Carbohydrates and Lipids

Carbohydrates
H O H OH H
C C
1 H C OH
1
H C OH C OH
2
H C OH
 H C OH
 C O
2
3 H C OH
3
H H
H
glyceraldehyde enediol intermediate dihydroxyacetone
tautomers

HC O HC O

H C OH HO C H

CH2OH CH2OH

D-glyceraldehyde L-glyceraldehyde
sterioisomers called enantiomers (mirror images)
FIG 9.5
Tetroses: enantiomers and diasteriomers
HC O HC O HC O

H C OH other chiral
H C OH HO C H
carbon
H C OH H C OH HO C H D-/L- chiral
carbon
CH2OH CH2OH CH2OH

sterioisomers that D-erythrose L-erythrose

are not mirror images:
diasteriomers mirror images: enantiomers

HC O HC O

HO C H H C OH

H C OH HO C H

CH2OH CH2OH
D-threose L-threose
FIG 9.9
aldoses
FIG 9.9
ketoses
 O

Rings of Pentoses furan ring

H O H O
O H
C C C
1 O

H C OH H C OH H C OH
2

H C OH H C OH H C OH pyran ring
3

H C OH H C OH H C OH
4
CH2 OH CH2 OH D- ribose CH2 OH
5


 
HO CH2 O HO CH2 O O
5
OH O OH
4 1
OH HO OH
3 2 HO HO OH
OH HO OH HO OH
HO

-D-ribofuranose -D-ribopyranose-D-ribofuranose -D-ribopyranose

56% 18% 20% 6%
 Rings of Hexoses
O H H O
C C

H C OH H C OH

HO C H
HO C H
H C OH
H C OH
H C OH
H C OH
CH2OH
CH2 OH


 O
CH2OH
CH2OH
O
O OH OH chair
OH
HO OH
HO OH
OH O

-D-glucopyranose -D-glucoyranose boat

-D-glucose: 64% -D-glucose: 36%
 Derivatives:
phosphate esters, acids and lactones
O
CH2OH -

⇌
CH2 O P O
O -
OH + ATP OO + H+
OH
HO OH
OH HO OH
OH
α-D-glucose α-D-glucose-6-phosphate
ΔGo’ = -16.7 kJ/mole

CH2OH CH2OH

⇌
O OH O
OH + 2 Cu2+ + 5 OH- OH + Cu2O + 3 H2O
C -
HO OH HO O
OH OH CH2OH

α-D-glucose D-gluconate
⇌ OH
O
O + OH-
HO
OH
D-δ-gluconolactone
 Derivatives:
alditols
O H
CH2 OH
C
H C OH
H C OH
HC O CH2OH
HO C H
HO C H
H C OH H C OH
H C OH
OH OH H C OH
H C H C
H HC OH
C OH
CH2OH CH2OH
CH2 OH CH2OH

D-erythrose erythritol D-glucose D-glucitol (sorbitol)

 Derivatives:
amino sugars
CH2OH CH2OH CH2OH
CH2OH
HO O OH O OH O OH
HO O OH OH
OH OH OH
HO HO
OH OH NH2
NH2

β-D-glucose β-D-glucosamine β-D-galactose β-D-galactosamine

CH2OH CH2OH CH2OH

O OH O OH O OH
OH
HO HO HO
NH NH2 NH
O - O -
C O O O C O
HC C HC C
CH3 O O CH3
CH3 CH3

β-D-N-acetylglucosamine muramic acid N-acetylmuramic acid

 Derivatives:
glycosides
CH2OH
CH2OH

HO
OH
O

OH
+ CH3OH ⇌ OH
O
+ H2O
HO O CH3
OH
OH
-D-glucose methyl-α-D-glucopyranoside

CH2OH
O O
OH CH2
C N hydrolysis
HO HC CN-
OH O O
OH
HO
OH

amygdalin
 Disaccharides
CH2OH CH2OH CH2OH CH2OH
O O O O
OH OH OH OH
HO OH HO OH HO O OH
OH OH OH OH

-D-glc + -D-glc maltose

-D-glucopyranosyl (14) -D-glucopyranose
CH2OH CH2OH CH2OH
CH2OH OH
O O CH2OH O
OH OH OH O
O HO CH2
HO OH HO OH HO OH OH
OH O OH
OH OH OH HO O
HO OH
OH

-D-glc + -D-glc trehalose O

-D-glucopyranosyl (11) -D-glucopyranose
CH2OH
CH2OH O
HO CH2 O OH OH
O
OH HO HO
CH2OH OH
HO OH O
OH HO HO CH2 O
HO
CH2OH
HO

-D-glc + β-D-fru sucrose

-D-glucopyranosyl (12) β-D-fructofuranoside
 Disaccharide: synthesis
CH2OH CH2OH CH2OH CH2OH

OH
O
+ OH
O
⇌ OH
O
OH
O
ΔGo’ = +15 kJ/mole
HO OH HO OH HO O OH
OH OH OH OH

-D-glc + -D-glc maltose

2 Pi

ATP ADP UTP PPi

CH2OH
CH2OH CH2OH
O
O O
UDP-glucose
OH
OH OH
HO OH
OH HO O PO3 2- HO O PO 3 -PO 3 - uridine
OH OH
CH2OH
-D-glc -D-glc-1-phosphate O
OH -D-glc
HO OH
OH

UDP
CH2OH CH2OH

OH
O
OH
O
maltose
HO O OH
OH OH
 Polysaccharides: amylose
CH2OH
O
OH -D-glucose
HO OH
OH

CH2OH CH2OH CH2OH CH2OH CH2OH CH2OH

O O O O O O
OH OH OH OH OH OH
HO O O O O O OH
OH OH OH OH OH OH

amylose: -D- glucose monomers with  (14) linkages

 Polysaccharides:
amylopectin and glycogen
CH2OH
O
OH -D-glucose
HO OH
OH

CH2OH CH2OH CH2OH CH2OH

O O O O
OH OH OH OH
HO O O O O
OH OH OH OH
CH2OH CH2OH CH2 CH2OH CH2OH CH2OH
O O O O O O
OH OH OH OH OH OH
HO O O O O O OH
OH OH OH OH OH OH

amylopectin: -D- glucose monomers with  (14) linkages

with  (14) linkages every 10-20 residues

glycogen: -D- glucose monomers with  (14) linkages with  (14)

linkages every (approximately) eight residues
 Polysaccharides:
CH2OH
cellulose OH
HO
O OH OH
OH
-D-glucose O OH
HO
OH CH2OH
flipped

CH2OH OH CH2OH OH CH2OH OH CH2OH OH

O O O O O O O O
OH OH OH OH OH OH OH OH
HO O O O O O O O OH
OH CH2OH OH CH2OH OH CH2OH OH CH2OH

cellulose: -D- glucose monomers with  (14) linkages;

every other monomer is flipped
FIG 9.22
cellulose
 Polysaccharides:
H
C
O
hemicellulose (xylans)
H C OH

HO C H
H
H C OH O OH
OH
H2C OH HO
OH

D-xylose -D-xylose
H H H H

O O O O OH
OH O OH O OH O OH
HO
OH OH OH OH

a typical xylan: -D- xylose monomers with  (14)

linkages; every other monomer is flipped
: often with groups added at C2 or C3
- COCH3 (acetyl)
- 4-O-Me--D-glc
 Polysaccharides:
hemicellulose (glucomannans)
CH2OH CH2OH
O OH O OH
OH OH HO
HO HO
OH

-D-glucose -D-mannose
CH2OH CH2OH CH2OH
CH2OH CH2OH
CH2OH
O O O OH
O O O OH HO
O OH O OH HO O OH
OH O OH HO O
HO OH
OH
OH

a typical glucomannan: -D-glucose and mannose

monomers with  (14) linkages; every
other monomer is flipped
: often with groups added at C2 or C6
- COCH3 (acetyl) (12 or 3)
- -D-galactose (16)
 Polysaccharides:
CH2OH OH chitin
HO
O OH
OH OH
O OH
HO
OH CH2OH

-D-glucose -D-glucose; flipped

CH3 CH3 CH3 CH3
C O C O C O C O
CH2OH NH CH2OH NH CH2OH
NH CH2OH NH
O O O O O O O O
OH OH OH OH OH OH OH OH
HO O O O O O O O OH
NH CH2OH NH CH2OH NH CH2OH NH CH2OH
C O C O C O C O
CH3 CH3 CH3
CH3

chitin: -D-glucose monomers with  (14)linkages;

every other monomer is flipped
: -NHCOCH3 (acetylated amino group) added at
each C2
Polysaccharides: glycosaminoglycans O
-

O S O
O
-
O chondroitin sulfate: disaccharide monomer
O S O
-
CH2
is β-glucuronic acid (1 –>3)
O O O HO O OH
CH2 C β-N-acetylgalactosamine-6-sulfate
- O
O O HO O O
OH NH
C O
O C O Disaccharides linked by β 1–>4
O OH
OH NH CH3 bonds
HO C O
OH -
O
CH3
O S O keratin sulfate: disaccharide monomer is
O
-
O
CH2
β-galactose (1 –>4) β-N-
O S O
HO
CH2OH
O OH acetylglucosamine-6-sulfate
O O OH
O
CH2
** error in text **
O
NH
HO
CH2OH
O OH
O OH
C O Disaccharides linked by
O
OH
NH
CH3 β 1–>3 bonds
OH
C O
CH3

-
CH2OH
hyaluronic acid: disaccharide monomer
O O O OH
CH2OH C O is β-glucuronic acid (1 –>3)
O
O
-
O O
OH
O
HO NH β-N-acetylglucosamine
C O O
O C O
O OH
OH HO NH CH3 Disaccharides linked by
HO C O
OH
CH3
β 1–>4 bonds
FIG 9.24
 Polysaccharides: heparin (a non-
structural glycosaminoglycan)

O
O
C
C
HO O
HO O -
O
O
-
O S O
heparin: disaccharide monomer is
O S O
HO O -glucuronic acid-2-sulfate
O O
HO
C
O
CH2
C CH2 (or -idouronic acid-2-sulfate
O OH
O O OH
O
OH (1 –>4)
OH OH O O
HO
O
O NH
β-N-acetylglucosamine-6-sulfate
O NH
O S O C O
O S O C O
O
-
CH3
O
-
CH3 Disaccharides linked by
β 1–>4 bonds
 Bacterial cell walls
CH2 OH
CH2 OH
CH2 OH O OH
O
O OH OH O
OH
HO O NH
HO
NH NH
H3C CH C O
C O C O
C CH3
CH3 CH3
H N O
H3C C H
NAG: N-acetylglucosamine L-alanine
C O
- N H
O
CH2 OH
C C H
O OH O D-isoglutamic
CH2
HO
CH2 acid
O NH
H3C CH C O C O
C CH3 N H
- +
O
O H3N CH2 CH2 CH2 CH2 C H L-lysine
C O
NAM: N-acetylmuramic acid N H
H C CH3
C
D-alanine
-
O O
 CH2 OH
CH2 OH
O OH
O
- O

Gram positive
OH
O HO O NH
C HC H NH
H3C CH C O
C O
O C CH3
CH2 CH3 H
N O
H3C C H
CH2 C O
- N H

L-lysine C O
O C C H
O
N H CH2
CH2
HN CH2 CH2 CH2 CH2 C H C O

C O C O N H

CH2 N H
HN
C O
CH2 CH2 CH2 CH2 C
C
H
O
L-lysine
1 H C CH3 CH2 N H

D-alanine
H C CH3
NH NH
- C C O O
- C
O
C O O O CH2
NH
CH2
2 C O

NH CH2
HN
C O C O

CH2 CH2

pentaglycine 3 NH
HN C O

bridge C O
CH2

NH

CH2
4 H C
C O
CH3

NH
+
N
C O
H
D-alanine
C O H3N CH2 CH2 CH2 CH2 C H

5 CH2
N H
C O L-lysine
CH2

NH O
CH2
C C H
-
O N H
C O C O
H3C C H
H C CH3
N H D-alanine CH3
C O
H N
C
O
CH3
H3C CH C O
C O HO
NH
O NH
+
H3N CH2 CH2 CH2 CH2 C H OH
O
O
O OH
HN H CH2 OH
CH2 OH
FIG 9.25
gram positive bacteria
 CH2 OH
CH2 OH

Gram
O OH
O
OH O
HO O NH
NH

negative
H3C CH C O
C O
C CH3
CH3 O
H N
H3C C H
C O
- N H
O
C C H
O
CH2
link CH2
C O
O N H
NH CH2 CH2 CH2 CH2 C H
D-alanine H C
C
CH3 C O
L-lysine
N H N H
C O H C CH3
+
H3N CH2 CH2 CH2 CH2 C H - C
O O
N H
C O
CH2
CH2
O
C C H
-
O N H
C O
H3C C H
H N O
CH3
C CH3
C O
H3C CH C O
NH
HO O NH
OH O
O
O OH
CH2 OH
CH2 OH
FIG 9.25
gram negative
 Penicillin
R
L-lys
H O C
H CH3
S
N C CH3 H N C HC C CH3
H
H
C N C CH3 H
C N C
O
H C O
- C
O O -
O O

Peptide chain – D-ala – D-ala penicillin

 Glycoproteins
asparagine threonine
O R CH2OH CH3 R
CH2OH
protein
O NH C CH2 CH chain HO O O CH CH
OH OH
R R
HO
NH oligosaccharide NH
C O chain C O

CH3 CH3

N-acetylglucosamine N-acetylgalactosamine

N-linked O-linked
 Blood Groups
O
sialic acid O O

N-acetylgalactose O
O O O
O CH2OH R O
O
R O R
D-galactose O HO O CH2OH O
O O
OH O HO O
OO OH O
NH
OO OO
C O OH

CH3
L-fucose N-acetylgalactose galactose

Type O Type A Type B

 Lipids: fatty acids
-
O O -
O
O
C C
CH2
hydrophilic CH2
H2C H2C
head
CH2 CH2
H2C H2C
CH2 CH2
H2C H2C
hydrophobic CH2 CH2
tail H2C C
H
CH2 C CH2
H2C CH2 CH2
H
CH2 CH2 CH2
H2C CH3
CH2
H2C
CH3

palmitic acid palmitoleic acid

(n-hexadecanoic acid) (cis-9-hexadecanoic acid)
16:0 16:1cΔ9
Lipids: fatty acid melting points
Fatty acid Melting point (oC)

capric (10:0) 31.6

lauric (12:0) 44.2
myristic (14:0) 53.9 trends?
palmitic (16:0) 63.1
stearic (18:0) 69.6
arachidic (20:0) 76.5
behenic (22:0) 81.5
lignoceric (24:0) 86.0
cerotic (26:0) 88.5
palmitic (16:0) 63.1
palmitoleic (16:1cΔ9) 0.0
stearic (18:0) 69.6
oleic (18:1cΔ9) 16.0
linoleic (18:2cΔ9, 12) 5.0
linolenic (18:3cΔ9, 12, 15) -11.0
arachidic (20:0) 76.5
arachidonic (20:4cΔ5, 8, 11, 14) -50.0
 Fats: triacylglycerides
H2C OH

HC OH
glycerol: not optically active
H2C OH

O R1
C
H2C O O
R2 triacylglyceride: optically active if R1 and R2
HC O C
(fatty acids) differ from one another
H2C O R3 (typically the case)
C
O
O O R1
R1
C C
O H2C O L-form exists naturally
H2C O O
R2
H C O C R2 C O C H

R3 H2C O R3
H2C O C
C
O O
R-triacylglyceride L-triacylglyceride
 Saponification:
Soaps and Detergents
O
R1
O C
R1 -
C K+/Na+O
H2C OH
H2C O O
R2 NaOH, KOH - + HC OH
HC O C + 3 H2O K+/Na+ O
C
R3

H2C O R3 wood ashes H2C OH

C O
(lye)
O O
- R2
K+/Na+ O C

Na+ and/or K+ salts of

fatty acids = soap
O
sodium dodecyl sulfate (SDS):
-
a detergent Na+ O S CH2 CH2 CH2 CH2 CH2 CH2
CH2 CH2 CH2 CH2 CH2 CH3
O
 Fats: triacylglycerides
H2C OH

glycerol HC OH

H2C OH

O CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH3

3 fatty acids + 3 C CH2 CH2 CH2 CH2 CH2 CH2 CH2
-
O

hydrophobic tail
hydrophilic
O
head CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH3
C CH2 CH2 CH2 CH2 CH2 CH2 CH2
H2C O O
CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH3
triacylglyceride HC O C CH2 CH2 CH2 CH2 CH2 CH2 CH2
H2C O CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH3
C CH2 CH2 CH2 CH2 CH2 CH2 CH2
O

+ 3 H2O
FIG 10.2
 not very hydrophilic
Waxes
O
- HO O
O O CH2
CH2
C C
CH2
CH2 CH2
CH2
H2C
H2C H2C H2C
CH2
CH2 CH2 CH2
H2C
H2C H2C H2C
CH2
CH2 CH2 CH2
H2C
H2C H2C
+ H2C
CH2 + H2O
CH2 CH2 CH2
HC
HC HC HC
CH CH2
CH CH2 CH CH2 CH CH2 CH2
CH2 CH2 CH2
H2C
H2C H2C H2C CH2
CH2 CH2 CH2
H2C
H2C H2C H2C CH2
CH2 CH2 CH2
H2C H2C
H2C H2C CH3
CH3
CH3 CH3

fatty acid long-chain alcohol wax

 Membrane lipids:
glycerophospholipids
H2C OH H2C OH

H C OH HO C H
O O
- -
O P O CH2 H2C O P O
- -
O glycerol-3-phosphate O

O O
R1 R1
C C
H2C O O O H2C O

H C O C R2 R2 C O C H
O O
R3 O P O CH2 H2C O P O R3
- -
O O
glycerophospholipid
 Membrane lipids:
glycerophospholipids
O
phosphatidic acid H R1
-typically ionized at pH 7 C
+
phosphatidylethanolamine H3N CH2 CH2 H2C O O

CH3 H C O C R2
O
+
phosphatidylcholine H3C N CH2 CH2 R3 O P O CH2
-
O
H3C
+
phosphatidylserine H3N CH CH2
C
-
O O

HO OH
phosphatidyl inositol
OH
HO
OH
 Membrane lipids: sphingolipids
CH CH2 CH2 CH2 CH2 CH2 CH2 CH3
HO CH CH CH2 CH2 CH2 CH2 CH2 CH2
HC NH2
-
sphingosine (D-trans-4-sphinganine
O HO CH2
C CH2 R
O
a fatty acid
CH CH2 CH2 CH2 CH2 CH2 CH2 CH3
HO CH CH CH2 CH2 CH2 CH2 CH2 CH2
HC NH C CH2 R

CH3 O HO CH2 O
+ -
a ceramide
H3C N CH2 CH2 O P O
-
H3C O

phosphocholine
CH CH2 CH2 CH2 CH2 CH2 CH2 CH3
HO CH CH CH2 CH2 CH2 CH2 CH2 CH2
CH3 O HC NH C CH2 R
+ O
H3C N CH2 CH2 O P O CH2
-
H3C O sphingomyelin
 Membrane lipids: glycosphingolipids
CH CH2 CH2 CH2 CH2 CH2 CH2 CH3
HO CH CH CH2 CH2 CH2 CH2 CH2 CH2
HC NH2
-
sphingosine (D-trans-4-sphinganine
O HO CH2
C CH2 R
O
a fatty acid
CH CH2 CH2 CH2 CH2 CH2 CH2 CH3
HO CH CH CH2 CH2 CH2 CH2 CH2 CH2
HC NH C CH2 R

HO CH2 O
O a ceramide

a saccharide
CH CH2 CH2 CH2 CH2 CH2 CH2 CH3
HO CH CH CH2 CH2 CH2 CH2 CH2 CH2
HC NH C CH2 R
O
O CH2 O

a cerebroside glycosphingolipid
 Membrane lipids:
glycosphingolipids
Tay-Sachs individuals
lack enzyme to cleave
terminal gal CH CH2 CH2 CH2 CH2 CH2 CH2 CH3
HO CH CH CH2 CH2 CH
2 CH
2 CH
2 CH2
HC NH C CH2 R
CH2OH CH2OH
HO O CH2 O
O O
OH CH2OH
O OH
O O
CH3
OH
C O
NH O OH
O

O
HOHC OH

HC OH
CH3
GM2: a ganglioside glycosphingolipid
Membrane lipids: glycoglycerolipids
O
R1
C
H2C O O

H C O C R2
CH2OH
HO O O CH2
OH

OH
monogalactosyl diglyceride

O
R1
C
H2C O O

O H C O C R2
-
O P O CH2
-
O
remember: this is called a glycerophospholipid,
or a phosphoglyceride
FIG 10.5
 Membrane lipids:Cholesterol
H3C H3C
21 22
20
CH3 CH3 24
23
12 18 CH3
CH3 17 25
11 13 27
CH3 H3C
CH3
19
C D 16
H3C
1 9 14
15 26
2 10 8
A B
3 5 7
HO HO 4 6
FIG 10.9
FIG10.10
FIG 10.11
FIG 10.12
FIG 10.14
FIG10.15
FIG 10.18
FIG 10.19
FIG 10.20
FIG 10.21
FIG 10.22
FIG 10.24
FIG 10.27
FIG 10.28
FIG 10.31
FIG 10.32
FIG 10.33
FIG 10A.1
FIG 10A.2
FIG 10A.3
FIG 10A.4
FIG 10A.6