啤酒酿造过程中萜烯醇类化合物变化规律

采用基于顶空固相微萃取-气相色谱质谱技术(HS-SPME/GC-MS)建立的啤酒中酒花物质的检测方法,跟踪了啤酒酿造过程中源自酒花的5种萜烯醇类香气化合物的变化规律,初步为啤酒厂酒花配方及工艺调整奠定了理论基础。通过对糖化过程中不同酒花配方、不同煮沸方式及酒花添加工艺对冷麦汁中萜烯醇类化合物含量影响的研究,发现冷麦汁中的萜烯醇类化合物主要受最后一次添加酒花的添加量和添加时机影响,最后一次酒花在煮终回旋前添加较煮终前10 min添加,更利于萜烯醇类化合物在冷麦汁中的保留,这与国外的late-hopping工艺相一致;与煮终前10 min最后一次添加相比,在煮终回旋前最后一次添加酒花能使冷麦汁中里那醇含量提高209.4%,α-萜品醇为91.2%,香叶醇为31.4%,橙花醇175.0%。通过研究发酵过程中萜烯醇类化合物的变化规律,发现5种萜烯在发酵过程中呈上升趋势,且它们之间可能被酵母相互转化。     

酒花香气成分的检测及富含典型酒花香气啤酒的试验研究

单萜类物质是贡献啤酒酒花香气的重要成分。本研究在100L中试规模,原麦汁浓度为14°P,苦味质为20BU的条件下,从不同酒花添加工艺、添加量和品种三方面分析了啤酒中8种单萜类酒花香气物质的含量,并进行感官品评,发现在发酵罐中添加l％o香花的效果最好,啤酒风格因酒花品种不同而有异。8种酒花香气物质中里那醇、香叶醇、口．香茅醇和α-萜品醇最为重要,其啤酒中的含量与酒花中里那醇和香叶醇含量密切相关,前三者与前人研究-致,但本研究发现“α-萜品醇”也是重要香气物质之-。但啤酒中的酒花香气物质含量高,酒花香味不-定强,这可能与其构型有关,因此,又研究了三种酒花在啤酒酿造过程中酒花香气物质的同分异构体,包括（R）-（-）-里那醇、（S）-（＋）-里那醇、（-）-α-萜品醇、（十）-α-萜品醇、（R]-（＋）-卢-香茅醇、（S）-（-）-卢-香茅醇的含量。研究发现酒花品种的差异会引起同分异构体含量及比例的显著差异,加上其阈值的变化。进-步验证了同分异构体对啤酒中酒花香味的影响。     

单萜醇类在啤酒发酵过程中的变化及对酒花香气的贡献

啤酒中的里那醇、香叶醇和β-香茅醇等单萜醇类物质是贡献啤酒酒花香气的重要成分,其在发酵过程中的变化对啤酒香气质量产生直接影响。结合感官品评和数理统计手段,发现在4%(v/v)乙醇溶液中,不同浓度的里那醇、香叶醇和β-香茅醇的单一物质香气及其协同作用香气呈现出的特性均不同。当含量不高于50μg/L时,混合不同浓度的3种物质,发现并非3者的浓度越高啤酒获得的香气强度就越大,且当里那醇浓度为12.5μg/L,香叶醇浓度为12.5μg/L,β-香茅醇浓度为25μg/L时,3者的协同作用可促使啤酒获得最突出的酒花香气。此外,里那醇、香叶醇和β-香茅醇在发酵过程中发生了生物化学变化,其中里那醇主要转化为α-萜品醇;香叶醇主要转化为β-香茅醇;β-香茅醇主要转化为乙酸香茅酯。3者总体损失率分别为36.6%、45.1%和38.1%。结合上述两方面研究,在采用发酵罐添加酒花的方式进行酿造时,控制好酒花的添加量,促使啤酒中里那醇、香叶醇和β-香茅醇的最终含量在12.5μg/L,12.5μg/L和25μg/L即可达到合理利用酒花香气资源的目的。     

三个国家Cascade酒花香气对比分析

采用顶空固相微萃取气相色谱-质谱（HS-SPME-GC-MS）联用的方法分析测定中国、美国和新西兰Cascade颗粒酒花中香气化合物的组成,分别与Cascade酒花在麦汁煮沸时添加酒花的酒样香气化合物和在啤酒储存期干投酒花的酒样香气化合物进行对比分析,同时分别进行感官品评。结果表明,三个国家Cascade酒花的香气化合物相比较,新西兰Cascade酒花在麦汁煮沸过程中添加,香气化合物减少17种,增加3种,在啤酒储存期干投香气物质减少19种,增加12种;美国Cascade酒花在麦汁煮沸过程中添加,香气化合物减少18种,增加2种,在啤酒储存期干投香气物质减少12种,增加12种;中国Cascade酒花在麦汁煮沸过程中添加,香气化合物减少12种,增加5种,在啤酒储存期干投香气物质减少11种,增加14种。减少的主要是萜烯类物质,增加的主要是醇和酯类物质。感官品评方面,在麦汁煮沸过程中添加Cascade酒花,中国的Cascade酒花具有突出的柑橘、柠檬、苹果或桃子的香味;在啤酒储存期干投Cascade酒花,生成较多的醇类物质,酒花的利用率较高。     

酯类物质对啤酒质量的影响

啤酒是以麦芽为主要原料,添加酒花,经酵母发酵酿制而成的一种含二氧化碳、低酒精度的饮料酒。啤酒中的高级醇类、醛类、双乙酰、有机酸、酯类和含硫化合物等均对啤酒的风味有着重要的影响,这些发酵副产物与酒精、二氧化碳共同组成啤酒的酒体,并形成啤酒特有的风味。当其中一种或多种物质含量过高时,就会改变啤酒的风味特性,导致啤酒风味缺陷,     

啤酒风味物质研究进展

近年来,啤酒产业不断发展,人们对啤酒的风味要求不断提高。啤酒的风味是衡量其品质的关键指标,种类繁多的挥发性和非挥发性成分是啤酒具有特有风味的主要原因。啤酒因原料、酵母、发酵工艺、贮藏等条件的不同,成品风味有很大差异。本文综述了啤酒风味物质的组成,从啤酒的香气成分、苦味成分和不良风味3个方面阐述风味物质的来源。啤酒花中萜烯类化合物、酵母发酵产生的酯和高级醇是啤酒重要的香气来源。麦汁、干加酒花、添加功能性原料、无醇的新型啤酒等新技术的应用也对啤酒的香气有一定协同作用。啤酒花中的α-酸、β-酸及多酚物质赋予啤酒特有的苦味。酒花添加量、添加时间,啤酒过滤和灭菌对啤酒苦味具有一定的影响。啤酒的酿造过程中产生的双乙酰、含硫化合物和贮藏期间产生的老化味会使啤酒产生不良风味。超高压技术对降低啤酒不良风味有一定作用。通过本综述,有望推动改进啤酒生产配方、提升啤酒风味、改进工艺和贮藏条件等方面研究的深入进行。     

西楚酒花对玫瑰香葡萄酒香气的影响

以玫瑰香葡萄为原料,探讨在葡萄酒酿造中加入西楚酒花后的香气特点。采用气相色谱-质谱联用技术(GC-MS)对添加不同浓度的西楚酒花玫瑰香葡萄酒中挥发性物质进行定性鉴定和定量分析,运用主成分分析法(PCA)分析不同浓度的西楚酒花玫瑰香葡萄酒的关键香气物质,并结合香气阈值确定各挥发性成分的相对气味活度值(ROAV)。结果表明:共检测到31种香气成分,包括13种酯类、11种醇类、1种酸类、6种其他类,其中醇类和酯类物质含量较高,对葡萄酒整体香气具有重要贡献作用;通过主成分分析得出,5个酒样在前3个主成分呈分散分布,说明添加西楚酒花的玫瑰香葡萄酒与普通酒样的香气成分种类之间差异明显;在酒样中,随着西楚酒花浓度的增加,同时玫瑰香葡萄酒的特征风味物质香茅醇的含量也在增加。综合得出,西楚酒花葡萄酒中能保留部分酒花香味物质,酒花香气物质与葡萄酒本身香气物质并不是简单叠加。     

黄桃酒发酵过程中风味物质的变化

为了研究黄桃酒发酵过程中风味物质动态变化,本研究采用顶空固相微萃取(HS-SPME)结合气相色谱-质谱联用(GC-MS)技术分析风味物质,结合香气活力值(OAV)确定主要风味物质。结果表明,发酵7 d制备的黄桃酒,酒精度14.50%(v/v)、总酸31.54 g/L、可溶固形物12.37 °Brix、总黄酮1.08 g/L。感官评价表明,所制备黄桃酒保留了桃果实的清香,同时又有酒的醇香和酯香。顶空固相微萃取-气相色谱与质谱联用(HS-SPME/GC-MS)结合分析得到:发酵过程中共检测出70种风味物质,含量较多的是酯类(29种)、醇类(15种);发酵过程中风味物质种类变化不大,但每类风味物质含量却有较大变化。酯类、醇类物质含量在主发酵过程中呈递增趋势,后熟时趋稳;醛类、酮类和酸类物质含量逐渐减少。通过计算香气活力值(OAV)确定16种物质对黄桃酒风味贡献较大,其中辛酸乙酯、γ-癸内酯和右旋萜二烯对黄桃酒香气贡献最大,活力值大于20。在发酵过程中,酯类、醇类物质的增加赋予黄桃酒浓郁的酒香,同时保留了黄桃的特征香气物质。     

陈酿时间对发酵型香菇酒香气成分及酒体风味的影响

采用顶空固相微萃取与气相色谱-质谱联用技术对发酵型香菇酒陈酿早期香气成分变化进行动态检测,通过峰面积归一法计算各香气成分相对含量,并结合相对香气活度值（relative odor activity value,ROAV）进行分析。结果表明：发酵型香菇酒在陈酿早期形成大量香气成分,检出54 种,其中1-辛烯-3-醇、异戊醇、癸酸乙酯等8 种挥发性香气化合物是发酵型香菇酒具有独特风味的主要原因。陈酿早期香菇酒香气成分变化较大,醇类与酸类香气物质的相对含量总体下降,酯类香气物质相对含量明显上升,其他类香气物质变化不大。陈酿60 d及陈酿180 d的成品香菇酒的香气成分相对含量及ROAV,差异不显著（P＞0.05）。证明在陈酿早期即形成了发酵型香菇酒的主体香,提示生产中可适当缩短发酵型香菇酒的陈酿时间,缩短生产周期,提高生产效率。     

酿造条件对酿酒酵母发酵香气的影响

采用顶空固相微萃取结合气相色谱-质谱联用技术,比较不同酿酒酵母菌株（CY3079、LA-FR、LA-RA、MST、OFC）在模拟葡萄汁中发酵产香性能,并分析不同酿造条件下各类发酵香气的变化规律。结果表明：LA-FR酵母菌株产酯类、萜烯类物质能力最强,产香性能最好,因而选用LA-FR酵母菌株研究氮源质量浓度、发酵温度、pH值、SO2添加量对各类香气物质的影响。当氮源质量浓度从1.0 g/L增加至2.0 g/L时,LA-FR菌株所产生的醇类、萜烯类物质含量分别降低36.41%和42.56%,酯类、酸类物质含量分别增加72.92%和26.86%;当发酵温度在18～28 ℃范围内变化时,较低温度发酵有利于酯类、萜烯类物质的积累,但不利于醇类、酸类物质的合成;当pH值从3.2升高至3.8时,酯类、萜烯类含量分别增加19.50%和67.43%,醇类、酸类含量分别降低30.24%和34.16%;SO2添加量与醇类、酯类合成量呈正相关,与酸类、萜烯类合成量呈负相关。多元回归分析结果表明,氮源质量浓度对醇类和酯类香气含量影响最大,发酵温度对酸类物质含量影响最大,SO2添加量对萜烯类香气含量影响最大,该研究结果可为深入研究复合因素对发酵香气的影响及葡萄酒香气风味调控提供理论依据。     

香型酒花对啤酒酿造质量的影响

啤酒花有两种基本类型:苦型和香型酒花.它赋予啤酒特有的苦味和香味,同时也影响啤酒的泡沫形成;酒花中含有酒花树脂、酒花油和多酚物质.本文主要就香型酒花在啤酒酿造过程中的风味变化以及对啤酒香味质量的影响进行了讨论.     

国产酒花香气成分及酿造特性的研究

为探究国产酒花在啤酒酿造中的酿造价值,将7种中国本土种植和培育的啤酒花（卡斯卡特、D1号、拿盖特、柯密特、青岛大花、哥伦布、哈拉道）在模拟啤酒酿造过程中添加,并在关键酿造节点取样,使用气相色谱-质谱（GC-MS）技术分析酒花在啤酒酿造过程中不同时期香气成分,并通过感官品评综合评估其酿造价值。结果表明,7种国产酒花香气成分均能满足啤酒酿造要求,除哥伦布为高α-酸酒花,青岛大花为苦型酒花外,其余品种均为苦香兼优型酒花,该类酒花既可煮沸时添加也可用于后期酒花干投,其中,卡斯卡特酒花与D1号酒花干投样品中月桂烯含量分别为0.458μg/L、0.324μg/L,远高于一般酒花,非常适合印度淡色艾尔啤酒（IPA）酿造。     

A Study of the Fate of Volatile Hop Constituents in Beer

SUMMARY— The volatile material from a pilot plant brewed beer (hopped) has been analyzed by the direct combination of capillary gas chromatography and mass spectrometry. None of the major volatile terpenoid hydrocarbons of hops (myrcene, caryophyllene, humulene) could be detected in the beer volatiles. The only volatile constituents in the beer which could be assigned to hops with some certainty were ethyl dec-4-enoate and ethyl deca-4,9-dienoate, which exist in the hop oil as the methyl esters.
A capillary gas chromatography analysis of a beer which was brewed without hops but with methyl dec-4-enoate (0.02 g/L) showed that this ester was converted to the ethyl ester by the fermentation.
A study was also carried out using model systems to parallel the "kettle boiling" step of brewing. This involved boiling hops with water for a set period and filtering the water extract from the hops. It was found that the pattern of volatile hop constituents in the filtrate (hopped water) was quite different from hop oil and consisted principally of free organic acids, humulene epoxide, humulenol, and other hop oil oxygenated components. With fine filteration through Celite, very little myrcene, humulene, or caryophyllene were transferred into the water, even though they form the major part of hop volatiles. If, however, only coarse filtration was used, a greater amount of these hydrocarbons were found in the filtrate.
It is concluded that the amount of volatile hop oil constituents reaching the final beer probably depends upon the exact conditions of the brewing process used. No evidence could be found in the present work to support the view that the tiny amounts that do survive in beer prepared by the typical American process could contribute more than a very minor amount to the characteristic beer aroma.     

Humulus lupulus – a story that begs to be told. A review

The hop cones of the female plant of the common hop species Humulus lupulus L. are grown almost exclusively for the brewing industry. Only the cones of the female plants are able to secrete the fine yellow resinous powder (i.e. lupulin glands). It is in these lupulin glands that the main brewing principles of hops, the resins and essential oils, are synthesized and accumulated. Hops are of interest to the brewer since they impart the typical bitter taste and aroma to beer and are responsible for the perceived hop character. In addition to the comfortable bitterness and the refreshing hoppy aroma delivered by hops, the hop acids also contribute to the overall microbial stability of beer. Another benefit of the hop resins is that they help enhance and stabilize beer foam and promote foam lacing. In an attempt to understand these contributions, the very complex nature of the chemical composition of hops is reviewed. First, a general overview of the hop chemistry and nomenclature is presented. Then, the different hop resins found in the lupulin glands of the hop cones are discussed in detail. The major hop bitter acids (α‐ and β‐acids) and the latest findings on the absolute configuration of the cis and trans iso‐α‐acids are discussed. Special attention is given to the hard resins; the known δ‐resin is reviewed and the ε‐resin is introduced. Recent data on the bittering potential and the antimicrobial properties of both hard resin fractions are disclosed. Attention is also given to the numerous essential oil constituents as well as their contributions to beer aroma. In addition to the aroma contribution of the well‐known essential oil compounds, a number of recently identified sulfur compounds and their impact on beer aroma are reviewed. The hop polyphenols and their potential health benefits are also addressed. Subsequently, the importance of hops in brewing is examined and the contributions of hops to beer quality are explained. Finally, the beer and hop market of the last century, as well as the new trends in brewing, are discussed in detail. Hop research is an ever growing field of central importance to the brewing industry, even in areas that are not traditionally associated with hops and brewing. This article attempts to give a general overview of the different areas of hop research while assessing the latest advances in hop science and their impact on brewing. Copyright © 2014 The Institute of Brewing & Distilling     

酒花老化评价的研究进展

酒花是啤酒生产的重要原料,确定酒花新鲜度更是保证啤酒酿造质量的关键。本文综述了国内外关于酒花老化评价的研究进展,根据酒花老化过程中苦味物质(α-酸和β-酸)、多酚和香气物质的变化情况,阐述了目前评价酒花老化程度的指标,为建立更为准确的酒花老化评价体系的研究提供一些理论参考。     

125th Anniversary Review: The Role of Hops in Brewing

Although hop technology has been a substantial part of brewing science for the last 130 years, we are still far from claiming to know everything about hops. As hops are considered primarily as a flavour ingredient for beer, with the added benefit of having anti‐microbial effects, hop research is focused on hops as a bittering agent, as an aroma contributor and as a preservative. Newer fields in hop research are directed toward the relevance of hops in flavour stability, brewing process utilisation, the technological benefits of hops in brewing as well as hops as a source of various substances with many health benefits. However the more we find out about the so‐called “spirit of beer” the more questions emerge that demand answers. While hop research was only an ancillary research field for decades, during the last ten years more universities and breweries have determined that hops must play a meaningful role in their research efforts. This article gives an overview of the up‐to‐date knowledge on hop aroma, hop derived bitterness, and the role of hops in flavour stability as well as light stability. Hop research is a wide field, therefore in this review only selected topics are reviewed. Other research areas such as hops utilisation, the antifoam potential of hops, or the advances in knowledge pertaining to the physiological valuable substances of hops go beyond the scope of this article.     

The effect of hopping regime,cultivar and β‐glucosidase activity on monoterpene alcohol concentrations in wort and beer

Previous studies show that the complexity of hop aroma in beer can be partly attributed to the hydrolysis of glycosidically bound monoterpene alcohols extracted from hops during the brewing process to release volatile aglycones. However, fundamental studies that examine the extraction of glycosides during brewing and their subsequent hydrolysis by yeast have not been performed. Furthermore, extraction of other hop‐derived compounds into beer shows a strong dependency on the hop cultivar being used and the point at which it is added. This study focused on the extent of glycoside extraction owing to hopping regime and cultivar, and their hydrolysis by yeast β‐glucosidase activity. Glycoside concentrations of wort made with three different hopping regimes and three cultivars were measured by the difference in volatile aglycone concentrations between samples treated with purified β‐glucosidase and untreated samples. Aglycone concentrations were measured by solid‐phase microextraction gas chromatography–mass spectrometry. Additionally, β‐glucosidase activities for 80 different yeast strains and their effect on aglycone concentration in wort were determined. Results showed that yeast have a wide range of abilities to hydrolyse glycosides with a maximum hydrolysis occurring after 3 days of fermentation regardless of yeast activity. Although it was shown that yeast are capable of glycoside hydrolysis, glycoside concentrations in wort are low and make small contributions to hop aroma. These results help explain the extent to which different brewing yeasts and hopping regimes contribute to hoppy beer aroma through the hydrolysis of non‐volatile hop‐derived compounds. Copyright © 2017 The Institute of Brewing & Distilling     

The Influence of Hopping on Formation of Carbonyl Compounds During Storage of Beer

Improving beer flavour stability is an important brewing goal. Pilot scale brewing trials (50 L) were performed that focused on the determination of the influence of hop pellet dosage and dosage timing on carbonyl compounds in stored beer. The reducing activity of experimental worts, beers and stored beers appeared to depend on the hop pellet dose. Brews with lower amounts of hop antioxidants showed an enhanced formation of carbonyl compounds over the course of beer storage. A correlation between DPPH reducing activity and the content of some carbonyls, including the important markers 2‐furfural and (E)‐2‐nonenal, was found. Fresh and aged beers hopped by different amounts of hop pellet doses were clearly distinguishable according to their carbonyl content using Cluster analysis. Results of the sensorial analysis corresponded to the analytical criteria values. Results of this study bring further evidence of the indispensable impact of hop antioxidants on the suppression of undesirable carbonyl compound formation in the course of beer staling, which can be significant in beers hopped by aroma hops. However, hop antioxidants are only one of many factors affecting beer staling.     

原料对麦汁酚酸抗氧化能力的影响

本文检测了不同啤酒麦芽及酒花品种中酚酸的含量,分析了酿造原料对麦汁抗氧化能力的影响。结果发现,加麦、澳麦、国产西北三种麦芽中,澳麦提供的抗氧化能力较小,同时提供的老化物质也最少,对提高啤酒的风味稳定性有利。以单位α-酸计,香花比苦花提供更多的酚酸和抗氧化能力。酒花老化过程损失相当多的酚酸,酿造过程中应尽量使用新鲜的酒花。     

酒花与啤酒中单萜化合物的研究进展

单萜化合物是酒花和啤酒中香气化合物的重要组成部分,具有典型的酒花香气特征,在自然界中以游离态和糖苷结合态两种形式存在。本文重点阐述了酒花中单萜化合物的生物合成途径、控制其合成的关键酶和基因以及酒花中单萜醇化合物相互转化关键酶的研究进展。此外,本文还综述了酒花与啤酒中单萜化合物的变化及其影响因素,糖苷结合态单萜化合物的结构、含量及其分析方法,并对单萜化合物在啤酒中的研究前景进行展望。