Melanoidins from coffee infusions. Fractionation, chemical characterization, and effect of the degree of roast

A method involving fractionation in ethanol aqueous solutions, anion exchange chromatography, and immobilized copper chelating chromatography was developed to obtain high molecular weight anionic melanoidin populations from coffee infusions. Six anionic fractions with different physicochemical properties (ethanol solubility and chelating ability) and chemical composition regarding carbohydrate as well as protein nature and content were isolated. Fractions with similar chemical composition were obtained for light-, medium-, and dark-roasted coffee infusions. These melanoidin fractions accounted for 30-33% of the cold-water soluble high molecular weight material, independently of the degree of roast in coffee. The nature and abundance of the different polysaccharides in each fraction were dependent on their ethanol solubility. The 50% ethanol insoluble melanoidin populations contained mostly galactomannan-like carbohydrates, and the fractions obtained with 75% ethanol contained mostly arabinogalactan-like carbohydrates. The melanoidin populations with chelating properties presented significantly lower carbohydrate content and, from these, the 75% ethanol soluble fractions were almost devoid of carbohydrate material. The results obtained suggest that the chelating ability of these coffee melanoidins is modulated by their carbohydrates.     

Chemical and sensorial characteristics of espresso coffee as affected by grinding and torrefacto roast

Grinding is a critical step in the preparation of espresso coffee (EC). The addition of sugar during the torrefacto roasting process could influence the degree of brittleness and grinding. The aim of this work was to study the influence of the grinding grades (coarse, fine, and very fine) in Arabica/Robusta 20:80, natural roasted (A20:R80), and Arabica/Robusta 20:80 with 50% Robusta torrefacto roasted (A20:R80 50% torrefacto) on the chemical and sensorial characteristics of EC in order to select the optimal espresso grinding grade. A higher percentage of coarse particles was found in A20:R80 ground coffee. In both ECs, the extraction of solids and soluble and aroma compounds increased inversely with particle size. Higher foam indices and extraction yields were found in A20:R80 50% torrefacto ECs probably due to the solubilization of caramelized sugar and melanoidins. It has been suggested that the range of an acceptable extraction yield could be extended to 25% in A20:R80 50% torrefacto ECs. In conclusion, the optimal grinding grade for the obtainment of an EC with A20:R80 was fine and that for A20:R80 50% torrefacto was coarse.     

Chemical characterization of the high-molecular-weight material extracted with hot water from green and roasted robusta coffees as affected by the degree of roast

The hot-water-soluble polymeric material from green and roasted Uganda robusta coffees submitted to different degrees of roasting was isolated and characterized, and the changes in structure and amount of galactomannans and arabinogalactans were determined and discussed in relation to the data already available for arabica coffees, obtained under the same experimental conditions. The content of arabinogalactans extracted from robusta green coffee was higher than that extracted from arabica. For roasted coffees, the amount of galactomannans extracted ranged from 0.66% to 0.92% (w/w). These values were near 50% of those obtained from the arabica coffees using the same extraction procedure. However, the amount of arabinogalactans extracted from robusta coffees (0.56-0.72%) was in the range obtained from arabica. The structures of arabinogalactans and galactomannans extracted from green and roasted coffees were not sufficiently different between robusta and arabica coffees to explain the observed differences in extraction yields for the arabinogalactans from green coffees and for the galactomannans from roasted coffees. The total polysaccharide content and the structures of the galactomannans and arabinogalactans in the two green coffee varieties investigated were also very similar. These differences in the extraction of high-molecular-weight polysaccharides between arabica and robusta roasted coffees may be related to the different susceptibility of the cell walls during the roasting process, known to result in a different porosity between arabica and robusta roasted coffees.     

Furan levels in coffee as influenced by species, roast degree, and brewing procedures

Brazilian green coffee beans of Coffea arabica and Coffea canephora species were roasted to light, medium, and dark roast degrees and analyzed in relation to furan content by using an in-house validated method based on gas chromatography coupled to mass spectrometry preceded by headspace solid-phase microextraction. Furan was not detected in green coffees, whereas levels between 911 and 5852 μg/kg were found in the roasted samples. Higher concentrations were found in Coffea canephora species and darker ground coffees. Some of the potential furan precursors were observed in significant amounts in green coffee, especially sucrose and linoleic acid, but their concentrations could not be correlated to furan formation. Additionally, coffee brews were prepared from roasted ground coffees by using two different procedures, and furan levels in the beverages varied from <10 to 288 μg/kg. The factor that most influenced the furan content in coffee brew was the brewing procedure.     

Chemical characterization of the high molecular weight material extracted with hot water from green and roasted arabica coffee

The polysaccharides present in coffee infusions are known to contribute to the organoleptic characteristics of the drink, such as the creamy sensation perceived in the mouth known as "body", the release of aroma substances, and the stability of espresso coffee foam. To increase the knowledge about the origin, composition, and structure of the polysaccharide fraction, the high molecular weight material (HMWM) was extracted with hot water from two green and roasted ground arabica coffees: Costa Rica (wet processed) and Brazil (dry processed). The polysaccharides present in the green coffees HMWM were arabinogalactans (62%), galactomannans (24%), and glucans, and those found in roasted coffees were galactomannans (69%) and arabinogalactans (28%). The polysaccharides of the HMWM of the roasted coffees were less branched than those of the green coffees. The major green coffee proteins had molecular weights of 58 and 38 kDa, and the 58 kDa protein had two subunits, of 38 and 20 kDa, possibly linked by disulfide bonds. The protein fraction obtained from roasted coffees had only a defined band with < or =14 kDa and a diffuse band with >200 kDa. The majority of the galactomannans were precipitated with solutions of 50% ethanol, and the size-exclusion chromatography of the roasted fractions showed coelution of polysaccharides, proteins, phenolics, and brown compounds. The use of strong hydrogen and hydrophobic dissociation conditions allowed us to conclude that the phenolics and brown compounds were linked by covalent bonds to the polymeric material.     

Chemical characterization and antioxidant properties of coffee melanoidins

Melanoidins, the brown polymers formed through Maillard reaction during coffee roasting, constitute up to 25% of the coffee beverages' dry matter. In this study chemical characterization of melanoidins obtained from light-, medium-, and dark-roasted coffee beans, manufactured from the same starting material, was performed. Melanoidins were separated by gel filtration chromatography and studied by MALDI-TOF mass spectrometry. Results showed that the amount of melanoidins present in the brews increased as the intensity of the thermal treatment increased, while their molecular weight decreased. The antioxidant activity of melanoidins isolated from the different brews was studied by using different methodologies. Melanoidins antiradical activity determined by ABTS(*)(+) and DMPD(*)(+) assays decreased as the intensity of roasting increased, but the ability to prevent linoleic acid peroxidation was higher in the dark-roasted samples. Data suggest that melanoidins must be carefully considered when the relevance of coffee intake in human health is studied.     

Gamma-tocopherol as a marker of Brazilian coffee (Coffea arabica L.) adulteration by corn

The adulteration of coffee with cereals, coffee twigs, etc. is apparently widespread in Brazil with corn being considered the most widely used. No adequate methods are available to detect such contamination in commercial coffee. A new method, based on high-performance liquid chromatography (HPLC) tocopherol determination was developed to detect coffee adulteration by corn. Percentages of alpha-, beta-, gamma-, and delta-tocopherol determined by HPLC in six coffee varieties were 29.0, 61.7, 3.3, and 6.0, respectively. Similar values were obtained in six popular coffee brands. The percentages of alpha-, gamma-, and delta-tocopherol in six corn samples were 3.6, 91.3, and 5.1, respectively. These differences could be applied to detect corn in a pure coffee sample intentionally contaminated with corn with the best result obtained with gamma-tocopherol. With this methodology, one coffee brand was apparently adulterated (8.9%), most likely with corn. Tocopherol fingerprinting offers the potential to detect adulteration.     

Chemical and biological characteristics of alkaline saline soils from the former Lake Texcoco as affected by artificial drainage

 Soils from the former Lake Texcoco are alkaline saline and were artificially drained and irrigated with sewage effluents since the late 1980s. Undrained soil and soil drained for 1, 5 and 8 years were sampled, characterized and incubated aerobically for 90 days at 22±1  °C while production of CO₂, available P and concentrations of NH₄ ⁺, NO₂ ^– and NO₃ ^– were monitored. Artificial drainage decreased pH_H2O, water holding capacity, organic C, total N, and Na⁺, K⁺, Mg²⁺, B, Cl^– and SO₄ ^2– concentrations, increased inorganic C and Ca²⁺ concentrations more than 5-fold while total P was not affected. Microbial biomass C decreased with increased length of drainage but bacteria, actinomycetes, denitrifiers and cellulose-utilizing bacteria tended to show opposite trends. CO₂ production was less in soils drained ≥5 years compared to undrained soil but more than in soils drained for 1 year. Emission of NH₃ was negligible and concentrations of NH₄ ⁺ remained constant over time in each soil. Nitrification, as witnessed by increases in NO₃ ^– concentrations, occurred in soil drained for 8 years. NO₂ ^– concentrations decreased in soils drained ≤1 year in the first 7 days of the incubation and remained constant thereafter. It was found that artificial drainage of soils from the former Lake Texcoco profoundly affected soil characteristics. Decreases in pH and Na⁺, K⁺, Cl^– and SO₄ ^2– concentrations made conditions more favourable for plant growth, although low concentrations of inorganic N and available P might be limiting factors. Received: 1 December 1999     

Cadmium sorption by two acid soils as affected by clearing and cultivation

Abstract

The objective of this study was to determine the effect of clearing and cultivation on the sorption of cadmium (Cd) by two acid soils from Zimbabwe with differing cultivation stories. In their original state, not cleared‐not cultivated (virgin soils), the two soils exhibited noticeable and similar capacities to sorb Cd. The Mazowe soil contains the highest level of organic matter (40 g kg^‐1) and a effective cation exchange capacity (ECEC) of 144 mmol_c kg^‐1. Yet, Bulawayo soil (23.5 g kg^‐1 organic matter and ECEC of 146 mmol_c kg^‐1) has higher pH and Mn and Fe oxide content and these characteristics seemed to counteract the effect of lower organic matter. After 50 years of cultivation, The Mazowe soil has lost 60% of its organic matter and ECEC, and consequently the ability of its soil matrix to bind Cd has proportionally decreased. In Bulawayo (cleared in 1983 and first ploughed in 1984), on the contrary, the organic matter and ECEC of the cultivated soil remains over 95% of the values on its virgin counterpart. In this soil, the retaining ability for Cd has not still been affected. In the two soils Cd sorption was highly pH‐dependent. The extent of sorption was minimal under acidic conditions and increased sharply as the pH was raised. The immediate reversibility of the sorption process proved to be very low. When sorption and desorption data were compared it was clear that soil characteristics like high organic matter and oxide content which showed to enhanced Cd sorption, contributed at the same time to slow down the backward reaction.     

表面活性剂与EDTA对紫色土镉的化学行为影响

Elemental composition and geochemical characteristics of iron-manganese nodules from nine main soils in China were studied by chemical and multivariate statistical analyses to better understand the reactions and functions of ironmanganese nodules in soils and sediment. Compared to the corresponding soils, Mn, Ba, Cd, Co and Pb had strong accumulation, Ni had moderate accumulation, while Ca, Cu, Fe, Na, P, Sr and Zn accumulated to a minor degree in the iron-manganese nodules. In contrast, Si, Al, K, Mg and Ti were reduced in the iron-manganese nodules. The contents of Ba, Cd, Co, Cu, Ni, Pb and Zn were positively and significantly correlated with that of MnO2 in the iron-manganese nodules, while the contents of Cr, Cu, Ni, Pb and Zn were positively and significantly correlated with that of Fe2O3 in soils. Based on a principle component analysis, the elements of iron-manganese nodules were divided into four groups： 1） Mn, Ba, Cd, Co, Cu, Li, Ni, Pb and Zn that were associated with Mn oxides, 2） Fe, Cr and P that were associated with Fe oxides, 3） Si, K, and Mg that were included in the elemental composition of phyllosilicate, and 4） Ca, Na, Al and Ti that existed in todorokite, birnessite, lithiophorite and phyllosilicate. It was suggested that accumulation, mineralization and specific adsorption were involved in the formation processes of soil iron-manganese nodules.     

Chemical discrimination of arabica and robusta coffees by Fourier transform Raman spectroscopy

This article deals with the potential of Fourier transform (FT) Raman spectroscopy in discrimination of botanical species of green and roasted coffees. There are two species of commercial importance: Coffea arabica (arabica) and Coffea canephora (robusta). It is recognized that they differ in their lipid fraction, especially in the content of the diterpene kahweol, which is present at 0.1-0.3% dry matter basis in arabica beans and only in traces (<0.01%) in robusta. The visual examination of the Raman spectra of the lipid fraction extracted from arabica, robusta and liberica samples shows differences in the mid-wavenumbers region: arabica spectra have two characteristic scattering bands at 1567 and 1478 cm(-1). The spectrum of the pure kahweol shows the same bands. Principal component analysis is applied to the spectra and reveals clustering according to the coffee species. The first principal component (PC1) explains 93% of the spectral variation and corresponds to the kahweol concentration. Using the PC1 score plot, two groups of arabica can be distinguished as follows: one group with high kahweol content and another group with low kahweol content. The first group includes samples coming from Kenya and Jamaica; the second group includes samples from Australia. The main difference between these coffees is that those from Kenya and Jamaica are well-known for growing at a high altitude whereas those ones from Australia are grown at a low altitude. To our knowledge, the application of Raman spectroscopy has never been used in coffee analysis.     

Discrimination between arabica and robusta coffee species on the basis of their amino acid enantiomers

This work reports the results for the composition of robusta and arabica coffee species in terms of their amino acid enantiomers in the green and roasted states. The analyses were conducted for the free amino acids, as well as for the amino acids obtained after acid hydrolysis. The amino acids were extracted/hydrolyzed and isolated by SPE on strong cation exchange columns, derivatized to their N-ethoxycarbonylheptafluorobutyl esters, and analyzed by gas chromatography/FID on a Chirasil l-Val column. Multivariate analyses applied to the results showed that the free amino acids can be used as a tool for discrimination between coffee species, with a special reference to l-glutamic acid, l-tryptophan, and pipecolic acid. There is also some evidence that these compounds can be used for discrimination between green coffees subjected to different postharvest processes. It is also shown that the amino acid levels observed after acid hydrolysis can be used for the same purposes, although displaying less discriminatory power.     

Chemical characterization and decomposition of organic matter from two contrasting grassland soil profiles

Particle size fractions of soils from the surface 6 cm of two adjacent grassland plots which, as a result of different fertilizer treatments since 1897, have either a mor or a mull humus form were analysed using solid-state ¹³C nuclear magnetic resonance spectroscopy and fractionation of organic N by steam distillation. In the mor humus soil, which had received 180 kg (NH⁴)²SO⁴ ha^?1 annually and was pH 4.3, there was more C and N in the larger particle size fractions than in the mull humus soil (pH 5.8). The NMR spectra of correspondingly sized soil fractions were similar for both soils. The intensities of NMR signals between 0 and 40 ppm (alkyl-C) and between 160 and 200 ppm (carbonyl-C) increased with decreasing particle size. The intensities of the NMR signals between 60 and 90 ppm (0-alkyl-C) and between 90 and 110 ppm (acetal- and ketal-C) decreased with increasing particle size. Comparison of the NMR spectra of the >2000 um fractions from both soils with those of dried grass litter from the same plots indicated the exclusive plant origin of the C in the largest size fraction of the soils. NMR resonances between 40 and 60 ppm were attributed to alkyl-amino-C because their intensities agreed with the amino-N determinations obtained during organic N fractionation. During incubation in soil microcosms, the larger sized fractions decomposed more rapidly than the smaller fractions. However, all the correspondingly sized particle fractions from the two soils decomposed at the same rate except the >2000 pm fractions. The largest size fraction from the mor humus soil decomposed faster than that from the mull humus soil. This difference in decomposition rate could not be attributed to differences in the chemical composition of the >2000 pm fraction.     

胶体态磷和溶解态磷在不同土壤磷饱和度稻田土壤中形态分布

Soil dissolved phosphorus (P) and colloidal P mobilization could be closely related to the degree of phosphorus saturation (DPS). Effects of a wide range of DPS on the distributions of dissolved P and colloidal P in a paddy soil profile were investigated in this study. Dissolved P and colloidal P in water-dispersible soil colloid suspension increased obviously with increasing DPS. The change point of DPS was at 0.12 by using a split-line model. Above the value, dissolved P (3.1 mg P kg-1 ) in soil profile would increase sharply and then transfer downward. Compared with dissolved P, colloidal P was the dominant fraction (78%-91%) of P in soil colloid suspension, and positively related to DPS without a significant change point. The high release of colloids in subsoils with low DPS was attributed to the low ionic strength and high pH value in subsoils. The DPS also had a significant and positive correlation with electrical conductivity (EC), but it showed a negative correlation with pH value. However, the concentration of colloidal P was not greatly correlated to the pH value, EC and optical density of the soil colloid suspension. The results indicated that DPS was an important factor that may affect the accumulation and mobilization of water-extractable colloidal P and dissolved P.     

Characterization and estimation of proanthocyanidins and other phenolics in coffee pulp (Coffea arabica) by thiolysis-high-performance liquid chromatography

Fresh and 3-day-old coffee pulp of the Arabica variety were analyzed for polyphenol composition followed by characterization by two different methods. The first method consisted in subjecting coffee pulp powder to direct thiolysis. For the second method, coffee pulp was subjected to successive solvent extractions, followed by thiolysis. Quantification of phenolic compounds was then achieved by high-performance liquid chromatography (HPLC) analysis of thiolysis products. Four major classes of polyphenols were identified: flavan-3-ols (monomers and procyanidins), hydroxycinnamic acids, flavonols, and anthocyanidins. Differences in concentration of procyanidins were observed between fresh and 3-day-old coffee pulp. Constitutive units were mainly epicatechin, representing more than 90% of the proanthocyanidin units, with average degrees of polymerization in the range of 3.8-9.1. Monomer to hexamer units of flavan-3-ols from fresh coffee pulp were separated by normal-phase HPLC. Molecular size of oligomeric proanthocyanidins was obtained by matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS). Results obtained confirm the presence of oligomers of the flavan-3-ol (-)-epicatechin.     

Effect of copper sprays oh the mineral nutrient content and growth of arabica coffee seedlings in Kenya

Abstract

Coffea arabica L. seedlings (cv. S.L.34) were sprayed with varying concentrations of cuprous oxide at 0.0, 0.25, 0.50 and 0.75% for 30 days. Significant increases in the total mean fresh and dry weight; rate of transpiration; stomatal apertures; the total leaf area and plant vigor were observed on the seedlings with increasing concentrations of Cu treatments. The content of N, K, Ca and Cu were significantly increased in the seedlings at Cu spray treatments of 0.50 and 0.75% It is possible that the growth promoting effects produced in coffee by spraying high concentrations of copper is partly nutritional. This is brought about by the catalysing effects of the absorbed Cu ions, by accelerating enzymatic activities within the plant and hence increasing nutrient uptake.     

不同养分和水分模式对水稻土化学和微生物学质量参数的影响

A field experiment was conducted from 1999 to 2002 to compare and evaluate the effects of nutrient and water regimes on paddy soil quality by investigating soil chemical and microbiological parameters. Four nutrient regimes, a control, chemical fertilizers only (CF), chemical fertilizers with swine manure (SM), and chemical fertilizers with wheat straw (WS), and two soil moisture regimes, continuous waterlogging (CWL) and alternate wetting and drying (AWD), were investigated. With SM and WS total organic carbon and total nitrogen in the paddy soil were significantly higher (P < 0.05) than those with CF. A similar effect for organic amendments was observed in the soil light fraction organic C (LFOC), water-soluble carbohydrates (WSC), and water-soluble organic C (WSOC). CWL, in particular when swine manure was incorporated into the paddy soil, markedly decreased soil redox potential (Eh) and increased total active reducing substances (ARS). Meanwhile, as compared to CF, SM and WS significantly (P < 0.05) increased soil microbial biomass C (MBC) and mineralizable carbon, with differences in AWD being higher than CWL. In addition, SM and WS treatments significantly (P < 0.05) improved rice above-ground biomass and grain yield, with AWD being greater than CWL. Thus, for ecologically sustainable agricultural management of paddy soils, long-term waterlogging should be avoided when organic manure was incorporated into paddy soil.     

Pearling of hull-less barley: product composition and gel color of pearled barley flours as affected by the degree of pearling

Barley grains from two hull-less varieties, Phoenix and Candle, were pearled to various degrees (10-80%). The composition (starch, protein, beta-glucan, lipid, and ash) of pearled grain (PG) and pearling flour (PF) was determined. Effect of pearling on Hunter L, a, and b color parameters of uncooked and cooked (gel) barley flour (milled from PG) was investigated over a 3 day storage at 4 degrees C.     

Seedling growth and chemical composition of two pistachio cultivars as affected by boron and nitrogen application

The combined effects of four nitrogen (N) levels (0, 50, 100, and 150 μg/g soil) and six boron (B) rates (0, 20, 40, 60, 80, and 100 μg/g soil) on the growth and chemical composition of Kale‐ghoochi, a cultivar of pistachio (Pistacia vera L.) semi‐tolerant to B toxicity, and Badami, a cultivar very sensitive to B toxicity, were studied in a calcareous soil under greenhouse conditions. The application of 20 μg/g B has beneficial effects on leaf growth of the Kale‐ghoochi cultivar. The toxic effect of B application greater than 40 μg/g on pistachio growth was alleviated by application of 50 and 100 μg N/g for Kale‐ghoochi and Badami cultivars, respectively. The rate of B accumulation in pistachio shoots was reduced about 39 % by N additions of 50 to 150 μg/g for Badami, and 24, 52, and 69% with N rates of 50, 100, and 150 μg/g for Kale‐ghoochi, respectively. Therefore, when pistachio is grown in B‐enriched soils and/or is irrigated with water of relatively high B content, it is recommended that the plants be supplied with adequate N.     

CH4 oxidation in two temperate arable soils as affected by nitrate and ammonium application

The short-term effect of NaNO₃ or (NH₄)₂SO₄ application on CH₄ oxidation was measured under laboratory conditions with sieved soils collected from the top layer (0–12 cm) of a loamy and a sandy soil. The soils were incubated in sealed flasks and the CH₄ and CO₂ concentrations in headspace were measured periodically. On each gas sampling date the soils were analysed for inorganic N, electro-ultrafiltration organic N, and pH. NH ₄ ⁺ application to the loamy soil inhibited CH₄ oxidation entirely whereas in the untreated control soils CH₄ concentration decreased linearly with a rate of-41 nl CH₄ l^-1 h^-1; NO ₃ ^sup- application to this soil caused a small but significant reduction in CH₄ uptake. The CH₄-oxidizing ability of the sandy soil was low, even in the control. This was mainly a result of the disturbed soil structure after sieving. Both NH ₄ ⁺ and NO ₃ ^sup- treatments completely inhibited CH₄ uptake in this ligh-textured soil. The adverse impact of NH ₄ ⁺ persisted during the entire incubation, although in the loamy soil only 17% of the NH ₄ ⁺ added was recovered after 168 h. The negative effect of NO ₃ ^sup- was probably caused by an increase in osmotic potential. Immediate inhibition of CH₄ oxidation after inorganic N addition was demonstrated in two arable soils, although the effect was directly related only in part to soil N transformations.