Chlorogenic Acid Lactones Research Articles

Metabolite Profiling of Premium Civet Luwak Bio-Transformed Coffee Compared with Conventional Coffee Types, as Analyzed Using Chemometric Tools.

Luwak (civet) coffee is one of the most precious and exotic coffee commodities in the world. It has garnered an increasing reputation as the rarest and most expensive coffee, with an annual production. Many targeted analytical techniques have been reported for the discrimination of specialty coffee commodities, such as Luwak coffee, from other ordinary coffee. This study presents the first comparative metabolomics approach for Luwak coffee analysis compared to other coffee products, targeting secondary and aroma metabolites using nuclear magnetic resonance (NMR), gas chromatography (GC), or liquid chromatography (LC) coupled with mass spectrometry (MS). Chemometric modeling of these datasets showed significant classification among all samples and aided in identifying potential novel markers for Luwak coffee from other coffee samples. Markers have indicated that C. arabica was the source of Luwak coffee, with several new markers being identified, including kahweol, chlorogenic acid lactones, and elaidic acid. Aroma profiling using solid-phase micro-extraction (SPME) coupled with GC/MS revealed higher levels of guaiacol derivatives, pyrazines, and furans in roasted Luwak coffee compared with roasted C. arabica. Quantification of the major metabolites was attempted using NMR for Luwak coffee to enable future standardization. Lower levels of alkaloids (caffeine 2.85 µg/mg, trigonelline 0.14 µg/mg, and xanthine 0.03 µg/mg) were detected, compared with C. arabica. Other metabolites that were quantified in civet coffee included kahweol and difurfuryl ether at 1.37 and 0.15 µg/mg, respectively.

Identification of subthreshold chlorogenic acid lactones that contribute to flavor instability of ready-to-drink coffee

Flavor instability of ready-to-drink (RTD) coffee during storage negatively impacts product quality. Untargeted liquid chromatography/mass spectrometry (LC/MS) analysis was applied to identify chemical compounds that degraded during storage and impacted the flavor attributes of RTD coffee. LC/MS chemical profiles of non-aged and aged coffee samples were modeled against the degree of difference sensory scores by orthogonal partial least squares with good fit (R2Y = 0.966) and predictive ability (Q2 = 0.960). The top five predictive chemical features were subsequently purified by off-line multidimensional Prep-LC, revealing ten coeluting chlorogenic acid lactones (CGLs) compounds that were identified by LC/MS and nuclear magnetic resonance (NMR). The concentrations of eight CGLs significantly decreased in the coffee during the 4-month storage. Sensory recombination testing revealed the degradation of 3-O-caffeoyl-ɣ-quinide and 4-O-caffeoyl-ɣ-quinide significantly impacted the flavor stability of RTD coffee at subthreshold concentrations.

Review: Peran Enzim dalam Meningkatkan Kualitas Kopi

Indonesia is the third largest coffee producing nation in the world after Brazil and Vietnam. The types and the characteristics of Indonesian coffee are different in each area but the main important factor of consumer acceptance depends on its bitterness level. Chlorogenic acid lactone is a compounds that play an important role as contributor to the coffee bitterness that are formed during the roasting process of coffee bean because of its precursor chlorogenic acid. Chlorogenic acid is commonly found in many plants. One of them can be found in coffee with high concentration. Chlorogenic acid lactone (bitter compound) can be hydrolyzed to chlorogenic acid (non-bitter compound) using hog liver esterase and chlorogenate esterase. This study aimed to analyze the use of these enzymes to decrease the level of bitterness in coffee. The results indicated that HLE and chlorogenate esterase effectively hydrolyzed chlorogenic acid lactones in coffee. Based on the sensory test, coffee extracts treated with enzymes were less bitter than the untreated coffee extracts. If it was associated with Indonesian local coffee then the method can be done with chlorogenate esterase that was in accordance with the legal guarantee of halal product.

Selective enzymatic hydrolysis of chlorogenic acid lactones in a model system and in a coffee extract. Application to reduction of coffee bitterness

Chlorogenic acid lactones have been identified as key contributors to coffee bitterness. These compounds are formed during roasting by dehydration and cyclization of their precursors, the chlorogenic acids (CGAs). In the present study, we investigated an approach to decompose these lactones in a selective way without affecting the positive coffee attributes developed during roasting. A model system composed of (3-caffeoylquinic acid lactone (3-CQAL), 4- caffeoyl quinic acid lactone (4-CQAL), and 4-feruloylquinic acid lactone (4-FQAL)) was used for the screening of enzymes before treatment of the coffee extracts. Hog liver esterase (HLE) hydrolyzed chlorogenic acid lactones (CQALs, FQALs) selectively, while chlorogenate esterase hydrolyzed all chlorogenic acids (CQAs, FQAs) and their corresponding lactones (CQALs, FQALs) in a non-selective way. Enzymatically treated coffee samples were evaluated for their bitterness by a trained sensory panel and were found significantly less bitter than the untreated samples.

Transformation of chlorogenic acids during the coffee beans roasting process

Due to the recently discovered biomedical activity of chlorogen acid, the interest in its physicochemical and pharmaceutical properties has increased. The plant product most frequently mentioned as remarkably rich in this compound is coffee beans. The present paper shows that the roasting process of coffee beans not only leads to the degradation of chlorogenic acid isomers to volatile components, the fact well known from the literature, but also causes their transformation to quinic acid and its epimer and to four chlorogenic acid lactones (basic and epimeric forms of 3- and 4-O-caffeoylquinic acid lactones) and changes the ratios between the amounts of chlorogen acid isomers and dicaffeoylquinic acids isomers. It is also shown that the increase of water content above its standard level in the initial green coffee beans slows down only the changes occurring during the roasting process.

The Physiological Effects of Dandelion (Taraxacum Officinale) in Type 2 Diabetes.

The tremendous rise in the economic burden of type 2 diabetes (T2D) has prompted a search for alternative and less expensive medicines. Dandelion offers a compelling profile of bioactive components with potential anti-diabetic properties. The Taraxacum genus from the Asteraceae family is found in the temperate zone of the Northern hemisphere. It is available in several areas around the world. In many countries, it is used as food and in some countries as therapeutics for the control and treatment of T2D. The anti-diabetic properties of dandelion are attributed to bioactive chemical components; these include chicoric acid, taraxasterol (TS), chlorogenic acid, and sesquiterpene lactones. Studies have outlined the useful pharmacological profile of dandelion for the treatment of an array of diseases, although little attention has been paid to the effects of its bioactive components on T2D to date. This review recapitulates previous work on dandelion and its potential for the treatment and prevention of T2D, highlighting its anti-diabetic properties, the structures of its chemical components, and their potential mechanisms of action in T2D. Although initial research appears promising, data on the cellular impact of dandelion are limited, necessitating further work on clonal β-cell lines (INS-1E), α-cell lines, and human skeletal cell lines for better identification of the active components that could be of use in the control and treatment of T2D. In fact, extensive in-vitro, in-vivo, and clinical research is required to investigate further the pharmacological, physiological, and biochemical mechanisms underlying the effects of dandelion-derived compounds on T2D.

Effect of polygalacturonase and feruloyl esterase from Aspergillus tubingensis on demucilage and quality of coffee beans

To explore the potential for the application of Aspergillus tubingensis enzyme extract in coffee processing, the effects of crude enzymes on coffee beans were studied. Yields of polygalacturonase and feruloyl esterases obtained from solid-state fermentation using A. tubingensis, with pectin and de-starched wheat bran as carbon sources, were 15.9U/mL and 2.44U/mL, respectively. Crude enzyme extracts removed the mucilage of coffee cherries within 3h, which is substantially more efficient than traditional fermentation. Additionally, the viscosity of coffee mucilage was reduced to 80% by a 3-h treatment with the crude enzyme extract at 50°C. The titratable acidity and organic acids in coffee beverages were also decreased to half the amounts of those in the traditionally fermented group. The total chlorogenic acid in the green beans decreased to 67.3%; however, a decline of only 14.3% was observed in the traditionally fermented group. On the other hand, chlorogenic acid lactones in the roasted beans were reduced to 63.9%, and a 37.2% decline in the chlorogenic acid content was detected.

Identification and quantification of bioactive compounds in coffee brews by HPLC–DAD–MSn

Coffee is a beverage widely consumed worldwide because of its organoleptic characteristics and stimulating and beneficial health effects. This paper presents the identification and quantification of chlorogenic acids and derivatives, trigonelline, nicotinic acid, 5-hydroxymethylfurfural, theobromine, theophylline, and caffeine in brews of 10 roasted ground coffee and 4 soluble coffee determined by HPLC–DAD–MSn. Among the chlorogenic acids and derivatives, 17 chlorogenic acids, 5 chlorogenic acid lactones, 2 cinnamoyl-amino acid conjugates, and 2 free cinnamic acids were identified. This is the first study that reports the presence of caffeoylferuloylquinic acid isomers, and cinnamoyl-amino acid conjugates in soluble coffee brews. Regular roasted ground coffee brews showed higher contents of chlorogenic acids (4162mg/100g), chlorogenic acid lactones (779mg/100g), p-coumaric acid (2.4mg/100g), trigonelline (2044mg/100g), nicotinic acid (100.4mg/100g), caffeine (4565mg/100g), and theobromine (12.5mg/100g) than regular soluble coffee brews. Decaffeinated coffee brews presented higher levels of chlorogenic acids, chlorogenic acid lactones, caffeic acid, and trigonelline when compared to the regular ones. Despite the differences in the levels of these compounds, brews of roasted ground coffee and soluble coffee, both regular and decaffeinated, represent an important source of bioactive compounds for habitual coffee consumers.

Does roasted coffee contain chlorogenic acid lactones or/and cinnamoylshikimate esters?

Coffee is one of the most popular and consumed beverages in the world with many positive health effects. In this study the chlorogenic acid lactones and cinnamoylshikimate esters, a subclass of phenolics, from seven commercial roasted Robusta coffee samples were detected and characterized by LC–MSn (n=2–4). This is the first time when cinnamoylshikimate esters are reported in roasted coffee based on their tandem MS data. We used a previously developed LC–MSn method to distinguish between chlorogenic acid lactones and cinnamoylshikimate esters. Chlorogenic acid lactones and their isomeric shikimate esters have identical m/z values in their MS spectra but different tandem MS spectra and retention times. Structures of these chlorogenic acid lactones and shikimate esters were assigned on the basis of LC–MS3 patterns of fragmentation, relative hydrophobicity and fragmentation analogy to the synthetic standards of mono-acyl chlorogenic acid lactones and shikimate esters containing moieties of ferulic, caffeic, p-coumaric and dimethoxycinnamic acids. Furthermore, 7 unknown and 52 known mono and diacyl chlorogenic acids were identified and characterized to their regioisomeric level. The study is relevant for profiling chlorogenic acids and their dehydration derivatives, shikimates and lactones, in roasted coffee.

Scavenging capacity of coffee brews against oxygen and nitrogen reactive species and the correlation with bioactive compounds by multivariate analysis

In the present work the scavenging capacity of coffee brews against ROS (ROO, H2O2, HO and HOCl) and RNS (NO and ONOO−) was evaluated and correlated with their bioactive compounds by multivariate analysis. It is the first time that the complete antioxidant capacity profile of coffee brews against different ROS and RNS is evaluated and that the capacity of coffee brews to scavenge NO is reported. The coffee brews were able to scavenge all the reactive species tested and possibly NO2 and CO3−. The capacity of the coffee brews to scavenge ROO (2523 to 3673μmol TE/g), HO (IC50=2.24 to 4.38μg/mL), NO (IC50=3.07 to 5.67μg/mL) and ONOO− (IC50=1.29 to 2.88μg/mL) was positively correlated to the contents of chlorogenic acids, chlorogenic acid lactones and p-coumaric acid, while the scavenging capacity against H2O2 (IC50=336 to 531μg/mL) was positively correlated to the content of browned compounds, mainly melanoidins. The coffee brews showed to be potent HOCl scavengers (IC50=5.12 to 11.20μg/mL), which was correlated to the contents of caffeic acid, 5-hydroxymethylfurfural and browned compounds. These results reinforce the hypothesis that the scavenging capacity against ROS/RNS is one of the mechanisms that can explain the association between the consumption of coffee brews and the decreased risk of chronic-degenerative diseases.

A New Method for the Preparative Isolation of Chlorogenic Acid Lactones from Coffee and Model Roasts of 5-Caffeoylquinic Acid

Chlorogenic acid lactones (CQL) are known to contribute to the bitter taste of roasted coffee. CQL might also have beneficial biological activities. Until now, there is a lack of pure standard compounds for quantification and biological testing. Using high-speed countercurrent chromatography, milligram amounts of lactones could be isolated. The structures of 3-O-caffeoyl-γ-quinide, 4-O-caffeoyl-muco-γ-quinide, and 5-O-caffeoyl-epi-δ-quinide were confirmed by 1D and 2D NMR spectroscopy including (13)C NMR data, which were previously not available from the literature. An UHPLC method was developed that enabled the separation of the lactones from roasted coffee in significantly shorter time than conventional HPLC.

How to distinguish between cinnamoylshikimate esters and chlorogenic acid lactones by liquid chromatography-tandem mass spectrometry

In this study, liquid chromatography-tandem mass spectrometry (LC-MS(n); n = 2-3) has been used to characterize and distinguish chlorogenic acid lactones from cinnamoylshikimate esters. This is the first time when an LC-MS(n) method has been developed to distinguish between these two isomeric classes of compounds formed in particular in food processing from chlorogenic acids at elevated temperature through loss of water. The structures of regioisomeric chlorogenic acid lactones and shikimate esters have been assigned on the basis of LC-MS(n) patterns of fragmentation, relative hydrophobicity, and fragmentation analogy with the synthetic standards of dimethoxycinnamic, ferulic, and caffeic acid containing monoacyl chlorogenic acid lactones and shikimate esters.

Roasted Coffees High in Lipophilic Antioxidants and Chlorogenic Acid Lactones Are More Neuroprotective than Green Coffees

Oxidative stress is involved in many neurodegenerative processes leading to age-related cognitive decline. Coffee, a widely consumed beverage, is rich in many bioactive components, including polyphenols with antioxidant potential. In this study, regular and decaffeinated samples of both roasted and green coffee all showed high hydrophilic antioxidant activity in vitro, whereas lipophilic antioxidant activities were on average 30-fold higher in roasted than in green coffee samples. In primary neuronal cell culture, pretreatment with green and roasted coffees (regular and decaffeinated) protected against subsequent H(2)O(2)-induced oxidative stress and improved neuronal cell survival (green coffees increased neuron survival by 78%, compared to 203% by roasted coffees). All coffee extracts inhibited ERK1/2 activation, indicating a potential attenuating effect in stress-induced neuronal cell death. Interestingly, only roasted coffee extracts inhibited JNK activation, evidencing a distinctive neuroprotective benefit. Analysis of coffee phenolic compounds revealed that roasted coffees contained high levels of chlorogenic acid lactones (CGLs); a significant correlation between CGLs and neuroprotective efficacy was observed (R(2) = 0.98). In conclusion, this study showed that roasted coffees are high in lipophilic antioxidants and CGLs, can protect neuronal cells against oxidative stress, and may do so by modulation of the ERK1/2 and JNK signaling pathways.

Rapid Screening and Identification of Polar Constituents from Brazilian Arnica Lychnophora sp. by LC-UV/DAD-ESI-MS and LC-UV/DAD-ESI-MS/MS Analysis

This paper describes an analytical method for the rapid screening and identification of the phenolic constituents present in the polar extracts of different Lychnophora spp. using LC-UV/DAD-ESI-MS and LC-UV/DAD-ESI-MS/MS. Compounds were identified based on UV, retention time, MS experiments and MS/MS of precursor ion or standard. On-line phytochemical investigation of Lychnophora spp. allowed for the identification of flavonoids, chlorogenic acid derivatives and lactones. Some of the observed compounds were for the first time identified in Lychnophora species in a fast analytical procedure. The data obtained here may be helpful to the investigation of polar constituents from other Lychnophora species.

Comprehensive analysis of major and minor chlorogenic acids and lactones in economically relevant Brazilian coffee cultivars

Coffee is the most consumed beverage in the world and a significant source of phenolic compounds, particularly chlorogenic acids (CGA). During coffee roasting, some CGA are partially transformed into chlorogenic acid lactones (CGL). Both CGA and CGL are important compounds for flavor and potentially beneficial to human health. In the present study, using LC–MS and synthetic standards, we investigated major and minor CGA and CGL isomers in green and roasted samples of economically relevant Brazilian Coffea arabica and Coffea canephora coffee cultivars. For the first time, in addition to nineteen previously identified CGA and CGL, 1-feruloylquinic acid, 1-feruloylquinic lactone and 3,4-diferuloylquinic acid were quantified in C. arabica and C. canephora, the contents of 3- and 4- p-coumaroylquinic lactones were reported in C. canephora and 3,4-di- p-coumaroylquinic acid was identified in C. arabica. Despite their low concentrations, the implications of these findings for flavor, cup quality and the biological properties of coffee merit further investigation.

Chlorogenic Acids and Lactones in Regular and Water-Decaffeinated Arabica Coffees

The market for decaffeinated coffees has been increasingly expanding over the years. Caffeine extraction may result in losses of other compounds such as chlorogenic acids (CGA) and, consequently, their 1,5-gamma-quinolactones (CGL) in roasted coffee. These phenolic compounds are important for flavor formation as well as the health effects of coffee; therefore, losses due to decaffeination need to be investigated. The present study evaluates the impact of decaffeination processing on CGA and CGL levels of green and roasted arabica coffees. Decaffeination produced a 16% average increase in the levels of total CGA in green coffee (dry matter), along with a 237% increase in CGL direct precursors. Different degrees of roasting showed average increments of 5.5-18% in CGL levels of decaffeinated coffee, compared to regular, a change more consistent with observed levels of total CGA than with those of CGL direct precursors in green samples. On the other hand, CGA levels in roasted coffee were 3-9% lower in decaffeinated coffee compared to regular coffee. Although differences in CGA and CGL contents of regular and decaffeinated roasted coffees appear to be relatively small, they may be enough to affect flavor characteristics as well as the biopharmacological properties of the final beverage, suggesting the need for further study.

Effect of Roasting on the Formation of Chlorogenic Acid Lactones in Coffee

Of all plant constituents, coffee has one of the highest concentrations of chlorogenic acids. When roasting coffee, some of these are transformed into chlorogenic acid lactones (CGL). We have studied the formation of CGL during the roasting of coffee beans in Coffea arabica cv. Bourbon; C. arabicacv. Longberry; and C. canephora cv. Robusta. Individual CGL levels were determined by comparison of HPLC peaks with those of synthetic CGL standards. Seven CGL were identified: 3-caffeoylquinic-1,5-lactone (3-CQL), 4- caffeoylquinic-1,5-lactone (4-CQL), 3-coumaroylquinic-1,5-lactone (3-pCoQL), 4-coumaroylquinic-1,5-lactone (4-pCoQL), 3-feruloylquinic-1,5-lactone (3-FQL), 4-feruloylquinic-1,5-lactone (4-FQL), and 3,4-dicaffeoylquinic-1,5-lactone (3,4-diCQL). 3-CQL was the most abundant lactone in C. arabica and C. canephora, reaching peak values of 230 +/- 9 and 254 +/- 4 mg/100 g (dry weight), respectively, at light medium roast ( approximately 14% weight loss). 4-CQL was the second most abundant lactone (116 +/- 3 and 139 +/- 2 mg/100 g, respectively. The maximum amount of CGL represents approximately 30% of the available precursors. The relative levels of 3-CQL and 4-CQL in roasted coffee were reverse to those of their precursors in green coffee. This suggests that roasting causes isomerization of chlorogenic acids prior to the formation of lactones and that the levels of lactones in roasted coffee do not reflect the levels of precursors in green coffee.

HPLC Analysis of chlorogenic acid lactones in roasted coffee

The identification of 3- (3-CQL) and 4-caffeoylquinic acid-γ-lactone (4-CQL) in roasted coffee is described. The lactones were separated from chlorogenic acids (CQA) by an isocratic reversed-phase (RP)-HPLC system and identified as caffeic acid derivatives using their ultraviolet spectra obtained on the fly with an diode array detector. Thermospray liquid-chromatography mass-spectrometry spectra (discharge ionisation, buffer ionisation) showed the quasi molecule ion and characteristic fragments (e.g. caffeic acid, quinide). The lactones were isolated from coffee by polyamide column chromatography followed by RP-HPLC on a semipreparative scale, and structures assigned using Fourier-transform infrared spectroscopy and various nuclear magnetic resonance techniques. There seems to be an equilibrium between the two lactones: isolation of 3-CQL and 4-CQL under the experimental conditions used yielded both lactones in the final product. The content of the caffeoylquinides in commercial coffee samples ranged from 1.5 to 3.5 g/kg dry matter.