Two novel betaine derivatives from Kancolla seeds (Chenopodiaceae)

Analysis of the polar extracts from kancolla seeds led to the isolation of five betaines: glycine betaine, trigonelline, trigonelline methylester, trigonelline glucosylester and 3-carboxy-1-(2-sulfoethyl)-pyridinium, the last two of which have not previously been reported in the literature. All structures were elucidated from spectroscopic [NMR (¹H, ¹³C, COSY, HOHAHA, HMQC, HMBC)] and mass spectrometric data (ESI-MS).     

Species,roasting degree and decaffeination influence the antibacterial activity of coffee against Streptococcus mutans

Coffee beverage has been associated with antibacterial activity against Streptococcus mutans, a cariogenic bacterium. This study aimed at identifying natural compounds in coffee that contribute to such activity and investigate the influence of species, roasting and decaffeination on it. Coffee chemical compounds and aqueous extracts of green and roasted regular and decaffeinated Coffea arabica and Coffea canephora beans were tested. MIC, biofilm inhibition and biofilm reduction results were correlated with the concentration of coffee compounds in the extracts. 5-Caffeoylquinic acid, trigonelline and caffeic acid solutions showed bacteriostatic activity (MIC = 0.8 mg/mL). Lighter and regular extracts showed higher inhibitory activity than darker and decaffeinated extracts, with an inverse correlation between bacterial colony-forming units and roasting degree. Only regular C. canephora extracts showed biofilm formation inhibition. The joint effect of chlorogenic acids, trigonelline and caffeine or other compounds removed by decaffeination seems to be one of the causes for coffee antibacterial activity against S. mutans.     

Evaluation of selected ubiquitous contaminants in the aquatic environment and their transformation products. A pilot study of their removal from a sewage treatment plant

A simple method using direct sample injection combined with liquid chromatography tandem mass spectrometry has been developed for the simultaneous analysis of six alkaloid compounds in environmental samples. The target list includes two psychostimulants (nicotine and caffeine), three metabolites (cotinine, nicotinic acid and paraxanthine) and a coffee chemical (trigonelline). The analytical method was evaluated in three different matrices (surface water, influent and effluent wastewater). The method developed showed an adequate sensitivity, below 0.6 μg L⁻¹ for wastewater and 0.1 μg L⁻¹ for river matrices, without any prior treatment of the samples. Finally, the methodology was applied to real samples for evaluation of their removal from a sewage treatment plant and their persistence/fate in the aquatic environment. All compounds studied in this work were detected at all sampling points collected along the Henares River. However, nicotinic acid was only detected three times in treated sewage samples at levels above its detection limit.     

Identification of Chemical Clusters Discriminators of Arabica and Robusta Green Coffee

The chemical parameters pH, soluble solids, caffeine, trigonelline, total chlorogenic acids, total caffeoylquinic acids, 3-O-caffeoylquinic acid, 4-O-caffeoylquinic acid, 5-O-caffeoylquinic acid, total dicaffeoylquinic acids, 3,4-O-dicaffeoylquinic acid, 3,5-O-dicaffeoylquinic acid, 4,5-O-dicaffeoylquinic acid, total feruloylquinic acids, 3-O-feruloylquinic acid, and 5-O-feruloylquinic acid were measured in Arabica (C. arabica) and Robusta (C. canephora) green coffees in order to determine discrimination parameters. In general, Robusta green coffee showed higher values for pH, soluble solids, caffeine, total caffeoylquinic acids, total dicaffeoylquinic acid, and total feruloylquinic acid, but the content of soluble solids was not significantly different in both species of green coffee. Through application of a multivariate analysis, it was concluded that these chemicals form three clusters, being the group of caffeine, trigonelline, 3-O-caffeoylquinic acid, 4-O-caffeoylquinic acid, 3-O-feruloylquinic acid, 5-O-feruloylquinic acid, 3,4-O-dicaffeoylquinic acid, 3,5-O-dicaffeoylquinic acid, and 4,5-O-dicaffeoylquinic acid highly discriminating for Arabica and Robusta green coffees.     

Fast simultaneous analysis of caffeine, trigonelline, nicotinic acid and sucrose in coffee by liquid chromatography–mass spectrometry

A rapid liquid chromatography–mass spectrometry method for the simultaneous quantification of caffeine, trigonelline, nicotinic acid and sucrose in coffee was developed and validated. The method involved extraction with hot water, clarification with basic lead acetate and membrane filtration, followed by chromatographic separation using a Spherisorb^® S5 ODS2, 5 μm chromatographic column and gradient elution with 0.3% aqueous formic acid/methanol at a flow rate of 0.2 mL/min. The electrospray ionization source was operated in the negative mode to generate sucrose ions and in the positive mode to generate caffeine, trigonelline and nicotinic acid ions. Ionization suppression of all analytes was found due to matrix effect. Calibrations curves prepared in green and roasted coffee extracts were linear with r² > 0.999. Roasted coffee was spiked and recoveries ranged from 93.0% to 105.1% for caffeine, from 85.2% to 116.2% for trigonelline, from 89.6% to 113.5% for nicotinic acid and from 94.1% to 109.7% for sucrose. Good repeatibilities (RSD < 5%) were found for all analytes in the matrix. The limit of detection (LOD), calculated on the basis of signal-to-noise ratios of 3:1, was 11.9, 36.4, 18.5 and 5.0 ng/mL for caffeine, trigonelline, nicotinic acid and sucrose, respectively. Analysis of 11 coffee samples (regular or decaffeinated green, ground roasted and instant) gave results in agreement with the literature. The method showed to be suitable for different types of coffee available in the market thus appearing as a fast and reliable alternative method to be used for routine coffee analysis.     

Urinary N-methylpyridinium and trigonelline as candidate dietary biomarkers of coffee consumption

Scope : In order to validate the in vivo function of putatively healthy molecules in foods, human intervention studies are required. As the subject's compliance concerning intake or abstinence of a given food is considered mandatory to be monitored by biomarkers, the objective was to identify analytical markers for coffee consumption. Methods and results : Urine samples collected from coffee drinkers were compared with those of non‐coffee drinkers using hydrophilic liquid interaction chromatography (HILIC)/time‐of‐flight mass spectrometry‐based metabolite profiling. Two urinary molecules, found to be contributing most to the dissimilarities between both groups, were identified as N‐methylpyridinium (NMP) and trigonelline and their suitability as coffee‐specific biomarkers was validated by means of a coffee intervention study. After the volunteers (five females and four males) consumed a single dose of coffee, morning urine was collected for 10 days while staying abstinent from any coffee. HILIC‐MS/MS‐stable isotope dilution analysis (SIDA) revealed elevated urinary concentrations of trigonelline and NMP for up to 48 (p=0.001) and 72 h (p=0.002), respectively, after coffee consumption when compared with non‐coffee drinkers. Conclusion : Analysis of urinary NMP allows to check for coffee consumption within a period of 3 days and is proposed as a dietary biomarker which might be used as an analytical probe to control compliance in human intervention studies on coffee.     

Correlation between cup quality and chemical attributes of Brazilian coffee

Brazilian arabica coffee is classified for trading according to the quality of the beverage obtained after roasting and brewing. In the present study, Brazilian green and roasted coffee beans were investigated for possible correlations between cup quality and the levels of sucrose, caffeine, trigonelline and chlorogenic acids, determined by HPLC analysis. Trigonelline and 3,4-dicaffeoylquinic acid levels in green and roasted coffee correlated strongly with high quality. To a lesser extent, caffeine levels were also associated with good quality. On the other hand, the amount of defective beans, the levels of caffeoylquinic acids (predominantly 5-caffeoyilquinic acid), feruloylquinic acids, and their oxidation products were associated with poor cup quality and with the Rio-off-flavor. The fact that similar correlations between cup quality and chemical attributes were observed in green and light roasted samples – the latter used for coffee cup classification – indicates that chemical analysis of green beans may be used as an additional tool for coffee quality evaluation.     

Chlorogenic acids and other relevant compounds in Brazilian coffees processed by semi-dry and wet post-harvesting methods

The levels of nine chlorogenic acids, caffeine, trigonelline and sucrose were determined by HPLC-UV and HPLC-RI systems in wet and semi-dry post-harvested coffee seeds from 17 Brazilian Arabica cultivars and progenies. Coffees processed by wet method showed higher contents of chlorogenic acids (p = 0.02) and trigonelline (p < 0.01), and lower content of sucrose (p = 0.02) compared to those produced by a semi-dry method. Regarding caffeine, no difference was observed between both methods. The implications of the differences observed in the chemical composition of coffee seeds treated by wet and semi-dry methods on cup quality deserve investigation.     

Kinetics of free protein amino acids, free non-protein amino acids and trigonelline in soybean (Glycine max L.) and lupin (Lupinus angustifolius L.) sprouts

A contribution for a better nutritional knowledge of lupin (Lupinus angustifolius L. var. zapaton) and soybean (Glycine max L. var. merit and var. jutro) sprouts about free protein amino acids (FPAA), free non-protein amino acids (FNPAA such as β-N-oxalyl-l-α,β-diaminopropionic acid (β-ODAP), α-aminoadipic acid, γ-aminobutyric acid (GABA) and β-alanine) and trigonelline content has been carried out. Seeds were germinated at 20 °C and darkness during several days in order to obtain good appearance sprouts. The content of FPAA and FNPAA varied among species and varieties. FPAA increased dramatically during germination and the lowest concentrations were found for G. max L. var. jutro. Cys was not detected as FPAA in seeds and seedlings of both legumes. Asn was present in the highest amounts in soybean and lupin seedlings. The α-aminoadipic acid gliotoxin, which was not present in raw soybean seeds, appeared in low amounts during germination. Later stages of germination caused significant increases of β-alanine and GABA, amino acids with beneficial properties. Germination also affected the content of the multifunctional plant hormone trigonelline and slight changes were observed. Highest levels of FPAA, beneficial FNPAA and trigonelline were found at 4, 6 and 9 days of germination for G. max L. var. jutro, G. max L. var. merit and L. angustifolius L. var. zapaton, respectively. Furthermore, these selected germination conditions showed low levels of the gliotoxic α-aminoadipic acid ensuring nutritional safety of the studied seedlings.