Question 6 (AME 1 2001 Question 7) Discuss the constituents of hops that are relevant to brewing an give a etaile e!

!planation of wh"# 'hat changes in (ualit" can occur uring storage of whole hops# $1%& $%&

!S) *" H*+S I, BR)WI,Althou#h hops have had a traditional minor role in medicine and ba.in#/ hops are no0 almost exclusively used to provide aroma and bitterness in beer/ 0ith the follo0in# properties1 Hops provide the bitter taste in beer 20ith alpha acid the principal precursor3 The oils provide aroma% Hops modify yeast performance durin# fermentation% Hops contribute to beer texture 2mouthfeel3 Hops have bacteroistatic properties 0hich protects beer a#ainst some biolo#ical spoila#e or#anisms% Hops reduce over foamin# durin# 0ort boilin#% Hops aid in protein coa#ulation durin# the boil% Hops act as a filter medium 0hen a hopbac. is used% Hops are a foam active a#ent in beer% (one Hops contribute tannins 0hich may increase the reducin# po0er of a beer/ and hence its resistance to oxidative stalin#% Tannins may also contribute to a tendency to produce chill ha4e% H*+ (H)MISTR5 The hop cone contains lupulin #lands consistin# of a mixture of hard and soft resin and hop essential oils/ other0ise the bul. of the hop cone is made up of ve#etative matter containin# cellulose/ proteins/ tannins etc% It is the soft resins 2soluble in hexane3 that are most important in bre0in#/ and these consist of alpha acids/ beta acids and uncharacterised soft resins%
Whole Hops

)xtraction of hop resins

diethyl ether and cold methanol
Solvents

Total Resins

Hexane Solvent
e bl lu so In

Soft Resins

Hard Resins

Methanolic Lead Acetate Lead Salt of Alpha Acids filtrate Beta Acids !ncharacterised Soft Resins

The alpha acid and the beta acids provide the bitterin# principals and exist as a mixture of different compounds% These acids are lar#ely insoluble in cold 0ater and/ 0hile they are more soluble in boilin# 0ater/ any material dissolved 0hile hot 0ill precipitate out on coolin#%

"i#ure $%&%'%$% (hemical extraction of hop resins

S ol ub le

6urin# 0ort boilin#/ ho0ever/ the alpha acids are isomerised into iso7alpha acids that are much more soluble 2 see "i#ure $%&%'%8%3% The beta acids are less soluble and are lar#ely unchan#ed durin# 0ort boilin#/ and hence contribute little to the final bitterness of the beer/ unless they are oxidised to hupulones in 0hich case they 0ill also contribute bitterness 2see section $%&%9%3% Isomerisation of alpha acids into iso7alpha acids%

Isomerisation of Alpha7Acids
*H *

H* * *H

*H

H*

trans7Isohumulone
* *H

2Iso7lpha7acids3
*H

H!M!L*,)
2Alpha7Acids3
*

H*

*H

cis7Isohumulone
2Iso7alpha7Acids3

Hops also contain beta acids 0hich are sparin#ly soluble and in fresh hops ma.e little contribution to beer bitterness% The beta acids are principally responsible for the antiseptic properties of the hops% In older hops after the beta acids have been oxidised they contribute more to the bitter character of the beer 2see fi#ure $%&%:%$3%

"i#ure $%&%'%; Structure of beta acids%

(omposition of Hops
Beta7Acids
* *

*H

Lupulone
; homolo#s n7/ co7/ ad7 minor contribution to beer bitterness 2hulupones3 $7$?= in hops trace solubility in 0ort 2ph &%83
Hops contain a 0ide ran#e of polyphenolic compounds of lo0 molecular 0ei#ht/ 0hich #enerally survive 0ort boilin# to #o throu#h to the final beer/ 0here particularly in the presence of oxy#en/ they convert slo0ly into products that contribute to chill ha4e and chemical and flavour instability% Ho0ever the tannins contribution from hops are #enerally considered to be less problematical than those contributed from the malt% Bet0een 87<= of the hop material consists of hi#her molecular 0ei#ht tannins>polyphenols 0hich to#ether 0ith a lar#er 2by 0ei#ht3 contribution from the malt tannins/ precipitate 0ith proteins durin# 0ort boilin# and help to improve the .ettle brea.%

)@TRA(TI,- BITT)R,)SS "R*M H*+S1 H*+ !TILISATI*,% The bitterin# principle forms only a small proportion of the total hop cone1 Table $%&%$?%$% Typical composition of (ommercial Hops% (omposition Water Total resin )ssential oils Tannins>polyphenols Monosaccharides +ectin Amino acids +roteins 2nitro#en x 9%8&3 Lipids and 0ax Ash (ellulose/ li#nin etc% T*TAL = $? $& ?%' < 8 8 ?%$ $& ; A <? $??

The maBority of the bitterin# from hops comes 0hen the alpha acids are isomerised durin# 0ort boilin#%% With bitterness playin# such a vital role in beer flavour/ it is important to achieve a consistent level of bitterness in the final beer% Table $%&%$?%;% sho0s the main factors that influence hop utilisation% Table $%&%$?%; "actors affectin# hop utilisation in bre0in#% Factor Wort pH Len#th of boil Hop addition rate Wort ori#inal #ravity "oamin# in .ettle "oam in fermenter A#e of hops Alpha acid content 2=3 Trub volume (old brea. volume 5east strain +ressure boilin# 2hi#her temperature3 Influence Increased pH Lon#er boil Hi#her addition Increased #ravity -reater foam -reater foam *lder hops Hi#her = alpha More trub More cold brea. Hi#her boilin# temp Utilisation Improved Initial improvement then decrease over '? mins% Lo0er Lo0er Lo0er Lo0er Lo0er Lo0er Lo0er Lo0er 5east dependent Cuic.er isomerisation

,ot all beers have the same de#ree of bitterness/ and the bitterness levels of beers vary substantially accordin# to the style of beer bein# bre0ed and the Duality of bitterness reDuired in different #eo#raphical areas%

H*+ AR*MA The essential oils in hops are the source of aroma compounds% These oils are volatile and 0ill be almost entirely vaporised from the .ettle if they are present from the start of a 9? to '? minute boil/ althou#h some 0ill be converted by heat or chemical reaction% To compensate for this/ many bre0ers 0ho 0ant beer 0ith a hoppy character add selected aroma varieties into the .ettle bet0een & and 8? minutes before the end of the boilE this #ives sufficient time to extract the hop aroma but ensures that all the oil is not lost in the vapour% Late hop character is often described as floral or citrus / but it can be unpleasant if present in too hi#h a concentration% The variety of hop/ the timin# of the addition/ as 0ell as the .ettle shape and the material of construction all have a maBor influence on the subtlety of the final beer aroma% Hops can also be added to beer after fermentation 7 to the maturation vessel or to the cas. for ales 7 to #ive beer a dry hop flavour often described as resinous spicy and citrus % Because the alpha acids are only sli#htly soluble in cold beer/ there is hardly any increase in the bitterness of beer 0ith dry hoppin#% Hops produce up to ;= of essential oils durin# the later sta#es of ripenin# after the bul. of the resin synthesis is complete% The composition of the oil reflects not only the variety but also the de#ree of ripeness% *ver ;?? hop oil compounds have been isolated and they are usually separated and identified usin# #as chromato#raphy 0ith mass spectroscopy 2-(MS3% The essential oils can be divided into three classes1 H56R*(ARB*,S 2comprisin# &? 7 A?= of the total3 The principal hydrocarbons are the monoterpene 2($?3 myrcene/ and the sesDuiterpenes 2($&3 caryophyllene and humulene% "arnesene and selinene occur in some varieties/ but not all/ and can be used as mar.ers for hop variety identification% All are very volatile and fe0/ if any/ hydrocarbons survive the 0ort boilin# process in to beer/ even 0hen added as a late hop addition to the .ettle% Traces of these compounds 0ill dissolve in dilute alcohol/ and both myrcene and humulene have been detected in beers 0hich have been dry hopped% *@5-),AT)6 (*M+*!,6S 2comprisin# 8? 7 &?= of the total3 Some of the oxy#enated compounds are produced by the esters of the correspondin# hydrocarbons 0hich produce a more polar and chemically complicated #roup of compounds% These are better able to survive 0ort boilin#/ particularly from a late .ettle hop addition/ and find their 0ay into beer% Ho0ever it is not .no0n precisely 0hich/ if any/ of these compounds are responsible for the desirable hop aroma since many of the compounds 0ill be volatili4ed durin# the last minutes of boilin#/ and those 0hich survive in to the 0ort may be lost 0ith (*8 pur#in# or be chemically modified durin# fermentation% S!L+H!R (*M+*!,6S 2comprisin# F $= of the total3 Althou#h the sulphur compounds are present in only very lo0 concentrations in hop oil they have potent aromas% "e0 sulphur compounds survive 0ort boilin#/ but late addition of hops can introduce trace amounts of sulphur compounds as can the addition of hop oils% Some of the sulphur compounds #ive coo.ed ve#etable/ onion7li.e/ rubbery sulphur aromas 0ith very lo0 perception thresholds%

It appears that hop flavours in the finished beer are a result of a syner#istic mixture of compounds% These may be modified by1 variety/ type of hop len#th and nature of boil oxidation and de#radation products durin# the bre0in# process yeast metabolism time and nature of hop stora#e% (olumn chromato#raphy of an oil rich carbon dioxide extract of hops #ave five fractions 0hich 0ere then added to beer1 -ivin# a hop aroma characacter to a beer not only reDuires selectin# an appropriate hop variety to provide the essential oils but also to add the hops so that at an appropriate sta#e in the process% KETTLE HOPS1 0hen hops are added at the be#innin# of the .ettle boil/ little if any aromatic oils persist into the finished beer% There 0ill be some chemical modification or combination of flavour compounds% LATE HOP ADDITION1 hops may be added at any sta#e from 8? to & minutes before the end of the boil/ or fresh hops added to a hop bac. to allo0 sufficient time for the extraction of some of the hop oils 0ithout them all bein# lost due to vaporisation% ,ot only 0ill some of the more volatile hop oils be lost in the last fe0 minutes of boilin# or 0hile 0aitin# for 0ort coolin#/ but the remainin# oils may be modified or lost durin# fermentation% It is usually the heavier esters and .etones 0hich are retained to #ive the fruit citrus characters found in many late hop la#ers% The extent to 0hich these characters persist depends on the .ettle desi#n as 0ell as the hop variety% DRY HOP1 appropriate hop varieties may be added durin# maturation or to cas. to impart a hop aroma and taste particularly to traditional ales% A 0ider ran#e of hop oils is extracted than durin# late hoppin#/ 0hich imparts a floral fra#rant note to beer often 0ith spicy characters 0hich can be astrin#ent if overdone% When 0hole hops are added to a cas. the extraction and chemical reaction of the oils 0ill continue throu#hout the drin.in# life of the cas. 0hich produces a constantly evolvin# chan#e in palate over time% H*+ +R*6!(TS Beside 0hole hops 2hop cones3 and pelletised hops/ other hop products and extracts are used either as alpha acids added to the .ettle or as isomerised iso alpha acids added to the .ettle or after fermentation% Also hop oils and hop bitterin# products can be added after fermentation to #ive a dry hop character/ or to modify the character of the final beer% +rocessed hop products represent a convenient and controlled system for addin# both bitterness and aroma character to beer/ and can be very useful for adBustin# beers produced outside specification% The benefits include1 Reduced bul. Reduced transport costs Reduced stora#e costs +otential for automatin# hop addition in the bre0ery !niformity 7 2can be standardised to = a alpha value3

 -reater stability 2lon# term stora#e3 Improved utilisation 2pellets up to $?=1 +ost fermentation bitterness up to :?= improvement3 Reduced beer and 0ort losses Improvements in beer Duality and consistency 6ecreased level of polyphenols>tannins 6ecrease 2or absence3 of nitrates 6ecrease 2or absence3 of pesticide residues These potential benefits have to be balanced a#ainst1 ) Increased production>processin# costs ) +ossible inclusions of solvents and toxic residues 2not 0ith (*8 extract3 ) +urist>public attiudes to the use of processin# and solvents ) +ossible adverse effects on beer Duality and taste% All of the products are derived from 0hole hops in the first instance/ and are #enerally used to help the Bre0er overcome the effects of a#ein#/ stora#e and consistency problems% Hop storage The common practice is to purchase hops/ particularly bitter varieties/ on the 0ei#ht of alpha acid 20hich may vary bet0een &= and $<= dependin# on variety3 rather than the 0ei#ht of hops themselves% Specialist aroma varieties 0hich have lo0er = alpha acid 28%&= 7 9= approximately3 are #enerally purchased by 0ei#ht of hop and command a premium for their aroma characters% There are four principal methods used for measurin# the alpha acid content in the laboratory1 lead conductance value L(G 2lead salt formation 0ith lead acetate solution3 7 principally measures the alpha acid content ultraviolet li#ht absorption 7 spectrophotometry 7 measures alpha acids and beta acids% optical rotation of polarised li#ht 7 polarimetry 7 measures only the alpha acids hi#h performance liDuid chromato#raphy 7 measure both alpha and beta acids as 0ell as many of the modified hop compounds 0hich are increasin#ly findin# favour for hop bitterin#% The lead conductance value method is still 0idely used in )urope to purchase hops/ althou#h spectrophotometry is the usual method in the !SA% Hops/ and alpha acid in particular/ under#o oxidation and de#radation durin# stora#e% Some varieties sho0 more rapid loss of alpha acid than others/ for example Tar#et/ althou#h the rate is affected by the form and conditions of stora#e% Since hops are only harvested in the autumn/ unless some are imported from the other hemisphere/ they need to be .ept in #ood condition for the Bre0er for at least $A months% To minimise deterioration/ 0hole hops are stored in a cold store/ and many hops are processed into hop pellets or hop extracts to improve stora#e and usa#e characteristics% As hops oxidise/ the percenta#e of soft resin decreases and the percenta#e hard resin increases/ 0ith a reduction in alpha and beta acids% The oxidative cleava#e of the acyl side chains of the hop resin #ive rise to volatile fatty acids

0hich produce the cheesy flavours in old hops% Many of the hop oils 0ill deteriorate and chan#e either throu#h evaporation/ oxidation or internal reactions 7 chan#in# the overall balance of the aroma and flavour characteristics of the hop/ unless the hops are stored cold or processed to reduce the exposure to oxidation% Althou#h there is a decrease in alpha acid as measured by lead conductance/ the oxidation of the beta acid into hulupones #ives a ne0 soluble bitterin# a#ent 0hich reduces the loss of perceived bitterness as sho0n in fi#ure $%&%9%$% When usin# old hops/ the perceived bitterin# value 0ill be #reater than that expected from the alpha acid determination% "i#ure $%&%:%$% (han#es in alpha acid analysis values and percieved bitterin# value durin# stora#e

6eterioration of hops 0ith stora#e

H Ambient Tempratures Total Bitterin# value

(hloro form as So lv
tolu ene as

ent

Solv ent

leadconductance value

alpha acid content

Alpha acid by H+L( Time *xidation of alpha acids decreases the bitterin# value *xidation of beta acids to hulupones enhances the bitterin# value chan#es in alpha acid analysis values and percieved bitterin# value durin# stora#e

Bitterin# value can be measured/ but the character and aroma Duality of aroma hops can only be satisfactorily determined throu#h bre0in# trials%