FATTY ACIDS IN ISOMERIZED HOP EXTRACTS AND GUSHING

A procedure is described for the analysis of fatty acids (C₁₂-C₁₈ individually and C₁₈₊ as a group) in hops, hop extracts and isomerized hop extracts, and analytical results are quoted for twenty-one different samples of hops or hop products. Isomerized extracts varied widely in their content of fatty acids and isomerization and processing of hops appeared to eliminate some fatty acids selectively so that isomerized extracts were enriched in palmitic acid, linoleic acid and linolenic acid. Some hop extracts had a surprisingly high content of lauric acid. The analytical results are discussed in relation to gushing.     

PAPER STRIP ANALYSIS OF SUBSTANCES DERIVED FROM HOPS

Reasonably satisfactory methods exist for the analysis of α acids in hops. The analysis of iso α acids in beer is not so well developed. The same determinations for hop extracts and isomerized hop extracts are much more difficult. A new method for these determinations is now described. It is based on a chromatographic technique using buffered paper strips and is applicable not only to hop extracts, isomerized or not, but also to hops and to beer. The percentage of α acids and iso α acids can be determined in one analysis. Eventually the determination of humulinic aci ds β acids and hulupones will also be possible. After separating these substances from one another their amounts are determined spectrophotometrically. The method is very fast and is more accurate than any other known method.     

RAPID SPECTROPHOTOMETRIC METHOD FOR DETERMINATION OF THE BITTERING VALUE OF ISOMERIZED HOP EXTRACTS

A method is described which allows the rapid determination of the bittering value of isomerized hop extracts. The method is also applicable in the case of isomerized hop extracts containing impurities such as α-acids and β-acids.     

异构酒花颗粒在啤酒酿造中的应用研究

对异构酒花颗粒和普通酒花颗粒进行了对比研究。结果表明,添加异构酒花颗粒可减少苦味物质的损失,酿造出的啤酒优于只采用普通酒花颗粒酿造出的啤酒,特别是酒花香突出,泡特性好。     

THE HIGH PERFORMANCE LIQUID CHROMATOGRAPHY OF HOP RESINS

Hop resins are eluted from a specially developed weak anion exchange bonded phase silica using citric acid, methanol, water, mixtures as eluent. Fresh and deteriorated hops and isomerized extracts have been examined. The ratio of the humulone congeners in different hop varieties and the conversion of α-acid to iso-α-acid during the hop boil have been measured.     

QUANTITATIVE ANALYSIS OF HOPS AND HOP EXTRACTS BY HIGH PRESSURE ION EXCHANGE CHROMATOGRAPHY

A new analysis for hop acids in hops and hop extracts is described. It is based on recent developments in high pressure liquid chromatography using pellicular anion exchange column filling material. Quantitative evaluation of α-acids, β-acids and oxidation products in hops and hop extracts is carried out by standard addition of pure humulone. The α-acids are completely separated from other hop substances before quantitation. The results of α-acids determinations must therefore be more accurate than was formerly possible and they are compared with conductometric titration results which are systematically higher. This is to be expected as it becomes more and more obvious that paper strip and conductometric analysis are not selective enough and determine fractions as “α-acids” which are in fact oxidation products of the hop acids.     

THE SUPPRESSION OF GUSHING BY THE USE OF HOP OIL

The addition to beer of small amounts of hop oil provides a means of suppressing gushing, without adversely affecting foam stability. The hydrocarbon fraction of hop oil is a more effective gushing suppressor than the oxygenated fraction.     

QUANTITATIVE DETERMINATION OF HOP BITTER SUBSTANCES AND THEIR DERIVATIVES IN HOP EXTRACTS BY THIN LAYER CHROMATOGRAPHY

A method is described which allows the separation of hop bitter components and derivatives present in hop extracts by thin-layer chromatography on a mixture of silica gel and cellulose. This method can be used to evaluate the purity of hop extracts, isomerized hop extracts and complementary base extracts.     

HOP RESINS AND BEER FLAVOUR V. THE SIGNIFICANCE OF OXIDIZED HOP RESINS IN BREWING

Oxidation products of α- and β-acids have been used to flavour beers. Ion-exchange chromatographic examinations of extracts of these beers are described. Examination of old hops has revealed the presence of certain oxidation products of hop resins.     

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.     

THE EFFECT OF HOP SUBSTANCES ON THE PRODUCTION OF FUSEL OIL

Unhopped beers contain more fusel oils than the corresponding normally hopped beers when certain strains of yeasts are used during fermentation. Water soluble fractions of hops and some soft resin constituents can influence fusel oil production. When hops are completely replaced by isomerized hop extracts the use of some additional hop fraction in the copper leads to the resulting beer having a similar fusel oil content to one hopped in the usual way. Partially hopped beers (0·25 lb./brl.) usually have similar fusel oil contents to beers produced using the normal quantity of hops (1·0 lb./brl.).     

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.     

Induction of Gushing with Recombinant Class II Hydrophobin FcHyd5p from Fusarium culmorum and the Impact of Hop Compounds on its Gushing Potential

Malt‐induced gushing is a problem that has been known for many years. Mechanisms and inducing agents are still not fully understood and identified. Hydrophobins produced by various filamentous fungi are currently under discussion as biological gushing‐inducing compounds. In the current study the class II hydrophobin FcHyd5p, from the cereal pathogen Fusarium culmorum, was employed in beer and other carbonated beverages for gushing experiments and the influence of hop compounds on gushing potential was examined. It was demonstrated that this protein strongly induces gushing in various carbonated beverages, including beer. It was further demonstrated that the resulting gushing volume is susceptible to certain hop compounds and can be decreased significantly by the addition of these substances.     

PREPARATION OF HOP EXTRACTS WITHOUT USING ORGANIC SOLVENTS

Extraction of hops with liquid carbon dioxide at ambient temperature provides an attractive means of producing hop extracts which are rich in α-acids and free from hard resins, polyphenols, pigments and residual organic solvents. The resulting yellow extracts give beer with a clean bitter flavour when they are added during wort boiling. Manufacturing costs using the process are likely to be substantially less than in a conventional hop extraction plant.     

EFFECTS OF PRODUCTS FROM SEEDLESS AND SEEDED HOPS ON BEER QUALITY

Comparative semi-industrial brewing trials with standard Continental lager beers have been carried out in Switzerland using hop pellets and hop extracts made from seeded and seedless hops. It has been demonstrated that the products from seeded hops containing 8% and 9% of seeds have no adverse effect on beer quality and that the flavour of all the beers was acceptable.     

The Oxygenated Sesquiterpenoid Fraction of Hops in Relation to the Spicy Hop Character of Beer

Hop‐derived sesquiterpenoid‐type oxidation products have been associated with a spicy or herbal hoppy beer character. However, the flavour threshold values of hitherto identified oxygenated sesquiterpenes are generally much higher than their estimated levels in beer. By applying two‐step supercritical fluid extraction of hop pellets using carbon dioxide, followed by chromatographic purification of the enriched sesquiterpenoid fraction, highly specific varietal hop oil essences containing all main oxygenated sesquiterpenes were obtained. Post‐fermentation addition (at ppb levels) of these purified sesquiterpenoid essences from various European aroma hops led to distinctive spicy or herbal flavour notes, reminiscent of typical ‘noble’ hop aroma. It is concluded that a spicy hop flavour impression in beer depends significantly on minor constituents of the natural sesquiterpenoid hop oil fraction.     

NON-IMPLICATION OF HOP α- AND β- ACIDS AS SOURCES OF SULPHUR COMPOUNDS IN BEER

Whereas hop oil terpenoids can give rise to organoleptically undesirable sulphur compounds in beer brewed using hops dressed on the bine with sulphur, the hop resin α- and β-acids and their transformation products appear incapable of reactions with sulphur under analogous conditions. The evidence indicates that the hop resins are not potential sources of sulphur compounds in beer     

USE OF EXTRACTS PREPARED WITH LIQUID CARBON DIOXIDE AS A SUBSTITUTE FOR DRY HOPS

Liquid carbon dioxide hop extracts were prepared for use as a substitute for dry hops. Many of these extracts were oil rich fractions containing up to 14% (w/w) hop oil. Extracts of Styrian Golding, Wye Target and Wye Northdown hops were used to treat ales prior to completion of beer processing and subsequent packaging. Emulsion/suspension systems were developed as carriers to facilitate addition of these extracts to beers before the chilling process. A loss of hop character from beer was found to occur during fining and filtration. Beers, treated with the extracts, exhibited natural though varietally distinct dry hop character. Production scale trials using these extracts have been successfully carried out to dry hop a brewery conditioned draught bitter and to match a traditionally dry hopped premium pale ale. The quantities of extract used indicated that economies in hop usage can be achieved when substituting liquid carbon dioxide hop extracts for dry hops.     

Impact of Different Hop Compounds on the Overfoaming Volume of Beer Caused by Primary Gushing

When weather conditions favour the growth of moulds on barley, beers brewed from the resulting malts often tend to gush. Certain Fusarium species (e.g., F. graminearum and F. culmorum) may cause this problem. Supersaturated with CO₂, a primary gushing beer contains an overcritical concentration of microbubbles; these are reputed to be stabilised by Fusarium‐derived hydrophobins. Research with varying brewhouse parameters has been performed to investigate the factors of primary gushing. As hops are known to contribute to a wide range of both gushing positive and negative substances in beer, the hopping regime has emerged as an important aspect. This paper examines the impact of different hop varieties on gushing. Hop oils and unsaturated fatty acids are reputed to be gushing‐suppressors. Compounds such as dehydrated humulinic acid can intensify the effect. Hop pellets, with a prevalent range of conductometric values (5–10% α‐acid), commonly employed in breweries to adjust bitterness and aroma were selected. By working with the same “gushing malt”, the spectrum of compounds in the finished beer only differed through the hop product used. The overfoaming volumes of different samples were determined according to MEBAK guidelines. Respective hop oil and fatty acid concentrations (by GC) and iso‐α‐acid contents (by HPLC) were compared and a chronological sequence of the changing percentages of beer loss is shown.     

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.