today’s topics: carbohydrate chemistry polyhydroxy aldehyde/ketones
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Today’s topics: Carbohydrate chemistry polyhydroxy aldehyde/ketones chirality and optical isomers – diatereomers & enantiomers hemiacetals and anomers – the cyclic forms of sugars acetals and glycosidic bonds – disaccharides to polysaccharides. Allosteric enzymes ……. - PowerPoint PPT PresentationTRANSCRIPT
Today’s topics:
Carbohydrate chemistry polyhydroxy aldehyde/ketones chirality and optical isomers – diatereomers & enantiomers hemiacetals and anomers – the cyclic forms of sugars acetals and glycosidic bonds – disaccharides to polysaccharides
Allosteric enzymes …….a) Have two distinct folded conformationsb) Have quaternary structurec) Have a sigmoidal v vs. [S] plotd) all of the above
Allosteric enzymes …….a) Can only be turned on one timeb) Can be regulated only to decrease activityc) Require an ‘activating’ enzyme.d) Can have incremental alterations in activity.
CH = O |CH — OH | CH2 — OH
C3H6O3 or…C3(H2O)3
Opposite amino acids, nature typically makes only D carbohydrates.
A carbohydrate is a polyhydroxy aldehyde or ketone and their derivatives (e.g. hemiacetals)Although initially named for having the general formula Cn(H2O)n, this is no longer required for something to be classified a carbohydrate.
Name some carbohydrates.
Carbohydrates you might be familiar with include: sugars (monosaccharides) like glucose, and fructose.
Disaccharides like sucrose, maltose, and lactose ….
Polysaccharides like starch, glycogen, and cellulose.
Monosaccharides3-carbon or triose
4-carbon or tetrose
5-carbon pentose
6-carbon hexose
# optical isomers = 2n
C=O | H - C - OH |HO - C - H | H - C - OH | H - C - OH | CH2 - OH
H
Glucose
C=O | H - C - OH |HO - C - H |HO - C - H | H - C - OH | CH2 - OH
H
Galactose
C6H12O6
Fructose
CH2 - OH | C = O |HO - C - H | H - C - OH | H - C - OH | CH2 - OH
Does glucose exhibit optical isomerism? a) yes b) no How many chiral carbons? a) 1 b) 2 c) 4 d) 6
DiastereomersOptical isomers that are not mirror images of each other.
C=O | H - C - OH |HO - C - H | H - C - OH | H - C - OH | CH2 - OH
H
D- Glucose
EnantiomersOptical isomers that are
mirror images of each other. C=O |HO - C - H | H - C - OH |HO - C - H |HO - C - H | CH2 - OH
H
L- Glucose
All natural sugars are D isomers
Hemiacetals and Hemiketals
C=O | H - C - OH |HO - C - H | H - C - OH | H - C - OH | CH2 - OH
H
D- Glucose b – D - Glucose
a – D - Glucose
Anomers
OOH
OHOH
OH
OH
b – D - Galactose
OOH
OHOH
OHOH
a – D - Glucose
OOH
OHOH
OH
OH
b – D - Glucose
OOH
OH
OHOH
OH
L - Glucose
Anomers – diasteromers that interchange in solution
Enantiomers the optical isomer that is the mirror image
Diastereomers optical isomers that aren’t mirror images
OOH
OHOH
OHOH
a – D - Glucose
OOH
OHOH
OHOH
OOH
OHOH
OH
O
OOH
OH
OHOH
maltose – a – 1,4 glycosidic bond
Lactose (milk sugar)Galactose + Glucose b -1,4
OHOH
O
OH
OHO
OH
HOOH
OHO
Sucrose (Table Sugar)
OH
HO
OH
OOH
O
OH
O
1
2a - 1, b - 2
HO
OH
OH
Common PolysaccharidesChitin
N-acetylglucosamine b-1,6 insect exoskeleton & fungal cell walls
GlycogenGlucose - a-1,4 & a-1,6 Animal glucose storage
Cellulose Glucose - b-1,6 Plant cell walls
StarchAmylose: glucose a-1,4
Amylopectin: glucose a-1,4 & a-1,6
Plant glucose storage
Polysaccharides
Chitin ― insect exoskeleton & fungal cell walls
Glycogen : Animal glucose storage
Cellulose : Plant cell walls
Starch : Plant glucose storage
Starch & glycogen store glucose in plants & animals. They contain mostly a-1,4 glycosidic bonds.
OH HO
OH
OHO
O
OH
OH
OHO
O
OH
OH
OHO
Oetc.
O
OHOH
OH
OHO
O
OH
OH
OHO
O
OH
OH O
Glycogen (& amylopectin of starch)
etc.
O
OHOH
OH
OHO
O
OH
OH
OHO
a-1,6a-1,4
Glycogen (& amylopectin of starch)
a-1,6
a-1,4
etc.Cellulose ― b-1,4 Linkage
OH
OH
OHO O
OH
OH
OHO O
OH
OH
OHO O
GLYCOGEN
Carbohydrate – protein/peptide combinationscarbohydrate groups can be attached to peptides, polypeptide chains or proteins to form …..
Peptido glycans – bacterial cell walls – penicillin antibiotics inhibit construction
Proteoglycans – Protein + glycosaminoglycans - lubricants in connective tissue cartilage = proteoglycan + collagen
Glycoproteins – Proteins with oligosaccharides attached to hydroxyl groups erythropoietin (EPO) – hormone that stimulates RBC production Blood group determinants Even Hemoglobin can be glycosylated – evidence of prolonged hyperglycemia Glycosylation of eye crystallins induce cataracts – connection with diabetes
O – CH2 HOOH
OHOH
OH
Glycoproteins
O H || N - C – CH2 -HO
OH
OHHO
NHC=OCH3
O-linked
N-linked
Ser
Asn
Man Man
Man
GlcNAc
GlcNAc
Asn
N-linked core
Blood Types & Glycosyl Transferases (EC 2.4)
Fuc
Gal
GlcNAc
Gal
Ser
GalNAcFuc
Gal
GlcNAc
Gal
Ser
Fuc
Gal
GlcNAc
Gal
Ser
Gal
O A B
Early stop codon mutation in glycosyltransferase gene results in nonfunctional enzyme
A vs. B glycosyltranferase enzymes differ in sequence in only 4/354 residues.
H-antigenRBC glycoprotein
gene probability Mother Father Type probabilityO 0.68 O O O 0.46A 0.26 A O B 0.06 O A A 0.42(-) 0.18 A A B O O B B 0.09 B B A B AB 0.03 B A
What is your blood Type? a) A b) B c) O d) ABe) don’t know
What is your RH factor? a) + b) - c) don’t know
“There are no known natural effects of these differing blood types. People with A, B, AB and O phenotypes do not differ in fitness in any major way that we have been able to detect. This suggests that the complete absence of the enzyme (null mutation) is neutral in the current human population and so is the switch from one form of the enzyme to another. (Suggestions that blood type determines susceptibility to some infections are common in the scientific literature. Most of them have not held up. The best correlation is a possible association between blood type O and susceptibility to cholera. This looks pretty good but the cause-and-effect relationship is still up in the air.) “
Laurence Moran – Professor of Biochemistry – University of Toronto
Flu virus’ gain entry into their host cell by bindingTo (sialic acid) glycoproteinsUsing the hemagglutinin (H).
New viral particles exit by Hydrolyzing the sialic acid offThe host glycoprotein using theirNeuraminidase (N)Tamiflu is a competitive inhibitor of this process.
The H1N1 designation of the flu indicates the type of these two proteins.
Did you get a flu shot?a) Yes b) no