ISOMERIZED HOP EXTRACTS IN EXPERIMENTAL BREWING

The later that isomerized hop extracts were added during the brewing process the better was the utilization. Thin layer chromatography of the beers produced from a range of experimental brews using isomerized hop extracts showed that the ratios of the various bitter substances derived from hops differed only slightly. The utilization of isomerized extract is enhanced if residues normally discarded during the manufacture of extracts are added to wort.     

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.     

INSTITUTE OF BREWING ANALYSIS COMMITTEE ANALYSIS OF HOP EXTRACTS AND ISOMERIZED HOP EXTRACTS

It is recommended that hop extracts should be examined qualitatively before the method of analysis is decided. Extracts would normally be analysed by the E.B.C. conductance method (and the results called “lead conductance values”) with a chromatostrip method as the alternative. Isomerized hop extracts should also be examined qualitatively, quantitative analysis being by the method of Wood, Lloyd & Whitear with countercurrent distribution as the recommended reference method.     

ORIGIN AND ESTIMATION OF THE GUSHING POTENTIAL OF ISOMERIZED HOP EXTRACTS

Two types of gushing promoter have been isolated from isomerized hop extracts. One type is a humulinicacid dehydration product which occurs rarely insuch extracts. The other type of gushing promoter consists of a mixture of oxidation products of hop resins, and is present in all the isomerized extracts examined. The higher the concentration of these oxidation products in a beer the greater is its tendency to gush. α-Acids and cohulupone have been shown to be effective gushing inhibitors. The gushing potential of an isomerized extract appears to be determined mainly by the relative proportions of oxidized materials and unchanged α-acid, present as contaminants. A method for determining the gushing susceptibility of a beer is described.     

ISO-α-ACIDS CONTENT OF ISOMERIZED HOP EXTRACTS

Two chromatographic procedures for the analysis of iso-α-acids in isomerized extracts have been tested. Although one of the methods—a variant of the Hansen, Hetzel & Miller procedure—performed better than the other, it still falls short of the demands of commercial transactions. The methods available for the assay of iso-α-acids are reviewed.     

ANALYSIS OF ISOMERIZED HOP EXTRACTS PART I. ESTIMATION OF ISOHUMULONES

A rapid spectrophotometric method for the estimation of the isohumulone content of isomerized hop extracts is described. This method has given acceptable reproducibility even in the hands of inexperienced personnel; it also gives results in close agreement with those obtained by counter-current distribution techniques, which are also described.     

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.     

PREPARATION OF HOP EXTRACTS RICH IN PARTICULAR CONSTITUENTS*

When a column containing powdered hops is extracted with liquid carbon dioxide, chromatographic separation of hop components occurs. They are extracted in the order essential oils, β-acids, α-acids; and the separation is enhanced when finely milled hops are extracted. Early fractions (～0·5 hour) contain a high proportion of the available essential oils when hops are extracted at ?20°C and such extracts are suitable as a replacement for dry hops. Fractions can be obtained from extractions at ～7°C which are rich in α-acids and contain low levels of β-acids. Small amounts of fats and waxes are normally present in fractions collected towards the end of a run when seeded hops are extracted.     

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.     

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.     

THE DEHYDRATION OF HUMULINIC ACID BY ALKALI

Humulinic acid has been dehydrated, by refluxing in aqueous sodium hydroxide, to 2-isovaleryl-5-(3-methylbut-2-eneylidene) cyclopentane-l,3-dione, which was isolated as a crystalline solid having m.p. 86–87° C.     

THE STABILITY OF HOP OILS IN LIQUID CARBON DIOXIDE EXTRACTS OF HOPS

Portions of extracts obtained by treating three varieties of hops with liquid carbon dioxide were stored in the cold and at ambient temperature for 18 months. During this period the composition of nop oils remained stable, except for the formation of two terpene methyl sulphides in extracts from all three varieties. Ales were ‘dry-hopped’ using portions of the stored extracts and, despite formation of the two sulphur compounds, the resulting hop character was satisfactory in all cases.     

THE MANUFACTURE OF HOP CONCENTRATES AND EXTRACTS*

Manufacture of the traditional hop concentrate (i.e., a product containing the chemically unchanged natural hop constituents apart from useless inert material) is increasing both in Europe and in America; this traditional concentrate, which is added to the copper, retains the varietal characteristics of the parent hop. In determining replacement ratios it is important to assess bitterness by tasting trials, as analytical assessments of bitterness may give misleadingly low results when concentrates are used. Although chemically pre-isomerized extracts can be prepared for addition to sweet beer, it is improbable that this type of extract will be used extensively until a great deal more is known about transformations which take place during hop boiling; such an extract, however, does allow maximum utilization of hop bittering principles. The selection of hops for high α acid content and the separate addition of the flavour components such as hop oil appears to be a desirable development for the near future.     

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.     

ANALYTICAL EVALUATION OF α-ACIDS IN HOP EXTRACTS AND IN HOPS*

The results of new investigations on hop extract analysis are presented. The main findings are:

• 1 The specific extinction (257) of α-acids at 276 nm in iso-octane used at present in CCD and paper strip analyses is 3·5% too high: analytical results have therefore been too low. The new extinction value to be used is 248.
• 2 The result of paper strip analysis depends very much on the amount of α-acids placed on the strip. The three-point paper strip method can only partly correct this. In general, figures with paper strip analysis have a tendency to be too high.
• 3 Conductometric titration of α-acids produces a figure about 2 to 10% too low. This can be partly corrected by adding 20% dimethylsulphoxide or dimethylformamide to the titration medium.
• 4 Conductometric analysis of hop extracts with removal of “iso-α-acids like material” before titration is possible by a very simple procedure (pH 7 buffer extraction).

New photometric and conductometric procedures based on these results give figures which are in agreement for something which must be practically true α-acids.     

ANALYSIS OF HOP EXTRACTS BY SIMPLIFIED COUNTER-CURRENT DISTRIBUTION METHODS

Simplified counter-current distribution procedures are described which allow correct analysis of the α acids and iso α acids content of hop extracts.     

ON THE ANALYSIS OF HOP BITTER ACID

A High Performance Liquid Chromatography (HPLC) method for automated routine analysis of the hop bitter acids is described. It allows the simultaneous determination of α-acids, β-acids, cohumulone and colupulone. This analysis based on two chromatographic runs takes less than 1/2 h. With this new method as reference, the defects of existing conductometric titration techniques were studied and a new improved conductometric method based on toluene-buffer extraction was developed. The new methods are applicable to all forms of hop products containing α- and β-acids. Analysis for α-acids with ether-acid aqueous methanol extraction gives results which are too high because of several basic defects.     

ESTIMATION OF LEAD CONDUCTANCE VALUES FOR HOP EXTRACTS CONTAINING WATER-SOLUBLE FRACTIONS

A rapid method is described for estimating the lead conductance values of hop extracts containing water soluble fractions.     

ADDITION OF HOP EXTRACTS TO BEER USING LIQUID CARBON DIOXIDE*

A method is described for imparting hop character to beer using extract prepared by treating hops with liquid carbon dioxide. The long contact times required for conventional dry-hopping techniques are avoided, and the use of liquid carbon dioxide as a medium for dispersal of the extract obviates problems due to residual organic solvent or emulsion stabilizers. Beers in which hop character was introduced in this way were found to be similar in flavour to control beers treated with portions of the same hop extract dissolved in ethanol.     

THE OCCURRENCE OF HOP RESINS IN HOP OIL

Appreciable amounts of α and β acids have been found in the essential oil obtained by steam distillation of hops.