Most economical to reduce microbial populations · 2019. 9. 12. · 2-Acetylthiazole popcorn 1...
Transcript of Most economical to reduce microbial populations · 2019. 9. 12. · 2-Acetylthiazole popcorn 1...
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Most economical to reduce microbial populations
Also inactivates certain enzymes but …
induces chemical reactions
Acid catalyzed reactions – unsaturated terpenes
Maillard reaction – complex mixture of products
Thermal decompositions/reactions
produce sulfur volatiles
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Formation of sulfur volatiles – degrades flavor
dimenthyl sulfide
methanethiol
hydrogen sulfide
Non sulfur volatiles formed
4-vinyl guaiacol (ferulic acid)
alpha-terpineol (limonene)
Furaneol (sugars + ascorbic acid)
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0
1
2
3
4
5
Gra
pefr
uit- o
Passio
n F
ruit- o
Mo
ldy- o
Cooked
- o
Me
dic
ine
- o
Gra
pefr
uit-r
Passio
n F
ruit -
Mold
y-r
Co
oke
d-r
Me
dic
ine
-r
Sw
eet
Acid
Bitte
r
Canned OJ vs Fresh Squeezed OJ
0
1
2
3
4
5
Gra
pefr
uit-o
Passio
n F
ruit-o
Mo
ldy-o
Cooked
-o
Me
dic
ine
-o
Gra
pefr
uit-r
Passio
n F
ruit -
r
Mold
y-r
Cooked
-r
Medic
ine
-r
Sw
eet
Acid
Bitte
r
Gra
pefr
uit-o
Passio
n F
ruit-o
Mo
ldy-o
Cooked
-o
Me
dic
ine
-o
Gra
pefr
uit-r
Passio
n F
ruit -
Mold
y-r
Cooked
-r
Medic
ine
-r
Sw
eet
Acid
Bitte
r
Canned OJ (blue) Fresh Squeezed OJ (red)
No Naringin!!
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1.8
1-M
eth
an
eth
iol
2.2
7- D
ime
thyl
su
lfid
e
4.3
9- 2
-me
thyl-
3-f
urn
ath
iol
9.0
0-N
ot
aro
ma
ac
tive
15
.15
16
.92
18
.33
2 4 6 8 10 12 14 16 18
Time (min DB-5)
PF
PD
Re
sp
on
se
5.3
0- M
eth
ion
al
3.6
3- 3
-me
rca
pto
-2-b
uta
no
ne
6.6
6-D
ime
thyltr
isu
lfid
e
13
.61
-1
-P
MT
Pérez-Cacho, P. R.; Mahattanatawee, K.; Smoot, J. M.; Rouseff, R., Identification of sulfur volatiles in canned orange juices lacking orange flavor. Journal of Agricultural and Food Chemistry 2007, 55, 5761-5767.
CH3
CH3 SH
CH3
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Widely distributed in Foods
Are found in many chemical forms
Typically found at trace concentrations
Have extremely potent aromas
Are difficult (BUT IMPORTANT) to measure
GC-olfactometry
Sulfur specific GC detectors - PFPD
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Sulfur in Cooked Foods
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Sulfur in Fruits
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N
S
N
S
SS
S
CH3S
CH3 CH3S
SCH3
CH3S
H
sulfide dissulfide thiol
thiazole thiazolines thrithiolane
Sulfur Structures
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Sulfur Off-Flavor Structures
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Sulfur Off-Flavors
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Relative Aroma Strength
Rough rule – many exceptions
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Compound Odor
Description
Odor Threshold (µg/L)
Hydrogen sulfide Rotten egg, sulfurous 10
Methional Cooked potato 1.8
2-Acetylthiazole popcorn 1
Methanethiol Sulfurous 0.2
Dimethyl disulfide cabbage 0.16
2-Acetylthiophene sulfury 0.08
2-Furfurylthiol Roasted, coffee like 0.005
2-Methyl-3-furanthiol Boiled meat 0.005
Bis(2-methyl-3-furyl)-disulfide beef like 0.00002
Sulfur Aroma Thresholds
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How to measure at trace levels?
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Atomic Emission
Sulfur Chemilluninesence
Flame Photometric detection
Pulsed Flame Photometric Detection, PFPD
Selected Ion Monitoring, SIM
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PF
PD
Res
po
nse
(S
qrt
mo
de)
H2S
S
O2
MeS
HD
MS
E
MS
(IS
)
2-M
eth
iop
hen
e
Met
hio
nal
DM
TS
IPD
S (
IS)
2,8-
epit
hio
-cis
-p-m
enth
ane
1-p
-men
then
e-8-
thio
l
8-S
H-p
-men
than
-3-o
ne
(IS
)
DM
DS
3-S
H h
exyl
ace
tate
11
14 15
1716 18
400 600 800 1000 1100 14001200 1500900700 1300
Bis
-2-m
eth
yl-3
fury
l-d
isu
lfid
e *
ZB-5 column
Sulfur compounds in GFJ (canned RFC)
3-M
eth
iop
hen
e
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PFP
D R
esp
on
se (
Sqrt
)
Time
2-M
eth
iop
hen
e D
MD
S
DM
TS
3-M
eth
iop
hen
e
Met
hio
nal
3-S
H h
exyl
ace
tate
2,8
-ep
ith
io-c
is-p
-men
than
e
1-p
-men
then
e-8
thio
l
H2S
SO2
MeS
HD
MS
CS 2
Thermal generation of GFJ VSC’s
Fresh Juice
Heated @ 90°C 2 hrs
Heated @ 90°C 6 hrs
Heated @ 90°C 15 hrs
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Mechanism for 1-PMT formation
SH
H S H
+-limonene
citrus
1-p-menthen-8-thiol
Grapefruit – character impact
+H+
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Thiam ine (vitam in B1)
N H2N
N N
S
O H
+
bis (2-m ethyl-3-furyl)-disulfideO
S S
O
threshold = 2 parts in 1014
parts w ater
Thiamine Decomposition
Dreher, J. G.; Rouseff, R. L.; Naim, M., GC-Olfactometric Thermal Degradation of Thiamin in Model Orange Juice. Journal of Agricultural and Food Chemistry 2003, 51, 3097-3102.
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CH3
S COOH
NH2
CH3
SCHO
methionine methional
Tasteless-odorless Cooked potato
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MethionineCysteine Glutathione
S-Methyl Methionine
OH
O
NH2
SH NHHOOC
O
NH2
SH
NH
O
COOHSOH
NH2
O
SOH
NH2
O
+
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Non-pathogenic bacteria
Associated with fruit juice off-flavorsflavor defect in apple and orange juices
Produces flat/sour type spoilagestorage temperature critical
no gas produced
Off-aromamedicinal
antiseptic
disinfectant
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Aro
ma
Inte
nsi
tyFI
D R
esp
on
se
can
dy,
sw
eet,
fru
ity
alco
ho
l
ber
gam
ot
cucu
mb
erfr
esh
,flo
wer
pu
nge
nt,
spo
ilage
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bag
e
pap
er
sco
tch
tap
e
bee
f b
roth
oil
y,fr
ied
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tch
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ean
ise ?
ho
spit
al
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,fri
edcl
ove
mild
ewy
clea
ner
h
erb
ace
ou
s
ran
cid
oil
mea
ty
swea
ty
10.0 11.0 12.0 13.0 14.0 15.0 16.0 17.0
Time - Minutes
GU
AIA
CO
L
2,6
-D
CP
2,6
-D
BP
me
dic
ine
me
dic
ine
me
dic
ine
,an
tise
pti
c
A. Cycloheptanicus Day 28
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0
1
2
3
4
5
6G
C-O
Aro
ma P
eak H
eig
ht
Day 0 Day 14 Day 28
2,6-DBP
2,6-DCP
guaiacol
0
1
2
3
4
5
6
GC
-O A
rom
a P
eak H
eig
ht
Day 0 Day 14 Day 28
2,6-DBP
2,6-DCP
guaiacol
Incubation Time (Days)
Perez-Cacho, P. R.; Danyluk, M. D.; Rouseff, R., GC-MS quantification and sensory thresholds of guaiacol in orange juice and its correlation with Alicyclobacillus spp. Food Chemistry 2011, 129, 45-50.
Gocmen, D.; Elston, A.; Williams, T.; Parish, M.; Rouseff, R. L., Identification of medicinal off-flavours generated by Alicyclobacillus species in orange juice using GC-olfactometry and GC-MS. Letters Applied Microbiology 2005, 40, 172-77
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min0 10 20 30 40 50 60 700
10
20
30
40
50
Met
hio
nin
e
MM
S
Fresh Satsuma juice
Time (min)
Flu
ore
scen
ce I
nte
nsit
y
ASP
ASn Gln
Thr
Arg
Lys
L-a-ala
Phe
Ser
SOH
NH2
O
+
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Screen incoming juices for precursors
mandrins have highest MMS
orange and grapefruit lower MMS
Sakamoto, K.; Inoue, A.; Nakatani, M.; Kozuka, H.; Ohta, H.; Osajima, Y., S-
methylmethionine sulfonium in fruits of citrus hybrids. Bioscience Biotechnology and
Biochemistry 1996, 60, 1486-1487.
Direct “at risk” juices to ref. storage
Pass juice through cation exchange resinManabe, T., Dimethyl sulfide as a factor of off-flavor in heat-induced Satsuma
mandarin orange (Citrus unshiu) juice and its precursor. Hiroshima Nogyo Tanki
Daigaku Kenkyu Hokoku 1979, 6, 145-52.