啤酒花浸膏中α-酸异构化反应影响因素研究

α-酸是啤酒花的主要成分,也是啤酒苦味的主要物质,通过改变外界因素提高α-酸异构产率增加啤酒的泡沫稳定性,提高啤酒质量。采用单因素筛选试验研究了催化剂种类、催化剂含量、加热时间、加热温度、加热时pH对α-酸异构化产率的影响。影响α-酸异构化的最佳异构化工艺参数为:催化剂种类为MgCl_2、催化剂质量分数4%、反应时间180 min、温度80℃、pH为10.05,α-酸的异构化率达78.6%。试验获得的α-酸异构化最佳反应条件,为工业开发啤酒花产品、提高α-酸异构化率有重要参考价值。     

啤酒酒花颗粒异构化研究

啤酒苦味的主要来源是α-酸,在麦汁煮沸过程中α-酸会转变成苦味更强、溶解性能更好的异α-酸.以单因素和响应面试验设计为基础,啤酒花颗粒为原料,反应温度/压力、酒花添加量、缓冲液pH值和催化剂使用量为因素,研究探讨对α-酸异构化的影响.结果表明,当实际温度为116℃,酒花添加量2g,pH值11,催化剂添加量3%时,异α-酸转化率最高,达到116.03%.在实际生产过程中,α-酸的异构化率并不是很高,若在麦汁煮沸过程中加入预异构化的异α-酸会使酒花制品利用率提高.     

分光光度计法检测异α-酸

今天,大量的异构化和还原化酒花浸膏被应用于苦味啤酒的酿造,例如:异α-酸、ρ-异α-酸、四氢异α-酸和六氢异α-酸,它们都能够通过分光光度计来进行检测.由于异构化和还原化α-酸能够吸收紫外光和可见光,所以对于实现酒花浸膏的定量分析来说,分光光度计无疑是一个简单而有准确的工具.尽管酒花制品广泛应用于啤酒酿造已经超过30年,但并没有关于采用分光光度计法测定其有效成分的报道.本文的主要内容是建立一个简单、便捷的分光光度计实验方法,使用碱性甲醛来检测异构化和还原化α-酸.     

二氢异构化啤酒花浸膏的工艺优化

二氢异构化啤酒花浸膏是啤酒花中的一个主要的软树脂成分α- 酸经异构化成异α- 酸后氢化还原制备的产物,具有苦味平和、无后苦味等特点,是异α- 酸的还原产物中溶解度最好的一个产品。在正交试验的基础上,通过进一步的单因素试验考察异α- 酸加氢还原为二氢异α- 酸的工艺条件。结果表明,反应温度、催化剂NaBH4的用量、KOH 与异α- 酸的物质的量比及反应时间等都与反应产物二氢异α- 酸的收率有直接关系,其影响程度依次减弱,合成二氢异α- 酸的最佳工艺条件为氢氧化钾与异α- 酸的物质的量比1:1、NaBH4 与异α- 酸的物质的量比0.25:1、反应温度100℃、反应时间2h。在此条件下,进一步的放大实验证明,反应收率可达97% 以上。     

啤酒花及其制品的苦味物质初探

啤酒花是啤酒苦味最重要的来源。本文就酒花及其制品的苦味物质进行浅显探讨。1酒花苦味物质1．1苦味物质组成酒花中含有14％-18．5％的苦味物质,由许多酸和树脂组成。酒花树脂由硬树脂和软树脂组成,其中软树脂由α-酸、β-酸及未定性树脂组成。     

啤酒酿造过程中异α-酸变化的初步研究

本文利用高效液相色谱法检测啤酒及麦汁中的异α-酸,分析异α-酸在啤酒酿造过程中的变化。麦汁煮沸过程中,异α-酸含量与煮沸时间、温度呈正相关关系,是体现啤酒花中α-酸利用率的重要指标。啤酒发酵过程中,异α-酸的损失率12.7%～33.7%。又进一步研究了成品啤酒贮藏过程中异α-酸的降解与啤酒老化之间的关系。     

啤酒酿造过程酒花苦味物质利用率的研究

本研究采用三种不同酒花添加方案,考察啤酒酿造过程中酒花苦味物质的异构化率、利用率和损失率、在煮沸开始添加相同α-酸量的条件下．不论使用的是C02酒花浸膏还是45型酒花颗粒．它们的异构化率都为53％、研究中,另一试验在回旋沉淀槽添加100g／hL（38BU）酒花颗粒（香型）,其苦味质含量相比前四组的苦味质提高了3．5BU,而晚加酒花的异构化率仅为9．2％、研究中．发酵与过滤后酒花的苦味物质损失21．2％到32．7％．使用酒花颗粒的损失率要略高于使用酒花浸膏,酒花颗粒存在较高的多酚含量．会沉淀较多的蛋白质形成热、冷凝固物,酒花苦味物质α-酸与异α-酸会随着热、冷凝固物而被一同去除。酿造试验的最终酒花利用率范围为20．6％到23．2％。     

异构酒花浸膏中异α-酸氢化工艺优化

采用单因素筛选试验考察了氢化温度、pH值、氢气压力、氢化时间、催化剂用量、浸膏中异α-酸浓度对异α-酸氢化的影响。再利用Plackett-Burman设计研究了各因素对异α-酸氢化的影响。结果表明,底物异α-酸浓度、氢气压力和pH对异α-酸酒花浸膏氢化效果影响显著;在此基础上,采用L9(34)正交设计法对影响异α-酸酒花浸膏氢化的3个主要因素异α-酸浓度、氢气压力、pH进行了参数优化试验。结果表明,影响异α-酸酒花浸膏氢化的主次因素顺序为异α-酸浓度>氢气压力>pH值,异α-酸氢化的最佳工艺参数为:异α-酸的浓度55mg/mL,氢气压力0.2 MPa,pH值10,催化剂Pb/C用量3%,氢化时间4h。浸膏中四氢异α-酸的浓度达到58.89%,异α-酸氢化转化率达到89.73%。     

酒花添加方法对啤酒苦味一致性和风味稳定性的影响

通过试验，研究α-酸、异α-酸与酒花添加方法及啤酒老化时间的关系。色谱分析表明，在啤酒老化过程中，啤酒中的α-酸、异α-酸，和二氢异构铲酸都是不稳定的，同时也反映在啤酒的感官方面。在实验条件下，发现啤酒中四氢异构α-酸带有的独特苦味很稳定。同时，整体的风味稳定性也有明显改进。这些结果证明了酒花产生的苦味，包括二氢异α-酸，在啤酒储藏过程中对风味恶化起着非常重要的作用。     

麦汁煮沸过程中酒花α-酸异构化与降解机理的动力学研究

α-酸异构化为异α-酸的速率决定于α-酸在90～130℃煮沸阶段中的变性速率。用12mL的不锈钢管取样（pH5．2的α-酸缓冲水溶液），用于测定特定温度下不同时间的变化。α-酸和异α-酸的浓度通过高压液相色谱（HPLC）测定。异构化反应的首要因素是反应速率为温度的函数。通过试验得到：α-酸转变为异α-酸的速率常数k1=（7．9-10^11）e^（-11858／T），α-酸非特性降解的速率常数k2=（4．1-10^12）e^（-12997/T）。试验检测到异构化的活化能为98．6kj／mol，降解反应的活化能为108．0kj／mol。若α-酸的浓度降至二次半衰期时仍在持续煮沸，就会导致异α-酸发生降解而损失。     

The impact of different hop compounds on the growth of selected beer spoilage bacteria in beer

Beer spoiling lactic acid bacteria are a major reason for quality complaints in breweries around the world. Spoilage by a variety of these bacteria can result in haze, sediment, slime, off-flavours and acidity. As these bacteria occur frequently in the brewing environment, using certain hop products that inhibit the growth of these spoilers could be a solution to prevent problems. To investigate the impact of seven different hop compounds (α-acids, iso-α-acids, tetrahydro-iso-α-acids, rho-iso-α-acids, xanthohumol, iso-xanthohumol and humulinones) on the growth of six major beer spoilage bacteria (Lactobacillus brevis. L. backi, L. coryniformis, L. lindneri, L. buchneri, Pediococcus damnosous), two concentrations (10 and 25 mg/L) of each hop substance were added to unhopped beer. The potential growth of the spoilage bacteria was investigated over 56 consecutive days. A comparison of the results shows a strong inhibition of growth of all spoilage bacteria at 25 mg/L of tetrahydro-iso-α-acids closely followed by α-acids as the second most inhibitory substance. The results showed a high resistance of L. brevis to all hop compounds as well as an inhibition of L. coryniformis and L. buchneri at low concentrations of most hop components. In comparison with the control sample, L. lindneri showed increased growth in the presence of some hop compounds (rho-iso-α-acids, xanthohumol, iso-xanthohumol, humulinones). © 2020 The Authors. Journal of the Institute of Brewing published by John Wiley & Sons Ltd on behalf of The Institute of Brewing & Distilling     

ESTIMATION OF α-, β- AND ISO-α-ACIDS IN HOPS,HOP PRODUCTS AND BEER USING HIGH PERFORMANCE LIQUID CHROMATOGRAPHY

Methods are described in which high performance liquid chromatography (HPLC) is used to estimate α-, β- and iso-α-acids in hops, hop products and beer. The chromatography relies on an isocratic elution of components from a polythene ‘cartridge’ column, and the method is calibrated with the pure substances as primary standards. Using such a column over 1000 analyses have been carried out without any significant loss in resolution or precision. The procedures are sufficiently rapid for use in commercial transactions and for quality control purposes. For hops and hop extracts coefficients of variation (%) of 2·5 and 0·8 were obtained respectively for α-acids. Values of 0·9 and 0·3 were obtained for iso-α-acids in isomerised extracts and beers respectively. For some isomerised extracts it has been observed that peaks in addition to those given by the iso-α-acids are present on the chromatogram. The current method recommended by the EBC over estimates the iso-α-acid content since these other constituents are included in the analysis.     

酒花制品中异α-酸浓度的测定方法

采用分光光度法探索测定异α 酸、四氢异α 酸异构体、六氢异α 酸异构体等酒花制品中异α 酸的浓度 ,利用该方法对已知标准样品中异α 酸浓度进行检测 ,其重复性与精密度的结果表明 ,该方法的变异系数≤ 1 %,回收率在 99 8%～ 10 0 5 %之间 ;方法操作简单 ,可作为啤酒企业衡量评价异α 酸、四氢异α 酸异构体、六氢异α 酸异构体等酒花制品中异α 酸浓度的检测方法     

Analysis of hop acids by capillary electrophoresis

Micellar electrokinetic chromatography (MEKC) was used to separate components of hop extracts. The separation of a sample of iso-α-acids by MEKC was better and faster than by an established HPLC method, giving <0.8% RSD on migration times and 5–10% RSD on peak areas. MEKC was also successfully used to separate the oxidation products of the α- and β-acids and thus to monitor the stability of hop products containing them. Furthermore, MEKC distinguished among samples of reduced iso-α-acids (rho-, tetrahydro- and hexahydro- derivatives).     

ABEO-ISO-α-ACIDS

During boiling, substantial amounts of hop α-acids are transformed into oxidation products containing the same cyclopentane nucleus as the iso-α-acids: these oxidation products, which have been called abeo-iso-α-acids I, II and III, are separable by countercurrent distribution. Lager beers contained between 88 and 160 mg. of abeo-iso-α-acids per litre. Although the abeo-iso-α-acids are almost devoid of bitterness, they have strong foam-producing properties.     

Potential impact of medium characteristics on the isomerisation of hop α-acids in wort and buffer model systems

Many brewing variables, e.g., pH, boiling time, temperature, and the presence of metal catalysts, are essential in view of the isomerisation of hop α-acids into iso-α-acids. In this work, a comparative study on the impact of several selected factors on α-acids isomerisation was performed in both buffer model solutions and wort, in order to find out enhanced boiling conditions for higher isomerisation yields.     

HUMULINIC ACID IN ISOMERIZED HOP EXTRACTS

Humulinic acid, which is not bitter, behaves similarly to iso-α-acids in some analytical estimations of beer bitterness. The humulinic acid content of a number of isomerized hop extracts was estimated using thin layer chromatography.     

Hop bitter acids inhibit carbohydrate metabolism,enhance biogenic amine metabolism and alter L-malic acid,glutamic acid and arginine metabolism of Lactobacillus brevis 49

Beer contains only limited amounts of readily fermentable carbohydrates and amino acids. Beer spoilage lactic acid bacteria have to come up with metabolic strategies in order to deal with selective nutrient content. The research was performed to investigate the influence of iso-α-acids on the metabolism of organic acids, biogenic amines (BAs), off-flavour compounds, carbohydrates and amino acids of Lactobacillus brevis 49. Only glyoxylic acid and ethyl formate in de man, rogosa, sharpe broth was consumed, and multiple organic acids, BAs and off-flavour compounds were produced. By supplementing a series of concentrations of hop iso-α-acids, consumption of L-malic acid, glutamic acid and arginine and generation of BAs were found benefit for bacteria to develop hop-resistance. In the metabolism of carbohydrates, glucose was preferred over maltose and maltriose, and hops significantly inhibited the utilisation of carbohydrates. The results provide comprehensive information of metabolites of L. brevis 49 under various concentrations of hop stress.     

EFFECT OF STORAGE ON HOP EXTRACTS

Representative commercial hop extracts suffered no appreciable loss either of α- or β-acids or of bittering value when kept for 2 to 21 months in closed containers. Though there was loss of α- and β-acids on prolonged exposure of the extracts to air, it did not lead to a corresponding loss of bittering value. Of a range of commercial isomerized extracts, most proved satsifactorily stable on storage. However, when large losses of iso-α-acids did occur they were accompanied by corresponding reductions in bittering value. With reference to bittering compounds, there appeared to be no significant differences in the storage stability of beers bittered using hops or extracts of various types.     

COMPARISON OF TIME-INTENSITY WITH CATEGORY SCALING OF BITTERNESS OF ISO-α-ACIDS IN MODEL SYSTEMS AND IN BEER*

A 17-point non-numerical category scale indicated a direct, linear relationship between average perceived bitterness and concentration of iso-α-acids in water and in a commercial lager. Time-intensity (T-I) tracings yielded additional information: the rate of increase in bitterness after taking the sample into the mouth; the rate of decrease after reaching maximum intensity; the events associated with swallowing; and total duration, which ranged from 13 to 42 s across judges. The T-I curves revealed a burst of bitterness intensity immediately after swallowing, which was proportional to the concentration of iso-α-acids for water solutions, but not for beer. Addition of 2.6% ethyl alcohol to the lager enhanced bitterness, particularly at low levels of added iso-α-acids, whereas addition of 2.0% glucose reduced bitterness in the control as well as in beer with added iso-α-acids. In water, 20 and 30 ppm of iso-α-acids were more bitter and had a longer duration than in beer. Among judges there were marked differences in the patterns of the T-I tracings, but there was excellent reproducibility within judges across replications.