties: shear-thinning variability in gumfunctionality. concentration (1-2%) of AGP-based aggregates is mostly unavoidable and participates to the stability of gum solutions depending on environmental conditions. The formation of a small electrostatic and hydrophobic interactions. Building phase diagrams should allow predicting Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT
45 Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). 6. Literature stabilized microcapsules foraroma protection. nano/microparticles. This should open a lot of new applications as major texturing agents bottleneck and is to enzymes compatible with crosslink an industrial use then to optimize grafting gum processes. Finally, one molecules by or to graft carboxylate groups to increase the gum charge density. It remains to find efficient enzymes to form one 100% can imagine to graft lipids or oligopeptides to gum improve amphipathic properties of gums the most promising, is to graft onto the gum specific molecules or chemical groups. Then carboxylate groups removing methyl groups appears interesting. The second way, probably questioned. In particular, the activities possibility could to be found increase but the the enzymatic cocktails are actually available and must be screened. Enzymes questions with more specific concentration of of their availability charged and impaired by the hyperbranched characteristic of costs gums. Fortunately, a number of enzymes or should be surface properties. The use of glycosidases may be a solution, however their efficiency properties. is A major bottleneck is then to decrease the gum viscosity while maintaining high industry. However, protein-rich fractions are Acacia gums degraded, and to which significantly impairs decrease their their of viscosity, proteases which surface or/and is glycosidases. Proteases of have particular demonstrated use their in explored. ability The first one to concerns hydrolysis of gums. degrade This can be achieved either by the use Enzymes can potentially expand the modification possibilities of gums. Two ways should be to purify AGP, iii) to assemble them with proteins, iv) to graft lipids by chemical reaction. only way to propose new ingredients based on Acacia gums is i) to enrich them with AGP, ii) properties of Acacia gums clearly represents the best future way of innovation. Actually, the Enzymatic modification of Acacia gum: the possibility to modify the structure and functional conditions and heatingin largevolumesneedto beconsidered. Acacia gum-protein nano/microparticles at the be efficient at industrial the lab scale. scale. An important challenge Issues is the formation about expensive and way. Another stabilization way is of mixing protein denaturation by heating, which has been proven to to stabilize Acacia gum-protein microparticles has been reported, chemical treatments imply this either the use of enzymes or physical treatments. is Using enzymes a possible but assemblies are obtained through weak interactions, cross-linking stabilization without Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT
46 Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). Anderson, D. M.W.,&Stoddart, J.F. (1966). Studies on UronicAcid Materials. PartXV. Theuseof Anderson, D. M.W.,&Rahman,S. (1967). Studies on uronic acid materials. 20.Theviscosity Anderson, D. M.W.,Douglas, D. M.B.,Morrison,&W.P.(1990). N.A., Wang, Specifications forgum- Anderson, D. M.W.,&Dea, I.C. M.(1971).advancesin Recent thechemistryofAcaciagums. Journal Anderson, D. M.W.,Bridgeman, E.,Earquhar,J. G.K.,&Mcnab,C. G.A.(1983). Thechemical Anderson, D. M.W.(1978). Chemotaxonomic aspects ofthechemistryAcaciagum exudates. Kew Anderson, D.I. M.,Dea, C.Karamall.Ka,&Smith, J.F. (1968).Studies on uronic acid materials.24. L. Amy, (1934). Contribution dela àl'étudedespropriétéset structuresolutions desgeléesde et Shanbedi,Amiri, A., M.,Eshghi, H.,Heris, S. Z., &Baniadam, M.(2012). Highly Dispersed Multiwalled Ali, B. H.,Ziada,A.,&Blunden, G. (2009).Biological of effectsofreview somerecent gum arabic: A J.M.,Bergenstahl, B., &Nilsson, J.,Penarrieta, L.Alftren, (2012).Comparison of molecular and Al-Muhtaseb, A.H.,McMinn,T.R.sorption W.A.M.,&Magee, (2004).Water isotherms ofstarch C.,H.,& Al-Assaf, S.,Sakata,M.,McKenna, Aoki, Phillips, G.O. (2009).Molecular associations in Al-Assaf, S.,Phillips, G. O.,&Williams, P. A. (2005).Studies on acaciathe exudategums. Part I: Al-Assaf, S.,Phillips, T.G. O.,Sasaki,Y.,(2003). &Katayama, Modified gum Arabic. In (Vol. Al-Assaf, S.,Phillips, G. O.,Aoki,H.,&Sasaki,Y. (2007).Characterization and properties of Acacia Al-Assaf, S.,Andres-Brull,J.,&Phillips, M.,Cirre, G.O. (2012).Structural changesfollowing industrial Y.,Eda,S.,Akiyama, &Kato, K.(1984).Gumarabic isakind of arabinogalactan protein. Agricultural Adamson, A.W.,&Gast,P.(1997).Physical-Chemistry ofSurfaces(6thed.):John & Wiley sons, L., Jasniewski,J.,Gaiani,Aberkane, C.,Hussain, R.,Scher,J., &Sanchez,C. (2012).Structuration Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: , 104-114. 2, Research, Molecular-sieve Chromatography on Acaciasenegal gum (Gum Arabic). Carbohydrate molecular weight relationship for Acaciagums. Carbohydrate4 , 298-303. Research, Additives and Contaminants, 7(3),303-321. arabic (Acacia-Senegal) -Analytical data forsamplesand collectedbetween1904 1989.Food of Society of Cosmetic 61-76. Chemistry, 22, (L) Willd). International TreeCrops245-254. , Journal, 2 characterization ofthetestarticleused in toxicological studies of gumarabic(Acaciasenegal Bulletin, 32,529-536. 6(1),97-103. Research, An analytical study of differentformsof gum fromAcaciaSenegalWilld. Carbohydrate gomme., Université de Paris. of theThermophysical Properties.Journal ofPhysical Chemistry C,116 (5), 3369-3375. Carbon Nanotubeswith Decorated AgNanoparticlesinand Water Experimental Investigation Foodresearch. and Chemical Toxicology, 47 (1), 1-8. fractionation. Food Hydrocolloids, 26(1),54-62. emulsifying properties of gumarabic and mesquite gumusing asymmetrical flowfield-flow Engineering, (3),297-307. 61 mathematicalpowders -1: description Part ofexperimentaldata. Journal of Food acacia gums. Structural (2), 325-336. Chemistry, 20 molecular weightofAcaciasenegalgumexudate. Food Hydrocolloids, 19(4), 647-660. 20030407). JP20030103495 21(3), 319-328. produce ahydrogelformand convert poorinto agood emulsifier. Food Hydrocolloids, 1-ControlledPart maturation of Acaciasenegalvar.toincreaseviscoelasticity, senegal (L.) Willd. var.senegalwith enhanced properties (Acacia(sen)SUPERGUM(TM)): Cambridge: RSC Publishing. processing ofAcaciagums. InG. O. P.A. W. J.F. Kennedy (Ed.), GumArabic(pp. 153-168). and Biological Chemistry, 48(1),235-237. USA. Hydrocolloids, 29(1),9-20. mechanism of beta-lactoglobulin -acaciagumassemblies inof presence quercetin.Food 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT
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48 Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). Chikamai, W. B. N.,&Banks, (1993).Gum-arabic fromAcacia-Senegal (L) Willd in Kenya. Food Chevalier, A.(1924).Sur laproduction arabiquede la gomme enAfrique Occidentale.de Revue Charoen, R.,Jangchud,Harnsilawat, A., K., T.,Naivikul,D.O., &McClements, J. (2011). E. D.Charoen, R.,Jangchud,Harnsilawat, A.,&McClements, J. A., K., T.,Decker, (2012). Chandler, R.C.of (1941). Nature bound in water colloidal systems.PlantPhysiology, 273-291. 16, Chanamai, R.,&McClements,D.J. (2002).Comparison of gum arabic, modified starch,and whey Cecil, C. O. (2005). Gumarabic. Saudi AramcoWorld,56(2),36-39. Castellani, O.,Guibert,D., Al-Assaf, S.,Axelos,M.,Phillips, G.O., & Anton,M. (2010). Hydrocolloids Castellani, O.,Gaillard, C., Vie,V.,Al-Assaf,S.,M.,Phillips, Axelos, G. O.,&Anton, M. (2010). Castellani, O.,Al-Assaf,S., Axelos,M.,Phillips, G.O.,& Anton, M.(2010). Hydrocolloids with Castel, V.,Rubiolo, A.C.R.C., &Carrara, (2017).Droplet sizedistribution, rheological behavior and Cassini, A.L. S.,Marczak, D.C.F., &Norena, P.Z.adsorption (2006).Water isotherms of texturized Capataz-Tafur, J.,Trejo-Tapia, G.,Rodriguez-Monroy,M.,&Sepulveda-Jimenez, G.(2011). Caius, J.F., &Radha,K.S. (1942). Thegumarabic of thebazaarsand shops ofBombay. Journal of Cadden, A. M.(1988). Moisturesorption characteristicsoffood several fibers. Journal ofFood Butstraen, C., &Salaün, F. (2014). Preparationofmicrocapsules bycomplexcoacervation of gum D.Burgess, J.,&Singh, O. N.(1993).Spontaneous formation ofsmall-sized albumin Acaciacoacervate Bungenberg deJong,H.G. (1949b). Morphology In ofcoacervates. H.R.(Ed.), Kruyt Colloid Science Bungenberg deJong,H.G. (1949a). Crystallisation-coacervation-flocculation. InH. R. K. (Ed.) (Ed.), Buffo, R.A.,Reineccius,G.&Oehlert, W.(2001).Factors affectingtheemulsifying and Buffo, emulsions R.A.,&Reineccius,G. A.(2000).Beverage and theutilization ofgumacacia as T.Briggs, R.,&Schmidt, H. F. (1915).Experimentson emulsions. II. Emulsions andof water benzene. Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: Hydrocolloids, 7(6),521-534. Botanique Appliquée&d'AgricultureColoniale, 4,256-263. E165-E172. Emulsions: Protein,GumArabic, and Whey Modified Starch. Journal of Food 76(1), Science, Influence ofBiopolymer Emulsifier Typeon Formation and Stability of RiceBranOil-in-Water by biopolymer emulsifiers. Food Chemistry,131(4),1340-1346. Influence ofinterfacial composition on oxidative stability ofoil-in-water emulsions stabilized (1),120-125. Science, 67 protein isolate asemulsifiers: Influenceof pH,CaCl(2) andJournal temperature. of Food (TM)) Acaciasenegal.Food Hydrocolloids, (2-3),193-199. 24 conventional (Acaciasenegal(L.) Willd. var.senegal)and matured(Acacia(sen) SUPERGUM with emulsifying capacity.1-Emulsifying Part propertiesand interfacial characteristics of surface.air-water Food Hydrocolloids, 131-141. 24(2-3), Hydrocolloids withemulsifying capacity.3-AdsorptionPart and structural propertiesatthe Food Hydrocolloids, 24(2-3),121-130. emulsifying capacity.2-Adsorption Part propertiesatthen-hexadecane-Waterinterface. gum arabic. Food Hydrocolloids, 170-177. , 63 stability ofcorn oil emulsions stabilized byanovel hydrocolloid (Breagum)comparedwith soy protein. Journal of Food Engineering,77(1),194-199. vulgaris L. Plant Cell Tissue andOrgan Culture,106(1),169-177. Arabinogalactan proteins areinvolved in cell aggregationof suspension cultures ofBeta Bombay NaturalHistory Science,41,261-271. (4),1150-1155. Science, 53 Arabic and chitosan. Carbohydrate608-616. polymers,99, particles. Journal ofPharmacy andPharmacology, 45(7), 586-591. (Vol. ElsevierPublishing II, pp. 433-480).Amsterdam: Company. Colloid (Vol.Science pp.ElsevierPublishingII, 232-258).Amsterdam: Company. rheological properties of gumacaciainemulsions. beverage Food Hydrocolloids, 15(1),53-66. emulsifier/stabilizer. &Flavorist, ,24-44. Perfumer 25 Journal ofPhysical Chemistry,19, 478-499. 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT
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61 Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). indicates thecomposition of the mixture. Scale5m(unpublishedbar: data). with concentrations of 45% ethanol and 20 g.L the biphasic (II) region. Inset: Micrographs of Acacia senegal gum-ethanol-water Vis spectroscopy. The solubility system curve appears in red and delineates the monophasic (I) from cloud point method (pH 5 citrate buffer, 25°C). Appearance of turbidity was checked by UV- Figure 4: Phase diagram of Acacia senegal gum-ethanol-water system determined by the dot lines (Gaïaal.,areexponentialet 1981) fits of data(unpublished data). 30°C) and ionic strengths. Solid line (this paper), dashed lines (Gooycoolea et al., 1995) and geographical origins. Measurements corresponded to different pH (4-8), temperature (20- Rao (1999), Sanchez et al. (2002) and Li et Briggs (1941), al. Schleif et al. (1951), Williams et al. (1990), Goycoolea et 2009. al. (1995), Mothe and Gum samples were from different gum dispersions. Data were taken from Taft and Malm (1931), Riddell and Davies (1931), Figure 3: Effect of concentration on the relative newtonian viscosity (/ buildingassembly fromtheelementary blocks 1 and2(adapted fromRenardetal., 2014). attached to it. The self-similarity approach was then used to build the AGP macromolecular the overall symmetry, or self-ordering, of carbohydrate moieties and arabinoside oligomers consideration the quasi-palindromic nature of polypeptide backbones and as a consequence covalent interactions. The elementary of building the assembly blocks of 6 were building blocks 1 constructed and 8 linear taking arrangement building of five blocks building blocks 2 1. into (right) Three-dimensional by model of covalent AGP made and/or non- (AGP) macromolecular assembly from Acacia Senegal gum. Building block 2 was built by a Figure 2: (left) Elementary building blocks 1 and 2 used to build arabinogalactan-protein analysed (unpublishedseyal gumswere data). seyal (B) gums. 202 spray-dried and 100 raw A. senegal gums, 28 spray-dried and 6 raw A. Figure 1: R Figure captions Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: h conformation plots of spray-dried (black) and raw (red) Acacia senegal(A) and 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT
-1 gum. The arrow in the phase diagram 0 ) of Acacia senegal Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). Figure 1 offiguresList Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). Figure 2 Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). Figure 3 Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT Version postprint Sanchez, C.,Nigen,M., MejiaTamayo, V.,Doco,T., Williams,P., Amine, C.,Renard, D.(2018). Figure 4 Acacia gum: Historyof thefuture.Food Hydrocolloids, 78,140-160. ,DOI: 10.1016/j.foodhyd.2017.04.008 Comment citer cedocument: ACCEPTED MANUSCRIPT