MT3239 Polimer Hayati

(3 SKS)
Dr. Lia Asri & Steven, ST., MT.

lia.asri@material.itb.ac.id steven@material.itb.ac.id

Program Studi Teknik Material

Fakultas Teknik Mesin dan Dirgantara
 Rencana Pembelajaran

Pertemuan TOPIK (LIA) Pertemuan TOPIK (STEV)

1 Pendahuluan: Polimer dan 8 UTS
Biopolimer.
2 Protein 9 Bioplastik
3 Polisakarida: Starch 10 Bioplastik (Project)
4 Polisakarida: Lignoselulosa 11 Bioplastik
5 Polisakarida: kitin, kitosan, alginate 12 Biopolimer untuk aplikasi struktural
6 *Kuliah Tamu (24 Februari 2021) 13 Biopolimer untuk material maju
7 Biobased Polymer 14 Biopolimer untuk aplikasi biomedis
5 Polisakarida: kitin, kitosan, alginat a. Sumber kitin dan kitosan
b. Struktur kitin dan kitosan
c. Sumber alginate
d. Struktur alginate
e. Diskusi
6 Kuliah tamu* Dr. Alia Nur Oktaviani (Riken, Spidersilk)

7 Biobased Polymer a. Biobased polymer

b. Pro dan kontra biobased polymer
c. Sumber monomer
d. Produk biobased monomer
e. Diskusi
Chitin & Chitosan
Outlines
Part I Chitin and Chitosan
1. Origin and source
2. Isolation and chemical structure
3. Physiochemical properties
4. (Potential) Applications and uses

Part II Alginic acid (Alginate)

1. Origin and source
2. Isolation and chemical structure
3. Psychochemical properties
4. (Potential) Applications and uses
1. Origin and Source

Nagahama, et al., Carbohydr. Polym. 2008.

Nature Comment, vol 524, 2015
 Chitin in Fungi Cell Walls
What are fungi? [1]
Fungi have the following characteristics:
• Their main body is in the form of thin strands called mycelium
• Can not produce their own food through photosynthesis
• The major decomposer of organic matter
• Their cell walls are made mostly of chitin

Chitin in fungi
http://www.anselm.edu/homepage/jpitocch/genbios/31-01-FungalMycelia-L.jpg
⚫ Fungal chitin occurs as randomly oriented microfibrils
typically 10-25 nm in diameter and 2~3 μm long
⚫ Chitin is covalently linked to other polysaccharides, 0.1 μm
such as glucans, and forms chitin-glucan complex
⚫ The chitin content in fungi varies from 0.5% in yeast to
50% on filamentous fungi species

[1] Purves W.K. et al Life: The Science of Biology 6th edition. Sinauer Associates Inc. (2001)
SEM micrograph of chitin microfibrils
[2] Herth W. Zugenmaier P. Microbiology Letters, (1986) 263
(Poterioochromonas stipitata) [2]
Muzzarelli R. et al, Chitin in Nature and Technology. Plenum Press NY, 1985
 Chitin in Mollusks Shells
The fascinating mollusk shells!
• Optimized material properties due to its micro-
and nano-scale laminate composite structure
• Chitin is demonstrated in the shells of mollusk
species (105 species so far) The bivalve mollusk Mytilus galloprovincials
http://digilander.libero.it/conchiglieveneziane/bivalvi/immagini/MytilusGalloprovincialis1.jpg
• Chitin forms cross-linked chitin-protein complex
and distributes mainly in the hinge and edges of
the shell
• Bivalve mollusks deposit and orient the chitin in a
very defined manner
• The major role of chitin:
- mechanical strength
- integrate the flexible region Confocal laser scanning microscopy (LSM) image reveals a cross-linked
fibrous chitin-protein matrix. The samples are labeled with chitin-binding
- coordinating switch during shell formation GFP with decalcification and fixation. [1]

[1] Weiss I.M. Schonitzer V. The distribution of chitin in larval shells Journal of structural biology,153 (2006) 264
Muzzarelli R. et al, Proceedings of the 1st International Conference on Chitin and Chitosan. MIT Sea Grant Program (1977)
 Chitin in Arthropods Cuticles
What are arthropods? [1]

The arthropods constitute over 90% of the animal kindom

⚫ Exoskeleton composed mainly of chitin
⚫ Distinct parts of the body
⚫ Jointed legs and appendages
⚫ Bilateral symmetry

Classification of arthropods [2]

⚫ Trilobites are a group of ancient marine animals
⚫ Myriapods comprise millipedes and centipedes
⚫ Chelicerates include spiders, mites, scorpions
⚫ Hexapods comprise insects
⚫ Crustaceans include crabs, lobsters, shrimps and barnacles
http://evolution.berkeley.edu/evolibrary/images/arthropodphylogeny7.gif
 Arthropod cuticle:
multifunctional composite
seta

• Epicuticle
covered by a layer of wax, waterproofing barriers
• Exocuticle & endocuticle
pore canals
Main structural components of the cuticle
Resist mechanical loads
Multilayered chitin-protein composite embedded with
minerals Typical structure of arthropod cuticle [1]
• Exocuticle
epicuticle
Dense, stiffer, chemically inert, and relatively dehydrated
• Endocuticle exocuticle

Sparse, softer, hydrated, and readily soluble

• Membrane layer
• Pore canals endocuticle

Transport mineral ions, wax, nutrition during growth

Soft, ductile, can be highly deformed SEM micrograph of lobster cuticle [2]
[1] Neville A. C. Biology of the Arthropod Cuticle. Springer-Verlag NY (1975) 8
[2] Rabbe D. et al. Journal of Crystal Growth 283 (2005) 1-7
 The Hierarchical Structure of Cuticles
Chitin is a structural biopolymer whose role is analogous to that of collagen in the higher animals and cellulose in plants
American lobster claw Bouligand structure
bundles

proteins

chitin molecules
α-chitin chains nanofibrils fibrils
• In crustaceans, chitin is found to occur as fibrous material embedded in a six stranded protein helix
• Chitin occurs in nature as ordered crystalline microfibrils forming structural components in the exoskeleton of arthropods or in the cell
walls of fungi and yeast
Rabbe D. et al. The crustacean exoskeleton as an example of a structurally and mechanically graded biological nanocomposite material Acta Materialia 53 (2005) 4281
2. Isolation and Chemical Structure
 What is chitin?

• Chitin is a natural polysaccharide

• Chitin is a structural biopolymer
whose role is analogous to that of
collagen in the higher animals and
cellulose in plants
• The 2nd abundant organic source on
earth
• Structure similar to cellulose with
hydroxyl group replaced by acetamido
group (C2)
• N-acetyl-glucosamine units in β-
(1→4) linkage

Structure of Chitin, Chitosan, and Cellulose [1]

[1] Kohr E. Chitin: fulfilling a biomaterials promise. Elsevier Science, 2001

[2] http://invsee.asu.edu/Modules/yeast/structure.htm
 Chitin is a Co-polymer
⚫ Pure chitin does not exist in reality

⚫ Chitin and chitosan tend to form co-

polymer

⚫ # of N-acetyl-glucosamine units > 50%

=> Chitin

⚫ # of N-glucosamine units > 50%

=> Chitosan

⚫ Degree of N-acetylation,
DA = acetamido / (acetamido+amino)

⚫ Degree of N-deacetylation,
DD = amino / (acetamido+amino)
Structure of Chitin-Chitosan co-polymer

⚫ In nature, chitin is commonly 70~90%

Kohr E. Chitin: fulfilling a biomaterials promise. Elsevier Science, 2001
 Crystalline structure of Chitin
• Chitin has 3 polymorphic forms: α-chitin, β-chitin, γ-chitin
• α-chitin:
-the most abundant form
-anti-parallel configuration
[1]
-highly ordered crystalline structure
-strong H-bonding (N-H····O=C) : A hydrogen bond between the acetamide group
on the C2 carbons and the secondary alcoholic hydroxyl groups on the C3 carbon is
linked through a water molecule with the primary alcoholic hydroxyl groups on a C6
carbon.
-rigid, intractable, insoluble
• β-chitin:
- found in diatom spines and squid pens
- parallel configuration
- weak H-bonding
- unstable, soluble in water
• γ-chitin: H-bonding in α-chitin H-bonding in β-chitin
- mixture of α and β-chitin
[2]
- intermediate properties
[1] Muzzarelli R. Chitin. Pergamon Press, 1977
[2] Kohr E. Chitin: fulfilling a biomaterials promise. Elsevier Science, 2001
 What is chitosan?
6 6
4 4
5 5
• Chitosan is the N-deacetylated derivative of chitin 3
2
1
3
2
1

• N-glucosamine units in β-(1→4) linkage

• N-deacetylation of chitin into chitosan is achieved by
treating with 50% NaOH
• # of N-glucosamine units > 50% (DD>50%) => Chitosan
• "Chitosan“ is a general term for a series of N-
deacetylated chitins soluble in dilute aqueous acids.

Chitosan :
1. Reactive amino groups!!
2. Reactive hydroxyl groups available
3. Chelates many transitional metal ions. Structure of Chitin, Chitosan, and Cellulose [1]

[1] Kohr E. Chitin: fulfilling a biomaterials promise. Elsevier Science, 2001

[2] http://invsee.asu.edu/Modules/yeast/structure.htm
 Chitosan: Degree of deacetylation

%DD= 100 x n GlcN/(n GlcN + n GlcNAc)

• n GlcN =average number of D-glucosamine

units,
• n GlcNAc - average number of N-
acetylglucosamine units.
• In some works, degree of acetylation is used,
DA = 100 – DD
✓ The degree of deacetylation (%DD) can be
determined by NMR, FTIR, UV spectroscopy
✓ %DD in commercial chitosan ranges 60-100%
Chitin-Chitosan: Physiochemical properties
• Slightly crystalline in “native” state
• Whitish/ivorish color
• Odorless/tasteless
• Soluble in water at acidic pH (%DD) => Chitosan
Solubility
▪ Solubility affected by solvent mixing, %DD and chemical modification
▪ Viscosity affected by %DD, molecular weight, concentration , ionic strength

Chitin
✓ Owing to the semi-crystalline structure of chitin with extensive hydrogen bonding, the cohesive energy density and
hence the solubility parameter will be very high and so it will be insoluble in all the usual solvents
✓ The solubility of chitin can be enhanced by treatment with strong aqueous HCl where by a solid-state
transformation of α-chitin into β- chitin occurs
✓ Strong polar protic solvents such as trichloroacetic acid (TCA), dichloroacetic acid (DCA), etc. have been found to
dissolve chitin.
 Solubility

Chitosan
✓ Readily soluble in dilute acidic solutions below pH 6.0.

✓ "Chitosan“ is a general term for a series of N-deacetylated chitins soluble in dilute aqueous acids.

✓ If the deacetylation (%DD) of the amino group is 70-100%, the polymer will be water soluble in the acid salt
form. (or >50%)

✓ The average value of %DD effects the water solubility mostly by the hydrophilic properties of the amine group.

✓ At low pH, these amines get protonated and become positively charged and that makes chitosan a water-
soluble cationic polyelectrolyte

✓ Most generally it is represented by the acid base equilibrium between the free amine and its ammonium salt
form.
Reactivity
Chitosan Derivatives
Chitosan Derivatives
Chitin-Chitosan: Physiochemical properties

Kravanja et al., Molecules 2019

Chitin-Chitosan: Physiochemical properties
Chitosan-boehmite desiccant composite as a promising adsorbent towards heavy
metal removal

Rajamani et al., Journal of Environmental Management 2019

Aplikasi?
Packaging

https://www.thepackagingblog.com/active-packaging-antimicrobial-
antioxidant-nanotechnolgy-controlled-release-packaging/
Cazón et al, 2019
Biomedical Applications
Wound Dressing
• Wound dressings are used to protect wound skin form
insult, contamination and infection
• Chitin-based wound dressings
- Increase dermal regeneration
- Accelerate wound healing
- Prevent bacteria infiltration [1]
- Avoid water loss Chitosan wound dressings

• Chitin surgical threads - strong, flexible, decompose

after the heals

Anticoagulation
⚫ Anticoagulation is essential for open-heart
[2]
surgery and kidney dialysis
Cell culture compatibility ranking of wound dressing materials
⚫ Preventing blood from clotting during the surgery
⚫ Sulfated chitin derivatives have good
anticoagulant activity
[1] Kohr E. Chitin: fulfilling a biomaterials promise. Elsevier Science, 2001
[2] Khor E. Lee Y.L. Implantable applications of chitin and chtosan. Biomaterials 24 (2003) 2339
Biomedical Applications: Drug Delivery
Hydrogels
• Hydrogels are highly swollen, hydrophilic polymer networks that
can absorb large amounts of water
• pH-sensitive hydrogels have potential use in site-specific drug
delivery to gastrointestinal tract (GI)
• Chitosan hydrogels are promising in drug delivery system

Tablets
⚫ Chitin and chitosan have been reported to be useful [1]

diluents in pharmaceutical preparations Mechanism for pH-sensitive hydrogels

Microcapsules
⚫ Microcapsule is defined as a spherical empty particle
with size varying from 50 nm to 2 mm
⚫ Chitosan-based microcapsules are suitable for
controlled drug release [2]

Schematic structure of chitosan microcapsules coated

with anionic polysaccharide and lipid

[1] Park S.B. et al. A novel pH-sensitive membrane from chitosan — TEOS IPN. Biomaterials 22 (2001) 323
[2] Majeti N.V. Kumar R. A review of chitin and chitosan applications. Reactive & Functional Polymers 46 (2000) 1-27
Alginate
 Alginate
1. Structure of alginate
2. Source and extraction of alginate
3. Properties of alginate
4. Gelation of alginate
5. Applications
 1. Structure
✓ Alginates belong to the class of
linear heteropolysaccharides that
contain two sugar constituents.

✓ consisting of 1,4-linked 𝛽-D-

mannuronic acid (M) and 1,4 𝛼-L-
guluronic acid (G) residues.

✓ Alginate are arranged in

homogenous (poly-G, poly-M) or
heterogenous (MG) block-like
patterns.

✓ commercial alginate may differ in

composition and the sequence of G-
and M-blocks.

Figure 1:The structure of ALG: monomers (a), chain conformation (b), and blocks distribution (c).
 2. Source and extraction
Alginate distributed widely in the cell walls of brown algae and several bacteria strains
which is hydrophilic and forms a viscous gum when hydrated (hydrocolloids).
In seaweed, the alginate is present as a mixed salt of sodium and/or potassium, calcium, and magnesium.

Source:
• Brown algae
• Bacteria (Azotobacter, Pseudomonas)
 2. Source and extraction

✓ Alginate extraction process from seaweeds is uncomplicated but multistage procedure.

✓ usually starts with treating the dried raw material using diluted mineral acid.
✓ After further purification, the obtained alginic acid is converted into water-soluble sodium salt in the
presence of calcium carbonate, which is next transformed back into acid or its expected salt
✓ Among various Alginate, sodium alginate is one of the most widely investigated ones
✓ ALG extracted from different sources differ in M and G residues as well as the length of each block.
2. Source and extraction
 2. Source and extraction

Alginic acid

Sodium Alginate
 3. General Properties
1. possess a high degree of physicochemical heterogeneity which influences their
quality and determines potential applicability.
2. are commercially available in various grades of molecular weight, composition,
and distribution pattern of M-block and G-block
3. the factors responsible for their physicochemical properties such as viscosity,
sol/gel transition, and water-uptake ability
4. The molecular weight, expressed as an average of all the molecules present in
the sample, of commercial ALG varies between 33 000 and 400 000 g/mol.
 3. General Properties
• Generally, by raising the ALG G-block content
or molecular weight, more stronger and brittle
ALG gels may be achieved

• Alginic acid is insoluble in water and organic

solvents

• ALG monovalent salts and ALG esters are

water-soluble forming stable, viscous solutions

• ALG solubility is limited by the solvent pH (a

decrease in pH below pKa 3.38–3.65 may lead
to polymer precipitation), ionic strength, and
the content of “gelling ions”
 3. General Properties
• ALG with more heterogeneous structure (MG-blocks) are soluble at
low pH compared to poly-M or poly-G ALG molecules, which
precipitate under these conditions
• ALG capability of creating viscous solutions may vary according to
their concentration, solvent pH
• ALG can be easily formed into diverse semisolid or solid structures
under mild conditions because of their unique ability of sol/gel
transition.
 4. Gelation

• alginate gel will develop instantaneously in the presence of divalent cations like Ca2+, Ba2+ or Sr2+
• acid gels may also develop at low pH.
• Gelling occurs when the divalent cations take part in the interchain ionic binding between guluronic
acids blocks (G-blocks) in the polymer chain giving rise to a three dimensional network.
• Such binding zones between the G-blocks are often referred to as “egg-boxes”
 4. Gelation
• Control of the rate of salt addition is required to
produce a calcium alginate gel rather than a
fibrous precipitate
• The buckled shape of the this region allows the
cooperative binding of chains between G blocks.
• The alignment of these regions creates diamond
shaped holes containing a hydrophilic cavity that
binds calcium ions by multicoordinate linkages
with oxygen atoms.
• The result is that the calcium ions bind the chains
tightly together, while they sit like eggs in an egg
carton.
• The chain-chain interactions occur until a
completed three dimensional network is formed.
 4. Gelation
• alginates with a high content of G-blocks induce stronger gels.
stiff, transparent, brittle gels

• Gels made of M-rich alginate are softer and more fragile and may also have a lower porosity.
turbid gels low elastic modulus
This is due to the lower binding strength between the polymer chains and to the higher
flexibilities of the molecules.

Gelation depends on cation

Ba2+ > Sr2+ > Ca2+ > Mg2+
 4. Gelation
• Gel formation is driven by the
interactions between G-blocks
which associate to form tightly held
junctions in the presence of divalent
cations .
• In addition to G-blocks, MG blocks
also participate, forming weak
junctions
4. Gelation
 4. Gelation
Calcium crosslinking of alginates can be performed by
two methods:

1. “diffusion” method
• Crosslinking ions diffuse into the alginate solution
from an outside reservoir
• yields gels having a Ca2+ ion concentration gradient
across the thickness
• Dropping a Na-alginate solution into a CaCl2
 4. Gelation
Calcium crosslinking of alginates can be performed by two
methods:

2. “internal” setting
• the ion source is located within the alginate solution and
a controlled trigger (typically pH or solubility of the ion
source) sets off the release of crosslinking ions into
solution.
• gives gels with uniform ion concentrations throughout
• use insoluble calcium salts such as CaCO3 as a calcium
source.
• A change in the pH caused by a slowly hydrolyzing
lactone such as D-glucono-d-lactone (GDL) triggers the
release of Ca2+ ions internally and leads to gel formation.
 5. Applications
1. Alginate As an Ion Exchanger
2. Biomaterials
3. Others applications
 5. Applications
1. Alginate As an Ion Exchanger

• The primary mechanism for metal adsorption is ion exchange, although covalent bonding also
plays a role.
• Carboxylic groups are involved in this binding
• The affinity of the alginates for metal ions vary
• Alkali metal salts of alginate are soluble in water.
• When dibasic or polybasic cations are added to these solutions, a gelatinous or flocculant
precipitate forms, with the exception of magnesium ions which form a soluble salt.
 5. Applications
1. Alginate As an Ion Exchanger
Seaweeds alginates

• alginates prepared from Laminaria digitata

(high M content) have different affinities for
divalent cations than alginates prepared
from Laminaria hyperborea stipes (high G
content)

• G block sequences were the controlling The ability of any given alginate gel to take part in base
factor in determining metal binding exchange reactions can be expressed by a selectivity constant
selectivity (K)
 5. Applications
1. Alginate As an Ion Exchanger
• Sodium alginate can effectively eliminate heavy metal ions (e.g. Pb(II),
Cu(II), and Cd(II)) in aqueous solutions.
• However, sodium alginate gel beads with a loose network are limited
by the poor stability, weak water resistance, and serious thermal
degradation.
• Formation of beads or composites or crosslink alginate
• i.e Heavy metal sorption (Cu2+,Cd2+and Pb2+) by calcium alginate
beads
 5. Applications
1. Alginate As an Ion Exchanger

Halloysite/alginate nanocomposite beads

Chiew et al., Applied Clay Science 2016

 5. Applications
Alginate Beads
 Dental Materials5. Applications
1. Biomaterials

https://www.medicalexpo.com/prod/zhermack/product-74628-909943.html https://www.cavex.nl/en
 5. Applications
1. Biomaterials
3D plotting of alginate-based hydrogel scaffolds: (A) 3 wt% alginate without methylcellulose, four
layers; (B) 3 wt% alginate + 9 wt% methylcellulose (alg/MC), four layers; (C) alg/MC, 20 layers; (D)
alg/MC, 50 layers; (insert) top view.
Alginate Hydrogel Scaffold

Schütz, Journal of Tissue Engineering and Regenerative Medicine 2015

 5. Applications
1. Biomaterials

Kosik-Kozio et al, Biofabrication 2017

Alginate Scaffold
Alginate Hydrogel Scaffold
Alginate Scaffold
the internal gelation using CaCO3
alginate/bacterial cellulose
nanocrystals/collagen composite
hydrogel for tissue engineering

Yan et al, Polymer Bulletin 2018

Alginate Wound Dressing
Drug delivery
Bacterial Cellulose Nanofiber/ Sodium Alginate Hybrid Hydrogels
Drug delivery
Drug delivery