China Medical University

Miau-Rong Lee, PhD

Biochemistry Dept., School of Medicine
2023/11/3

For : Biochemistry in Daily Life

(General education course)
Goals

Students are expected to be able to

• Classify carbohydrates
• Describe the linear and cyclic structure of
monosaccharides
• Describe the formation and chemical properties of
oligosaccharides and polysaccharides
• Describe the structure and function of
glycoconjugates (glycosaminoglycans,
glycoproteins)
Outlines

1. Classification of carbohydrates
2. The structures and stereochemistry of
monosaccharides
• Configuration and Fischer projection fomula
• Cyclic structures, anomers, and Haworth
projection formulas
3. Formation of oligosaccharides and polysaccharides
• Structures and functions of cellulose, chitin,
starch and glycogen
4. Glycosaminoglycans, glycoproteins
1. The Structures and Properties of
carbohydrates
Carbohydrates serve as fuel and
building materials

What else?
Carbohydrates

• Carbohydrate:
a polyhydroxyaldehyde or polyhydroxyketone, or a
substance that gives these compounds on hydrolysis
• Monosaccharide: a carbohydrate that cannot be
hydrolyzed to a simpler carbohydrate
• Building blocks of all carbohydrates
– (CH2O)n ：They have the general formula CnH2nOn,
where n varies from 3 to 8
– Aldose: a monosaccharide containing an aldehyde group
– Ketose: a monosaccharide containing a ketone group
 Carbohydrates

CARBOHYDARTES

MONOSACCHARIDES POLYSACCHARIDES
OLIGOSACCHARIDES

Basic units of Non crystalline,

They can be non soluble in water,
carbohydrate
further hydrolyzed tasteless, on hydrolysis
Cannot be hydrolyzed
gives molecules of
into smaller units
a. Disaccharides monosaccharides
a. Based on the number e.g. starch, cellulose
b. Trisaccharides
of C-atoms c. Tetrasaccharides
b. Based on the type of
functional group
(Carbonyl group)
 Aldoses (aldehyde sugars) Ketoses (ketone sugars)

Monosaccharides Triose : 3 carbon sugars (C3H6O3)

• (CH2O)n
• Glucose (C6H12O6) :
the most common Pentose : 5 carbon sugars (C5H10O5)

• Classification
– aldose or ketose
– number of carbons
• D- and L- monosaccharides:
-- according to the configuration
at the highest-numbered chiral Pentose : 5 carbon sugars (C5H10O5)
carbon atom.

• epimers at C-4
差向異構體
 Cyclization of glucose
• anomers: carbohydrates that differ in configuration only at their
anomeric carbons
• anomeric carbon

trans

cis

A cyclic hemiacetal (半縮醛)

Anomeric Carbon

α- anomer β - anomer
Cyclization of sugars

𝛼 𝛽

a cyclic
Hemiketal
(半縮酮)

D-Fructose
(open-chain form)
The anomeric carbon is the carbon found in the ring next to the
oxygen and also attached to an oxygen outside the ring.
Anomeric pairs have all chiral carbons in the same configuration
except the anomeric carbon. Which of these listed below are
anomeric pairs?
1) 2)
A. 1, 2
B. 2, 3
C. 3, 4
D. 1, 4
E. 2, 4

3) 4)
Glycosidic Bond Formation

• Glycoside: a carbohydrate in which the -OH of the anomeric

carbon is replaced by –OR
• Glycosidic bond: the bond from the anomeric carbon to the
-OR group
• Formation of oligosaccharides and polysaccharides

anomeric carbon glycosidic bond

+ CH3OH + H2O

𝛼-D-Glucopyranose Methyl Methyl−𝛼-D-Glucopyranoside

(hemiacetal) A glycoside
alcohol
(full acetal)
Disaccharides

Free anomeric carbon

(reducing end)

Non-reducing sugar Reducing sugar

 Lactose

+
• A reducing sugar,
hydrolyzed by lactase
H2O
(human), -galactosidase
Acetal (bacteria).

𝛼 Anomer

Nonreducing end Reducing end

 Glycosidic linkages can take various forms
Disaccharides composed of glucose
C1  C4

≡
Cellobiose

C1  C4
C1  C6

C1  C1

Maltose
Gentiobiose

C = hemiacetal (a reducing sugar)

Trehalose
C = acetal (Non-reducing sugar)
A disaccharide of -D-glucose

𝜷,𝜷(11) Glycosidic bonds

A disaccharide of -D-glucose. Both anomeric carbons (C-1)

are involved in the glycosidic linkage.
Amino Sugars

𝑁-Acetyl-𝛽-D-giucosamine 𝑁-Acetylmuramic acid

Phosphoric Esters

• important in the metabolism of sugars to provide energy

– frequently formed by transfer of a phosphate group
from ATP
 Polysaccharides (Glycans)

• Homoglycans: glucan (starch, glycogen, cellulose), Fructan, Galactan

• Heteroclycans: hyaluronic acid, agar, chitin, peptidoglycans, etc.
• Serve as storage and structural roles
 Storage Polysaccharides
• Polymers of glucoses
• Starch, in plants: amylose & amylopectin
• Glycogen, in animals, Is stored mainly in liver and muscle cells
• They are hydrolyzed to release glucose when the demand for sugar
increases
 Structural Polysaccharides
• Cellulose, in plant cell walls, a polymer of glucose, but the
glycosidic linkages differ; β (14)
• Chitin, in the exoskeleton of arthropods and cell walls of many fungi
 Starch: Amylose and Amylopectin

Amylose

Amylases  (14)

Amylopectin

(16)

 (14)
Amylopectin:  (14) &  (16) linkage, branched
Glycogen

• Liver glycogen (90 g): converted to blood sugar

• Muscle glycogen (300 g): glucose for muscle use

• Glycogen:  (14) &  (16) linkage, branched

• Degrees of branching: glycogen > amylopectin
 Cellulose

Repeating disaccharide in cellulose ( 𝛽 -cellobiose) cellulase

• ~2800 D-glucose units

per molecule joined by -
1,4-glycosidic bonds
• major structural
component of plant cell
wall, insoluble fiber

extensive intra- and intermolecular

hydrogen bonding between chains
What would happen if a cow were given antibiotics
that killed all the prokaryotes in its stomach?
• The cellulose in human food passes through the digestive
tract as “insoluble fiber”
• Many herbivores, from cows to termites, have symbiotic
relationships with some microbes that use enzymes
(cellulases) to digest cellulose
 Chitin
• Chitin is composed of units of N-acetyl--D-glucosamine
joined by -1,4-glycosidic bonds
• the major structural component of the exoskeletons of
invertebrates, such as insects and crustaceans; in cell walls of algae, fungi,
and yeasts
CH2OH

(14) (14) (14)

N-acetyl- -D-glucosamine CCH3

• Biomedical materials -- chitosan

Chitin is used to make a strong and flexible surgical thread.
 Mannans
In plants, mannans have a structural role by binding cellulose, but also
they serve a storage function as a reserve carbohydrate in endosperm
walls and vacuoles of seeds and vacuoles in vegetative tissues

β-1,4-linked backbone containing mannose (linear mannan)

a combination of glucose and mannose residues (glucomannan)

occasional side chains of α-1,6-linked galactose residues

 Glycosaminoglycans

• Glycosaminoglycans: polysaccharides based on a

repeating disaccharide where one of the monomers is an
amino sugar and the other has a negative charge due to
a sulfate or carboxylate group
• Heparin: natural anticoagulant
• Hyaluronic acid: a component of the vitreous humor of the eye
and the lubricating fluid of joints
• Chondroitin sulfate and keratan sulfate: components of
connective tissue
• The hydrated GAGs serves as a flexible support for the
ECM (extracellular matrix), interacting with the structural
and adhesive proteins, and as a molecular sieve,
influencing movement of materials through the ECM.
 Glycosaminoglycan, Proteoglycan,
and Aggregates
糖醛酸 胺基糖
Alduronic acid Amino Sugars COO- CH2OH

n Hyaluronic
(proteoglycan aggregates) acid

(proteoglycan) NHCOCH 3
D-glucuronic acid N-Acetyl-D-galactosamine

COO- CH2OSO3-

Chondroitin
sulfate

NHCOCH 3
D-glucuronic acid N-Acetyl-D-galactosamine

CH2OH CH2OSO3-

Keratan
sulfate
NHCOCH 3
Galactose N-Acetyl-D-glucosamine
 Structure and Distribution of
Glycosaminoglycans (GAGs)
In cartilage,
tendons, Most heterogenous
ligaments, GAGs, KSI in corneas
and arota KSII in loose
connective tissue
proteoglycan
aggregates
glucuronic acid n n
Chondroitin 4-sulfate Galactose Keratan sulfate
In cartilage, Intracellular
tendons, component of
ligaments, mast cells,
and arota serves as
anticoagulant

n
N-acetylgalactosamine n
Heparin N-acetylglucosamine
Chondroitin 6-sulfate Heparan sulfate Unsulfated, not
COO- CH2OH covalentlly
In skin, attached to protein,,
blood vessel, also in bacteria
heart valves In synovial fluid of
joints, vitreous
humor of the eye,

L-iduronic acid
n HNCOCH 3 n umbilical core,
loose connective
Dermatan sulfate Hyaluronic acid tissue and cartilage
Extracellular matrix
Functions of Glycosaminoglycans

• mucous secretion
• synovial fluid of joints, vitreous humor of the eye, umbilical
core
• Connective tissues： loose connective tissue and cartilage,
skin, tendons, ligaments, blood vessel, heart valves, and
aorta
Cartilage 軟骨
Shock absorber

軟骨素 (chondrointin sulfate)

Functions of Glycosaminoglycans

 the “slippery” consistency of mucous secretion and synovial fluid.

 the resilience of synovial fluid and the vitreous humor of the eye.
Glycoproteins (糖蛋白)

• Oligosaccharide + Protein
̶ N-linked (Asn) & O-linked (Ser)
• Glycoproteins frequently play a role
in the immune response
Structures of Blood-Group Antigenic Determinants
Biochemical Connections: Glycoproteins and
Blood Transfusions
 Biochemical Connections:
Fruits, Flowers, Striking Colors, and Medicine

Cinnamaldehyde Vanillin
Cyanidin chloride

Red and blue color

The term digitalis is also used
for drug preparations that
contain cardiac glycosides,
particularly one called digoxin,
extracted from various plants
of this genus.  irregular
Laetrile
heart beat
for cancer therapy ???
Vitamin C Is Related to Sugars

An unsaturated lactone

Cyclic ester bond :

air oxidation
 hydrolyze this bond
Ascorbic acid (Vitamin C) and inactivates Vit C

Except guinea pig and human

2. Medicine and other Application
Biochemical Connections:
Lactose Intolerance: Why Do So Many
People Not Want to Drink Milk?

• Lactaid contains the enzyme

lactase.
• Lactase is a β-galactosidase
enzyme involved in the hydrolysis
of the disaccharide lactose into
the building blocks galactose and
glucose.
Biochemical Connections:
Low-Carbohydrate Diets

Glycemic index
Good carbs vs. Bad carbs
Low Carb Low fat diet
diet +
weight loss
drug
Body ↓ ↓
weight
Blood ↓ 50% ↓ 21%
pressure
Biochemical Connections:

Why Is Dietary Fiber So Good for You?

Complex carbohydrates

Soluble and insoluble fibers (amylopectin and other pectins),

bind water and increase satiety (filling the stomach)
Biochemical Connections:

An Apple a Day…. Why?

• The old adage, “An apple a

day keeps the doctor away”
has persisted over time due
to actual health benefits from
apples.
• Apples have a high pectin
content, a soluble fiber known
to be an effective GI regulator.

© Photodisc
What can Beano do?
Raffinose, a trisaccharide composed of galactose, fructose, and
glucose. Raffinose can be found in beans, cabbage, brussels
sprouts, broccoli, asparagus, other vegetables, and whole grains.
Beano contains the enzyme α-galactosidase.
It can digest raffinose. (a non-reducing sugar. )
Catalyze : raffinose + H2O  alpha-D-galactose + sucrose.
CH2OH

α-galactosidase

CH2
HOCH2

CH2OH
 Polysaccharide as a Promising Bioactive
Material for Drug Nanocarrier Systems
• Many properties of polysaccharides such as
biocompatibility, solubility, potential for modification,
and innate bioactivity provide great potential for
their use in drug delivery systems
• Polysaccharides have very low or no
toxicity levels
• Since polysaccharides are naturally
present in the body, most of them
are degraded enzymatically. As a
result, mechanism of release for
therapeutics associated with
polysaccharide-based carrier
systems is provided by enzymatic
degradation
• The functional groups of polysaccharides such as
hydroxyl and amine groups yield high aqueous
solubility. However, this solubility can often be
adjusted via monomer modification.
 白木耳（white jelly fungi）

銀耳(Tremella fuciformis Berk)，

俗稱白木耳（white jelly fungi）， α-1,3- mannan
屬真菌中擔子菌(basidiomycetes)，
銀耳目(Tremellales)，銀耳科
(Tremellaceae)，銀耳屬
(Tremella)；可食用部份為子實體。
β-D- glucuronic acid
銀耳所含多醣體(polysaccharides)可以降低老
鼠血糖與低密度膽固醇含量、抗發炎、促進淋
巴球增生與血小板細胞活性(8)及增加脾臟巨噬 β-(1,2)D- xylobiose
細胞的活性)、誘導人體產生致腫瘤壞死因子 銀耳多醣體主要結構（參考Fraser et al. 1973）
(tumor necrosis factor, TNF) ，及在抗腫瘤活
性上所扮演的角色等。
近年來，美國及日本等國也有多項以銀耳多醣
活性成分glucuronoxylomannan為訴求之專利
申請案通過，包括飲食補充劑、血管內皮細胞
促進劑、抗過敏藥劑以及皮膚用保濕材料等。

銀耳子實體
• 銀耳所含的透明膠質主要為多醣體，其分子量大小約為50萬
至600萬道爾頓(dalton)，主要化學結構（上圖）以α-1,3-甘
露聚醣(mannan)為主鏈，側鏈接有β-D-木糖(xylose)與β-D-
葡萄糖醛酸(glucuronic acid)，在C2 的位置接有β-(1,2)D-木
二糖(xylobiose)，屬於酸性異質多醣體(acidic
heteropolysaccharide)。
• 這樣的化學結構，與黑木耳及其他菇類，以β-(1,3) D-葡聚糖
(glucan)為主結構之同質多糖體(homopolysaccharide) 大不
相同。
• 根據文獻及試驗顯示，銀耳多醣體塗於皮膚上，可形成透明
薄膜，能提高皮膚保水率，為天然保濕素材，適合開發成皮
膚保濕保養品。
Future Medicine
Glycosaminoglycan-based resorbable polymer composites
in tissue refurbishment | Regenerative Medicine

Future Medicine
Glycosaminoglycan-based resorbable polymer composites in tissue refurbishment | Regenerative Medicine
Medical application of glycosaminoglycans: a review

The different applications of glycosaminoglycans

J Tissue Eng Regen Med, Volume: 12, Issue: 1, Pages: e23-e41, First published: 12 January 2017, DOI: (10.1002/term.2398)
3. Exercise
1. The carbohydrate shown is
a. a monosaccharide
b. a ketose.
c. a hexose.
d. all of these
e. none of these

2. The carbohydrate shown is

a. the D isomer.
b. the L isomer.
c.both D and L.
d. neither D nor L.
e. It's impossible to tell from a
picture which isomer this is.
3. Which of the following figures represents the Haworth
projection of the carbohydrate shown?

A. C.

B. D.
4. As shown below, epimers of D-Glucose include:
A. D-Fructose and L-Glucose
B. D-Glucose and L-Glucose
C. L-Glucose and L-Idose
D. L-Idose and D-Galactose
E. L-Glucose and D-Galactose
5. Which carbon of the open-chain form of a sugar becomes
the anomeric carbon in the cyclic form?
A. the carbonyl carbon
B. the highest numbered chiral center
C. the highest numbered carbon
D. It depends on the individual sugar.

6. A pyranose is a sugar that

A. contains a five-membered ring as part of its cyclic
structure.
B. contains a six-membered ring as part of its cyclic
structure.
C. is a five-carbon open-chain sugar.
D. is a six-carbon open-chain sugar.
7. The  and  forms of the same sugar are called
A. anomers.
B. diastereoisomers.
C. enantiomers.
D. epimers.
E. none of these

8. Glycosidic linkages between monosaccharide units may

vary based on
A. the anomeric form of the cyclic structure, i.e.,  or .
B. which ̶ OH group is involved.
C. both of these
D. none of these
9. Which of the following best describes the glycosidic
bond in the disaccharide shown?

A. (1-4)
B. (1-4)
C. (2-4)
D. (2-4)
E. None of the above.

10. Glycosidic bonds from sugars

A. always link to the other molecule through an oxygen atom
B. always link to the other molecule through a nitrogen atom
C. may link to the other molecule through either an oxygen
or a nitrogen atom
11. Which of the following statements associated with
cellulose is false?
A. It's a linear polymer of glucose.
B. The glycosidic linkage is b(1 ®4).
C. Hydrolysis is accomplished enzymatically by cellulase.
D. Most animals can easily digest this compound.

12. The main difference, on the surface of a red blood cell,

between the A-B-O major blood groups depends on
A. the presence or absence of a certain protein sequence.
B. the presence or absence of a certain sugar.
C. the presence or absence of an acetyl group on a sugar.
D. all of these
13. Which lettered subunit is the nonreducing end?
A) A B) B C) C
D) There is more than one nonreducing end on this carbohydrate
E) There are no nonreducing ends on this carbohydrate

the glycosidic bond 1. (2-6)

2. (1-4)
3. (2-4)
14. Cartilage and mucous are both slippery because:
A. Short polymers comprise these compounds.
B. The charge repulsion between the many acid groups
in these polymers.
C. The sticky nature of sugars.
D. Both charge repulsion of acidic groups and the
sticky nature of sugars.
E. All of these

15. Glycoproteins
A. are involved in the metabolism of sugars
B. are proteins to which sugars are covalently bonded
C. occur in the bloodstream of diabetics
D. have not been found in nature, but have been
synthesized in the laboratory