by photosynthesis - dongguk · 2014-01-10 · by photosynthesis the most abundant organic molecules...
TRANSCRIPT
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By photosynthesis◦ The most abundant organic molecules◦ >90% dry matter of plants
Significant contribution to the properties of foods Initial source of all food Provide◦ Energy (~4.5 Cal/g), Carbon and fiber
Cx(H2O)y 70-80% human energy needs (US~50%) Monomers and polymers
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Sweetness Precursors of aroma compounds Precursors of colored compounds Provide texture◦ Cellulose◦ Starch◦ Pectin
Build viscosity at low concentration◦ Starch◦ Gums◦ Cellulose fragments
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•Definition
•Polyhydroxyaldehyde or polyhydroxyketonehaving 2 or more hydroxyl groups
•Aliphatic polyhydroxy aldehydes, ketones and
their derivatives
•Food Carbohydrates: sugars, starches, gums, fiber, gels...
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◦ aliphatic: Open chain organic compounds and those cyclic compounds that resemble them (i.e. not aromatic)
OH
C
CH3
H
C
H
H
C
H
CH3 COOH
OH
OHHO
CH 2OHO OHAliphatic
molecules
Aromatic molecule
OH
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Cannot be broken down by mild acid hydrolysis C3-9 (esp. 5 and 6) Polyalcohols with aldehyde or ketone functional
group Many chiral compounds◦ C has tetrahedral bond angles
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◦ Categorized by chain length
Category # of Glycose Units Food Example
Monosaccharide 1 Sugars
Disaccharide 2 Sugars
Oligosaccharide 3 - 10 Sugars
Polysaccharide >10 Starch, Gums
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Classified as no. of carbons (typically 3-8) and carbonyl group◦ Aldehyde: aldose (carbonyl at C-1, -ose) ◦ Ketone: ketose(carbonyl at C-1, -ulose)◦ hexoses (6 carbons): most common◦ Major one: aldoses◦ Triose, tetrose, pentose, hexose◦ The most simple sugar: carbon 3 (glyceraladehyde,
dihydroxyacetone)
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Chiral carbon
OHHOHH
OHHHHO
CCCCCC
its mirror image is an "optical
isomer"
e.g. glucose
H2OH
HO 4 chiral centers e.g. at C2 carbon: This
structure has a non-superimposable mirror imageCHO
(CHOH) 3CH2OH
OHHC2
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Different compounds having same molecular composition
Constitutional isomers Stereoisomers
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Stereoisomer◦ 3-D orientation difference of atoms
Enantiomer◦ Non superimposable mirror image◦ Have same physicochemical properties except Optical
rotation Diastereomer: stereoisomer not Enantiomer◦ Cis, trans◦ Anomer, apimer• Different Physicochemical properties
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A carbon is chiral if it has four different groups
Chiral compounds have the same composition but are not superimposable
Display in Fisher projection
CH2OHH OH
CHO
CH2OHOH H
CHO
D-glyceraldehyde L-glyceraldehydeENANTIOMERS 18
An anomer is one of a special pair of diastereomericaldoses or ketoses ◦ At carbon of hemiacetal◦ α, β-form◦ Different Physicochemical properties
An epimer is one of a special pair of diastereomericaldoses or ketoses except on glyceraldehyde◦ mannose, glucose
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Optical activity
sample
Light source Polar meter
right: (+)left: (-)
Polarized light
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[α] = αㆍ100/(dㆍc)
α= observed rotationd = width (dm)c = conc of sample (g/100mL)
example (25°C, sodium lamp)[α]25
D = -13.52°
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“D” or “L” is up to the last chiral carbon’s conformation
◦ D conformation (i.e. D-glucose)◦ Most sugars: D conformation
H
H2OH
last chiral carbon C
CC
OCC
OH
HO
OHHO
H
HH
CH2OHH
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3
4 5
6
5 OHHOHH
OHHHHO
CCCCCC
HO1
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4 chiral centers —> 16 stereoisomers
OH
OHOH
CH2OHO OH
OHOH
OHCH2OH
O OH
D-mannose D-galactose D-gulose
OHOHOH
CH2OHO OH
OHHOHHHHO
CCCCCCH2OH
HO
HO H
OHH
HHO
CCCCCCH2OH
HO
HO
H OH
HOHH
OH
CCCCCCH2OH
HO
HO
H OH
HH
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◦Hemiacetal is formed when Carbonyl group was attacked by nucleophile◦ Monosugars: Aldehyde and alcohols hemiacetal(pyranose, furanose)
formation
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Hemiacetal: has -OH and -OR group at the same carbon
Acetal: has two OR group at the same carbon
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The most stable form: ring (cyclic) form
HC
CC
OCC
OH
HO
OHHO
H
HH
CH 2 OHH
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4 5
6-D-glucopyranose (glucose)—an aldose
a hexosean aldohexose
—4C1 chair conformation
C CO
CCH
H
COH
H
OHH
OHOH
CH2OH1
2
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6H
-D-fructopyranose (fructose)—a ketose
a hexulosea ketohexose
—2C5 chair conformation28
Anomer is formed
◦ nucleophilic C5 -OH can attack either up or down carbonyl group
HOH 2CH•••O
CC C
C
COH
H
CH2OH
C
CC
C
O
O•••HC
OH
OHHO
CH2OHO OH
OH
OHHO
CH2OHO
OH
CCCCCCH2OH
OH
H O
OHOH
HOH
HH
H
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“” or “” form anomeric carbon
OH
OHOH
CH2OHO
OHOH
OHOH
CH2OHO OH
or or
anomer anomer
HCC
C
OCC
OH
HO
OHHO
H
H
H
CH2OHH
12
3
4 5
6
HCC
C
OCC
OH
HO
OHHO
H
HH
CH2OHH
12
3
4 5
6
trans cis
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Various OH groups can be nucleophile
CH2OH
OHOHOH 2C
HO-D-fructofuranose
HO
OHHO CH2OH
O OH
-D-fructopyranose
HO
CC
CCCCH2OH
O
OHOH
HO
H2OH
HH
HHCC
CCCCH2OH
O
OHOH
HO
H2OH
HH
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Nomenclature:◦ Pyranose: hexagonal (six-membered) ring (a very
stable form due to optimal bond angles)◦ Furanose: pentagonal (five-membered) ring
OH
OHHO
CH2OHO OH
-D-glucopyranose
OH
HOHO CH2OH
O OH
-D-fructopyranose
1
12
234
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5
6
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In aqueous acid or base C-O bond is broken: straight chain form
OH
OHHO
CH2OH
OO•••H
OH
OHHO
CH2OH
OOH
OHH
OHH
OHH
HHO
C
C
C
C
C
C H2OH
H
O
1
5 5
5
1
1
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Straight chain form (glucose and fructose):
OHH
OHH
OHH
HHO
C
C
C
C
C
C H2OH
H
O
OHH
OHH
O
HHO
C
C
C
C
C H OH2
C H OH21
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3
4
5
6
D-glucose(an aldohexose)
D-fructose(an ketohexose)
1
2
3
4
5
6
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◦ Since carbonyl carbon is electron deficient Easy to be attacked by nucleophiles
1. if OH groups is nucleophile, rings formed2. formation of hemiacetal (alcohol adding to carbonyl group in nucleophilic attack)3. Reversible reaction is possible
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In solution, monosugars (e.g. D-glucose, D-fructose) are interchangeable◦ straight and ring form◦ different ring sizes◦ and anomeric isomers
mutarotation◦ Specific optical rotation of monocarbohydrate is change due
to the change of its structure◦ dynamic equilibrium◦ due to reversibility of reaction◦ Fig 3-2
straight chain
-furanose -furanose
-pyranose -pyranose
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Generally only a few isomers predominate
Straight chain form: lower than 1%!
0
10
20
30
40
50
60
70
80
% o
f all
isom
ers
D-glucose D-fructose D-mannose D-galactose
a-pyranoseb-pyranosea-furanoseb-furanose
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Straight form: the most reactive◦ free carbonyl susceptible to nucleophilic attack,
oxidation, reduction, isomerization◦ even small amounts allow reactions to proceed
Stereochemistry: effect on sweetness◦ different sugars and different isomeric forms vary
in sweetness!◦ -D-fructopyranose makes fructose sweeter than most sugars
Isomer stability◦ Affected by temp and solvent
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