International Journal of Biological Macromolecules 79 (2015) 377387

Contents lists available at ScienceDirect

International Journal of Biological Macromolecules

journal homepage: www.elsevier.com/locate/ijbiomac

Review

Alginate based polyurethanes: A review of recent advances and

perspective
Khalid Mahmood Zia , Fatima Zia, Mohammad Zuber, Saima Rehman,
Mirza Nadeem Ahmad
Institute of Chemistry, Government College University, Faisalabad 38030, Pakistan

a r t i c l e

i n f o

Article history:
Received 20 February 2015
Received in revised form 25 April 2015
Accepted 28 April 2015
Available online 9 May 2015
Keywords:
Alginates
Polyurethane
Hydrogels
Recent advances
Future perspectives

a b s t r a c t
The trend of using biopolymers in combination with synthetic polymers was increasing rapidly from
last two or three decades. Polysaccharide based biopolymers especially starch, cellulose, chitin, chitosan, alginate, etc. found extensive applications for different industrial uses, as they are biocompatible,
biodegradable, bio-renewable resources and chiey environment friendly. Segment block copolymer
character of polyurethanes that endows them a broad range of versatility in terms of tailoring their properties was employed in conjunction with various natural polymers resulted in modied biomaterials.
Alginate is biodegradable, biocompatible, bioactive, less toxic and low cost anionic polysaccharide, as a
part of structural component of bacteria and brown algae (sea weed) is quite abundant in nature. It is used
in combination with polyurethanes to form elastomers, nano-composites, hydrogels, etc. that especially
revolutionized the food and biomedical industries. The review summarized the development in alginate
based polyurethanes with their potential applications.
2015 Elsevier B.V. All rights reserved.

Contents
1.

2.
3.

4.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 377
1.1.
Polysaccharides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 378
1.2.
Reasons for choosing alginates and polyurethanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 380
Alginate: an overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 380
2.1.
Applications, development and limitations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 381
Alginate based polyurethanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 383
3.1.
PUAlg hydrogel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 383
3.2.
PUAlg blend . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 384
3.3.
PUAlg elastomer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 384
3.4.
PUAlg nanocomposite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 385
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 385
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 385

1. Introduction
All through the history, humans have much relied on biological
materials such as wool (protein bers), leather, cotton (vegetable
ber), wood, silk, etc. to meet their needs. Polymeric materials
play a crucial role both in material world and modern industrial

Corresponding authors. Tel.: +92 300 6603967; fax: +92 041 9200671.
E-mail addresses: ziakmpkpolym@yahoo.com (K.M. Zia),
pioneeravian@hotmail.com (M.N. Ahmad).
http://dx.doi.org/10.1016/j.ijbiomac.2015.04.076
0141-8130/ 2015 Elsevier B.V. All rights reserved.

economics [1,2]. Polymer materials are solid, nonmetallic compounds of high molecular weight [3]. Natural polymers (proteins,
nucleic acids, polyesters, polysaccharides), semisynthetic (hydrohalogenated rubber, cellulose nitrate) and synthetic polymers (PE,
PP, PU and PVA, etc.) are the three main categories when polymers
are classied on the basis of origin [4]. Natural polymers are further divided into two main categories, i.e. homologous biopolymers
such as proteins and heterologous biopolymers such as glycoproteins, i.e., it consists of carbohydrate and protein monomers [5].
Proteins and nucleic acids are available in large quantities
from renewable resources. The trademark associated with natural

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K.M. Zia et al. / International Journal of Biological Macromolecules 79 (2015) 377387

polymers is their biodegradability, bioactivity, easy availability and

nontoxic nature. With the progress in the research area of chemistry, biology, materials and modern sciences, a vast array of novel
synthetic polymeric materials have been introduced from last
ten decades. Synthetic polymers such as nylon, polyethylene and
polyurethanes have transformed daily life, are derived from nonrenewable fossil fuel resources [6]. Petroleum derived synthetic
polymers have been widely used in composites are not readily
biodegradable and resistant to microbial degradation thus accumulated in the environment and become a major source of waste
disposal [7,8]. Another problem is fossil fuel and petroleum prices
volatility that forced to replace commercial synthetic polymers
with natural biodegradable polymers such as polyesters, proteins
and polysaccharides [919]. Sustainability of resources cannot be
achieved if we will continue to use non-renewable resources.
Polyurethanes, from a synthetic class of polymers are receiving much attention as one of the most biocompatible material.
Due to their easy availability and propensity to modify their
properties, polyurethanes are used for various applications, e.g.
coatings, sealants, adhesives, elastomers, foams, textile nish [20]
and for biomedical applications due to having good biocompatibility [21,22]. Use of natural polymers for PUs modication gained
interest as they make them more environmentally green material.
Much research has been conducted on polysaccharides, proteins
and lipids based PUs with their respective applications in different
industrial elds especially for biomedical applications. The structure of PU results to form a phase segregated structure, which make
them available for their use in various ways such as adhesives,
coatings, biomedical materials and elastomers [23,24]. PU elastomers (PUEs) are having the capacity to use in various applications
because they are moldable, injectable and recyclable [25].
Morphological pattern of PUEs have been presented in the
established literature. The effect of the diisocyanate structure and
chain extender (CE) length using ,-alkane diols on the crystallinity, surface morphology and thermo-mechanical properties of
PUEs have also been investigated [2628]. Published materials are
also available on the synthesis, characterization and application of
chitin based PUs [2931]. In vitro biocompatibility and cytotoxicity
of chitin/1,4-butanediol blends based PUEs have been comprehensively reported [32,33]. Some documents are available on the structural characterization of chitin-based PUEs and their shape memory
characteristics [34,35]. XRD studies and surface characteristics of
UV-irradiated and non-irradiated chitin-based PUEs have also been
presented elsewhere [3641]. The microstructure of a PU block is
generally known to be composed of different phases, i.e., it is based
on domains which have been built of hard urethane-type segments
and on soft polyol segment [34]. A wide class of materials can be
obtained by controlling variables such as the functionality, chemical composition and the molecular weight of the different reactants.
Natural bio-macromolecules serve as basic template for cell
growth, are usually biocompatible, whereas, synthetic polymers
can impart other toxic compounds or impurities that do not allow
cell growth. Compared with natural polymers, however, synthetic
polymers have much better thermal and mechanical properties
[42]. The increasing interest in new polymeric material based on
blends of 2 or more natural bio-macromolecules and blends of natural bio-macromolecules and synthetic polymers can establish a
new form of materials called bio-articial or biosynthetic polymeric
materials with improved mechanical properties and biocompatibility compared with those of individual polymeric component
[4347].

organisms such as animals, bacteria, green plants and fungi hence

also referred as one of the main class of natural biodegradable
polymers [48]. Bio-macromolecules have potential array of applications in almost all segments of the economy and can be used as
adhesives, absorbents, lubricants, soil conditions, cosmetics, drug
delivery vehicles, textile, good strength structural materials, etc.
[6]. Polysaccharides are the most abundant organic materials found
in nature and are present in all living organisms where they carry
out one or more of their diverse functions [49]. In comparison
with other biopolymers, these molecules are characterized by their
chemical diversity, presence of large number of functional groups,
strong hydrophilicity and their rigidity [50]. Polysaccharides are
ubiquitous can be classied as either homo-polysaccharides or
hetero-polysaccharide and found in algae (e.g. alginate), plants
(e.g. starch, cellulose, glucomannan, pectin, guar gum), microbes
(e.g. dextran, xanthan gum), and animals (chitosan, chondroitin)
[5153].
Polysaccharides have some special characteristics which are not
available in other natural polymers which includes; water solubility, ow behavior, gelling potential and/or surface and interfacial
properties depending upon the difference in monosaccharide composition and linkage type [54]. Polysaccharides have been used
for decades in various industrial applications, e.g. pharmaceuticals, biomaterials, foodstuff and nutrition, and biofuels, growing
understanding and deeper investigations of the importance of

Fig. 1. (a) Cations form of calcium alginate, (b) gel formation of calcium alginate in
solution [86].

1.1. Polysaccharides
Bio-macromolecules are diverse and important class of polymeric materials formed in nature during the growth cycles of

Fig. 2. Alginate based impression material for dental applications [87].

K.M. Zia et al. / International Journal of Biological Macromolecules 79 (2015) 377387

379

Table 1
Different techniques for the synthesis and characterization of various alginate-based materials and their prospective applications in various elds.
Sr. No

Name

Techniques used for

characterization

Potential applications

Reference

1.

Sodium alginate/poly(vinyl alcohol) alloy

FT-IR, SEM, DSC, TGA

[97]

2.
3.
4.

PVAalginate
PVAalginate
PVAalginate

5.

PVAalginate

As a matrix for yeast immobilization

[101]

6.
7.

PVAalginate
PVAAlginate

FT-IR, SEM
FT-IR, EDAX
Potentiometric Kinetic
parameters
SEM, diffusion,
coefcients, stability
tests (pH)
EDX, FT-IR
FESM, EDX

Membrane for separation of dimethyl

formamide/water mixtures
Wound dressing membrane
For phosphate removal
Hydrolysis of pineapple waste

[102]
[103]

8.

PVAalginate

SEM

9.
10.

MgAl LDHalginate/polyvinyl alcohol

[A336][Mtba]/PVAalginate

XRD, FESEM
FTIR, SEM, TGA

11.
12.

Naalg/PVA composite
Maghemite PVAalginate Beads

13.
14.

Matrix for enzyme immobilization

For PV dehydration of isopropanol

[109]
[110]

18.
19.
20.

CelluloseAlginate
Carboxymethyl cellulosesodium alginate
NCCalginate

Employed for PV dehydration, esterication

reactions.
For drug (diclofenac sodium) delivery systems
A good candidate for alkaline direct methanol fuel
cells applications
Improved ethanol production
For separation of benzenecyclohexane mixtures
Biodegradable lms

[111]

16.
17.

PVAalginatesulfate
Glutaraldehyde/sodium
alginatepoly(vinyl alcohol)
Aluminum-rich zeolite beta incorporated
sodium alginate
Sodium alginate/poly(vinyl alcohol)
poly(vinyl alcohol)/sodium alginate

FT-IR, SEM
FESEM, XRD, FT-IR,
XPS, EDX
FESEMEDX, HPLC
SEM

Matrix for immobilization of invertase

Encapsulation of Fe2 O3 magnetic beads for
photocatalytic reduction of Cr(VI)
Effective removal of N,N-dimethyl formamide
from industrial efuents
For water remediation
For removal of divalent mercury from aqueous
solutions
Nano-ltration and/or desalination
Cesium removal from radioactive waste water

21.
22.

Chitosanalginate (CS/ALG)
Alginate/chitosan/PLA-H

Potential use for oral insulin delivery

Scaffolds for VEGF controlled release

[117]
[118]

23.

For adsorption of two important synthetic dyes, i.e.

Congo red and methyl Violet from water
For PV dehydration of ethanol

[119]

25.

Poly(acrylic acid-Co-hydroxyethyl
methacrylate) sodium alginate
Sodium alginatepoly(N-isopropyl
acrylamide)
PLGA/chitosan cellulose alginate

An emulsion stabilizer in synthesis of

biodegradable polymers.

[121]

26.
27.
28.

PLGA-alg-RGD MP.
Chitosanpoly (caprolactone)/alginate
Chitosanalginate

Delivery system for vaccination

For controlled delivering of VEGF
Drug delivery

[122]
[123]
[124]

29.
30.

Chitosanalginate
Alginatechitosan

Nanogels for vaccine delivery

A novel ber for wound care application

[125]
[126]

31.

Chitosanalginate

[127]

32.
33.

Carboxymethyl chitosanalginate
Chitosan/alginate nano-layered PET lm

34.
35.

Alginate/HPMC
Alginate-G-poly(sodium acrylate) and poly
(vinyl pyrrolidone)
Alginate/chitosan/titanium

ATRFTIR, XPS, SEM,

XRD, DTA
XPS, SEM

Used in the preparation of Pickering emulsion as

potent carriers in biomedical area
Site selective protein delivery in intestine
For preparation of multilayer lms
Coating biomedical appliances or multilayer edible
coatings
Improved in vitro release of BSA
Potential candidate for drug delivery systems and
water manageable materials
Potential applications in tissue engineering
scaffolds eld
Inhibit biolm formation

FT-IR, FESEM, XRD

Antimicrobial activity for brous mats

[134]

FT-IR, XRD, DSC, SEM

As a controlled release carrier for the food grade

peptide, nisin.
High potential to be used as high
Strength packaging materials.
As coagulant for wastewater treatment
For encapsulation of antioxidants
Bacterial encapsulation
For agrochemical delivery system
Potential and economical wound dressing material.
Photo-Fenton catalysts for water
Disinfection

[135]

15.

24.

36.
37.

39.

Minocycline loaded
chitosan/alginate/titanium
Carboxymethyl chitosan/organic
rectorite/alginate
Alginate/alginate-resistant starch

40.

Cellulosealginate

41.
42.
43.
44.
45.
46.

Aluminum sulfatealginate
Starchcalcium alginate
Alginatestarch
Starchalginate
Alginatesago starch-Ag-NP
Iron/montmorillonite/alginate

38.

FT-IR, SEM, UTM

FT-IR, XRD, SEM
XRD, TGA, DSC
IC, SEM, EWC, GC
FT-IR, XRD, DTA, SEM
FT-IR, SEM, XRD, DSC,
TGA
DLS, SEM, FT-IR
SEM, GPC, Mercury
porosimetry
FTIR, SEM, XRD,
DTATGA
FT-IR, TGA
Rheometery,
sonication. FESEM,
FT-IR, DSC, TGA
XPS, SEM
SEM
Sonication, SEM. FT-IR,
DSC
FT-IR, Optical
microscopy
SEM, optical
microscopy
SEM
SEM, DSC, TGA, water
contact angles

SEM, FT-IR

FESEM, XRD

DSC, FT-IR, SEM

FT-IR
TGA, SEM, TEM
ICP-MS, FT-IR

[98]
[99]
[100]

[104]
[105]
[106]
[107]
[108]

[112]
[113]
[114]
[115]
[116]

[120]

[128]
[129]

[130]
[131]
[132]
[133]

[34]
[136]
[137]
[138]
[139]
[140]
[141]

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K.M. Zia et al. / International Journal of Biological Macromolecules 79 (2015) 377387

Table 1 (Continued)
Sr. No

Name

Techniques used for

characterization

Potential applications

Reference

47.

Alginate-graft-poly(ethylene glycol)

SEM, NMR

[142]

48.

Calcium phosphatesodium alginate

49.

Sodium alginate/heteropolyacid
H14 [Nap5 w30 o110 ] (HPA)

Membranes for pervaporation

Dehydration of ethanol

[144]

50.
51.
52.
53.

Alginate/collagen-I
Alginatethiol-terminated peptides
Sodium alginatePNIPAM
Alginate/polyethyleneimine
and biaxially oriented poly(lactic acid)

FT-IR, XRD, SEM,

ICP-OES
FTIR, SEM, TGA, DSC,
UTM and contact angle
measurements
SEM
UV-VS, 1 H NMR
IR, NMR, SEM
UV-VIS, FESEM, AFM

Encapsulation and intracellular delivery of a

bioactive growth factor
Drug delivery carriers

[145]
[146]
[147]
[148]

54.

56.

Prosopis Juliora
Carbon/Ca/alginate
Hyaluronic acid/sodium
alginate
Sodium alginatepolyacrylamide

57.

AgNPsalginate

SEM, FT-IR, Water

contact angle
FTIR, NMR SEM,
DTATGA, XRD, PZC
FT-IR, SEM

Enhance wound healing properties

Potential application for tissue engineering
For biomedical applications
Promising alternative to non-biodegradable
synthetic food
Packaging materials
For the adsorptive removal of aniline
Blue dye (AB dye)
For pervaporation dehydration of ethanolwater
mixtures
For drug delivery systems

[152]

58.

Sodium alginate/superabsorbent polymer

FT-IR, TGA, SEM

59.

Ag/alginate

UVvis, FESEM

60.

FT-IR, SEM, NMR

63.
64.
65.

B-cyclodextrin/acrylic acid/sodium
alginate
Polycaprolactone (PCL)/alginate
Alginic acid/metal coordinated
carboxylated alginic acid
Alginatezirconium
Alginatelignin
Halloysite/alginate

Treatment process for antibacterial nishing and

textiles.
Effective recycling of textile dyes from textile
efuents
For tissue engineering scaffolds, soft tissue
implants, antimicrobial wound dressings
As an agricultural water retention agent in saline
soil
For biomedical applications
For deouridation process

[158]
[159]
[160]

66.

Methacrylated alginate/PEG

67.

AlginatePEGAc

SEM

68.

Calcium phosphate/alginate

69.

Alginate/HNT

73.

Znoalginate
Alginatesilicate
Alginatechitosanpoly(lactic-co-glycolic
acid)
Alginate-glass ceramics

Great potential for applications in tissue

engineering.
Controlled environment for antimicrobial activity
For decolorization of the azo dye, reactive Red 22
For protein delivery system

[164]

70.
71.
72.

optical microscopy,
ESEM, TEM, SEM, FT-IR
AFM, TEM, FTIR, XRD,
TGA
XRD, XPS
SEM
SEM

For deouridation of water

Scaffolds for tissue engineering
Applications including bioprocessing and tissue
engineering.
Bioadhesive for clinical use in biomedical
applications
Novel muco adhesive material for controlled drug
release
For protein imprinting

Useful for periodontal tissue regeneration

[168]

74.
75.

Alginate/polyacrylamide
Alginategelatin

Promising biomaterial for cartilage tissue

Membranes for enhancement of diffusion and
sorption

[169]
[170]

55.

61.
62.

FT-IR, SEM

FT-IR, SEM
FTIR, EDAX, SEM
FTIR, XRD, SEM, EDAX
SEM, Micro-CT
EDX, FT-IR, FESEM, TGA

SEM, EDAX, AFM, FTIR,

XRD
SEM
SEM, FT-IR, XRD, DSC,
PALS

polysaccharides in life science are driving the development of

polysaccharides for novel (bio-molecular) applications [5561].
1.2. Reasons for choosing alginates and polyurethanes
Alginates have a potential array of commercial applications, as
they are widely used in the food and textile industries as thickeners, stabilizers, gel-formers, lm-formers, etc. [62]. Due to the
abundance of algae in water bodies, there is a large amount of alginate material present in nature with its excellent biocompatibility,
biodegradability, non-toxicity, chelating ability and relatively low
cost [63,64]. Hence, there is signicant additional potential to
design sustainable biomaterials based on alginates. Alginate can be
easily modied in any form such as microspheres, microcapsules,
sponges, hydrogels, foams, elastomers, bers, etc. This property can
increase the applications of alginate in various elds such as tissue engineering and drug delivery [65]. Signicant research has
been conducted on application of alginate as a bone tissue engineering material [6669], therapeutic cell entrapment [7073],

[143]

[149]
[150]
[151]

[153]
[154]
[155]
[156]
[157]

[161]
[162]
[163]

[165]
[166]
[167]

nanoparticles of alginates for drug delivery systems and for enzyme

immobilization [74]. Notable amount of research article has been
published covering different aspects of alginates. Further PU has
shown excellent characteristic regarding biocompatibility with the
body cells. Following study has clearly demonstrates the potential of PU regarding its use without any cytotoxicity. In one of the
reported method, preparation of regenerated silk broin solution
(SF) Cocoons of B. mori silkworm was degummed 3 times in 0.5%
(w/v) Na2 CO3 solution at 98100 C for 30 min, rinsing with distilled water to separate proteins and waxes [75].
2. Alginate: an overview
In the very rst, alginate was reported by the British chemist E. C.
C. Stanford in 1881. Alginate an anionic and hydrophilic polysaccharide is one of the most abundant biosynthesized natural materials
that is derived primarily from two sources, marine plants, i.e. brown
sea weed (40% of dry matter) and bacteria. Commercially, alginates species are derived primarily from brown algae, included

K.M. Zia et al. / International Journal of Biological Macromolecules 79 (2015) 377387

381

Fig. 3. Chemical procedure for synthesis of PU(I) and PU-g-CaA (II) [113,178].

Laminaria hyperborea, Ascophyllum nodosum and Macrocystis

pyrifera. Alginates isolated from bacteria such as Azotobacter and
Pseudomonas species are usually not economically feasible for commercial applications and limited to small-scale research studies
[76,77].
In structural presentation, alginate contains linear blocks of
(1 4)-linked -d-mannuronic acid (M) and -l-guluronic acid
(G) monomers. Typically, the blocks are composed of three different
forms of polymer segments: consecutive G residues, consecutive M
residues and alternating MG residues. The copolymer composition,
sequence and molecular weights vary with the source and species
that produce the copolymer, also reected in their properties. Viscosity depends upon molecular size, the afnity for cations and
gel forming properties are mostly related to the block structure of
guluronic acid residue. The contents of G-blocks mainly contributed
to gel strength and stability [67,71,7883].
Alginates have four reactive sites for contribution in a chemical
reaction including carboxylic acid and hydroxyl functional groups,
and two relatively not sustainable bonds, i.e. 1 4 glycosidic
and internal glycolic bonds. The characteristics, e.g., hydrophilicity, solubility, and chemical and biological properties of alginate
derivatives may be modied by creating new functional groups into
the alginate backbone [84]. Carboxyl groups and hydroxyl groups
laterally on the backbone of the alginate enable remarkably several
modication approaches to enhance or tailor the properties such as
physicochemical, biological, mechanical, and other desired properties [85]. Sodium alginate is water soluble and when it trickled into
a solution containing Ca2+ ions, each Ca2+ ion knocks away the two

Na+ ions. The alginate molecule contains loads of OH group that can
be coordinated to cations (Fig. 1a).
When alginate is coordinated to Na+ , its a very exible chain and
when Na+ is replaced by Ca2+ however, each Ca2+ ion (black dots in
Fig. 1b) coordinates to two alginate chains, linking them together.
The exible chains become less exible and form a huge network
a gel within seconds after the alginate mixture is dripped into the
water bath with the Ca2+ ions [86]. Due to its hydrophilic nature,
alginate takes a good impression (Fig. 2) in a moist environment
and can use as dental material [87].
2.1. Applications, development and limitations
Alginate forms a solid gel under mild handling conditions which
allows it to be used for entrapping cells into beads and shapes [88].
Interestingly, cell encapsulation of some types of alginate beads
may actually enhance cell survival and growth. In addition, alginate has been explored for use in liver, nerve, heart, and cartilage
tissue engineering [8993]. Pharmaceutical, food (as additive) and
technical applications (such as in print paste for the textile industry) are quantitative hand the market for alginates. Alginate beads
immobilized on PU matrix increase the degradation of O-phthalates
by enhancing the activity of Bacillus sp. cells. Widely used phthalate is a plasticizer used in resins causing serious terrorism threats
formulation intended to environment [94].
In some recent studies, the MW of alginates (MW
30,000690,000) and the mole fraction (FM 0.690.86) of mannuronate residues present in alginate molecular chains were also

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Fig. 4. Chemical procedure for the synthesis of (a) cationic aqueous PU dispersion [181], (b) anionic aqueous PU dispersion [181], (c) ionic PU dispersion extended with
TBAAlg [182] and (d) non-ionic PU dispersion [182].

K.M. Zia et al. / International Journal of Biological Macromolecules 79 (2015) 377387

383

Fig. 5. SEM images of (a) CaA and (b) PU-g-CaA; (c) XRD pattern of CaA and PU-g-CaA; (d) the inuence of reaction temperature on the swelling degree of PU-g-CaA and CaA
microspheres [178].

identied as key factors relating to the immunological activity of

alginates [95]. Unfortunately, in the literature, some drawbacks
associated with alginates are poor cell adhesion and mechanical
weaknesses have been reported. As a remedy to overcome these
draw backs, the strength and cell behavior of alginate have been
enhanced by mixing it with other materials, including the natural
polymers agarose and chitosan [93,96]. Alginates based blends,
copolymers and composites have been presented in the established
literature (Table 1).
3. Alginate based polyurethanes
Functionalization of polyurethanes with natural polymers especially polysaccharide found to be a suitable process for biomaterials
development. Alginate-based polyurethanes are perhaps more
interesting options because alginates retain advantages like low
cost, abundance and range of applications [171176].
3.1. PUAlg hydrogel
PUalginate gel compositions are potential material for biomedical application and food industry with various constituent ratios
based on an anionic PU (APU) water dispersion (WD) and sodium
alginate (AG) prepared by cross-linking with Ca+ ions. By optimizing the degree of cross-linking, by varying the composition
ratio and Ca2+ quantity, systems with controlled thermo and pHsensitivity, swelling ratio, and strength indexes can be obtained. It
is worth to mention that the alginate contents increased the tensile strength of the material lms. Mixtures of APU and AG formed
structural non-Newtonian stable systems with higher viscosity in
comparison with initial components in the absence of divalent
cation [174].

The mechanical strength of alginate hydrogel is subject to

biodegradation and swelling [177,178]. Numerous attempts have
been made to control the swelling degree of alginate based materials by modifying its structure with various methods such as
blending, copolymerization, etc. [178]. Because of the crystalline
character of PU, it contains high tensile strength and anti-swelling
property [179]. The PU-grafted Ca+ alginate gel, therefore, can be
synthesized by 2-hydroxyethyl methacrylate (HEMA) and diethylene glycol (DEG) capped isophrone diisocyanate (IPDI) forming
crystallizing area in the matrix of polysaccharide (Fig. 3). Grafted
PU, side chains may affect the arrangement of alginates which may
formed highly ordered crystalline region, and provide alginate with
physical cross-linking points. As a result the thermodynamic properties such as stability and anti-swelling stability were improved
in PU-g-CaA samples due to intensied intermolecular force [178].
One recent application of PUalginate hydrogels is in molecules
imprinting such as sugars, amino acids and metal ions. For bovine
serum albumin (BSA) imprinting, the PU grafted calcium alginate
(PU-g-CaA) hydrogel microspheres were synthesized and characterized. It has been previously conrmed that the grafted PU side
chains have constructed physical cross-linking points and improve
the mechanical and chemical stability of hydrogel [178] which is
therefore expected to be beneted for protein recognition which
is conrmed by the enhanced imprinting efciency and selective
factors obtained at high grafting ratio. Compared with CaA, PU-gCaA MIPs exhibit higher rebinding selectivity and are more capable
of recognizing and separating target protein molecules, having
promising applications as advanced material for chemical sensing
and bio-separation [180]. Preparation of alginate-based PUs had
been a signicant challenge because of the nal polymers tendency
to the phase separation [174]. Alginate and PU are two incompatible polymers with different glass transition temperatures.

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K.M. Zia et al. / International Journal of Biological Macromolecules 79 (2015) 377387

Nevertheless, the development of such methods to improve the

compatibility between the two polymers is a challenge.
3.2. PUAlg blend
Keeping in view the aim of improving compatibility of two
polymers, aqueous PU dispersion sodium alginate compositions
(PUD/SA) were synthesized. PU dispersions were prepared with
polytetramethylene glycol (PTMG) and isophorone diisocyanate
(IPDI), extended with dimethylol propionic acid (DMPA) (Fig. 4a
and b). Both storage modulus and tan versus temperature showed
identical Tg and other thermal transition for control PUD and
its blends with sodium alginate. The SEM and EDX showed the
presence of alginate and its distribution as agglomerations in
PU matrix. The surface properties including contact angle values
decreased with increasing sodium alginate content that ascribed
increase in the hydrophilicity of the blends. Such transformation
was attributed to the presence of hydrophilic carboxylate, hydroxyl
and ether functional groups attached to the alginate molecules
[171]. Another approach for the preparation of compatible alginate based polyurethane with desired properties was the synthesis
of novel soluble alginate-based PUs in common aprotic organic
solvent by the reaction of NCO-terminated PU prepolymer and tributyl ammonium alginate (TBA-Alg) for the rst time (Fig. 4c).
The presence of TBA-Alg into the backbone of PU was revealed
by specic peaks of uronic acid residues in 1 H NMR. The ionic nature
of PU backbone not only effects on thermal properties of samples,
but also changes the morphology of chemically-bonded alginate.
Both polyether and polyester based non-ionic PUs extended by
TBA-Alg illustrated the distinct alginate, i.e. aggregate-like structures of alginate into the matrix of PU (Fig. 4d) whereas those
ionomers extended by alginate were appeared as continuous systems at nanoscale [182].
The PU segment had a very important impact on the morphology of gel surface as shown in Fig. 5a and b. The Ca+ alginate
(CaA) hydrogel microspheres possessed coarse surface and big cavity while PU-g-CaA showed a dense and smooth surface. As shown
in Fig. 5c, the CaA exhibits characteristic 2 values at 13.1 , 25.06
and 39.42 , which is due to the stronger hydrogen as well as polar
intramolecular and intermolecular interactions. In this study, sharp
peak observed at 18.46 correspond to PU-g-CaA in-spite of 39.42 ,
which is attributed to the addition of carbamate groups and ether
bond. Apart from above, PU interferes with the arrangement of CaA
forming highly order crystal region, which indicate that PU was
grafted on to the CaA. The relationship between reaction temperature and swelling degree of PU-g-CaA is presented in Fig. 5d. It can
be observed that the increase in of reaction temperature results
to rst swelling degree decreased and then increased. Such phenomenon is mainly attributed to PU side chains that intense the
intermolecular interaction, forming crystal structure and facilitating the loss of inner water. Meanwhile, the hydrophobic nature of
PU also resists water from inward diffusion.
3.3. PUAlg elastomer
Modication in the chemical structure of PU to improve the
incompatibility of alginate based PU was previously focused
in researches [181184]. The role of emulsier on the nal
properties of composites containing PUDs and alginates was relatively a new strategy, studied by Daemi et al. [181,182]. Two
different anionic and cationic PUs samples using DMPA and Nmethyldiethanolamine emulsiers respectively were synthesized.
A series of the alginate-based PUEs were formulated by solution
blending of the PUDs and sodium alginate. The nano-composite
elastomers of cationic PUs and SA showed excellent miscibility,
excellent mechanical properties with high elongation at break and

Fig. 6. In vitro test of rat broblast cell (a) the cells grown in cell culture media only,
(b) the cells grown in EGF-loaded AHP treated media for 48 h [185].

increased hydrophilicity that may be due to formation of tertiary

ammonium carboxylate salts produced from electrostatic interaction between cationic PU and poly-anionic alginate while the
anionic ones were appeared as the relatively incompatible ingredients and their elongation was signicantly dropped because of
the immiscibility of the SA and anionic PUs [181]. Alginates and
other natural polysaccharides can be used in different applications in drug delivery and control release systems as they can
be used as micro and nano encapsulation agents [183,184]. Some
investigation has been reported for drug delivery application of
PUAlg elastomer/hydrogel [185189], in vitro test of rat broblast cells, the cells grown in cell culture media only and the cells
grown in epidermal growth factor (EGF)-loaded AHP treated media
were studied. The EGF-treated, EGF-loaded alginate hydrogel, and
EGF loaded alginate hydrogel polyurethane (AHP) cells were proliferated 2.7, 2.5, and 2.2 times compared with cell only group,
respectively [185]. Fig. 6 shows that AHP treated well group was
much more packed with cells. However, EGF-treated cells were the
most proliferated, hydrogel-treated cells were the next, and AHPtreated cells were the last order. Regarding the EGF release proles
from alginate hydrogel and AHP at four different pH conditions;
the cumulative release increased rapidly with time and reached an
equilibrium value after a certain time. In general, the release behavior of EGF was similar with that of BSA since both of these drugs are
protein drug [185]. However, EGF release rate from alginate hydrogel only and AHP was different. EGF release rate from AHP was
slower than that from alginate hydrogel because of its composite
structure.

K.M. Zia et al. / International Journal of Biological Macromolecules 79 (2015) 377387

385

Fig. 7. (a) Scheme of the elementary unit of APU, (b) schematic performance of alginate unit [174].

3.4. PUAlg nanocomposite

Compatible aqueous cationic PUDsodium alginate nanoparticles (CPUD/SA) elastomers were prepared by solution blending of
cationic PUDs based on PTMG and IPDI extended with N-methyl
diethanolamine (MDEA), 1,4-BDO chain extenders and sodium
alginate (SA). Pristine CPUD and its nano-composite elastomers
with SA showed excellent miscibility that arise from different
charges of both anionic alginate and cationic PU and hydrogen
bonding which was supported by DMTA and FTIR results. The
prepared composites indicated two interesting nano-bead (low
molecular weight SA) and nano-rod (higher molecular weight SA)
morphologies in respect of different molecular weights of sodium
alginate samples proved by SEM and EDX. The phase separation of
PU segments decreased resulting in lower elongation and higher
mechanical strength, in the presence of greater amounts of Na alginate. Moreover, with increasing alginate content in the elastomers,
the thermal stability and hydrophilicity increases because of the
presence of quite thermally stable uronic acid residues and presence of hydrophilic carboxylate and hydroxyl groups [172]. While
progressing in another study, anionic water based PU (APU) was
formed (Fig. 7) as a result of interaction of an isocyanate precursor on the basis of oligo(oxytetramethylene) glycol (MM1000) and
aliphatic diisocyanate (HMDI) (1:2) with dianhydride of pyromellitic acid and dihydrazide of dicarbonic acid in acetone solution
followed by carboxylic groups transfer to a salt form and consecutive dispersion in water [174].
In a study [174], the APU and aqueous solution of alginate
(5 wt.%) were mixed in various compositions and the sample lms
were cast by pouring the compositions on glass substrates, dried
at room temperature for 72 h, and then dried at 60 C to constant
weight in a vacuum oven. The prepared material was used for various potential applications.

4. Summary
From the last few decades the trend of utilization of polysaccharide in various industrial elds owing to their structural diversity,

biodegradability, biocompatibility, abundance, non-toxicity and

specic bioactive properties is rapidly increasing. The most abundant marine polysaccharide, alginate, with their inherent well
known gelling and stabilizing properties proved to be a potential candidate for synthetic modied biomaterials. However certain
limitations associated with this unique polymer can be overcome
either by modication in their structure or blending with other
natural and synthetic polymers. Polyurethanes/alginate hydrogels,
elastomers and nanocomposites systems with novelty in their
properties are making the alginates a potent polymer to be explored
further.

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