915 ) 1 − † 280 g kg ∼ ducts in this article is solely for the tional Foods Research Unit, National al Center for Agricultural Utilization rch,USDA,ARS,1815NUniversityStreet, on and does not imply recommendation however, food applications of ), with only a small amount of 1 − and is in the public domain in the USA 11,12 700 g kg ∼ ) bran and corn Correspondence to: George E Inglett, Func CenterforAgriculturalUtilizationResea Peoria, IL 61604, USA. E-mail: [email protected] Mention of trade names or commercial pro purpose of providing specific informati or endorsement by the US Department of Agriculture. Functional Foods Research Unit,Research, Nation USDA, ARS, 1815 N University Street, Peoria, IL 61604, USA Traditional uses for these co-products of corn processing largely ∗ † lts in a number of low-value co-products. Two of the major ommercialization of processes for the isolation or production include animal feed,Therefore which research is does constantly under notthese way products. command to expand Lucrative a the applicationsprovide use high of of much price. these needed economic productsrevenue relief would for and farmers would bydecreasing increasing benefit fuel and manufacturers food costs. andthe Much of consumers utilization the of by research concerning cornconversion bran to and fuel corn ethanol; fiber has centered on its and hemicellulose ( COMPOSITION OF CORNFIBER BRANThe AND chemical composition of corn CORN branTable and 1. corn fiber Clearly, is the shown majority in dietary of fiber, both which corn is bran nearlydietary completely and fiber in insoluble. corn corn The fiber bran insoluble is is composed of cellulose ( these co-products may alsothis review provide the added composition value.discussed of and Therefore then corn current in and bran prospective and researchthe surrounding corn utilization fiber of will cornfood be fiber components will and be addressed. corn bran in the production of e production of food ingredients or additives, including corn rn fiber contain potentially useful components that may be e utilization of corn fiber and corn bran in the production of ides and ferulic acid. Components of corn bran and corn fiber may t 6 tof 10 6 Of the , while 1 × 10 − 2,3 total corn and Sean X. Liu × Zea mays 1 0 ∗ − . tofcornfiber 6 and the kernels 10 1 − 4 × 43 . Corn bran, however, currently 6 In comparison, 68 t of corn was wet-milled, while 1 6 Thus about 2 10 4 The profitable products of wet-milling × 7 6 t of rice were produced in 2008. . : 915–924 www.soci.org This article is a US Government work 6 90 10 t of corn bran were produced. × ) is a major crop in the USA, with 329 6 2010; Both corn bran and corn fiber are mainly composed 24 The major purpose of dry-milling is to recover the 10 . 7 maize; co-products; corn fiber gum; vanillin; ferulic acid; xylo-oligosaccharides t was dry-milled. ) to separate its component parts: endosperm, germ In 2008, 25 × 1 5,6 6 −

10 9,10 Zea mays 341 . 8 ×

Corn bran is produced in yields of about 60–70 g kg The processing of corn for food use requires one of two milling 24 . wheat and 9 endosperm fraction for use asthe corn germ may grits, be meals harvested for and oil. flours, while corn fiber is produced in yields of about 80–110 g kg and bran. and 0 techniques: dry-milling or wet-milling.the Corn traditional dry-milling milling of involves clean, tempered200 grain g (moisture kg content of the pericarp (bran); however,material corn fiber from also the containsbran. cell endosperm, wall which is not contained in corn J Sci Food Agric

INTRODUCTION Corn ( fiber in the production of food components co-products produced by this operationfocuses are corn on bran current and cornpotentially and fiber, prospective higher-value which currently research food have low surrounding components. commercial th Corn value. This bran review and co Abstract The milling of corn for the production of food constituents resu Devin J Rose, George E Inglett (www.interscience.wiley.com) DOI 10.1002/jsfa.3915 Utilisation of corn ( harvested through physical, chemical or enzymatic means for th Review Received: 20 July 2009 Revised: 11 December 2009 Accepted: 17 December 2009 Published online in Wiley Interscience: 9 March 2010 Keywords: fiber oil, corn fiber gum, cellulosic fiberalso gels, xylo-oligosacchar be converted to food chemicalsof such food as products vanillin from and corn xylitol. bran C improves or corn the fiber production has of been these met components withPublished from numerous 2010 corn technical by bran challenges, John or therefore Wiley further corn & research fiber Sons, that is Ltd. needed. are softened to facilitategluten, separation fiber of and the germ. components: starch, has low valuecombination and with corn germ is cake or often mealpressed (germ after or used oil has extracted). been for Wet-milling of animalthe corn grain feed involves first in alone steeping moisture water or content and in increases sulfur to about dioxide. 450 During g kg this process the total domestic corn use,went 52% to was devoted ethanol to productionallocated animal for (fuel the feed, production and 37% of food beverage) products. and 11% was kernel. produced domestically in 2008. 5 are the starch (endosperm) andCo-products oil of (germ) wet-milling from include thesteeping solids, corn corn which kernel. fiber, are sometimes corn combinedgluten gluten and feed. sold and as corn 32 44 and layer have 31 30 40 m) and µ and then : 915–924 Therefore 90 37 36 . Unfortunately, found that corn 1 2010; − 33 Because corn bran . substituted corn bran 48,49 et al flour showed decreases 40 34 demonstrated that bran 1 . − 39 . et al and enzyme treatment and decreases loaf volume, J Sci Food Agric et al 38,39 Xylanase addition to bread dough gave the lowest breaking strength, 41–43 1 − flour in muffins resulted in significant indicating that extrusion did not change 39 In cookies, medium (212–425 1 − 35 m). 41,45–47 38 µ and Ozturk . Holguin-Acuna m) particle sizes gave better spread ratios, color 1 µ 38 − . 212 -xylanases (xylanases; EC 3.2.1.8) in bread making. hypothesized that the poor performance of corn β < withtheaimofincreasing thedietaryfibercontentof et al 35 32 flour showed a 20% reduction in loaf volume, . 4)- 1 − → et al -(1 In attempts to utilize other cereal brans, treatments such as Enzyme treatment may also affect the quality of baked goods In more recent experiments, Mendonca De Kock Artz decreases in flavor, mouthfeel,compared texture with muffins containing and the same overall level of acceptability wheat bran. in most sensory scores, including texture, color and flavor, careful control of particle size the baking properties of corn bran in this application. incorporated the extruded corn branpanelists into cookies. Unfortunately, were abletriangle tests to comparing control correctly cookiesextruded with corn cookies identify bran but containing were the not ablesample to in odd correctly triangle identify tests comparing the cookies sample odd containing extrudedunextruded or in corn bran, bransignificantlydecreasedtheradialexpansionratio,appearance and general acceptability of extruded snacks containingat corn bran 150–320 g kg particle size affects qualityIn bread, when smaller added particle sizes tolarger decreased bread loaf particle volume and sizes. more cookies. than they extruded corn bran using a twin-screw extruder for oat flour in an extrudedbran breakfast cereal. at They 300 found that and corn 400 g kg with added cereal brans.endo The best example of this is the use of During bread making,increases the presence water of absorption insoluble arabinoxylans and tested these two cereals in a sensorythe panel. Panelists cereal preferred that contained corn bran at 300 g kg ISOLATION ANDNENTS UTILISATION OF CORN BRAN OF ANDCorn CORN bran and FIBER corn fiber COMPO- contain potentially valuable components, including oil, phytosterol esters, dietary fiber and phenolic thus diminishing breadpositive quality. impact on Soluble breaddough arabinoxylans quality viscosity, owing have to air a theirvolume entrapment contribution and and to texture. the improvement of loaf andmuffins bran in baked goods could be improved by extrusion. cakes containing corn bran at 300 g kg shown some promise; therefore theseor treatments corn with fiber corn may also bran be beneficial,applicable. although perhaps not directly widelyconsumedfoods.Unfortunately,thisresultedinundesirable changes in200 product g kg quality: bread containing corn bran at can convert a portionoligosaccharides and of improve the loaf volume. insoluble arabinoxylans to soluble corn bran at 250 g kg the authors did not comparecontaining no this corn sample bran. with a control product and corn fiber contain substantial levels of arabinoxylansadding (Table 1), xylanase to breadmay improve fortified its loaf with volume corn andextend sensory bran to attributes. other This or may products also such corn as fiber cookies. coarse (425–850 and overall sensory scores compared with cookies madeparticle with sizes finer ( 31 25,26 18 18 22,23 16,17 16,17 21 21 12,16 12,16 12,16 21 17 16,17 cakes 21 22 NR NR 2 30 16 16 6–20 30–40 78 www.soci.org DJ Rose, GE Inglett, SX Liu ND–3 ND–8.4 100–130 150–200 526–735 526–732 113–117 176–213 300–372 1.02–18.5 17.2–36.8 0.61–1.28 35.9 This article is a US Government work 3) to the main and is in the public domain in the USA -arabinofuranosyl L → - elegantly described α 29 13,19,20 19,20 13,14 13,14 13,15 13–15 13,14 18 14,18 13–15 13–15 13–15 15,24 13,14 14,15 19,20 13 15 13,14 0.2 2) or (1 50–115 → 128–178 182–248 eported in polysaccharide form. Because of its complex structure, )ofcornbranandcornfiber while corn bran contains two times 1 − b 18 13,27,28 -glucuronic acid or oligosaccharide side D The importance of these compounds will be ). The hemicellulosic fraction is composed of 1 23 − c 6.25. d × Composition (g kg 4)-xylopyranosyl backbone and 10 g kg Side units of a → ∼ -Coumaric acid 3–4 p MannoseGalactoseGlucose Uronic acidsLignin 44–51 3 39–42 7–10 Arabinose Xylose 217–243 14 Diferulic acid 6.8–32 Soluble fiberInsoluble fiber 706–863 2–26 Ferulate phytosterol esters Ferulic acid 28–31 -(1 Indentation indicates that this component is a component of the non-starch glucose. Nitrogen Neutral sugars and uronic acids r The remainder of corn bran and corn fiber comprises residual β Constituent Corn bran Corn fiber above constituent but is still reported asbran a or proportion corn of fiber the entire product. corn c d ND, not detected; NR,a not reported. b Total phenolics 55 Total dietary fiber 732–860 StarchOilAsh 40–112 13.2–19 6–10 Protein Table 1. this hemicellulosic fraction may be referred tobecause the as structure a is mainly heteroxylan composed or, of xylosyl and arabinosyl units, an arabinoxylan. Saulnier and Thibault more ferulic acid. a the interactions between thesecomponents heteroxylans and within other corn cell pericarp:the wall the spaces heteroxylan between fractioncrosslinked the fills with cellulosic each microfibrils, otherdi- and which and other triferulate are bridges, cell then solidifying wallrendering the components the cell heteroxylan via wall’s insoluble. structure and starch, lipid, protein, ash,phytochemicals phenolic (Table compounds 1). and Subtlethese other components differences are trace apparent. in Most notably, the cornmore fiber amounts than contains twice as of much ferulate phytosterolrecovered esters, which in can be corn fiber oil, discussed further in later sections. residues as side units linked (1 chain. www.interscience.wiley.com/jsfa UTILISATION OF WHOLE CORN BRAN AND CORN FIBER Research on the utilizationproducts began with of the addition corn-milling of corn bran co-products to breads, in food Some of themoiety arabinofuranosyl esterified side to units O-5. contain a ferulic acid lignin ( chains containing galactose, xylose and arabinose also occur.

916 917 10 therefore Therefore 57 59 showed that 62 . et al and Yadav The molecular weights of the two 24 . www.interscience.wiley.com/jsfa 59,60 the latter being more efficient. et al isolated corn fiber gum from corn bran 58 61 59,60 . of available heteroxylan) and the cellulose-rich 1 et al − Delignification occurs optimally at pH 11.5; 57 showed that these CFGs were better emulsifiers than gum 380 g kg < 59 . As stated previously, corn fiber includes cellular material from Perhaps the most substantial difference between the corn fiber Recently, Carvajal-Millan Few differences in chemical composition and physical proper- Another approach to producing a lighter-colored corn fiber the whole grain,pericarp while and corn does branendosperm. not Thus is include differences composed the inmay mainly cell structure occur or wall of physical between material the milling properties corn from co-products, fiber the depending gumsthe on isolated endosperm whether from have heteroxylans different thesepericarp. from Yadav characteristics two than those in the subtle differences in heteroxylanendosperm branching and pericarp may heteroxylans, exist althoughferences these between are minor certainly dif- not as variedgrains as such for as heteroxylans wheat. from other gums isolated from theseand two co-products CFG-2 was from that cornthan both fiber CFG-1 the same were products significantlyet al isolated better from emulsifiers corn bran. In fact, Yadav hydrogen peroxide can be added to the alkali during extraction arabic in orange oil emulsions.protein They content attributed of this to the thesuggests samples higher that originating from proteins corn mayheteroxylans fiber. be in the This more endosperm than intimately in associated the pericarp. with or the solubilized corn fiberperoxide gum after extraction, may be treated with hydrogen some ferulic acid remains esterified to solubilized corn fiber gum ties between these four fractions (CFG-1 and CFG-2and from corn corn fiber) were bran evident. and corn fiber using thedirect same extraction comparison. procedure, They allowing for boiledsodium each hydroxide starting and materialwas calcium in then hydroxide. treated dilute with Theand hydrogen soluble peroxide the and corn extract partially fiberThey acidified gum termed was this recovered isolate by CFG-1.extraction ethanol The residue precipitation. was left after further dilutehydrogen alkali peroxide extracted treatment to with obtain CFG-2. a more severe alkaline gum has been to usethe colored hydrogen lignin peroxide. compounds to This soluble converts organicremoved. acids much that can of be residue remaining after cornunusable. fiber Higher gum yields extraction with was greatercorn hard fiber purity and gum were was obtained extracted with when the potassium extract hydroxide was and treated then with calcium hydroxide. low ( CFG-1s were 290 000 and 334 000 Da whenand isolated corn from fiber corn respectively, bran while the molecular weightsCFG-2s of were the 491 two 000 and 452 000 Daisolated respectively. Corn from fiber gums both sourcesand showed CFG-2 from low corn viscosities,CFG-2 bran with from being corn CFG-1 slightly fiber. lower TheCFG-2 isolated than arabinose/xylose from CFG-1 ratios corn of and branfiber CFG-1 were and 0.70 0.55 and and 0.60 0.67 andoriginating respectively. from from This corn the suggests endosperm are that slightlythose heteroxylans more from branched the than pericarp owingtios to in the heteroxylans higher from arabinose/xylose corn ra- fiberheteroxylans) compared (which with contained corn bran endosperm (which did notdosperm contain en- heteroxylans). This was furtherheteroxylan fraction substantiated was when isolated from the coarse corn fiberwithout (corn the fiber endosperm fraction), which gave arabinose/xylosetios ra- of 0.60 and 0.64 for CFG-1 and CFG-2 respectively. 1 − These 56 and is in the public domain in the USA (Table 1). Usually, Calcium hydroxide 1 − A substantial portion 10 28 Unfortunately, yields were 54 17 of available heteroxylan were used response surface experi- however, the native structure The product thus obtained has 1 14 50 . − 10,14 26 et al The first stage involves treatment with a : 915–924 This article is a US Government work 90 51,52 53 2010; found that potassium hydroxide and ammonium C. ◦ 17 Brownies prepared with Z-Trim containing 40% less fat C. Using saturated calcium hydroxide, maximum yields 55 ◦ A myriad of treatment conditions have been used to solubilize One example of Z-Trim’s success was reported by Warner and Cellulosic fiber gel from corn bran has found commercial suc- Hespell Applications of corn co-products www.soci.org hydroxide produced dark extracts, probablypounds due to produced colored at com- theThis high phenomenon was temperatures also shown with used sodium hydroxide. for extraction. base to completely disintegrate the cell wall structureThe of corn bran. solids are thenperoxide recovered to and produce treated a colorless againcorn product. with Cellulosic bran hydrogen fiber exhibits gel high from gel-like hydration structure. capacity, high viscosity and a may be disrupted incellulosic a fiber gel. two-stage high-shear process to yield a of this heteroxylan mayor be corn removed bran by with treatmentby alkali acidification of or to corn pH alkaline fiber 4.0–4.5 hydrogenA) (to peroxide and remove followed ethanol insoluble hemicellulose precipitation. similar to those with19 h potassium at 97 hydroxide were obtained after dark-colored heteroxylan products wouldowing to likely their be influence undesirable on product color. corn fiber gum. Chanliaud Inglett. cess. Marketed under the tradefat name mimetic Z-Trim, or flour it substitute is andments, promoted is dairy as used foods a in and baked processed goods,Furthermore, meats condi- (http://www.ztrim.com). Z-Trim is findinghelp applications meet the in strict school nutritional guidelines lunches outlinedSchool to in Lunch the Program National set forth by theof Food the and US Nutrition Department Service of Agriculture. J Sci Food Agric at 100 Cellulosic fiber gel Corn bran contains about 200 g cellulose kg antioxidants. Therefore some researchers have explored the useprocessing of technologies to harvest theseon components. the Research extraction,components production will be and discussed separately. utilization of each of these been termed corn fiber gum. mental design in twotype experiments and studying concentration, the time, effects temperatureon corn and of fiber liquid/solid alkali gum ratio yields. Whenimum using yields potassium hydroxide, of max- about 870 g kg Corn fiber gum As mentioned, the dietarycorn fiber fiber is fraction composed in largelyowing both of to heteroxylan, corn its which di- bran is and and insoluble triferulate crosslinks. than control brownies and 50% flour replacementby were evaluated trained panelists.significantly The different from Z-Trim thechocolate control brownies brownies flavor, were with sweetness, respect ratedflavor. to bitter In as addition, flavor, the not Z-Trim stalenessfor brownies and rated moistness, significantly cereal higher densitycharacteristics in and a fudge-like cohesiveness, brownie. which are desirable obtained with alkali concentrations between 1.2 and 1.5 mol L produced a corn fiber gumcolor that and was dissolved free easily of in impurities, water. lighter in cellulose exhibits undesirable characteristics in foodsdesirable and has functional few properties; C C, 97 In 82 At ◦ ◦ 88 84 98–100 of total 1 : 915–924 − 83 90 Unfortunately, 72 2010; ), but it contained a more 1 of xylan occurred at 210 − Notably, corn bran contains 1 − 66 J Sci Food Agric Under these conditions, about XOSfromcornbranorcornfiber 85 89 fungi resulted in a 2.0–2.5-fold increase and, despite the antimicrobial effects of ferulic Cfor2min. In preliminary animal studies, XOS have been In the large bowel of rats, microbial esterases ◦ 87 94 although this has not been shown in all cases. 90–92 Aspergillus Thus XOS with bound ferulic acid from corn bran Prebiotics are indigestible oligosaccharides that of arabinoxylan was released into solution in the form 96 80,81 86 When corn fiber was used as a starting material, a This has potential implications for the prevention of 1 − in vitro do not appear to inhibit the growth of probiotic bacteria 95 84,85 C, xylan yield was lower (200 g kg 93 ◦ Short-chain XOS from other agricultural products are potential Twostudieshavereportedtheuseof autohydrolysistosolubilize Autohydrolytic treatment has the advantage over enzymatic In addition to prebiotic activity, XOS may contain antioxidant of oligo- and polysaccharides.by These a monosaccharide liquors contamination were of accompanied about 100 g kg acid, maximum solubilization of 300 g kg prebiotics. neutral sugar residuessuggest in that the cornproduction starting of XOS bran material. by autohydrolysis These owing may to higher studies be yields. a better candidate for the have the potential to exhibit higher antioxidant activityisolated than from those other agricultural products. Corn fiber oil Most corn oil for human consumption comes from the germ; 3.2.1.55) from in the releasecleaves of xylan. the A esterunits feruloyl linkages on esterase between heteroxylans, (EC ferulic mayof 3.1.1.73), acid also the which increase and xylanase enzymatic arabinosyl accessibility towardmore the XOS, heteroxylan fraction, thus releasing in pure culture. more ferulic acidvegetables. than many common cereal brans, fruits and a portion offiber. the heteroxylan fraction from corn bran or corn inflammatory diseases and cancer. are able tolocal release antioxidant the or ferulic maytissues. be acid absorbed moiety, and where transported it to other acts as a shown to stimulate the growth of bifidobacteriaoligosaccharides, more than the fructo- most common and studied prebiotics. however, in recentowing years, to corn its fiber ability oil to lower has cholesterol received in attention animal studies. treatment in that it does notenzymes require that the can contribute use substantially of to harsh cost. chemicals or While more XOSenzymes, may their structures and be consequently their releasedantioxidant prebiotic and/or properties with may change the substantially. addition of these 500 g kg autohydrolysate liquors containmust a be variety removed. of These contaminantsby contaminants activated that are charcoal, ultrafiltration, commonly ion exchange, removed etc. selectively stimulatebifidobacteria the and growth lactobacilli)healthy of persons. in beneficial the gastrointestinal bacteria tract (e.g. of for 10 min or 200 desirable range of molecular weights. Using corn branmaterial, as a starting maximum solubilization of xylan occurred at 180 activity. Depending onfrom production cereal brans may parameters, retain esterified XOS ferulicsolubilized acid produced moieties oligosaccharides. on These the XOS exhibitactivity high antioxidant exhibit similar structures to these prebiotic XOS,confer and prebiotic this properties. may also a study with agedSuntory men Ltd, using Osaka, a Japan), commercial concentrationsincreased of XOS after bifidobacteria 3 (Xylooligo were weeks 95P, on XOS. 180 but a substantial amount of monosaccharides was produced. B. 76 63 at in situ and prone Trichoderma 71,72 www.soci.org DJ Rose, GE Inglett, SX Liu This article is a US Government work 67,68 and is in the public domain in the USA and bound phenolics 64 and gel formation, 78 were the most active 60 Xylanases from families C) to partially hydrolyze ◦ 76 Bacillus subtilis, Aspergillus T. virde although family 10 is more able and Second, ferulic acid has received 77 However, previous researchers have Enzymatic treatment proceeds by 63 showed that arabinofuranosidases (EC 73,74 71,72 79 . of available heteroxylan may be released 1 such as emulsification were the most active on insoluble substrates, − et al A. aculeatus 70 Therefore new xylanases that are more specific for their activities on soluble and insoluble xylan 23 screened xylanases from A. niger 75 . 69 a region chronically under oxidative attack and and provide radical-scavenging activity in this region of the et al 66 65 Some researchers have shown that the enzymatic production Fewstudiesexistontheuseofcornbranorcornfiberas Corn fiber gum has not enjoyed the commercial success that One of the most important factors to consider in the enzymatic aculeatus, Aspergillus niger, Trichoderma viride heteroxylan polymers and yield soluble hydrolysates. from the starting materialon with processing conditions. xylanase treatments, depending shown that corn bran orsubstrate corn fiber for heteroxylan enzymatic is degradation a comparedas more with wheat difficult others bran. such considerable attention owing toferulic its acid bound antioxidant to properties, solubleimportant and corn bran for gum may deliveringfor be disease beneficial particularly prevention. antioxidants Indeed,absorbed while to in free the the phenolics upper are gastrointestinal colon tract, rapidly of XOS caninstance, de be Vries increased by adding accessory enzymes. For starting material for theon enzymatic the production of production XOS. ofthat Research XOS 250–450 from other g kg cereal brans has revealed has been afforded cellulosic fiberthis gel product (discussed has several above). promising Because characteristicsof similar exudate to gums, those to disease. to hydrolyze highly branched arabinoxylans. utilizing microbial xylanases, while high-temperatureemploys processing hydronium ions and organic acids generated www.interscience.wiley.com/jsfa For the production of XOS, family 11 mayto be lower more desirable production owing of xylose, Xylo-oligosaccharides Xylo-oligosaccharides (XOS)soluble are xylan fragments partially thatcorn may fiber hydrolyzed, and be other obtained water- agriculturaltemperature from products treatment. corn by enzymatic bran, or high- as described above,applications more of this research polysaccharidecommercialization aimed gum as may at the eventually market broadening leadcould base explore the its widens. to use in New expanded snacks, applications bakedspecialty goods, beverages, foods, edible coatings, supplements and the like. after alkali treatment. This is an importantFirst, finding in for the two reasons. presence offiber hydrogen peroxide gum and that peroxidase, contains corn crosslinking, ferulic which can acid substantially can affectand its form physical gels potential properties via applications. oxidative for corn heteroxylan are needed. production ofselectivity XOS of the from xylanase.xylanases Direct with agricultural high enzymatic substrate hydrolysis productsMoers selectivity requires toward is insoluble xylan. substrate can be released by microbial esterases in the lowertract gastrointestinal colon, 10 and 11 are active on heteroxylans such as those in corn bran. subtilis while those from on soluble xylan. Xylanasesfamilies are based on also their catalytic classified activity. into a number of substrates. They found that the enzyme preparations from longibrachiatum high processing temperatures (160–220

918 919 1 13 − 121 115 . . thus other et al et al sodium 116,118,119 1 27,28 120 corn bran − 1 Tilay − Cfor1h,the ◦ 14 Feruloyl esterases C for 2 h, while only whereas corn bran of esterified ferulic ◦ suggests the former 1 13 I-1472. However, when . − Types A and D are able to . Interestingly, rice bran 107,111 116–118 et al 107 116 Unfortunately, ferulic acid in A. niger 96 www.interscience.wiley.com/jsfa ferulic acid (Table 1) and is the best of insoluble ferulic acid from corn were only able to release 30 g kg 1 ferulic acid, − 1 15 . − 1 − et al sodium hydroxide at 30 sodium hydroxide at room temperature for 1 1 − − C for 24 h led to a 1.3-fold increase in the level of ◦ found a maximum release of ferulic acid from corn 13 thus releasing ferulic acid into solution. In this case, . 13 et al Ferulic acid can also be liberated from corn bran by microbial Microbial feruloyl esterases alone are not sufficient to release Much of the research surrounding ferulic acid utilization from the corn bran was treated by autoclaving at 160 enzymes were able to release 903 g kg oil contains 10–20 g kg acid from theby fraction autoclave of treatment. corn Using bran that Novozym had 342, been Saulnier solubilized contains more than 30 g kg bran with 0.5 mol L ferulic acid recovered compared with the unoptimizedwhich procedure, was 2 mol L enzymes, namely feruloyl esterases. explanation. significant amounts of ferulic acid from corn bran; cleave ferulic acid dimers such ascorn those pericarp that form cell the walls, crosslinks while in allacid. classes Type are able A to shares releaseB ferulic sequence is similarity similar with tosequence lipases, carboxylic while esterase similarities type family with 1.respectively. chlorogenate Types C esterase and and D xylanase show corn bran is largely bound to cell wall components, ferulic acid fromhas natural been sources produced desirable. commerciallythe Indeed, in product ferulic Japan of acid by rice saponification bran of oil refining of insoluble, esterified ferulic acid from cornwith bran an when enzyme incubated preparation from solubilized only 300 g kg Feruloyl esterases have beenbased classified on into their types specificity A,similarities for with B, other aromatic enzyme C classes. substrates and and D sequence Saulnier used response surfaceof ferulic methodology acid to from corn maximize bran. They the found that release 4 mol L source of ferulic acidand among common other cereals, agricultural fruits, products. vegetables 24 h. The authors reported ferulic acid at 191.1 g kg treatments and cellconcert wall-degrading with feruloyl esterases enzymes if sufficient must yields areFor to be example, be realized. Bonnin used in ferulic acid andseparated corn by fiber precipitating gum the are corn co-solubilized fiber and gum can with be ethanol. catalyze the cleavage ofand the the arabinosyl ester moiety linkageenzymes on between arabinoxylans. are ferulic These produced acid extracellular when grown from on substrates a containing bound ferulic number acid. of bacteria and fungi under the optimized conditions. These levels aretypically much lower reported than for(Table corn 1). bran, Therefore but thesecorn comparable authors fiber to may instead unknowingly of corn corn haveold fiber bran, and used undergone or significant the storage-related corn oxidation.that The bran fact the may have optimized been those extraction reported previously conditions by are Saulnier so different from 30% of the corn bran gum fractionbran was co-solubilized. gum Thus, is if corn also desired,release a harsher the alkali heteroxylan treatment is fraction required in to higher yields. hydroxide at 21.6 corn bran has focusedprocess on similar its to release theabove), from corn production bran its may of be bound treated corn state.crosslinks, with fiber alkali In to gum cleave a the (discussed ferulate creating technological challenges for its isolation from corn bran. 114 The Corn 111 -casein, 102 κ 111 Ferulic acid -tocopherol. γ Because of its and is in the public domain in the USA 112 used fine grinding 109,110 Therefore, before this 105 In comparison with other 102 -glucosidase. They found treated corn fiber that had β 107 104 . As a supplement or drug, ferulic et al 113 m) were highest in ferulate phytosterol µ tested the effects of heat treatments in 96 : 915–924 This article is a US Government work 30 106 . < 90 explored the effects of adding different sulfates et al 2010; 103 . Ferulic acid also possesses antimicrobial activity against the most predominant being sitostanyl ferulate. et al 108 101 Commercially, ferulic acid can be synthesized by a condensation Ferulic acid may also be used in the production of vanillin, in Singh Acids or enzymes added to the corn fiber itself may affect oil Non-chemical treatments to increase oil yield of corn fiber -tocopherol (an antioxidant) in corn fiber oil. Applications of corn co-products www.soci.org spoilage and pathogenic micro-organisms. reaction of vanillin with malonic acid catalyzed by piperidine. edible films, as a crosslinking agent and as a supplement. been conventionally wet-milled withof sulfuric cellulase, acid amylase, or xylanase a and mixture use of ferulic acidwill as be discussed a in precursor a forbeen later shown section. to natural increase In tensile vanillin strength edible and films, production per centbreak ferulic elongation and at acid decrease water has vapor permeability and gas permeability in edible films created from soy protein isolate. Ferulic acid Ferulic acid is a phenolic antioxidant. They concluded that the decreases in phytosterols wereinsignificant practically and that theγ treatments were useful for increasing conventional, vacuum andnone microwave ovens. of They thethat found treatments the that substantially conventionaldecreased phytosterols impacted and and substantially increased oil vacuum yield oven but treatments slightly acid may theoretically bedisease, useful diabetes, some in cancers, hypertension, the atherosclerosis and treatmentinflammatory of diseases. Alzheimer’s J Sci Food Agric However, the cost of this procedure,the environmental concerns desire and for naturally derived food additives make isolation of This is most likelyesters, a result of high levels of ferulate phytosterol addition to milk has been shown to enhance heatby stability, possibly crosslinking nucleophilicthus amino preventing dissociation. acid residues on fiber contains three to sixcorn times bran more (Table of 1). Unfortunately, these the componentscompared amounts than are with still quite the low bran-derived levels oils of such similar as type rice compounds bran oil. in other product can obtain commercial application,oil ways yield to and increase phytosterol the content of the oil must be examined. antioxidant and antimicrobialpotential properties, for ferulic use in acid the food has industry as great a preservative. and air classification tothe finest fractionate particles ( corn fiber. They found that esters. Moreau naturally occurring antioxidants, including gallic acid,malvidin, caffeic acid, delphinidin, catechin, epicatechin, rutinferulic and acid quercetin, has been shownlipid to be the and most efficient proteinsystem. in inhibiting oxidation in a lecithin/liposome oxidation or acids to the steepof water during corn. the None wet-milling of of thesulfate two sulfates hybrids increased increased oil ferulate yield,tested, phytosterol but acetic ammonium ester and yield. hydrochloriceffective at Of acids increasing oil appeared the yield and to acids phytosterol content be of the the oil. most yield and composition. Singh that each of thesecontent treatments increased of the the oiland and corn removing phytosterol a fiber portion bycellulose, of hemicellulose). the up non-oil to components (e.g. sevenfold starch, by hydrolyzing have been investigated. Wu and Norton 1 A. − NRRL 131 : 915–924 ). even corn 1 The ferulic Pycnoporus 90 − Streptomyces 23 then converted N. spinosa 129,130 and thus must be 2010; enzymes released In these industries Owing to the desire 27,28 132 A.niger , which had been grown 128,129 of total ferulic acid as free 1 − J Sci Food Agric P. cinnabarinus C for 3 h and recovering the ◦ A. niger recently reported a possible non- used a three-step process to convert 137 For a natural claim, ferulic acid and other 137 131 . 136 ), tobacco and citrus fruits; et al Andrews) pods and occurs at 10–30 g kg Vanillin also occurs at lower concentrations in a , the molar yield increased to 43% when cellobiose Hence, owing to its high ferulic acid content, corn however, ferulic acid obtained in this manner cannot Today, synthetic vanillin is produced from guaiacol containing the soluble feruloylated oligosaccahrides 128 of total ferulic acid originally present in the corn 129 hypothesized that, under these conditions, some of 1 Between the 1930s and 1980s in the USA, most of − 13,115 133–135 ATCC 391 161. After 12 h, 43% of the ferulic acid had been 131 itself, rather than its enzymes, was used to release ferulic Pinus ponderosa 128 Lesage-Meessen In the food, pharmaceutical and cosmetic industries, vanillin is As mentioned, the ferulic acid in corn bran is covalently linked to Buranov and Mazza As discussed previously, enzyme extracts from Vanilla planifolia using petroleum as the carbon source. the synthetic vanillinhowever, was owing to produced environmental concerns, from this processabolished. has spent been sulfite liquors; ferulic acid fromautoclaving corn bran corn to bran vanillin. at The 140 first step involved be considered natural. an important flavor and aroma compound. potential food additives must be obtainedor by microbiological physical, means. enzymatic bran. Enzymes harvested from arabinosyl moieties as a glycosidic conjugate bran may playbiosynthesis a of vanillin. critical role in supplying ferulic acid for the ferulic acid from corn bran without pre-treatment. wide variety of other agriculturalpine ( products, including ponderosa Vanillin Vanillin is the major( flavor component in properly cured vanilla microbiological method ofthat converting would still ferulicconversion be acid considered of to natural. boundlow-polarity This vanillin ferulic involves water acid the extraction to direct extraction). (also vanillin In known this using process, asunder pressurized water subcritical sufficient at pressure high water temperature topassing was maintain through kept it a in columnMazza containing its the liquid sample. state Buranov while and whole bean. bran itself contains a small amount of vanillin (55 g kg the demandvanilla for beans; vanillin thereforeused. far synthetic (or outweighs artificial) its vanillin is production often from for natural vanillin productionresearchers with have less turned environmentalmaterial, to impact, which can ferulic be acidmeans. converted as to vanillin a by possible microbiological starting the ferulic acid was liberated from its bound state by cleavage acid thus obtained wassetonii then added to aconverted culture to of vanillin; however,and substantial other levels contaminants were of also vanillic produced. acid solubilized feruloylated300 g oligosaccharides, kg which represented liberated from its bound state. Alkalinethis hydrolysis task; can accomplish on sugar beet pulp, werecinnabarinus then added to aobtained from culture autoclaved corn of bran. The 185 were able to release 988 g kg the ferulic acid from itsfree carbohydrate ferulic moiety acid and tothe converted vanillic the vanillic acid; acid toniger vanillin with aacid molar and yield convert of itP. 22%. to cinnabarinus When vanillic acid, followedand by XAD-2 resin conversion were with also added to the culture medium. , 1 1 − 123 124 − Using 122 Candida 23 however, NRRL 185, 200 g kg of insoluble, www.soci.org DJ Rose, GE Inglett, SX Liu ∼ 1 125 11,12 This article is a US Government work esterified) and − and is in the public domain in the USA This costly and + 124 C for 1 min, 800 g kg ◦ This is because, in general, Neosartorya spinosa 15,121 were able to release 988 g kg 23 . et al To overcome the effects of inhibitors, Buhner and As with the conversion of pentose sugars to ethanol, treatedcornfiberhydrolysateswithactivatedcharcoal 126 126 127 . 124 C for 1 h or flash-explosion at 190 ◦ Xylose from acid hydrolysates must be purified prior to chemical Commercially, the majority of xylitol is produced by chemical hy- The above studies used a mixture of cell wall-degrading a crude enzyme preparation from however, Shin technically challenging step, asrelated well to as chemical environmental hydrogenation, concerns microbial has conversion sparked of interestto in xylose the the production to ofis xylitol ethanol. hydrolyzed in In using this a dilutethe case acid resulting process the or syrup similar starting enzyme is material treatment fermented and with then a yeast such as tropicalis Agblevor Table 1), which is comparable to that of hardwoods. hydrogenation, because the presence of otherthe materials impedes conversion and crystallization of xylose. drogenation of xylose, usually obtainedCorn from wood bran hydrolysates. and cornxylose harvest fiber owing offer to promising their starting high materials xylose content for ( enzymes in addition to pre-treatmentsto of facilitate the corn enzymatic bran attack. in order to remove these inhibitors.was They effective at found removing thatImproved inhibitors activated and processes charcoal increasing and xylitol yeastsxylitol yield. would for be important. the conversion of xylose to www.interscience.wiley.com/jsfa In the food industry, xylitol is usedsweetener as a with low-calorie, bulking non-cariogenic properties similarXylitol to is those not of used sucrose. thus by does plaque-causing not bacteria promote in dentalfoods the caries; owing mouth it to and is its alsoindex. slow useful absorption for and diabetic low impact on glycemic Most of thefiber research has focused on on bioconversion the production of of fuel corn ethanol; bran and corn BIOCONVERSION OF CORN BRANFIBER COMPONENTS AND CORN of insoluble ferulic acid was solubilized (free bran, and about one-third ofto the arabinose. ferulic Upon acid pre-treating remained the160 esterified corn bran by autoclaving at Novozyme 342 was then ableferulic to acid release as free about ferulic two-thirds acid. ofcombination When feruloyl that with esterases other are enzymes, used the in acid increased is the release result of of the ferulic production ofwhich short-chain are feruloylated XOS, soluble and more accessible to feruloyl esterases. yields of xylitolof inhibitors are such generally ashydrolysis. low furfural and because hydroxymethylfurfural of during the formation corn bran hasdegradation proven compared a with more others such difficult as substrate wheat for bran. enzymatic esterified ferulic acid aspre-treatment. free ferulic acid from corn bran without Xylitol Xylitol is a five-carbon polyalcohol that occurs widely in nature. components of thesechemicals co-products that may would beuse be converted of important to corn to other additive/chemical bran production the has numerous or potential food advantages corn industry.such fiber The as as aincreased reduced revenue starting for producers material environmental of corn for products. impact, food ‘natural’ label and

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Previous research has been devoted to direct addi- With the exception of cellulosic fiber gel (Z-Trim) produced from Applications of corn co-products www.soci.org food applications may increasereduce the agricultural value waste of and theseproducts. Two decrease mill of these streams, the major cost co-productsfiber. are of corn bran major and corn corn tion of these mill streams to food, tosterol esters, may help lower cholesterol, The authors suggest that yieldsprocessing conditions may and/or be adding improved ‘green’ by additives. optimizing corn bran, gels with properties similar to shortening in baked goods. acids, richly contained intives, as corn crosslinking bran, agents, maynatural as be vanillin supplements or used production. as as precursors preserva- to co-product can be fractionated to yield corn fiber gum withcosity low vis- and excellent emulsifying properties the corn bran starting material contained 25.1 g ferulic acid kg heteroxylan fraction can betial partially prebiotics hydrolyzed to yield poten- flow rate of 5 mL min J Sci Food Agric REFERENCES CONCLUSIONS Wet-milling and dry-millingproducts of that corn are resultlow-value in commodities. currently a sold variety as of animal co- feeds and other corn bran) was obtained using water at 220 of its aliphatic doubleproducing bond vanillin. rather The than highest the vanillin ester production linkage, (1.68 g thus kg has not been realized owing to thein numerous challenges involved working withresearch these may co-products. include Importantbeyond areas the extrusion of following: forco-products future (1) increasing improved in functionality foods; techniques and of (2) ways maximize these to the whole for increase phytosterol the corn solubilization content; or fiber (3)corn partial improved bran oil hydrolysis methods or of yield corn thecost-effective fiber heteroxlyans to ways in yield of cornother liberating fiber gum and phenolic or purifying acids; XOS;hydrolysis ferulic (4) (5) more of improved acid heteroxylans for and methods conversionchemicals; for to (6) xylitol identification the or of other complete moreorganisms food productive that strains are of micro- capablebran to of potentially useful converting food products. components of corn ingredients. of eachponents co-product to recover potentially useful com- these componentscals. to other commercially important chemi- Mol JAgric :46–52 Process Progress xylanase 26 : 915–924 J Biotechnol :1239–1243 :1139–1150 90 Anal Biochem 41 30 Cellulosa :175–180 (2007). :408–411 (1998). 2010; 84 Mol Nutr Food Res 75 Trends Food Sci Technol :2942–2951 (1997). 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