A Cross-Flow Ultrasound-Assisted Extraction of Curcuminoids from Curcuma Longa L.: Process Design to Avoid Degradation

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A Cross-Flow Ultrasound-Assisted Extraction of Curcuminoids from Curcuma Longa L.: Process Design to Avoid Degradation foods Article A Cross-Flow Ultrasound-Assisted Extraction of Curcuminoids from Curcuma longa L.: Process Design to Avoid Degradation Arianna Binello 1 , Giorgio Grillo 1 , Alessandro Barge 1 , Pietro Allegrini 2, Daniele Ciceri 2 and Giancarlo Cravotto 1,* 1 Dipartimento di Scienza e Tecnologia del Farmaco, University of Turin, Via P. Giuria 9, 10125 Turin, Italy; [email protected] (A.B.); [email protected] (G.G.); [email protected] (A.B.) 2 INDENA S.pA., Viale Ortles, 12, 20139 Milan, Italy; [email protected] (P.A.); [email protected] (D.C.) * Correspondence: [email protected]; Tel.: +39-011-6707183; Fax: +39-011-6707162 Received: 9 May 2020; Accepted: 2 June 2020; Published: 4 June 2020 Abstract: Rhizomes of Curcuma longa L. are well known for their content of curcuminoids, which are compounds with interesting biological activity against various inflammatory states and diseases. Curcuminoids can degrade during processing. This piece of work investigates fast, efficient and cost-effective metabolite recovery from turmeric under ultrasound-assisted extraction (UAE). An analytical evaluation of curcuminoid stability under sonication in different solvents is reported for the first time. HPLC and quantitative 1H-NMR were used. Under the applied conditions, EtOAc was found to be the optimal extraction medium, rather than EtOH, due to its lower radical generation, which facilitates better curcuminoid stability. Kinetic characterization, by means of the Peleg equation, was applied for single-step UAE on two different rhizome granulometries. Over a time of 90 min, maximum extraction yields were 25.63% and 47.56% for 6 and 2 mm matrix powders, respectively. However, it was observed that the largest portion of curcuminoid recovery was achieved in the first 30 min. Model outcomes were used as the basis for the design of a suitable multi-step cross-flow approach that supports and emphasizes the disruptive role of cavitation. The maximum curcuminoid yield was achieved over three steps (92.10%) and four steps (80.04%), for lower and higher granulometries, respectively. Finally, the central role of the solvent was further confirmed by turmeric oleoresin purification. The EtOAc extract was purified via crystallization, and a 95% pure curcuminoid product was isolated without any chromatographic procedure. No suitable crystallization was observed for the EtOH extract. Keywords: Curcuma longa L.; curcuminoid stability; multi-step extraction; ultrasound-assisted extraction; extraction kinetic 1. Introduction In recent years, non-synthetic and biologically active compounds from vegetal sources have gained increasing interest because of their important role in health-care systems worldwide; pigments have found use as additives or supplements in food, pharmaceutical and cosmetic industries. One of the most widely studied sources of natural pigment plants is Curcuma longa L., a perennial rhizomatous shrub belonging to the Zingiberaceae family. Also known as turmeric, this plant is commonly used as a coloring and flavoring agent in the food industry and, in particular, it is known as the ‘golden spice of life’, and constitutes the main component of curry [1]. However, it is also appreciated in traditional medicine for its biological properties, which are mainly related to its curcuminoids; chemical Foods 2020, 9, 743; doi:10.3390/foods9060743 www.mdpi.com/journal/foods Foods 2020, 9, 743 2 of 19 components that include curcumin (CUR), demethoxycurcumin (DMC) and bisdemethoxycurcumin Foods 2020, 9, x FOR PEER REVIEW 2 of 20 (BDMC) (Figure1)[2]. Figure 1. Chemical structures of curcuminoids: (a) curcumin (CUR), (b) demethoxycurcumin (DMC), (cFigure) bisdemethoxycurcumin 1. Chemical structures (BDMC). of curcuminoids: (a) curcumin (CUR), (b) demethoxycurcumin (DMC), (c) bisdemethoxycurcumin (BDMC). Although these substances can be chemically synthesized, is worth noting that the Joint FAO/WHO ExpertAlthough Committee these on Foodsubstances Additives can (JECFA) be chemically specifications synthesized, only allow is curcuminoidsworth noting extractedthat the fromJoint naturalFAO/WHO source Expert material Committee to be used on as Food food Additives additives [(JECFA)3]. specifications only allow curcuminoids extractedTurmeric from has natural curcuminoid source material contents to ofbe 2–9%used as depending food additives on its [3]. growing conditions and origin. The mainTurmeric biological has curcuminoid activities exhibited contents byof these2–9% depending compounds on are its antioxidant,growing conditions anti-inflammatory, and origin. antibacterial,The main biological antiviral, activities antifungal, exhibited anticancer, by immune-stimulatorythese compounds are and antioxidant, neuroprotective anti-inflammatory, [4–7]. antibacterial,The most antiviral, common antifungal, techniques anticancer to obtain curcuminoids, immune-stimulatory from turmeric and neuroprotective involve solvent [4–7]. extraction followedThe most by column common chromatography. techniques to obtain However, curcuminoids the choice from of turmeric the solvent involve and solvent the conditions extraction appliedfollowed must by column take into chromatography. account the safety However, of the finalthe choice use to of which the solvent these and compounds the conditions are intended, applied formust example, take into their account acceptability the safety in the of foodthe fina industry.l use to Soxhlet, which ultrasonic-assistedthese compounds extractionare intended, (UAE) for andexample, microwave-assisted their acceptability extraction in the (MAE)food industry. are currently Soxhlet, the mostultrasonic-assisted commonly used extraction methods, (UAE) although and othermicrowave-assisted techniques, such extraction as pulsed-ultrasonic (MAE) are andcurrentl supercritical-fluidy the most commonly extraction, used are alsomethods, reported although to be eotherfficient techniques, processes [such8–10 ].as Itpulsed-ultrasonic is worth noting that and UAE superc is nowritical-fluid widely extraction, used in vegetal-matrix are also reported extraction to be thanksefficient to processes its efficiency, [8–10]. which It is wo allowsrth noting it to: (1)that enhance UAE is now extraction widely yields used in and vegetal-matrix rates; (2) make extraction use of alternativethanks to its solvents; efficiency, (3) reducewhich allows costs and it to: required (1) enhance extraction extraction times; yields and (4)and preserve rates; (2) heat-sensitive make use of compounds.alternative solvents; Several cavitation (3) reduce devices costs and are available,required extraction including bath,times; probe and and(4) preserve flow systems, heat-sensitive and can providecompounds. huge Several process-type cavitation flexibility, devices such are as availabl scalability,e, including and the usebath, of counter-currentprobe and flow orsystems, co-current and systemscan provide [11]. huge In particular, process-type the co-current flexibility, cross-flow such as scalability, approach and is a relativelythe use of simple counter-current sequential-step or co- protocolcurrent thatsystems is used [11]. in solid In /particular,liquid extraction the co-current for different cross-flow purposes, suchapproach as decontamination, is a relatively leaching simple andsequential-step food washing. protocol Essentially, that theis used solid in to besolid/l extractediquid isextraction mixed with for freshdifferent solvent, purposes, then recovered such as anddecontamination, drained. The extractedleaching and solid food then washing. meets fresh Essentially, solvent the and solid is recovered to be extracted and drained is mixed again. with fresh The highersolvent, the then number recovered of steps, and the drained. more the The matrix extract approachesed solid then depletion meets [fresh12]. solvent and is recovered and Adrained great dealagain. of The metabolite-extraction higher the number research of steps, has the investigated more the matrix this mechanism,approaches anddepletion it has [12]. been describedA great using deal Fick’s of metabolite-extraction second law of diffusion research [13,14 has]. However,investigated a deeper this mechanism, modeling and of the it has kinetics been underlyingdescribed using the solid–liquid Fick’s second extraction law of diffusion processes [1 is3,14]. not However, common ina literature;deeper modeling mathematical of the kinetics assets, suchunderlying as useful the engineering solid–liquid tools, extraction are needed processes to cast is lightnot common on method in applicabilityliterature; mathematical and optimization. assets, Desorptionsuch as useful processes, engineering on the tools, other are hand, needed are to commonly cast light on interpreted method applic by mathematicalability and optimization. descriptors inDesorption literature, processes, and Peleg’s on Modelthe other is onehand, of are the commonly best known interpreted [15]. The commonby mathematical principles descriptors shared by in dehydrationliterature, and/rehydration Peleg’s Model phenomena is one and of metabolite the best known extraction [15]. allow The the common ability of principles this model shared to render by UAEdehydration/rehydration kinetics to be investigated phenomena [16,17]. and metabolite extraction allow the ability of this model to renderAn UAE equation kinetics that to describes be investigated the time-dependent [16,17]. trend of a system can ensure the understanding necessaryAn equation to define that the fastestdescribes
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