Changes in key aroma compounds of Criollo cocoa beans during roasting

Application of a comparative aroma extraction dilution analysis on unroasted and roasted Criollo cocoa beans revealed 42 aroma compounds in the flavor dilution (FD) factor range of 1-4096 for the unroasted and 4-8192 for the roasted cocoa beans. While the same compounds were present in the unroasted and roasted cocoa beans, respectively, these clearly differed in their intensity. For example, 2- and 3-methylbutanoic acid (rancid) and acetic acid (sour) showed the highest FD factors in the unroasted beans, while 3-methylbutanal (malty), 4-hydroxy-2,5-dimethyl-3(2H)-furanone (caramel-like), and 2- and 3-methylbutanoic acid (sweaty) were detected with the highest FD factors in the roasted seeds. Quantitation of 30 odorants by means of stable isotope dilution assays followed by a calculation of odor activity values (ratio of the concentration/odor threshold) revealed concentrations above the odor threshold for 22 compounds in the unroasted and 27 compounds in the roasted cocoa beans, respectively. In particular, a strong increase in the concentrations of the Strecker aldehydes 3-methylbutanal and phenylacetaldehyde as well as 4-hydroxy-2,5-dimethyl-3(2H)-furanone was measured, suggesting that these odorants should contribute most to the changes in the overall aroma after roasting. Various compounds contributing to the aroma of roasted cocoa beans, such as 3-methylbutanoic acid, ethyl 2-methylbutanoate, and 2-phenylethanol, were already present in unroasted, fermented cocoa beans and were not increased during roasting.     

Factors affecting formation of methyl nitrite in soils

The formation of CH₃ONO in 11 soils treated with HNO₂ or NaNO₂ in a closed system, was studied by measuring the concentration in the gas space above the soil and by absorbing CH₃ONO in HI. The gaseous concentration of CH₃ONO increased and then decreased following additions of HNO₂ or NaNO₂, and the production of CH₃ONO increased with increasing concentrations of HNO₂ or NaNO₂ added to soils.
The amounts of CH₃ONO trapped in HI were 13.5 to 20.4 times higher than those determined by integrating under the net production curves. The evolved CH₃ONO amounted to 0.4 to 3.5% of added NO₂⁻, and 4.2 to 50% of the gaseous forms of N absorbed by acidic KMnO₄ solution. The CH₃ONO evolved from soils was positively correlated with the methoxy content of the soils, and inversely related to soil pH, with negligible amounts being evolved from alkaline soils. The results show that CH₃ONO is a product of NO₂⁻ decomposition in soils, and indicate that small concentrations of the gas may be produced in N–fertilized soils in which NO₂⁻ accumulates.     

Modeling the formation of some polycyclic aromatic hydrocarbons during the roasting of Arabica coffee samples

Roasting is a critical process in coffee production, as it enables the development of flavor and aroma. At the same time, roasting may lead to the formation of nondesirable compounds, such as polycyclic aromatic hydrocarbons (PAHs). In this study, Arabica green coffee beans from Cuba were roasted under controlled conditions to monitor PAH formation during the roasting process. Roasting was performed in a pilot-spouted bed roaster, with the inlet air temperature varying from 180 to 260 degrees C, for roasting conditions ranging from 5 to 20 min. Several PAHs were determined in both roasted coffee samples and green coffee samples. Different models were tested, with more or less assumptions on the chemical phenomena, with a view to predict the system global behavior. Two kinds of models were used and compared: kinetic models (based on Arrhenius law) and statistical models (neural networks). The numbers of parameters to adjust differed for the tested models, varying from three to nine for the kinetic models and from five to 13 for the neural networks. Interesting results are presented, with satisfactory correlations between experimental and predicted concentrations for some PAHs, such as pyrene, benz[a]anthracene, chrysene, and anthracene.     

Flavanol and flavonol contents of cocoa powder products: influence of the manufacturing process

Major brands of cocoa powder products present in the Spanish market were analyzed for monomeric flavanols [(+)-catechin and (-)-epicatechin] and flavonols [quercetin-3-glucuronide, quercetin-3-glucoside (isoquercitrin), quercetin-3-arabinoside, and quercetin]. In addition, the influence of the manufacturing process of cocoa powder products, in particular, the alkalinization treatment ( Dutching), on the original content of these flavonoids has been studied. (-)-Epicatechin was in the range of 116.02-730.26 microg/g, whereas (+)-catechin was in the range of 81.40-447.62 microg/g in the commercial cocoa products studied. Among flavonols, quercetin-3-arabinoside and isoquercitrin were the major flavonols in the cocoa powder products studied, ranging from 2.10 to 40.33 microg/g and from 3.97 to 42.74 microg/g, respectively, followed by quercetin-3-glucuronide (0.13-9.88 microg/g) and quercetin aglycone (0.28-3.25 microg/g). To our knowledge, these results are the first quantitative data in relation to the content of individualized flavonol derivatives in commercial cocoa powder products. The alkalinization treatment resulted in 60% loss of the mean total flavonoid content. Among flavanols, (-)-epicatechin presented a larger decline (67%, as a mean percentage difference) than (+)-catechin (38%), probably because of its epimerization into (-)-catechin, a less bioavailable form of catechin. A decline was also confirmed for di-, tri-, and tetrameric procyanidins. In the case of flavonols, quercetin presented the highest loss (86%), whereas quercetin-3-glucuronide, quercetin-3-arabinoside, and isoquercitrin showed a similar decrease (58, 62, and 61%, respectively). It is concluded that the large decrease found in the flavonoid content of natural cocoa powder, together with the observed change in the monomeric flavanol profile that results from the alkalinization treatment, could affect the antioxidant properties and the polyphenol biovailability of cocoa powder products.     

Identification of the key aroma compounds in cocoa powder based on molecular sensory correlations

Isolation of the volatile fraction from cocoa powder (50 g; 20% fat content) by a careful extraction/distillation process followed by application of an aroma extract dilution analysis revealed 35 odor-active constituents in the flavor dilution (FD) factor range of 8-4096. Among them, 4-hydroxy-2,5-dimethyl-3(2H)-furanone (caramel-like), 2- and 3-methylbutanoic acid (sweaty, rancid), dimethyl trisulfide (cooked cabbage), 2-ethyl-3,5-dimethylpyrazine (potato-chip-like), and phenylacetaldehyde (honey-like) showed the highest FD factors. Quantitation of 31 key odorants by means of stable isotope dilution assays, followed by a calculation of their odor activity values (OAVs) (ratio of concentration to odor threshold) revealed OAVs>100 for the five odorants acetic acid (sour), 3-methylbutanal (malty), 3-methylbutanoic acid, phenylacetaldehyde, and 2-methylbutanal (malty). In addition, another 19 aroma compounds showed OAVs>1. To establish their contribution to the overall aroma of the cocoa powder, these 24 compounds were added to a reconstructed cocoa matrix in exactly the same concentrations as they occurred in the cocoa powder. The matrix was prepared from deodorized cocoa powder, which was adjusted to 20% fat content using deodorized cocoa butter. The overall sensory evaluation of this aroma recombinate versus the cocoa powder clearly indicated that the 24 compounds represented the typical sweet, cocoa-like odor of the real sample.     

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.     

Factors affecting sulfate adsorption,organic sulfur formation,and mobilization in forest and grassland spodosols

Forest and grassland soils that contained varying amounts of Fe and Al were collected from England and Wales. Fractionation of free Fe and Al was accomplished to determine which components affected sulfate adsorption. Organic Fe and Al were the dominant fractions in most soil horizons and high amounts of these organically bound metals and, to some extent, crystalline Fe oxide were associated with high sulfate adsorption potentials. These adsorption potentials reflected naturally occurring amounts of absorbed sulfate and ester sulfate. Overall, the C content exhibited a positive relationship with sulfate adsorption potentials. Soils with a high C content also exhibited high rates of organic S formation. The rate of organic S mobilization was greater in soils with higher amounts of soluble sulfate. Organic S was the largest pool and, typically, sulfonate S was the most abundant constituent of the organic pool.     

Coffee roasting and aroma formation: application of different time-temperature conditions

The impact of time-temperature combinations of roasting processes on the kinetics of aroma formation in coffee was investigated. The development of 16 aroma compounds and the physical properties of coffee beans was followed in a commercial horizontal drum roasting process and in laboratory scale fluidizing-bed roasting processes at high temperature-short time and low temperature-long time conditions. All trials were run to an equal roast end point as defined by the lightness of coffee beans. In addition, the effect of excessive roasting on aroma composition was studied. Compared to low temperature-long time roasting, high temperature-short time roasting resulted in considerable differences in the physical properties and kinetics of aroma formation. Excessive roasting generally led to decreasing or stable amounts of volatile substances, except for hexanal, pyridine, and dimethyl trisulfide, whose concentrations continued to increase during over-roasting. When the drum roaster and the fluidizing bed roaster were operated in the so-called temperature profile mode, that is, along the identical development of coffee bean temperature over roasting time, the kinetics of aroma generation were similar in both processes.     

Factors affecting the formation of dark, thick epipedons beneath forest vegetation, Michigan, USA

Extremely gravelly, coarse-textured soils (frigid Udorthents and Rendolls) with different thicknesses of Oa+A horizon sequences were studied to identify factors that have influenced their genesis. These well-drained, forested soils occur on geomorphic surfaces that range in age from 3200 to 6000 years BP. The soils all have more than 500 g kg^?1 coarse fragments by mass; most contain less than 300 g kg^?1 fine earth. In the lower solum of most pedons, content of cobbles increases and amount of fine earth decreases. Most coarse fragments are dolomite and chert. Thick, gravelly Oa and A horizons are weakly correlated with parent material characteristics such as high pH and carbonate contents. Organic matter concentrations in, and thicknesses of, upper horizons are enhanced by an abundance of coarse clasts, as soils with the most gravel exhibited the thickest and darkest epipedons. Relatively high amounts of crystalline clasts in the fine gravel fraction, as well as feldspathic minerals in the fine sands, also appear to promote the development of mollic epipedons.     

Factors affecting chlamydospore formation by Fusarium solani f. cucurbitae in pure culture

A study was made of several factors affecting the production of chlamydospores by Fusarium solani f. cucurbitae in pure culture. Lysis of macroconidia and chlamydospore formation is favoured by the absence of glucose in liquid culture media. Both low pH and addition of ammonium chloride to the culture medium reduces lysis of macroconidia and inhibits chlamydospore formation. Chlamydospores formed in media lacking glucose were produced from macroconidia in a manner resembling their formation in soil. They were examined by light and electron microscopy. When placed into natural soil, they acted as survival structures.     

Factors affecting the soil sorption of iodine

Iodine-129 is an important radionuclide released from nuclear facilities because of its long radioactive half-life and its environmental mobility. Its retention in surface soils has been linked to pH, organic matter, and Fe and Al oxides. Its inorganic solution chemistry indicates I will most likely exist as an anion. Three investigations were carried out to provide information on the role of the inorganic and organic chemistry during sorption of I by soil. Anion competition using Cl^? showed that anion exchange plays a role in I sorption in both mineral and organic soils. The presence of Cl decreased the loss of I^? from solution by 30 and 50% for an organic and a carbonated sandy soil respectively. The I remaining in solution was associated primarily with dissolved organic carbon (DOC). The loss rate from solution appears to depend on two reactions of I with the soil solids (both mineral and organic) creating both a release to and a loss from solution, and the reaction of I with the DOC (from very low to high molecular weight). Composition analyses of the pore water and the geochemical modelling indicate that I sorption affects the double-charged anion species in solution the most, particularly SO₄ ^?. Iodide introduced to natural bog groundwater at three concentrations (10^?3, 10^?1 and 10 meq L^?1) remained as I^? and was not lost from solution quickly, indicating that the association of I with DOC is slow and does not depend on the DOC or I concentration. If sorption of I to soil solids or DOC is not sensitive to concentration, then stable I studies, which by necessity must be carried out at high environmental concentrations, can be linearly extrapolated to radioactive I at much lower molar concentrations.     

Factors affecting the retention of rennet in cheese curd

The coagulant retained in cheese curd is a major contributor to proteolysis during ripening. The objective of this study was to quantify the effects of several milk-related factors and parameters during cheese manufacture on the retention of coagulant in cheese curd. The amount of coagulant retained in curd was determined by its activity on a synthetic heptapeptide (Pro-Thr-Glu-Phe-[NO2-Phe]-Arg-Leu) using reversed-phase HPLC. The retention of chymosin in cheese curd increased significantly when the pH of milk was reduced at rennet addition below pH 6.1, the pH at whey drainage below pH 5.7, or the average casein micelle size in milk and when the ionic strength of milk was increased. The casein content of milk and the quantity of chymosin added to milk had no significant effect on the retention of chymosin in curd; the quantity of coagulant bound per gram of casein remained unchanged.     

精原细胞分化与凋亡的影响因素

人们对哺乳动物精子发生过程已经有了相当多的了解，但对精子发生过程的调控机制仍然了解甚少。生殖激素及原癌基因和肿瘤抑制基因的表达产物对维持正常精子发生中各类细胞的存活、增殖和凋亡，以及各类细胞受损伤后的清除均具有十分重要的作用。本文论述了促卵泡激素、雌激素、雄激素、干细胞因子、Bcl-2家族蛋白及p53蛋白在原细胞的分化和凋亡中的作用，以便人们进一步了解精子发生的调控机制。     

植物残体分解过程中微生物群落变化影响因素研究进展

植物残体是土壤有机质的重要来源,研究分解植物残体的微生物群落结构及其演替规律日益受到重视。本文综述了影响植物残体分解过程中微生物群落结构和功能变化的3个主要因素:植物残体的性质、土壤和气候环境因素、农艺措施,这些因素通过影响微生物本身的活性和植物残体分解过程中化学组成的变化从而导致微生物群落的变化,同时植物残体腐解过程中微生物群落存在明显的演替现象。以上因素的影响并不是孤立的,而是相互联系和制约的。未来针对野外田间条件下植物残体的分解过程,仍需深入研究关键微生物群落的演替规律以及不同影响因素的交互作用机制。     

Quantitative precursor studies on di- and trihydroxybenzene formation during coffee roasting using "in bean" model experiments and stable isotope dilution analysis

The objective of this study was to investigate the potential of various raw bean components as precursors of pyrogallol (1), hydroxyhydroquinone (2), catechol (3), 4-ethylcatechol (4), 4-methylcatechol (5), and 3-methylcatechol (6) under quasi "natural" roasting conditions by using the recently developed "in bean" model roast experiments. Freeze-dried, fully extracted bean shells were loaded with aqueous solutions of either single coffee compounds or fractions isolated from the raw bean solubles. After freeze-drying, these reconstituted beans were roasted, aqueous coffee brews were prepared, and the target phenols were quantified by means of a stable isotope dilution assay with LC-MS/MS detection. On the basis of the quantitative data, it can be concluded that upon coffee bean roasting, catechol (3) is primarily formed by degradation of caffeoylquinic acids from both the caffeic acid and the quinic acid moiety of the molecule, as well as from Maillard-type reactions from carbohydrates and amino acids. In contrast, pyrogallol (1) and hydroxyhydroquinone (2) are efficiently generated from carbohydrates and amino acids and, in addition, from free or chlorogenic acid bound quinic acid moieties. 4-Ethylcatechol (4) is exclusively generated upon thermal breakdown of caffeic acid moieties. 3-Methylcatechol (6) is formed primarily from the Maillard reactions and, to a minor extent, also from various phenolic precursors, whereas 4-methylcatechol (5) is produced in trace amounts only from all of the different precursors investigated. On the basis of this precursor study, reaction routes explaining the formation of the target phenols are proposed.     

Factors affecting the cropping potential of reinstated soils

Abstract. Comparisons of crop production on recently reinstated soil in Northumberland have shown that the reduced yield potential of such soil may not be inevitable. Storage of soil in bunds did not greatly reduce subsequent crop yields, but failure to drain the land did. Provided an effective drainage scheme was installed, arable and grass crops could be grown successfully, responding very well to additions of nitrogen fertilizer and other normal good husbandry practices. To date it seems that neither deep cultivation nor the use of grass leys were as effective in the restoration process as had been expected.     

Factors affecting the release of flavor encapsulated in carbohydrate matrixes

The effects of water content and temperature variation on the release of flavor components into the headspace over flavors, encapsulated by an extrusion process, in low water content carbohydrate matrixes is studied. The largest amounts of release occurred when the matrix was above its glass transition temperature, whether this was due to increased water content or elevated temperature. Under these conditions up to 70% of the sucrose in the matrix crystallized over a period of 10 days, as quantified using Fourier transform Raman spectroscopy. Smaller amounts of headspace release occurred when the water content of the encapsulated flavor system was decreased from 3. 5 to 3.1% w/w. Small amounts of release occurred from the "as prepared" materials, which were associated with the presence of small amounts of unencapsulated flavor oil with direct access to the headspace. It was concluded that release due to matrix permeability was relatively slow as compared with the above mechanisms.