The multisensory perception of hop essential oil: a review

Hops are a key ingredient to add bitterness, aroma and flavour to beer, one of the most consumed beverages worldwide. Essential oils from different hop varieties are characterised by similar classes of chemical compounds and complexity, but their contribution to sensory characteristics in beer differs considerably. Volatiles in hop oil are categorised into several chemical classes. These induce diverse aroma and flavour sensations in beer being described as ‘floral’, ‘fruity’ (e.g. contributed by alcohols, esters, sulphur-containing compounds), ‘spicy’, ‘woody’, ‘herbal’ (sesquiterpenes, oxygenated sesquiterpenoids), and ‘green’ (aldehydes). The perception of hop volatiles depends on their concentrations and combinations, but also on threshold levels in different beer matrices or model systems. Several studies attributed modified taste and mouthfeel sensations to the presence of hop volatiles contributing to a multisensory perception of hop flavour. Linalool is frequently observed to show additive and synergistic-type behaviour and to affect aroma perception if combined with geraniol. Linalool has also been found to be involved in aroma-taste interactions, modifying the perception of bitterness qualities in beer. Particularly oxygenated sesquiterpenoids are suggested to be responsible for an irritating, tingling sensation indicating the activation of trigeminal receptors. The majority of these sensory interactions have been discovered almost by accident and a systematic research approach is required to gain a broad understanding of these complex phenomena. This review provides an overview of factors affecting the perception of hop derived volatiles involved in different sensory characteristics of beer, while illustrating the latest advances and highlighting research gaps from a sensory science perspective. © 2020 The Authors. Journal of the Institute of Brewing published by John Wiley & Sons Ltd on behalf of The Institute of Brewing & Distilling     

Changes in the hop-derived volatile profile upon lab scale boiling

Hop terpenes might be oxidized during kettle boiling into more water soluble compounds that could contribute to ‘hoppy’ aroma of kettle hopped lager beers. Our current research proves that the boiling process induces significant changes in the hop oil volatile profile. The discrimination between volatile profiles of unboiled and boiled hop essential oil was evaluated via principal component and cluster analysis (PCA and CA). HS–SPME–GC–MS analysis revealed quantitative changes (e.g. increases in the levels of oxygenated α-humulene and β-caryophyllene derivatives) as well as qualitative changes (i.e. detection of compounds, not found in unboiled hop essential oil) in the hop oil volatile profile upon boiling. Many of these compounds were previously found in lager beer and may therefore contribute to beer flavor. Interestingly, the analytical difference between unboiled and boiled hop essential oil proved to be more pronounced as the initial hop essential oil concentration used for boiling was increased. In addition, lager beers spiked with boiled hop oil were described as ‘hoppy/spicy’ during sensory evaluations. Therefore, the newly formed products and hop oil constituents that are characterized by an increased recovery after boiling, are candidate compounds for ‘hoppy’ aroma in real brewing practice.     

Influence of hop harvest date of the ‘Mandarina Bavaria’ hop variety on the sensory evaluation of dry‐hopped top‐fermented beer

To impart a special hop aroma to beer, dry‐hopping is a technique that is becoming more and more popular with commercial breweries. Nevertheless, until now little was known about the factors that influence the reproducibility (and consistent product quality) of dry‐hopping with flavour varieties. One factor that could influence the sensory impressions and aroma profile compositions of dry‐hopped beers is the hop harvest date. Therefore, to determine the effects of different harvest dates of the flavour variety ‘Mandarina Bavaria’ on the aroma of top‐fermented beer, laboratory‐scale dry‐hopping trials were performed. Besides tasting sessions of brewed beers, relative quantities of selected hop‐derived, as well as beer‐originated aroma compounds, were investigated by headspace–solid‐phase microextraction–gas chromatography–mass spectrometry. Duo–trio tests between the beers hopped with pellets of different harvest dates showed no significant differences (α = 0.05) between them. In addition, these beers had similar profiles in a five‐point profile tasting scheme. On the other hand, relative concentrations of some hop‐derived aroma compounds – especially myrcene, which is known to be able to contribute to beer flavour – increased corresponding to a later harvest date, while beer originated volatiles were not different between the beers. Analytical results combined with the results of sensory evaluations led to the conclusion that the harvest date of Mandarina Bavaria was not a dominant factor in the dry‐hopping aroma of top‐fermented beers. High amounts of fermentation by‐products are likely responsible for masking effects resulting in no sensory distinctness between the samples with different hop aroma compound concentrations. Copyright © 2016 The Institute of Brewing & Distilling     

Modulation of the Phytoestrogenicity of Beer by Monoterpene Alcohols Present in Various Hop Oil Fractions

The estrogenicity of beer, due to prenylated flavonoids, mainly 8‐prenylnaringenin, can be modulated under suitable conditions, whereby monoterpene alcohols present in hop oils act as precursors for prenylation of flavonoids. Four hop oil fractions, ‘citrussy’, ‘estery’, ‘floral’, and ‘spicy’, respectively, were investigated as potential sources. The main constituents were separated and identified by gas chromatography ‐ mass spectroscopy (GC‐MS). They were related to 8‐prenylnaringenin via their MS features, while the ability to deliver a prenyl residue was evaluated by selected ion monitoring of fragment ions m/z 69 and m/z 41. In particular, the citrussy hop oil fraction proved to be a rich source of precursors for prenyl residues and linalool, the main constituent in the citrussy and spicy hop oil fractions, was shown to be most prominent. The process was highlighted by an increase in the content of 8‐prenylnaringenin on forced ageing of acidified beer spiked with naringenin and linalool.     

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 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.     

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.     

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.     

RAPID GAS CHROMATOGRAPHIC EXAMINATION OF BEER FLAVOUR

Gas chromatographic analysis of the headspace vapour of beer permits rapid measurement of the concentration of myrcene and the principal volatile alcohols, esters and carbonyl compounds in beer. In some cases the results obtained can be correlated with differences in flavour associated with changes in brewing procedure. The strength of the hop aroma of beers which had been dry-hopped, or to which hop oil had been added, was broadly reflected by the content of myrcene, which varied from 7 to 120 μg. per litre. A similar range was found in wort, the content depending on the conditions of boiling. However, the major part of this was lost during fermentation.     

PREPARATION OF OIL RICH HOP EXTRACTS AND THEIR ADDITION TO BEER ON THE PILOT-SCALE USING LIQUID CARBON DIOXIDE*

The introduction of carbon dioxide hop extracts dissolved in liquid carbon dioxide to green beer during transfer from fermentation vessel to cold conditioning tank results in a sound dry hop flavour in the finished product. A system has been developed for injecting a solution of extract into a beer main. Extracts which are rich in hop oils are particularly suitable for imparting hop character to beer and a liquid-liquid countercurrent procedure is described for producing extract fractions containing enhanced levels of essential oil.     

HOP PRODUCTS

Hop products have established an important and permanent position in the brewing raw materials market. Hop pellets and hop extract offer significant advantages to traditional brewers. However, the ultimate hop product is the isomerised hop extract, which can now be produced without the involvement of organic solvents. Still to be resolved and hence controlled is the contribution of the hop oil fraction to beer flavour.     

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     

TRACE VOLATILE CONSTITUENTS OF BEER. HOP SEED OIL

The fatty acid profile of hop seed oil has been examined and shown to be very similar to the fatty acid profile of the lipid fraction of both hops from which the seeds have been removed and seedless hops. The fates of the hop lipids and in particular the fatty acid fraction, both in conventional hopping procedures and in the preparation of an isomerised extract are discussed with reference to their possible effect on beer flavour.     

The Role of Malt and Hop Polyphenols in Beer Quality,Flavour and Haze Stability

Pilot‐scale brewing trials of a 12°P pale lager beer were conducted to look at the effect of a modified dose of hop and malt polyphenols on haze, flavour quality, and stability. Results confirmed that malt polyphenols, and particularly hop polyphenols, in the course of wort boiling, improved reducing activity values and the carbonyl content in fresh and stored beers. Hop polyphenols significantly increased reducing activity and decreased the formation of carbonyls (TBA value) in fresh and stored beer. Reduced content of malt polyphenols, combined with the use of hop CO₂ extract, caused an increase in the TBA value in beer. PVPP stabilized beers tended to be lower in reducing activity. Both malt and hop polyphenols affected the intensity of “harsh taste” in fresh beers and a significant influence from PVPP stabilization of beer was not observed. The staling degree of forced‐aged beers depended on the polyphenol content in the brewhouse. Both hop and malt polyphenols had a positive impact on flavour stability. PVPP treatment of beer had a positive effect on the flavour stability of heat‐aged beers. Polyphenols, especially hop polyphenols, slowed down flavour deterioration during the nine month storage period, but the primary effect was seen during the first four months of storage. Storage trials did not show any unambiguous effects for PVPP stabilization on beer flavour stability. Results confirmed the negative impact of malt and hop polyphenols on haze stability, and PVPP stabilization minimized differences in shelf life prediction values between beers prepared with the modified dose of polyphenols.     

The Contribution of Geraniol Metabolism to the Citrus Flavour of Beer: Synergy of Geraniol and β‐Citronellol Under Coexistence with Excess Linalool

The behaviour of hop‐derived monoterpene alcohols during fermentation by lager yeast was previously investigated in this laboratory. It was suggested that the concentration of geraniol and β‐citronellol in the finished beer increased depending on the initial concentration of geraniol in the wort. In addition, an additive effect among linalool, geraniol and β‐citronellol was found and 5 ug/L of geraniol and β‐citronellol was enough for this effect. In this paper, conditions regarding the enrichment of the initial concentration of geraniol in the wort were investigated. From the screening of various hop cultivars, Citra hop was selected as a geraniol‐rich cultivar. In addition, it was observed that coriander seed, which can be used in beer production as a flavourant, contained not only linalool but also geraniol at high levels. The use of Citra hop or coriander seed was effective for enriching the concentration of geraniol and β‐citronellol in the finished beers. In the Citra beer and in the coriander beer, the content of linalool was excess in comparison with the content of geraniol and β‐citronellol. Therefore, the synergy of geraniol and β‐citronellol, under coexistence of excess linalool, was examined. It was found that the flavour impression of excess linalool became more fruity and citrus by coexistence with geraniol and β‐citronellol and that the coexistence of all three monoterpene alcohols was effective for this synergy. The flavour characteristics of the Citra and coriander beer and the importance of geraniol metabolism for a citrus flavour in beer are discussed.     

Volatile constituents of roasted tigernut oil (Cyperus esculentus L.)

BACKGROUND: Volatile compounds play a key role in determining the sensory appreciation of vegetable oils. In this study a systematic evaluation of odorants responsible for the characteristic flavour of roasted tigernut oil was carried out. RESULTS: A total of 75 odour‐active volatiles were identified. From these, 13 aroma compounds showing high flavour dilution factors in the range of 16 to 128 were quantified by their odour activity values (OAVs). On the basis of high OAVs in oil, the following aroma compounds [vanillin (chocolate, sweet vanilla), 5‐ethylfurfural (caramel, spicy), 2,3‐dihydro‐3,5‐dihydroxy‐6‐methyl‐4H‐pyran‐4‐one (caramel), phenyl acetaldehyde (honey‐like), ethanone, 1‐(4‐hydroxy‐3‐methoxyphenyl) (faint vanilla)] were elucidated as important contributors to the overall chocolate, sweet vanilla, butterscotch aroma of the oil. CONCLUSION: Odorants with high concentrations in the roasted tigernut oil such as 5‐hydroxymethylfurfural, ethyl hexadecanoate, n‐propyl‐9,12‐octadecadienoate gave relatively low OAVs, so their contributions to the overall orthonasal aroma impression of roasted tigernut oil can be assumed to be low. © 2012 Society of Chemical Industry