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Dry HoppingMyths versus Reality
1
Major volatile compounds
after main fermentation
(at start of dry hopping !)
2
Compounds present in beer after main fermentation
IR CPSil5 Compounds Flavour Samples
T 0 Day
C (ppm)
bièreFD
730 isobutylacetate banana, fruity 0.037 128
774 ethylbutyrate banana, fruity 0.058 512
812 3-methylbutanoic acid cheese 0.101 512
852 isoamylacetate Banana, apple 0.843 128
921 4-methylpentanoic acid cheese 0.009 <128
957 hexanoic acidDry leaves, goaty,
fatty acids0.094 512
974 2-methyl-2-pentanoic acid grassy, acid 0.056 <128
982 β-myrcene lemon, sweet 0.014 <128
1001 hexylacetate + sulfitic grassy, hop 0.002 512
1018 phenylacetaldehyde sweet, hony 0.010 <128
1088 linalool lemon 0.009 <128
1101 β-phenylethanol rose 6.672 512
1226 citronellol lemon 0.037 <128
1260 4-ethylguaiacol spicy 0.011 ND
1294 4-vinylguaiacol cloves 0.70 <128
YEAST
HOP
GLYCOSILES PRECURSORS
CYSTEINES BY PRODUCTSACTION ON FATTY ACIDS
BA
CK
GR
OU
ND
IN
FOR
MA
TIP
ON
3
IR CPSil5 Compounds Flavour Samples
T 0J
C (ppm)bière
FD
808 3-methyl-2-buten-1-thiol (MBT) hop, cheese ND 512
850 3-mercaptopropanol potatoes ND 512
890 2-mercaptoethylacetate grilled meat ND 512
905 4-mercapto-4-methyl-2-pentanone catty ND <128
1374 beta -damascenone cooked apple ND <128
1432 gamma-decalactone peach ND <128
1465 delta-decalactone coconut ND <128
1441 4-vinylsyringol Cloves ND <128
1578 ethyldodecalactone grassy ND <128
1687 delta-dodecalactone fruity, olive ND <128
4
YEAST
HOP
GLYCOSILES PRECURSORS
CYSTEINES BY PRODUCTSACTION ON FATTY ACIDS
Compounds present in beer after main fermentation
Analysis performed
at the lab of Prof Sonia Collin
UCL
5EBC HOP SYMPOSIUM GDX/JMR/SDK/2009
6
ALCOHOLS
ALDEHYDES
LACTONES
TERPENES
Monoterpenes
Sesquiterpenes
MCF-ACIDS (Medium chain fatty acids)
LCF-ACIDS
GLUCOSIDE OF TERPENES
Monoterpenes
Sesquiterpenes
GLUCOSIDE OF PHENOLS
Phenolic acids
Polyphenols
7
ACIDS
ALCOHOLS
TERPENES
Monoterpenes
Sesquiterpenes
VOLATILE PHENOLS
CYSTEINE DERIVATIVES (THIOLS)
MCF-ACIDS
LACTONES
GLUCOSIDE OF TERPENES
Monoterpenes
Sesquiterpenes
GLUCOSIDE OF PHENOLS
Phenolic acids
Polyphenols
Fate of major beer volatiles
by dry hopping (maturation) in presence of S.cerevisiae
8
MONOTERPENES
MAJOR BEER VOLATILES
CITRUS FLAVORS
9
IR CPSil5 Compounds Flavour Samples
TERPENEST 0J T 14J T 21J
C (ppm)bière
FD C (ppm)bière
FD C (ppm)bière
FD
982 β-myrcene Citrus, sweet 0.014 <128 0.014 <128 0.040 <128
1088 linalool Citrus 0.009 <128 0.05 >128 0.06 >1024
1226 citronellol Citrus, fresh 0.037 <128 0.020 <128 0.118 512
YEAST
HOP
GLYCOSILES PRECURSORS
10
CITRUS FLAVORS
IR CPSil5 Compounds Flavour Samples
T 0J T 14J T 21J
C (ppm)bière
FD C (ppm)bière
FDC (ppm)
bièreFD
982 β-myrcene Citrus, sweet 0.014 <128 0.014 <128 0.040 <128
1088 linalool Citrus 0.01 <128 0.05 >128 0.06 >1024= dil 1024x
1226 citronellol Citrus, fresh 0.037 <128 0.020 <128 0.118 512
TERPENES
11
DRY HOPPING: evolution of linalool
Influenced by :
- Time
- Temperature
- Hop variety (oil content)
- Hop quantity added
- Hop dispersion methods
(static /dynamic)- Beer type and yeast type
12
Linalool
CITRUS FLAVOURS
IR CPSil5 Compounds Flavour Samples
TERPENEST 0J T 14J T 21J
C (ppm)bière
FD C (ppm)bière
FD C (ppm)bière
FD
982 β-myrcene Citrus, sweet 0.014 <128 0.014 <128 0.040 <128
1088 linalool Citrus 0.009 <128 0.034 >128 1.192 >1024
1226 citronellol Citrus, fresh 0.037 <128 0.02 <128 0.12 512= dil 512x
13
DRY HOPPING: evolution of citronellol
Influenced by :
- Time
- Temperature
- Hop variety
- Hop quantity
- Hop dispersion methods
(static /dynamic)
- Beer type and yeast type
14
15
METABOLISM CASCADE OF MONOTERPENE ALCOHOLS BY LAGER
AND ALE YEASTS PROPOSED BY KING AND DICKENSON. THE ASTERIC
INDICATES A CHIRAL CENTER.
PRESENCE OF CITRONELLOL
16
IN LATE HOPPED WORT
(10 min before end of boiling)
Citation :
HAPPOSHU
17
G
Fate of the other volatile compounds
as the …
• Acids
• Esters
• Alcohols
• Aldehydes
• Lactones
• Thiols
• Others
18
CHEESY FLAVOURS
IR CPSil5
Compounds Flavour Samples
SHORT CHAIN FATTY ACIDST 0J T 14J T 21J
C (ppm) bière FD C (ppm) bière FD C (ppm) bière FD
812
3-methylbutanoic
acidcheesy
0.101 512 0.102 512 0.179 >1024
921
4-methylpentanoic
acidcheesy
0.009 <128 0.003 <128 0.018 512
957 hexanoic acid mild cheesy0.094 512 0.102 512 0.179 >1024
974
2-methyl-2-
pentanoic acidgrassy, acid
0.056 <128 0.037 <128 0.160 512
YEAST
HOP
19
HOP CONDITIONNING AND STORAGE CONDITIONS
CHEESY : linked to bad storage of hop bales and/or pellets and to the use of aged hop (presence of degradation products as 2-methyl-propionic acid/ isobutyric acid and of 2-methyl-butyric acid/ isovaleric acid)
20
FRUITY, FLORAL FLAVOURS
IR CPSil5 Compounds Flavour Samples
ESTERST 0J T 14J T 21J
C (ppm)bière
FD C (ppm)bière
FD C (ppm)bière
FD
730 isobutylacetate banana, fruity 0.037 128 0.065 512 0.096 >1024
774 ethylbutyratebanana,
fruity, flowery0.058 512 0.113 >1024 0.156 >1024
852 isoamylacetatebanana,
sweet0.843 128 1.086 128 1.821 >1024
1001 hexylacetate grassy, hop 0.002 512 0.002 512 0.011 512
YEAST
HOP
21
FRUITY, FLORAL FLAVOURS
YEAST
HOP
GLYCOSILES PRECURSORS
CYSTEINES BY PRODUCTS
ACTION ON FATTY ACIDS
IR CPSil5 Compouds Flavour Samples
HIGHER ALCOHOLST 0J T 14J T 21J
C (ppm)bière
FD C (ppm)bière
FD C (ppm)bière
FD
1101 ββββ-phenylethanol rose 6.672 512 6.532 512 11.685 >1024
22
IR CPSil5 Compouds Flavour Samples
ALDEHYDEST 0J T 14J T 21J
C (ppm)bière
FD C (ppm)bière
FD C (ppm)bière
FD
1018phenylacetaldehyde sweetened,
honey0.010 <128 0.015 <128 0.022 512
23
IR CPSil5 Compounds Flavour Samples
LACTONEST 0J T 14J T 21J
C (ppm)bière
FD C (ppm)bière
FD C (ppm)bière
FD
1432gamma-
decalactonepeach ND <128 ND <128 ND 512
1465delta-
decalactonecoconut ND <128 ND <128 ND 512
1578Ethyl-
dodecalactonegrassy ND <128 ND <128 ND 512
1687delta-
dodecalactone
fruity,
oliveND <128 ND <128 ND 512
FRUITY, FLORAL FLAVOURS
YEAST
HOP
GLYCOSILES PRECURSORS
CYSTEINES BY PRODUCTS
ACTION ON FATTY ACIDS
24
FRUITY FLAVORS
WHY LACTONES ?
25
FRUITY FLAVORS
YEAST PEROXISOME
BIOSYNTHESIS
26
FRUITY FLAVORS
YEAST PEROXISOME
BIOSYNTHESIS
27
IR CPSil5 Compounds Flavour Samples
T 0J T 14J T 21J
C (ppm)bière
FD C (ppm)bière
FD C (ppm)bière
FD
8083-methyl-2-buten-1-thiol
(MBT)
hop,
cheeseND 512 ND >1024 ND >1024
850 3-mercapto-propanol potatoes ND 512 ND >1024 ND >1024
890 2-mercapto-ethylacetategrilled
meatND 512 ND >1024 ND >1024
9054-mercapto-4-methyl-
2-pentanonecatty ND <128 ND <128 ND 512
YEAST
CYSTEINES BY PRODUCTS
SULFITIC FLAVOURS
28
Concentration of
major non-volatile compounds
after maturation in presence of raw hops• Polyphenols
• Glucosides
29
Non volatile compounds extractedPOLYPHENOLS
30
Year 2008
POLYPHENOLS
MOST INTERESTING PHENOLIC COMPOUNDS
• Phenolic acids
• Flavonoids
Flavanoids
Proanthocyanidin = anthocyanogen
• Resveratrol
31
IR CPSil5 Compounds Flavour Samples
PHENOLST 0J T 14J T 21J
C (ppm)bière
FD C (ppm)bière
FD C (ppm)bière
FD
1260 4-ethylguaiacol spicy 0.011 ND 0.000 ND 0.067 >1024
1294 4-vinylguaiacol Cloves, dentist 0.70 <128 1.32 <128 3.36 >1024
CLOVES AND SPICY FLAVORS
YEAST
ACTION ON PHENOLIC ACIDS
PRESENCE OF “POF or PAD YEASTS”
(Phenolic acid decarboxylase activity)
Several TOP fermenting yeasts
ONLY IF PRESENCE OF
BRETTANOMYCES sp
(Vinyl reductase activity)
POLYPHENOLS PHENOLIC ACIDS
HOP
32
FERULIC ACID = Phenolic acid
(Barley, Hops)
Formation of vinylguaiacol vinylphenol and styrene
from phenylalanine by S. cerevisiae !
33
POLYPHENOLS
FLAVANOIDS
WHY ARE “FRESH” FLAVANOIDS INTERESTING !
34
BECAUSE….
Non volatile compounds extracted
- POLYPHENOLS
- GLUCOSIDES35
NON VOLATILE COMPOUNDS
EXTRACTED
POLYPHENOLS
PHENOLIC ACIDS
FLAVANOIDS
GLUCOSIDES
GLYCOSIDES
• IMPORTANCE OF THE HOPS
• INFLUENCE OF THE YEAST STRAINS
• CULTURE YEASTS
• WILD YEASTS
Brettanomyces sp
36
- GLUCOSIDES
A few theory…
Glucosidic bound can be hydrolysed by :
- High temperature
- Enzymatic activity
- endogenous presence (yeast by
maturation, bottle refermentation)
- (addition of exogenous beta-
glucosidase during the process) –
No
n v
ola
tile
co
mp
ou
nd
s e
xtr
act
ed
37
No
n v
ola
tile
co
mp
ou
nd
s e
xtr
act
ed- GLyCOSIDES
In beer, the aglycon part is liberated by two
different types of activities
- by ββββ -1-3-glucanase activity in case of S. cerevisiae strains
- by β β β β -glucosidase activity in case of Brettanomyces sp. strains
38
Glycosidic bounds hydrolysed by endogenous
presence (by yeast during maturation and/or during bottle fermentation)
Preferential links detected in hopsTerpenes
• TERPENIC SUB – UNIT + SUGAR : FLAVOUR PRECURSOR
linalool - β-D- glucoside
α – terpineol – β – D - glucoside
1- octen-3-ol- β – D – glucoside
3 – hydroxy – β – damascenone – D – glucoside
• PHENOLIC SUB – UNIT + SUGAR : SHELF – LIFE PROTECTOR PRECURSOR
Flavonoids
Kaempferol and Quercetin – 3 – glycosides
glycosidic sub-unit : mono or di- glycosides – glucose , galactose, rhamnose
Flavanoids
As yet, flavanol dimers or multimers glucoside aren’t detected nor described
No
n v
ola
tile
co
mp
ou
nd
s e
xtr
act
ed
39
Glucosidic bound hydrolyses by endogenous presence (yeast by maturation, bottle refermentation)
No
n v
ola
tile
co
mp
ou
nd
s e
xtr
act
ed
• Importance of the yeast strain and
yeast species
40
41
LEGEND :SC : S.CEREVISIAE (ALE YEAST)
BB : BRETTANOMYCES BRUXELLENSIS
BC : BRETTANOMYCES CUSTERSII
*SC + D : S. CEREVISIAE + CARBOHYDRATE
SOURCE (GLUCOSE)
AR : AR 2000 GLYCOSIDASIC CONCENTRATE OF
ASPERGILLUS NIGER (COMMERCIALLY AVAILABLE)
TYPICAL YEASTS ββββ-glucanase and ββββ glucosidase activities
of different yeast strains and yeast species
Influence of hop quantity and of yeast strain
Glucosidic bound hydrolyses by endogenous presence (yeast by maturation, bottle refermentation)
• Importance of the aglycon moiety
(glucoside of higher alcohols)
1-octen-3-ol
No
n v
ola
tile
co
mp
ou
nd
s e
xtr
act
ed
cis-3-hexen-1-ol
42
YEAST
HOP
GLYCOSILES PRECURSORS
1374beta -
damascenone
cookedapple, rose
ND <128 ND <128 ND >1024
IR CPSil5 Compounds Flavour Samples
OTHERST 0J T 14J T 21J
C (ppm)bière
FD C (ppm)bière
FD C (ppm)bière
FD
43
FRUITY, FLORAL FLAVOURS
BEER DRY HOPPING IS A CONFLICTUAL ART
WHEN RAW HOP EXTRACTION TAKES PLACE IN PRESENCE OF ACTIVE YEAST
ACTIVE YEAST BY DRY HOPPING IMPROVES THE BEER VALUE BY :
- PROTECTING BEER FROM OXIDATION BY CAPTURING MOLECULAR OXYGEN
- PROTECTING BEER BY EXERTING A REFRESHING EFFECT
- IMPROVING (IN A FIRST STEP) THE BEER FLAVOUR BY :
• increasing the content of citronellol
• synthesizing nice flavours as lactones
• liberating aglycons from glucosides :
- Linalool, Geraniol,…
44
BEER DRY HOPPING IS A CONFLICTUAL ART
WHEN RAW HOP EXTRACTION TAKES PLACE IN PRESENCE
OF ACTIVE YEAST
ACTIVE YEAST by dry hopping
DECREASES THE BEER VALUE BY :
- LIBERATING ESTERASES THAT DECREASE THE AROMA
- METABOLIZING H+ ACCEPTORS AS SOME ALDEHYDES
AND OTHER POTENT SUBTILE FLAVOURS AS LACTONES
45
46
BEER DRY HOPPING IS A CONFLICTUAL ART
WHEN BOTTLING TAKES PLACE IN PRESENCE OF ACTIVE YEASTs
Sierra Nevada
Orval
47
TRADITIONNAL EUROPEAN METHODS
Methods by batch dry hoppingA
B
C
D
E
A : Parts of 4 KG of dried hop cones are compacted under inert gas (N2) in onion bags that are sealed in aluminium packets by the hop supplier. of 4 KG. These are stored in the fridge of the brewery at + 2 /+ 4°C. B : Just before use, the aluminium packets are opened and the onion bags containing the hop cones are decompressed.C : Before introduction in the empty tank,the hop cones are decompacted tooD : In order to improve the contact between the beer and the hop bells, the hop bag can be attached to the tank. E : Hop plugs of 5 Oz ( 140 Gr) are also available by hop suppliers and can be added to beer casks directly.
48
Pneumatic Method
= dry methodOut- Indoor hop
cellar canoon
Lagunitas Brewery
Methods by continuousextraction in separated vessels
1.2. by hop pelletsStone Brewery (designed plant)
New Belgium Brewery
1.1. by hop conesSierra Nevada Brewery
NEW AMERICAN METHODS
With authorization of Steven Pauwels, CBC Dry hopping subcommittee
HOP and BEER
49
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