Investigation of chocolate produced from four different Brazilian varieties of cocoa (Theobroma cacao L.) inoculated with Saccharomyces cerevisiae

Properly conducted cocoa fermentation is an important step for the production of high-quality chocolate. The aim of this work was to investigate the effect of four cocoa varieties (CCN51, PS1030, FA13, and CEPEC 2004) inoculated with Saccharomyces cerevisiae CA11 on microbial communities and the profile of volatile compounds and sensory characteristics of chocolate. The S. cerevisiae population increased significantly (p < 0.05) during the fermentations. The microbial communities varied according to cocoa variety fermentation as assessed by denaturing gradient gel electrophoresis (DGGE). The dominant yeasts were S. cerevisiae and Hanseniaspora guilliermondii, while Lactobacillus casei and Gluconobacter oxidans were the predominant bacteria in the four different fermentations analyzed. Sixty-one volatile compounds—including aldehydes (11), ketones (10), esters (14), acids (8), alcohols (8), pyrazines (5), furans (3), and others (caffeine and heptadecane)—were detected and quantified by GC–MS in the different chocolates. The sensory analysis showed that caramel was perceptible in the chocolate of PS1030, while CEPEC2004 was related to astringency, bitterness, and chocolate flavor attributes. The chocolates produced from FA13 and CCN51 were more similar in terms of sour and chocolate aroma. A “temporal dominance of sensation” (TDS) analysis showed that although the bitter attribute was dominant, the fruity, sweet, sour, astringent, and cocoa attributes were also perceptible, depending on the cocoa variety. These results suggest that the cocoa varieties had an influence on the chocolate's quality, which should be considered to obtain chocolate with different sensory characteristics or for better standardization of the process, even when using yeast as a starter culture.     

固相微萃取虾味香精中风味化合物的研究

以虾下脚料酶解液、L-精氨酸、L-丙氨酸、还原糖、硫胺素盐酸盐等为原料制备热反应虾味香精;采用固相微萃取技术并结合GC-MS检测技术对产物进行分析,总共获得61种挥发性化合物,尤其是鉴定出了二甲基二硫醚、吡嗪、3-甲基噻唑、2,5-二甲基吡嗪、2,6-二甲基吡嗪、2,3-二甲基吡嗪、三甲基吡嗪、二甲基三硫醚、甲基吡嗪、苯乙酮、噻唑醇、2-呋喃甲醇等文献报道对虾香味有贡献的化合物。     

Monitoring of cocoa volatiles produced during roasting by selected ion flow tube-mass spectrometry (SIFT-MS)

Selected ion flow tube-mass spectrometry (SIFT-MS) was used to measure the real-time concentrations of cocoa volatiles in the headspace during roasting. Alkalized and unalkalized Don Homero and Arriba cocoa beans were roasted at 120, 150, and 170 °C in a rotary roaster. The concentrations of total alcohols, acids, aldehydes, esters, ketones, and alkylpyrazines increased, peaked, and decreased within the timeframe used for typical roasting. The concentrations of alkylpyrazines and Strecker aldehydes increased as the roasting temperature increased from 120 to 170 °C. For most of the volatile compounds, there was no significant difference between Arriba and Don Homero beans, but Arriba beans showed higher concentrations of 2-heptanone, acetone, ethyl acetate, methylbutanal, phenylacetaldehyde, and trimethylpyrazine. For unalkalized Don Homero beans (pH 5.7), the time to peak concentration decreased from 13.5 to 7.4 min for pyrazines, and from 12.7 to 7.4 min for aldehydes as the roasting temperature increased from 120 to 170 °C. Also, at 150 °C roasting, the time to peak concentration was shortened from 9 to 5.1 min for pyrazines, and from 9.1 to 5 min for aldehydes as the pH increased from 5.7 to 8.7. PRACTICAL APPLICATION: SIFT-MS allows for real-time monitoring of the key volatile compounds contributing to chocolate flavor, with minimal sample preparation, thus can be used to facilitate adjusting the roasting conditions, such as temperature and time, to optimize chocolate flavor during roasting. Real-time monitoring during roasting can also be used to evaluate the flavor quality of different types of beans by comparing the concentrations of key flavor compounds.     

顶空固相微萃取结合GC-O与GC-MS技术鉴定可可粉中特征风味化合物

利用顶空固相微萃取(HS-SPME)结合GC-O与GC-MS技术鉴定可可粉中的特征致香成分,鉴定出有39种化合物参与构成可可风味,分别是:7种醛、3种醇、3种酮、8种酯、2种酸、4种吡嗪、2种胺以及其他一些特殊的挥发性物质。其中具有典型可可风味(坚果,可可香)的关键化合物有3种,分别为2,5-二甲基吡嗪、2,3,5-三甲基吡嗪以及2,3,5,6-四甲基吡嗪。     

Effects of reaction parameters on generation of volatile compounds from the Maillard reaction between L‐ascorbic acid and glycine

The formation of volatiles from the reaction between L‐ascorbic acid (ASA) and glycine (Gly) at different reaction parameters, such as temperature, time and pH, were reported and 20 different volatile compounds were identified using solid‐phase microextraction–gas chromatography–mass spectrometry (SPME‐GC‐MS). The results showed that the reaction parameters had the different effects on formation of volatiles, while the effect of pH was the most remarkable. When the initial solution pH was 4.5, the major volatiles were found to be furfural or derivatives of furan; while when pH ranged from 6.8 to 9.5, the major volatiles were found to be derivatives of pyrazines, including 2,5‐dimethyl‐pyrazine, 2‐ethyl‐5‐methyl‐pyrazine, trimethyl‐pyrazine, 3‐ethyl‐2,5‐dimethyl‐pyrazine and 2,3‐diethyl‐5‐methyl‐pyrazine. The quantity of 2,5‐dimethyl‐pyrazine and 2‐ethyl‐5‐methyl‐pyrazine reached the maximum when pH was 8.0. Finally, a possible reaction mechanism of ASA and Gly and the pathway for the formation of the various kinds of volatile products were proposed.     

Flavor Chemistry of Cocoa and Cocoa Products—An Overview

Cocoa originates from beans of the cocoa tree (Theobroma cacao L.) and it is an important commodity in the world and the main ingredient in chocolate manufacture. Its value and quality are related to unique and complex flavors. Bulk cocoas (Forastero type) exhibit strong basic cocoa notes, whereas fine varieties (Criollo, Nacional) show aromatic, floral, or smoother flavor characteristics. About 600 various compounds (alcohols, carboxylic acids, aldehydes, ketones, esters, and pyrazines) have been identified as odor‐active components. The specific cocoa aroma arises from complex biochemical and chemical reactions during the postharvest processing of raw beans, and from many influences of the cocoa genotype, chemical make‐up of raw seeds, environmental conditions, farming practices, processing, and manufacturing stages. There has been much research on cocoa flavor components. However, the relationships between all chemical components that are likely to play a role in cocoa flavor, their sensory properties, and the sources and mechanisms of flavor formation are not fully understood. This paper provides an overview on cocoa flavor from a compositional and a sensory perspective. The nonvolatile and volatile chemical components of cocoa and chocolate flavor, and their sensory properties correlated to the main influences involved in flavor formation, are reviewed.     

Improving chocolate flavor in poor-quality cocoa almonds by enzymatic treatment

Abstract: This paper proposes a method to enzymatically treat poor‐quality cocoa almonds (known as “slate”) to ensure the formation of chocolate flavor precursors. The production of flavor precursors improves the quality of these almonds, which are usually responsible for the low quality of the liquor produced. Proteases and carboxypeptidases from different sources were tested under various conditions. The different treatments were evaluated by chemical analysis (hydrolysis efficiency) and sensory analysis of the treated material compared to good‐quality cocoa almonds. The results show that it is possible, through the use of microbial enzymes, to generate the mixture of compounds that will release, after roasting, the characteristic chocolate flavor in poor‐quality almonds. However, it is necessary to optimize the conditions of enzymatic treatment to obtain better results and thus establish a process that can be used for industrial purposes for manufacturing cocoa and chocolate. Practical Application: The basidiomycete Moniliophtora perniciosa is the causative agent of witches’ broom disease (WBD) of the cocoa tree, whose seeds are the source of chocolate. It is the most important phytopathological problem of cocoa‐producing areas of the American continent, and has decimated the Brazilian cocoa industry. In Bahia (Brazil), M. perniciosa was identified in 1989 and, as a consequence of its spreading, the annual production of cocoa almonds dropped from 450000 to 90000 tons within 12 y, reducing export values from an all‐time high of about US$ 1 billion to 110 million. The high incidence of WBD incapacitates Brazil to produce enough cocoa almonds even for the internal market, leading the country to import low‐quality cocoa almonds mainly from African countries. Our work proposes an enzymatic treatment to increase the quality of that cocoa almonds and, consequently, to improve the quality of the chocolate produced and consumed in the country.     

Flavor of tomato and tomato products

Abstract

The characteristic sweet‐sour taste of tomato and its overall flavor intensity are due to the following components: reducing sugars (fructose and glucose), free acids (mainly citric’ acid), their ratio, as well as some volatile substances, not identified so far, and the interplay between the above‐mentioned groups of compounds. Of the minerals, potassium (by influencing the free acid content) and phosphate (due to its buffering capacity) indirectly affect the taste. The effect of the free amino acids (glutamic acid, glutamine, gamma‐aminobutyric acid, and aspartic acid) is not unambiguously proven.

The characteristic tomatolike flavor is predominantly determined by volatile substances. Volatile substances develop partly during ripening, partly during the comminution of the ripe fruit, as an effect of the enzymes activated. Volatile substances characterizing fresh tomato flavor are derived mainly from fatty acids and amino acids. Differences between the flavors of different varieties, the less characteristic, weaker flavor of hothouse‐grown tomatoes or artificially ripened ones, are explained by the different quantitative proportions of the volatile substances. So far no key substance playing a decisive role in the flavor of tomato has been detected. Of the approximately 400 volatile compounds so far identified, several were found, however, which have an important role in the flavor of fresh tomato (cis‐3‐hexenal, trans‐2‐hexenal, 2‐isobutylthiazole, hex‐anal, cis‐3‐hexen‐1‐ol, 2E,4E‐decadienal, 6‐methyl‐5‐hepten‐2‐one, etc.).

In the course of tomato processing the flavor substances undergo substantial qualitative and quantitative change, which may or may not be favorable. Depending on the extent of heat treatment and its duration, the reducing sugar and amino acid content decreases while the acid content (by the formation of pyrrolidone carboxylic acid) increases. A part of the volatile substances (mainly those providing “green” smell) evaporates and at the same time—traceable back to the breakdown of sugars and carotenoids—new components, among them those which characterize the “cooked” smell of tomato products, are formed (e.g., dimethyl sulphide, acetaldehyde). Although our knowledge as to the qualitative and quantitative composition of tomato flavor, the factors affecting it, and the effect of certain compounds on it has substantially increased, we are still not in the position to consciously develop the flavor during cultivation and processing. To achieve this further systematic research work is necessary.     

Effects of milk fat, cocoa butter, or selected fat replacers on flavor volatiles of chocolate ice cream

Selected volatile compounds of chocolate ice creams containing 0.6, 4.0, 6.0, or 9.0% milk fat or containing 2.5% milk fat, cocoa butter, or one of three fat replacers (Simplesse, Dairy Lo, or Oatrim) were analyzed by gas chromatography and gas chromatography-mass spectrometry using headspace solid-phase microextraction. The headspace concentration of most of the selected volatile compounds increased with decreasing milk fat concentration. Fat replacers generally increased the concentration of volatiles found in the headspace compared with milk fat or cocoa butter. Few differences in flavor volatiles were found between the ice cream containing milk fat and the ice cream containing cocoa butter. Among the selected volatiles, the concentration of 2,5-dimethyl-3(2-methyl propyl) pyrazine was the most highly correlated (negatively) with the concentration of milk fat, and it best discriminated among ice creams containing milk fat, cocoa butter, or one of the fat replacers.     

模式体系Maillard反应合成热加工肉类(牛肉)风味料的研究

以牛肉酶解物、L 半胱氨酸盐酸盐、DL 丙氨酸、D 木糖、盐酸硫胺素等为模式体系反应制备热加工肉类风味料 ,采用固相微萃取 (SPME) GC MS对反应产物进行分析 ,共分离鉴定出 71种挥发性化合物 ,尤其是分离鉴定出 2 ,5 二甲基 4 羟基 3 (2H) 呋喃酮、2 乙基 4 羟基 5 甲基 3(2H)呋喃酮、甲基吡嗪、2 ,5 二甲基吡嗪、2 ,6 二甲基吡嗪、4,5 二甲基噻唑、2 乙酰基 3 氨基噻吩、3 甲基 2 噻吩羰基醛、甲基 (2 甲基 -3 呋喃基 )二硫醚、反式茴香醚、5 乙烯基 4 甲基噻唑、四氢 3 甲基 1 ,3 二硫醇 (4 ,5 b)呋喃、十六醛等肉香或特征性牛肉风味化合物。     

新疆哈萨克熏马肠煮制过程中汤汁中游离氨基酸和挥发性物质分析

熏马肠是我国哈萨克族居民加工的一种传统肉制品,煮制成熟的熏马肠和汤汁都深受人们的喜爱,为了量化熏马肠煮制过程中滋味和挥发性风味物质的释放,对不同煮制时间汤汁中的游离氨基酸、主体风味特征、味觉特性和挥发性风味物质组分进行分析。结果显示,汤汁中的游离氨基酸总量呈增加趋势,煮制105 min和120 min时游离氨基酸总量显著高于煮制初期(P<0.05),而不同煮制时间的呈鲜、呈甜和呈苦味氨基酸百分比差异不显著(P>0.05)。汤汁咸味值、鲜味值、丰富度、苦味值、苦味回味值均随时间的延长呈增加趋势,涩味值和涩味回味值的变化规律不明显。不同煮制时间汤汁的挥发性成分具有明显差异,挥发性物质总量呈先增加后降低的趋势。汤汁主体风味成分在PC1和PC2上的方差贡献率为97.06%,风味特征明显,且在LD1和LD2上的方差贡献率为85.27%,通过风味主体成分可以区分不同的样品。煮制105 min时游离氨基酸含量较高,主体风味得到一定保持,涩味值未显著升高,较适宜用作熏马肠的熟制。     

Volatile compounds of black cumin seeds (Nigella sativa L.) from microwave-heating and conventional roasting

The volatile compounds in raw, conventionally roasted and microwave roasted black cumin (Nigella sativa L.) seeds at 0.45 kW for 2, 4, and 8 min, were analyzed by headspace-SPME gas chromatography-mass spectrometry. Among the 38 volatile compounds identified, the major compounds were thymoquinone and p-cymene in all samples. The levels of these compounds decreased with roasting. However, concentrations of pyrazines and furans increased significantly as a result of roasting and these compounds may affect the flavor of roasted black cumin seeds. Methyl pyrazine and 2,5-dimethylpyrazine were major pyrazines, formed at high concentration in seeds roasted for 8 min and in conventional roasting.     

Fluidized bed roasting of cocoa nibs speeds up processing and favors the formation of pyrazines

Roasting is an important step in cocoa processing causing water loss and generating volatile compounds responsible for chocolate aroma like nitrogen-heterocycles. In this study, the comparison of two techniques, oven roasting, and fluidized bed roasting, in terms of effective water diffusivity (De) and activation energies of formation (Ea) of nitrogen-heterocycles was achieved with cocoa nibs. Fluidized bed roasting, recognized for its energy efficiency and low-footprint synthesis, was 16 times faster than oven roasting. The order of magnitude of De in fluidized-bed-roasted nibs was −8, while it was −9 in the oven-roasted nibs. Moreover, the a_w was 50% higher in fluidized-bed-roasted nibs than in the oven-roasted ones. The Ea of nitrogen-heterocycles ranged roughly between 40 and 80 kJ/mol. Those values were lower under fluidized bed roasting than under oven roasting. The more effortless water mobility within fluidized-bed-roasted cocoa demanded lower Ea, and favored the formation of nitrogen-heterocyclics.Industrial relevanceThis study can inspire cocoa manufacturers and equipment designers to pursue the formation of nitrogen-heterocycles during the roasting process of cocoa. It can be done either by adapting and scaling the current fluidized bed coffee roasters to cocoa beans or nibs; or by exploring other alternatives capable of leading enough water diffusivity and water activity in the cocoa nibs, as reported here. These physicochemical conditions undoubtedly boosted the formation of volatile compounds responsible for chocolate aroma, e.g., the pyrazines, without carrying the formation of typical-burn volatile compounds. This natural way of favoring the generation of pyrazines in cocoa nibs could contribute to clean labels by reducing or avoiding the subsequent use of flavorings. The implementation of efficient heat-transfer techniques during roasting, e.g., fluidized bed roasting, could reduce the processing cost and improve sustainability. Studies in the matter of sensory profile, and energy consumption/conversion are called for future research.     

PRODUCTION AND EVALUATION OF CHOCOLATE BARS FROM ROASTED AND UNROASTED AFRICAN BREADFRUIT, AND BAMBARA GROUNDNUT FLOURS

Bambara groundnut (Voandezia subterranea) and African breadfruit (ABF) (Treculia africana) were procured, and then processed into flours by roasting or without roasting. The flours and cocoa powder were analyzed for functional properties. The flours of 25, 20 or 15 g were mixed with 15, 20 and 25 g of cocoa powder plus 40‐g sugar, 30‐g milk and 10‐g margarine, respectively, and heated for 20 or 10 min, then molded into bars. The chocolate bars produced were evaluated for nutrient composition and sensory properties. Results showed higher bulk density (67 g/mL) and water absorption capacity (2.1 mL/g) in cocoa powder than the substitute flours while the roasted ABF flour had the highest oil absorption capacity of 1.6 (mL/g). There was a considerable increase in protein, ash, fat, soluble carbohydrate, minerals and vitamin, except for the total lost of vitamin C in the bars. Protein varied significantly P < 0.05 per samples, where sample UG3 had the highest protein content at 8.25%, while sample RA1 the least at 3.80%. Chocolate bar from unroasted ABF (UA2) at 20:20 g combination had the best taste, and most samples were accepted by the taste panelist, indicating that these legumes could be used in the food industries to substitute for cocoa powder in chocolate bar production at levels of 50:50%.     

酶解联合高温处理对可可粉风味的影响

本文考察了酶解和高温联合处理对可可风味的作用。首先以游离氨基酸含量为评价指标,研究了5种蛋白酶对脱脂可可粉酶解液中游离氨基酸的影响,并进一步采用顶空-气相色谱-质谱联用（headspace gas chromatography mass spectrometry,HS-GC-MS）结合香气活力值（odor activity value,OAV）以及感官评价研究了高温（90~180 ℃）对可可挥发性物质的作用。结果表明,酶解处理提高了总氨基酸含量,为酶解前的1.4~5.0倍,且与未经酶处理的对照样（12种挥发物）相比,5种联合处理的样品分别检测出29（天冬氨酸酶）、31（酸性蛋白酶）、29（风味蛋白酶）、30（菠萝蛋白酶）、32（木瓜蛋白酶）种挥发物,挥发性物质种类明显增加。当反应温度达到150 ℃以上更有助于可可中具有坚果和奶油香气的杂环化合物的生成;由感官评价可得,经风味蛋白酶处理并在150 ℃反应2 h的可可风味最佳。基于OAV与感官评价的偏最小二乘（partial least squares,PLS）模型验证可得:酶解和高温处理使可可在保持原有巧克力香气的同时增加花果香和奶香风味,有助于提升可可整体香气品质。     

腌制及烤制时间对蜜汁烤鸭腿风味物质的影响

利用电子舌、高效液相色谱、氨基酸自动分析仪、顶空固相微萃取-气相色谱-质谱联用技术对不同加工阶段（腌制和烤制阶段）烤鸭腿样品的主要滋味物质和挥发性风味物质进行检测分析。结果表明：蜜汁烤鸭腿中关键滋味物质主要为呈鲜物质的5’-肌苷酸、5’-腺苷-磷酸、天冬氨酸及谷氨酸;共鉴定出61 种挥发性化合物,其中关键挥发性风味物质为7 种醛类化合物、2 种酯类化合物、1 种醇类化合物以及1 种杂环类化合物。在腌制阶段,5’-肌苷酸、5’-腺苷-磷酸含量减少,天冬氨酸、谷氨酸含量增加,挥发性风味物质的种类从29 种增至40 种;烤制阶段,5’-肌苷酸、5’-腺苷-磷酸、天冬氨酸含量显著上升,挥发性风味物质种类从40 种增至50 种,主要为醛类、酯类,其含量在烤制中期急剧增加,在烤制后期显著降低。综上所述,腌制阶段及烤制中后期为蜜汁烤鸭腿风味形成的关键时期。     

Factors influencing quality variation in cocoa (Theobroma cacao) bean flavour profile — A review

This review examined the factors that influence flavour volatiles of cocoa beans and the volume of work that needs to be done on these factors and their impact on the flavour volatiles of commercial cocoa beans. Cocoa bean flavour is one of the most important quality attributes as flavour is central to acceptability of cocoa beans and cocoa products such as chocolate. The complex composition of cocoa bean flavour depends on bean genotype, postharvest treatments such as pulp pre-conditioning, fermentation and drying, industrial processes such as roasting as well as the type of soil and age of cocoa tree. The bean genotype determines the chemical composition of the bean, specifically the contents of bean storage proteins, polysaccharides, and polyphenols. This determines the quantities and type of precursors formed during fermentation and drying processes leading to flavour formation, hence, influencing both flavour type and intensity. Cocoa bean fermentation and drying result in the breakdown of the storage proteins by endogenous proteases into amino acids and short chain oligopeptides while the polysaccharides are also degraded by invertase to glucose and fructose. The amino acids, oligopeptides, glucose and fructose react with each other during the roasting process to produce the typical cocoa flavour volatiles. Polyphenols are also oxidized by polyphenol oxidase during fermentation and drying which reduce the astringency and bitterness of the beans, thus, enhancing the flavour of cocoa beans. However, the extent to which other factors such as age of the cocoa tree and soil chemical compositions influence the formation of flavour precursors and their relationships with final flavour quality remains unclear. With increasing demand for sustainable production of high quality cocoa beans, greater understanding of factors contributing to the variations in flavour character would have significant commercial implications.     

Effect of Pretreatment with Dehulling and Microwaving on the Flavor Characteristics of Cold‐Pressed Rapeseed Oil by GC‐MS‐PCA and Electronic Nose Discrimination

Raw and dehulled rapeseeds were treated with microwave energy (800 W) from 1 to 8 min with 1‐min intervals at a frequency of 2450 MHz to investigate the influence of microwaving and dehulling pretreatment on the flavor characteristics of rapeseed oil extracted by pressing. Headspace solid phase microextraction was used to isolate the volatile compounds of rapeseed oil, which were then identified by gas chromatography‐mass spectrometry analysis. The results indicated that microwave and dehulling pretreatment of rapeseed can significantly influence the kinds and content of volatile compounds. The key flavor compounds in rapeseed oil were oxidized volatiles, heterocyclic compounds, and degradation products of glucosinolates. A pungent compound, 4‐isothiocyanato‐1‐butene, was reduced by 97% in rapeseed treated for 3 min with microwaves energy when compared to the rapeseed oil without any treatment. The pyrazine compounds in the oil appeared after 6 min of microwave pretreatment and give a pleasant roasting flavor when compared to crude oils. Principal component analysis was able to differentiate between oils obtained using 4 pretreatment processes based on volatile compounds and electronic nose. The results showed that dehulling pretreatment could improve the flavor, yet microwaving had a greater effect on the flavor of rapeseed oils.