4
CONTENTS
PART 1.
Preface
2
1.1. CARBOHYDRATE FUNDAMENTALS: MONOSACCHARIDES
10
1.1.1. The Fisher projection
10
1.1.2. D-‐ and L-‐sugars
10
1.1.3. Ring
formation
(alcohol + aldehyde = hemiacetal):
α
-‐ and
β
-‐forms and
the
Haworth
formula
12
1.1.4. Definition of
α
and
β
(Haworth) –
the anomeric
carbon:
13
1.1.5. Fisher-‐Haworth
interconversion
rules:
13
1.1.6. Example: Alginate
14
1.1.7. Epimers and anomers.
14
1.1.9. The
shape of hexoses
16
1.1.10. How
to determine whether a
sugar
is
1
C
4
or
4
C
1
16
1.1.11. A
strategy
for determining
the
ring
form:
17
1.2. ALGINATES
19
1.2.1.
Introduction
19
1.2.2. General
19
1.2.3. Structure of alginates
20
1.2.4. Content and distribution of M and G
in alginates
23
1.2.5. Examples: Composition of
some algal alginates
27
1.2.6. Bacterial alginates:
28
1.2.7. Determination of
composition and
sequence
in alginates
29
1.2.8. NMR of alginates – a brief
course
for polysaccharide
chemists
30
1.2.9. The
1
H-‐NMR
spectrum of D-‐glucose
(in D
2
O):
33
1.2.10. Alginates: The
1
H-‐NMR
spectrum
35
1.2.11. Chain
length
(DP
n
)
from NMR
37
1.2.12. Studying alginate
structure and
epimerization by NMR
38
1.2.13. Epimerization: Macromolecular
consequences
39
1.2.14. Gelation with
calcium
ions: Cross-‐linking of G-‐blocks
41
1.2.15. Alginate, alginic acid: different
salt
forms
42
1.2.16. Size and
shape of alginate molecules
in
solution
42
1.2.17. Alginates: Properties and uses
44
1.2.18. Gelation with Ca
++
: Gel
strength and Young’s modulus
44
1.2.19. Cell
immobilization and
encapsulation
45
1.2.20. Homogeneous gels –
controlled
release of
calcium
ions
(in
situ gelation)
47
1.2.21. Alginate
foams: 3D
cell
cultures
48
1.3. Chitin and
chitosans
49
1.3.1. General
49
1.3.2. Chitin
49
1.3.3. From
chitin
to
chitosan: Chemical de-‐N-‐acetylation
50
1.3.4. Chain geometry
50
1.3.5. F
A
: The
fraction of A
(GlcNAc)
residues
51
1.3.6. Polyelectrolyte properties
51
1.3.7.
Interactions with polyanions
(polyelectrolyte
complexes)
52
1.3.8.
Solubility
of
chitosans
52
1.3.9. Chitosans: Free amine
form and
salts
53