Extraction Of Chlorogenic Acid Research Articles

Caffeine, chlorogenic acid, and catechin extraction from coffee cherry waste using green solvent as natural deep eutectic solvent

Caffeine, chlorogenic acid, and catechin extraction from coffee cherry waste using green solvent as natural deep eutectic solvent

Green synthesis of water-compatible molecularly imprinted resin on graphene oxide for highly selective extraction of chlorogenic acid in aqueous systems

A green one-pot synthetic strategy was proposed to design a water-compatible surface molecularly imprinted composite with specific selectivity and high adsorption capability for selective extraction of chlorogenic acid from aqueous systems.

Computational simulation-assisted design and experimental verification of molecularly imprinted polymers for selective extraction of chlorogenic acid

Chlorogenic acid (CGA) is an active ingredient in honeysuckle with a broad-spectrum of antibacterial activity, suppressing tumor growth and other pharmacological effects. However, it is susceptible to damage during traditional extraction and separation processes. Therefore, developing selective and efficient extraction methods of CGA is essential. Based on computational molecular simulations, a reliable and efficient molecularly imprinted polymers (MIPs) were successfully developed for selective extraction of CGA. MIPs and non-molecularly imprinted polymers (NIPs) were synthesized using a precipitation polymerization method, employing three different functional monomers: [methacrylic acid (MAA), 4-vinylpyridine (4-VP), and methyl methacrylate (MMA)], with CGA serving as the template molecule. To simulate the polymers and predict the optimal ratio between the template and functional monomer, the computational studies and adsorption performance experiments were carried out. The adsorption characteristics and thermal stability of polymers were evaluated by isothermal adsorption, adsorption kinetics, selective adsorption and thermogravimetric analysis, aiming to obtain the MIPs with specific recognition and selectivity for CGA. When the molar ratio of template CGA to functional monomer 4-VP was 1:8, the prepared MIPs was found to have the maximum adsorption capacity (14.85 mg g−1) and the highest imprinting factor (1.74) at the CGA concentration of 100 mg L−1. These results were consistent with those obtained by computational molecular simulation. This study not only provides good guidance for developing separation materials for extracting CGA from natural plants but also inspires the application of computer simulation and molecular docking techniques in the preparation of specific MIPs materials.

NADES-Assisted Extraction of Polyphenols from Coriander Seeds: A Systematic Optimization Study.

Coriandrum sativum L. seeds are widely recognized for their traditional use in medicine. Among the most investigated components, the terpenoid linalool and monounsaturated petroselinic acid have attracted interest for their nutritional value. Instead, minor attention was paid to the polyphenolic fraction, resulting still being incomplete today. This study aimed to develop a systematic approach in which green natural deep eutectic solvents (NADES) were combined with conventional (maceration, MAC) or non-conventional (ultrasound-assisted extraction, UAE) techniques in a one-step methodology to recover polyphenols from coriander seeds. The NADES system choline chloride-citric acid (ChCl:CA, 1:1) was firstly evaluated, coupled with MAC or UAE, and then compared with ChCl-Urea (ChCl:Ur, 1:1) and ChCl-Glucose (ChCl:Glu, 1:1) under optimal conditions (20 min extraction time). The system ChCl:Ur UAE significantly improved the extraction of chlorogenic acid and its isomer (453.90 ± 4.77 and 537.42 ± 1.27 µg/g, respectively), while the system ChCl:Glu UAE improved the extraction of protocatechuic, caffeic and p-coumaric acids (131.13 ± 6.16, 269.03 ± 4.15 and 57.36 ± 0.06 µg/g, respectively). The highest levels of rutin were obtained with ChCl:CA-based NADES when the MAC technique was applied (820.31 ± 28.59 µg/g). These findings indicate that the NADES composition could be appropriately modulated to tailor extraction towards higher levels of a desirable bioactive for further applications.

Exploring the potential of Ilex paraguariensis coproduct: High concentration of chlorogenic acids and enhanced thermal stability

Five tons, per hectare, of thick stems of Ilex paraguariensis are generated each harvest the external part of these (IPC) has a high concentration of chlorogenic acids but is not yet commercially exploited. Thus, it is hypothesized that the coproduct of I. paraguariensis when submitted to optimized extraction conditions will result in extracts rich in chlorogenic acids. Furthermore, optimized encapsulation by anti-solvent precipitation with zein ensures improved thermal stability. Multivariate strategies were successfully employed to obtain extraction of 10.16 g chlorogenic acids per 100 g IPC in 75 % ethanol. The mixture of IPC extract (15 mL) and zein (1.36 g) dripped (18.14 mL h−1) on the water under stirring (4 rpm) results in encapsulated with 94 % efficiency and thermal stability of up to 357.5 C. We show that it is possible to optimize the extraction of chlorogenic acids and encapsulate them in a fast and efficient way for easy industrial expansion. The high amount of chlorogenic acids and the thermal resistance of the encapsulates indicate that applications in foods exposed to heat are highly promising for the valorization of this natural resource not commercially exploited, in line with the concepts of the circular economy.

Solid-liquid extraction of chlorogenic acid from Eucommia ulmoides Oliver leaves: Kinetic and mass transfer studies

Chlorogenic acid is an important natural active compound in Eucommia ulmoides Oliver leaves. A second-order kinetic model was considered applicable for the solid-liquid extraction process and revealed the positive effects of reducing the particle size, increasing the liquid-solid ratio and temperature on accelerating the extraction rate and increasing the equilibrium yield. An empirical model on the studied variables was developed to predict the extraction process and its feasibility was verified. The activation energy was 19.67 kJ mol−1. The mass transfer process was investigated based on Fick’s second law, where the extraction rate depends on the internal diffusion of the compound and the internal resistance was the main factor affecting the extraction process. Temperature and liquid-solid ratio significantly changed the effective diffusion coefficient and mass transfer coefficient in different ways, and the Biot number was related to the liquid-solid ratio. Overall, these findings provided fundamental datas and theoretical guidances for the extraction of chlorogenic acid.

An integrated process by ultrasonic enhancement in the deep eutectic solvents system for extraction and separation of chlorogenic acid from Eucommia ulmoides leaves

This study established an integrated process for the extraction and enrichment of chlorogenic acid(CGA)from Eucommia ulmoides leaves in a deep eutectic solvent system via ultrasonic wave-enhanced adsorption and desorption practices utilizing macroporous resins. Although deep eutectic solvents (DESs) have the advantages of chemical stability, good dissolving capacity, and nonvolatilization, routine solvent recovery operations are not suitable for subsequent separation in this solvent system. Based on the above characteristics, this study integrated the extraction and enrichment processes, in which DESs extracts directly loaded onto the macroporous adsorption resin, avoiding the loss of target components in solvent recovery and redissolution processes. The screening results of solvents and resin types further showed that choline chloride-malic acid (1:1) was the optimal DES, and the NKA-II resin had high adsorption and elution performance for CGA. The viscosities of the DESs were much higher than those of water and conventional organic solvents; thus, the mass transfer resistance was large, which could also affect the adsorption behaviour of the macroporous resin. The thermal and mechanical effects of ultrasound could effectively enhance the efficiency of the mass transfer, adsorption, and desorption in the DES systems. When compared to no sonication treatment, the CGA adsorption at various ultrasonic powers (120–600 W) was examined. At optimal ethanol concentration (60%), the effect of the ultrasonic treatment on the recovery of the DESs (water eluting process) and the desorption capability of CGA were confirmed. The use of three volumes of water elution could recover the DESs without loss of CGA. The adsorption process significantly differed depending on the ultrasonic settings, and the absorption balance time and experimental adsorption capacity at equilibrium were enhanced. Additionally, the adsorption procedure of the NKA-II macroporous resin for CGA under ultrasonic treatment could be clarified by the pseudo second order kinetic equation and the Freundlich isotherm model. Thermodynamic and dynamic parameters indicated that physical adsorption was the main process of the entire procedure, and it was a spontaneous, exothermic, and entropy-reducing physical adsorption process. This study potentially indicates that the use of ultrasonication, as a high-efficiency, environmentally friendly method, can enhance the features of the macroporous resin to better purify target chemicals from a DES extract.

Preparation and application of caffeic acid imprinted polymer.

In the present study, molecularly imprinted polymers were synthesized using caffeic acid (CA) as a template molecule and then used for the extraction of CA and chlorogenic acid (CLA) from complex matrices. Syntheses were carried out in tetrahydrofuran as porogenic solvent using 4-vinyl pyridine, methacrylic acid, acrylamide, and 1-vinyl imidazole as monomers, ethylene glycol dimethacrylate as crosslinker and 2,2'-azobisisobutyronitrile as initiator. In polymerization processes, different ratios of the template:monomer:crosslinker (T:M:CrL) were used to obtain the most suitable polymer. Caffeic acid:4-vinylpiridine:ethylene glycol dimethacrylate's 1:4:16 mole ratio of MIP was determined as the most convenient polymer for CA recognition. In addition, nonimprinted polymers (NIPs) without templates were prepared. Dynamic and static adsorption tests were applied to determine the absorption features of the NIPs and CA-MIPs. Separation and purification studies of CA and CLA were performed with molecular imprinted solid phase extraction (MISPE) application. All steps of MISPE (loading, washing, elution) were optimized by HPLC analysis.

Study of the chlorogenic acid extraction with choline chloride‐based deep eutectic solvents and its non‐covalent interactions analysis

AbstractThe microwave‐assisted extraction of the main phenolic component of green coffee beans, chlorogenic acid (CGA), was carried out employing deep eutectic solvents based on choline chloride and five different hydrogen bond donors (HBD) in a 1:2 ratio. The best performance for the extraction process of CGA was reached by the mixtures of choline chloride/ethylene glycol and choline chloride/urea. To understand the various interactions between the phenolic compound and the two most efficient deep eutectic solvents, computational calculations were carried out at the density functional theory (DFT) level, as well as Atoms in Molecules (AIM) and Non‐Covalent Interactions (NCIs) analyses. In that way, a variety of hydrogen bond types were found in every structure. Nevertheless, the CGA does not disrupt the hydrogen bond network established between ChCl and the HBD. Among the strongest interactions are those hydrogen bonds between the quinic acid moiety and the ethylene glycol or the urea. In addition, the thermochemistry of the formation of the two main deep eutectic solvents and their corresponding complexes with CGA was calculated, where the formation of urea‐based structures was slightly more effective by ~3 kcal/mol.

Yerba Mate (Ilex paraguariensis) Processing and Extraction: Retention of Bioactive Compounds.

Ilex paraguariensis is a native tree from South America known for the presence of bioactive compounds, and its processed leaves are consumed as hot and cold infusions. After harvest (step 1), the leaves are subjected to flame blanching to inactive the enzymes (step 2), followed by drying and milling (step 3). The impacts of I. paraguariensis processing on leaf composition were investigated by extracting the major compounds (chlorogenic and isochlorogenic acids (3-CQA, 4-CQA, 5-CQA, 3,4-DQA, 3,5-DQA and 4,5-DQA), p-coumaric acid, caffeine and rutin) using different ratios of ethanol and water as extraction solvent (EW 25:75, 50:50, and 75:25 (w/w)). The solvent ratio of EW 50:50 was more effective in extracting the chlorogenic acids isomers, with retention of chlorogenic acids of 3463, 9485, and 9516µg mL- 1 for steps 1, 2, and 3, respectively. Rutin and p-coumaric acid exhibited similar behavior with the increment of processing steps; however, p-coumaric acid was only detected in steps 2 and 3 for the solvent ratios EW 50:50 and 25:50. The caffeine extraction from I. paraguariensis varied from 936 to 1170µg mL- 1 for all processing steps, with emphasis on its concentration extracted in step 1. The evolution of processing steps led to a higher retention of phenolic compounds from I. paraguariensis, which was not observed when using different solvent ratios, and the solvent ratio EW 50:50 was more effective for the extraction of chlorogenic acids. The successful extraction of chlorogenic acids from I. paraguariensis in this study proved to be a promising alternative for the use of yerba mate beyond the cuia cup.

Cleavage of macromolecule (protein/polysaccharide)-phenolic bond in soybean cell wall through Lactobacillus casei and Lactobacillus helviticus mixed culture solid-state fermentation for chlorogenic acid extraction

Out of the available dietary sources use for chlorogenic acid extraction, soybean is new and cheap that could offer cost-effective chlorogenic acid production under solid-state fermentation (SSF). Consequently, the study aimed at investigating the cleavage of protein/carbohydrate-phenolic bond in heilong48 soybean (HS) variety via solid-state fermentation by Lactobacillus casei and Lactobacillus helviticus mixed culture for chlorogenic acid extraction with high yield and increased biological activity. A simplistic two-pot bioproduct optimization approach was used; first, screening (Plackett-Burman design) of SSF conditions and second, optimizing (Box-Behnken design) the significant SSF conditions obtained from the former design. The liquid-solid (liquid:solid) ratio of 32:68 (0.47), incubation time of 48 h, pH of 5, and temperature of 50 °C were the best-optimized SSF conditions obtained from the chronological combinatory screening and optimization methods. These conditions gave a satisfactory SSF model, and correspondingly acceptable chlorogenic acid yield (9.20 ± 0.17 mg/g), fermentation efficiency (37.26 ± 0.73%), and 2,2-diphenyl-1-picrylhydrazyl free radical-scavenging activity (DPPH) (65.21 ± 2.05 μmol AA eq/g dry sample) results. The L. casei and L. helviticus mixed culture fermented heilong48 soybean (MCFHS) sample (under optimized SSF conditions) had high (p < 0.05) chlorogenic acid yield and 2,2-diphenyl-1-picrylhydrazyl free radical-scavenging activity than the raw heilong48 soybean flour (RHSF) sample. The effectiveness of the optimized solid-state fermentation conditions on the structural modifications of heilong48 soybean sample was confirmed by scanning electron microscopy, atomic force microscopy, and Fourier transform infrared results.

Green solvents for the selective extraction of bioactive compounds from by-products of the coffee production chain

Approximately 15–20 million tonnes of by-products were generated globally in the coffee production chain during the 2020/21 season. The current uses for these by-products are inadequate or contribute to environmental degradation. This work reports the screening of hydrophilic and hydrophobic solvents, including deep eutectic solvents (DES), for their ability to extract the valuable metabolites caffeine and chlorogenic acid (markers in commercial extraction) from four coffee-related by-products. Water was the best solvent for recovering caffeine and chlorogenic acid from defective green coffee beans, while all hydrophilic DES surpassed water in the extraction of chlorogenic acid from coffee pulp. For the two remaining by-products, at least one DES was as good or better at extracting the caffeine or chlorogenic acid compared to water. The array of hydrophobic solvents tested here showed different selectivities, allowing the annotation of 12 compounds that have not been previously reported in coffee by-products. These results demonstrate the ability to obtain a new and controllable range of extracts from coffee by-products using green and functional solvents.

Optimization of Ultrasound-Assisted Extraction of Chlorogenic Acid from Potato Sprout Waste and Enhancement of the In Vitro Total Antioxidant Capacity.

Potato sprouts, an underutilized by-product of potato processing, could be exploited for the recovery of caffeoyl-quinic acids (CQAs), a family of polyphenols with well-recognized biological activities. In this work, the predominant compound of this class, 5-CQA, was extracted by Ultrasound-Assisted Extraction (UAE) under conditions optimized by an Experimental Design. The investigated variables solid/solvent ratio (1:10-1:50 g/mL), water content in ethanol (30-100% v/v) and UAE time (5-20 min) highlighted a critical influence of the last two factors on the extraction efficiency: extracts richer in 5-CQA were obtained with lower water content (30%) and time (5 min). The addition of ascorbic acid (1.7 mM) as anti-browning agent to the extraction solvent improved the extraction efficiency of 5-CQA compared to acetic and citric acids (3158.71 μg/mL, 1766.71 μg/mL, 1468.20 μg/mL, respectively). A parallel trend for the three acids and an increase in 5-CQA recovery was obtained with the use of freeze-dried sprouts (4980.05 μg/mL, 4795.62, 4211.25 μg/mL, respectively). Total antioxidant capacity (TAC) in vitro demonstrated UAE being a more valuable technique than conventional maceration. Furthermore, three-times-higher values of TPC (7.89 mg GAE/g) and TAC (FRAP: 24.01 mg TE/g; DPPH: 26.20 mg TE/g; ABTS 26.72 mg TE/g) were measured for the optimized extract compared to the initial one. An HPLC-DAD method was applied to monitor 5-CQA recovery, while an LC-HRMS/MS investigation allowed us to perform analyte identity confirmation along with detection of the glycoalkaloids α-solanine and α-chaconine. This evidence underlines the necessity to develop purification strategies in order to maximize the potential of potato sprout waste as a source of 5-CQA.

A green and novel strategy based on CO2 -responsive surfactant-functionalized multi- walled carbon nanotubes with microwave- ultrasound assistant to improve extraction and enrichment of phytochemicals from plant waste

In this study, a noval method was developed based on CO2 -responsive surfactant-functionalized multi-walled carbon nanotubes with microwave -ultrasound assistance extraction (CRS-MWN-MUAE) for obtain value-added compounds from plant waste. The single-factor experiments were applied to obtain the best experiment conditions: ultrasound power of 600 W, ultrasound time of 25 min, microwave time of 20 min, microwave power of 500 W, solid-to-liquid ratio of 20 mg/mL, and multi-walled carbon nanotubes (MWN) concentration of 4 g/L. The representative flavonoid and stilbene from pigeon pea leaves were orientin and cajaninstilbenes acid (CSA). The representative triterpenoid from cili fruits was roxburic acid. The representative flavonoid from cili leaves was quercetin. The representative anthocyanin from blackcurrant fruits was cyanidin 3-O-glucoside (C3G). The representative organic acid from blackcurrant leaves was chlorogenic acid. The orientin, CSA, roxburic acid, quercetin, C3G, chlorogenic acid extraction yields were: 4.42 mg/g, 9.43 mg/g, 1.56 mg/g, 0.15 mg/g, 2.24 mg/g, and 1.07 mg/g. Under these conditions, the solvent system possessed higher efficiencies from various plant wastes compared with other extraction method. The contents of target compounds have increased 1.1–20 folds. Meanwhile, the green surfactants could be recycled and achieved no significant loss in six operation cycles. Moreover, density functional theory and molecular dynamics simulation investigated the surfactant could be well compatible with target compounds because of the weak interactions among moleculars. Thus, the method was a green, efficient, novel, and ecofriendly extraction method for extracting and enriching high value-added compounds from cili, pigeon pea, and blackcurrant wastes.

Application of Chlorogenic acid as a substitute for antibiotics in Multidrug-resistant Escherichia coli-induced mastitis.

Mastitis affects animal welfare and causes economic losses in the dairy industry. It is caused mainly by bacterial pathogens, among which Escherichia coli (E. coli) is one of the prominent causative agents. To treat bovine mastitis, antibiotics were widely used. However, their extensive and uncontrolled use has led to the emergence of multi-antibiotic-resistant strains. Indeed, a superbug of E. coli was successfully isolated from a mastitis-suffering cow and found resistant to at least 10 antibiotics. Therefore, the development of a universal therapeutic agent used as a replacement for the antibiotic is an immediate need in the dairy industry. To do so, we examined whether chlorogenic acid (CGA), a natural and herbal extract, could be a perfect alternative in mastitis treatment. In this study, we observed that the combination of CGA and antibiotic had an additive or synergistic effect; CGA fought against the superbug by directly targeting bacterial cell wall and membrane; CGA can significantly alleviate the mastitis caused by the superbug E. coli via its antimicrobial, antioxidant and anti-inflammatory activities. Collectively, these data indicated that CGA had a true potential to replace antibiotics during mastitis treatment.

Natural deep eutectic solvent extraction of chlorogenic acid from Eucommia leaves: high extractability, stability, antibacterial, and antioxidant activity

Chlorogenic acid (CGA) is a natural compound with potent antioxidant and antibacterial properties that can be extracted from Eucommia leaves (EL).

Optimization of Glycerol Extraction of Chlorogenic Acid from Honeysuckle by Response Surface Methodology

Using honeysuckle as raw material, chlorogenic acid (CGA) was extracted with different alcohols. Based on the single-factor experiment design, the relationship between each parameter and the response value was explored by Box–Behnken method to optimize the process conditions. Best extraction results were obtained under the conditions of solid-to-liquid ratio of 1:20, the ultrasonic time of 40 min, the ultrasonic vibrator power of 240 w, and the CGA extraction rate of 2.98%. The experimental data show that the extraction rate of CGA is related to the length of the alcohol carbon chain and the number of hydroxyl groups in the extractant. The results from this work can provide technical basis for the safe and efficient production of CGA from honeysuckle.

Antibacterial Activity of Bioactive Compounds of Green Coffee Beans on Periodontogenic and Nosocomial Bacteria

The emergence of antimicrobial resistance and the side effects of synthetic drugs have raised an interest in searching for new antimicrobial compounds. The present study aims to evaluate in vitro antibacterial activity of green coffee and its active compounds (chlorogenic acid extract and caffeine extract) against some periodontogenic and nosocomial bacteria. The bioactive compounds, viz. chlorogenic acid and caffeine, were extracted through soxhlet extraction using methanol and water, respectively, and HPLC UV quantified these compounds. The study reported 3 CQA, 4 CQA, and 5 CQA as the significant chlorogenic acids in green coffee beans. Aqueous extract of green coffee beans (AGCB), which is dominant in caffeine, has been found to be the least effective against both periodontal and nosocomial bacteria. The result of our study revealed that the methanol extract of green coffee bean (MGCB), rich in chlorogenic acid, exhibits the highest inhibitory activity against periodontogenic bacteria, followed by the ethanol extract of green coffee bean (EGCB) and AGCB extract. EGCB extract was significantly effective against Staphylococcus epidermidis among selected nosocomial pathogens. AGCB extract was least effective against all bacteria. The results highlight that green coffee polyphenols, especially chlorogenic acid, could be used as antimicrobial agents in different biotechnological applications. The antibacterial property of green coffee highlights its potential as a naturally active antibacterial compound.

Valorization of Raw Coffee Beans (Coffea arabica and Coffea canephora) through Solvent Development and Extraction of Bioactive Compounds

Raw coffee beans are seen as valuable sources of bioactive compounds, such as alkaloids and chlorogenic acids. In this study, an efficient and eco-friendly method for the simultaneous extraction of caffeine, trigonelline, and chlorogenic acids from raw beans of two coffee species was developed, using green solvents and an unconventional method of extraction (assisted by ultrafast rotary disintegrator/homogenizer (UT-AE)). The experimental extraction conditions were optimized according to a completely randomized design (CRD), considering the following variables: solvent type (four deep eutectic solvents (DESs), water, and aqueous choline chloride solution (50 wt.%); temperature (25, 45, and 65 °C); and extraction technique (solid-liquid extraction with agitated heating and assisted by ultrafast rotary disintegrator/homogenizer). The extract obtained with choline chloride solution (50 wt.%) exhibited high total phenolic compounds and the highest antioxidant capacity. An analysis using high-performance liquid chromatography with a diode array detector (HPLC-DAD) indicated the presence of chlorogenic acids, caffeine, and trigonelline in all the extracts, in different amounts. The results obtained by the analysis of phenolic compounds and HPLC indicated that the aqueous solution of choline chloride (50% wt.%) was the most suitable solvent for the extraction of chlorogenic acids, while the water-based extracts showed high values of caffeine and trigonelline. DESs, in turn, seems to promote a protective effect on the antioxidant activity of biomolecules.

Modulatory Effect of Chlorogenic Acid and Coffee Extracts on Wnt/β-Catenin Pathway in Colorectal Cancer Cells.

The Wnt/β-Catenin pathway alterations present in colorectal cancer (CRC) are of special interest in the development of new therapeutic strategies to impact carcinogenesis and the progression of CRC. In this context, different polyphenols present in natural products have been reported to have modulatory effects against the Wnt pathway in CRC. In this study, we evaluate the effect of two polyphenol-rich coffee extracts and chlorogenic acid (CGA) against SW480 and HT-29 CRC cells. This involved the use of MTT and SRB techniques for cell viability; wound healing and invasion assay for the evaluation of the migration and invasion process; T cell factor (TCF) reporter plasmid for the evaluation of transciption factor (TCF) transcriptional activity; polymerase chain reaction (PCR) of target genes and confocal fluorescence microscopy for β-Catenin and E-Cadherin protein fluorescence levels; and subcellular localization. Our results showed a potential modulatory effect of the Wnt pathway on CRC cells, and we observed a reduction in the transcriptional activity of β-catenin. All the results were prominent in SW480 cells, where the Wnt pathway deregulation has more relevance and implies a constitutive activation of the signaling pathway. These results establish a starting point for the discovery of a mechanism of action associated with these effects and corroborate the anticancer potential of polyphenols present in coffee, which could be explored as chemopreventive molecules or as adjunctive therapy in CRC.