Current Research On The Blends of Natura

Progress in Polymer Science 36 (2011) 1254–1276
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Progress in Polymer Science

journal homepage: www.elsevier.com/locate/ppolysci
Current research on the blends of natural and synthetic polymers

as new biomaterials: Review
Alina Sionkowska
Faculty of Chemistry, Nicolaus Copernicus University, 87-100, Torun, Poland
a r t i c l e i n f o a b s t r a c t
Article history: This review reports recent advances in the field of the blends of natural and synthetic poly-
Received 11 August 2010 mers as new biomaterials. These materials have attracted both academic, and, for several
Received in revised form 4 May 2011
blends, industrial attention because they exhibit improvements in properties required in
Accepted 4 May 2011
the biomedical field. Herein, the structure, preparation and properties of the blends of natu-
Available online 25 May 2011
ral and man-made polymer are discussed in general, and detailed examples are also drawn
from scientific literature and practical work. The most common natural polymers: collagen,
Keywords:
Polymer blends chitosan, elastin, keratin and silk are discussed as a components of blends with man-made
Biopolymers polymers.
Biomaterials © 2011 Elsevier Ltd. All rights reserved.
Collagen
Chitosan
Elastin
Silk
Keratin
Nanocomposites
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1254
2. Polymer blending . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1255
3. Collagen as a biopolymer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1257
4. Collagen blends with synthetic polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1258
5. Chitosan as a biopolymer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1262
6. Chitosan blends with synthetic polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1265
7. Other natural polymers for potential blending with man-made polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1268
8. Blends of natural and synthetic polymers as a matrix for micro- and nanoparticles incorporation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1269
9. Critical comparison of the existing knowledge in the field of bioartificial blends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1270
10. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1271
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1271
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1271
1. Introduction
Polymeric materials are widely applied in the biomed-

ical field. Although it is much easier to use synthetic
E-mail address: [email protected] polymers in the biomedical field, natural polymers are also
0079-6700/$ – see front matter © 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.progpolymsci.2011.05.003
A. Sionkowska / Progress in Polymer Science 36 (2011) 1254–1276 1255
required due to their biocompatibility and biodegradabil- preparation of biomaterials [190–209], but soluble forms of
ity. Another method of preparation of polymeric materials silk are not easily obtained. There are also very few papers
for biomedical applications is to blend synthetic polymers in scientific literature regarding new materials based on
with natural ones. Increasing interest in new materi- the blends of silk with other polymers [193–209]. More
als based on blends of two or more polymers has been recently keratin has been widely studied as a potential
observed during the last three decades. Blends of synthetic material for biomedical applications [210–218].
and natural polymers can form a new class of materials Studies with biodegradable starch-based polymers have
with improved mechanical properties and biocompatibil- demonstrated that these materials have a range of proper-
ity compared with those of single components. They have ties which make them suitable for use in several biomedical
been called bioartificial or biosynthetic polymeric mate- applications, ranging from bone plates and screws to drug
rials [1–4]. Natural polymers are usually biocompatible, delivery carriers and tissue engineering scaffolds. How-
whereas synthetic polymers can contain a residue of initia- ever, since this review article is focused on animal-derived
tors and other compounds/impurities that do not allow cell polypeptides, protein and polysaccharides, applications
growth [5,6]. Synthetic polymers have good mechanical focused on biopolymers from plant origin as the main com-
properties and thermal stability, much better than sev- ponent of the blend are not emphasized.
eral naturally occurring polymers. There is also a limitation
in the performance of several natural polymers in com- 2. Polymer blending
parison to synthetic polymers. Synthetic polymers can be
processed into a wide range of shapes, whereas for natural The field of synthetic polymer blends, has experi-
polymers several shapes are not easily obtained; for exam- enced an enormous growth in size and sophistication over
ple, high temperatures imposed in processing can destroy the past three decades in terms of both the scientific
their native structure. Newly developed polymeric materi- base and application, summarized in several publica-
als based on the blends of natural polymers and man-made tions [7,8,10,15,20,39,54,59,120,123,152,154]. A thorough
ones should be biocompatible while, at the same time, pos- review of biopolymeric blends and composites and their
sess good thermal and mechanical properties for use in applications in various industries is also available [120].
biomedical applications. The aim of bioartificial blending is to produce man-made
The main biopolymers used in preparation of materials blends that confer unique structural and mechanical prop-
for biomedical applications are collagen, chitin, chitosan, erties on the base of the specific properties of natural
keratin, silk and elastin, all natural polymers derived from polymers and synthetic polymers. By bioartificial blend-
animals body. There is also a group of natural polymers, ing the concept of biomimicry of several materials can be
derived from plants, such as starch, cellulose and pectin. developed and can lead to a new generation of scaffolds.
Several synthetic polymers can be blended with naturally In general biopolymers are more expensive than synthetic
occurring polymers to develop new materials. Moreover, polymers, but natural polymers are abundant and some
the polymeric blends can be strengthened by minerals, may be obtained at a relatively low cost. Usually, high cost
which nucleate and grow in a polymeric matrix to produce is connected with the purification of biopolymers from nat-
the appropriate size, shape and distribution of individual ural sources. To develop modified materials based on the
crystals, similar to hard tissue. blends of a natural polymer and a man-made polymer the
Natural polymers, such as collagen and elastin are usu- two components of the blend need to be combined into
ally insoluble in both water and organic solvents. The one versatile material. The components can be combined
exception is collagen extracted from the tissue of young in the molten state (melt mixing) and/or can be dissolved
animals, which is soluble in dilute acetic acid. Chitosan in the same solvent. One of the most promising meth-
is soluble in dilute acetic acid solution, but the concen- ods of solid-phase modification of polymers is the joint
tration that can be reached is rather low and depends action of high pressure and shear deformation on the blend
strongly on the molecular weight of the biopolymer. The of solid components. Under these conditions, the react-
solubility of collagen and chitosan in acetic acid provides ing material is subjected to plastic flow with an unlimited
the possibility to blend them with other water soluble strain [120]. However, melt-mixing and reaction between
polymers [7–10]. Silk, elastin and keratin are highly insol- solids at high pressures combined with shearing can be
uble natural polymers and hence the processing of these dangerous for proteins which possess hierarchical struc-
biopolymers is problematic, but these may be hydrolysed ture, i.e., high pressure and high temperature can lead to
to aid solubility. Mixtures of collagen with synthetic poly- denaturation and degradation of such biopolymers. The
mers as well as with other natural polymers has been preparation of a biopolymer blend by dissolution in the
widely studied as biomedical materials [1,2,7–9,11–58], as same solvent can avoid denaturation of the protein. The
have been collagen itself [60–80]. This trend has continued problem is that since many naturally occurring polymers
in the recent literature [81–100]. Chitosan has been widely are insoluble in common solvents it is necessary to obtain
studied as a potential biomedical material [101–119], as a soluble derivative of natural polymers (in the appropriate
have blends of chitosan with synthetic and/or other natu- temperature condition) or to hydrolyse the macromolecule
ral polymers [5,8–10,14,15,41,43,49,120–179]. Elastin has to shorter chains, which are usually water-soluble. Once
been considered for biomaterial preparation, but in prac- a water-soluble biopolymer has been achieved, it is nec-
tice it is seldom used for blend preparation [180–189], with essary to decide what kind of synthetic polymer should
only a few papers on blends of elastin with other poly- be combined with the natural one. This choice requires a
mers [183–185,188,189]. Silk is a good biopolymer for the detailed knowledge of the properties of both natural and
1256 A. Sionkowska / Progress in Polymer Science 36 (2011) 1254–1276
synthetic polymers. After preparing the two component is:

mixture in a suitable solvent one has to study the inter- smp
c
2
action between the natural and synthetic polymers in the = []2
c c
solution. Miscibility of the components is an important
c (b c2 + b c2 + 2b c c )
aspect in determining the properties of the blend. Meth- 3 22 2 33 3 23 2 3
+ []3 + c (6)
ods for the experimental study of polymer miscibility may c c2
be divided into several main groups: (i) methods based
on the determination of optical homogeneity of the mix- spm
= []2 w2 + []3 w3 + (b22 w22 + b33 w32 + 2b23 w2 w3 )c
ture, (ii) methods for the determination of glass transition c
temperatures, (iii) methods for the direct determination of (7)
interactions on molecular levels, and (iv) indirect methods
for the miscibility. Some of these techniques may be com- where w designates the normalized weight fraction of poly-
plicated, costly and time consuming. Hence, it is desirable mer (w2 = c2 /c, w3 = c3 /c).
to identify simple, low-cost and rapid techniques to study The equation for ideal mixed polymer solution:
the miscibility of polymer blends. The main method for

spm = []2 c2 + []3 c3 + b22 c22 + b33 c32 + 2 b22 b33 c2 c3
investigating the number of amorphous phases in polymer
blends is the determination of the number of glass transi- (8)
tion temperatures Tg , because each Tg corresponds to one
amorphous phase. The most commonly used experimen-
The preceding derives from Krigbaum and Wall [219],
tal method for Tg determination is differential scanning
and will result if Eq. (2) applies to the mixture, with kH a
calorimetry (DSC). DSC provides a reasonably fast, although
constant and [] given by Eq. (5).
expensive, method for the determination of the number of
Polymer mixtures might exhibit positive or negative
phases that coexist in a polymer blend. The problem is that
deviations from the defined ideal behavior because of the
sometimes it is not easy to determine Tg for biopolymers
existence or absence of interactions. The polymer–polymer
and moreover, several biopolymers do not have Tg .
miscibility can be determined by a parameter b:
Viscometry is also a simple, quick and inexpensive
method to evaluate miscibility [7,34,59]. The following

b = b23 − b22 b33 (9)
equations have been used in calculations to evaluate mis-
cibility: where b23 is obtained experimentally by substituting all
the terms in Eq. (4). A condition for miscibility is then given
sp
= [] + bc (1) by the inequality, as postulated by Krigbaum and Wall, by
c
analogy to other mixing “laws” [219]:
where [] is the intrinsic viscosity and b is the
polymer–polymer interactions term at finite concentration b > 0 (10)
related to the Huggins coefficient kH by The viscosimetry method can be used to investigate
b = kH []2 (2) polymer–polymer interactions and for assessment of the
miscibility between natural and synthetic polymers.
Eq. (1) has been adopted to a ternary system containing Fourier transform infrared (FTIR) spectroscopy is one
a solvent (component 1), and two polymers (components 2 of the many techniques that have been applied to inves-
and 3). For the ternary system, the total polymer–polymer tigate specific molecular bonding interactions in polymer
interactions (bm c2 ) are given by c2 (c2 b22 + c3 b23 ) for com- blends. When two polymers are in separate and distinct
ponent 2 and c3 (c2 b23 + c3 b33 ) for component 3: phases (complete immiscible systems), it can be assumed
that the two components do not interact in IR spectral
bm c 2 = b22 c22 + b33 c32 + 2b23 c2 c3 (3)
terms (except perhaps at the interfact of the two phases). In
where c2 and c3 are concentrations of components 2 and 3, that case, the spectrum of the blend reflects the appropriate
respectively, in a mixed polymer solution, c is the concen- addition of the IR spectrum of the two individual compo-
tration of mixed polymer solution, b22 and b33 are specific nents. In the case of miscible or partially miscible polymer
interaction coefficients of components 2 and 3 in a single blends, the IR spectrum may show the formation of new
polymer solution, b23 represents the interaction between bands as the results of miscibility; and disappearance of
different type polymer molecules in a mixed polymer solu- some component bands. Shifts in the specific bands would
tion. give information on the switches from component specific
bonds to the bonds between components [34].
(b22 c22 + b33 c32 + 2b23 c2 c3 )
bm = (4) Several studies have been published regarding misci-
c2 bility of collagen with other polymers [7,8,10,15,20,34,
The intrinsic viscosity of mixed polymer solution: 39,51,54,55,59]. The miscibility in polymer blends is
c c assigned to specific interactions between polymeric com-
spm 2 3
[]m = = []2 + []3 (5) ponents, which usually give rise to a negative free energy of
c c→0 c c→0 c c→0
mixing in spite of the high molecular weight of polymers.
The intrinsic viscosity of a mixture of two polymers is The most common interactions in the blends are hydrogen
the weight average of the intrinsic viscosity of the two poly- bonding (when polymers contain chemical groups capable
mers taken separately. For a ternary system the equation of forming hydrogen bonds), ionic and dipole, pi-electrons
and charge-transfer complexes. Most polymers in the blend fibrils, exhibits its mechanical strength in the plane of the
are immiscible with each other due to the absence of network. The differences in strength that have been found
specific interactions. Sometimes two polymers are par- for skin are due to the fibril orientation rather than the fibril
tially miscible: they are miscible only in solution, but they type [60,61,63–65]. Collagen is a highly crosslinked mate-
are immiscible after solvent evaporation. Several methods rial which is usually insoluble in water. The age-related
have been employed to assess the interactions between differences in solubility of skin collagen were examined by
two components in the blend and then the miscibility of susceptibility to pepsin digestion. It was found that solu-
two polymers [1–3,7,8,34,59]. bility in acetic acid decreased rapidly during maturation
While the miscibility of two or more synthetic poly- and then slowly with age [66]. The ageing processes can
mers has been studied, the miscibility of natural polymers result in collagen crosslinking that has a deleterious effect
with synthetic polymers is poorly understood. The main on the mechanical properties of tissues. Furthermore, it has
problem is to find a solvent suitable for both natural and been reported that exposure to UV irradiation can induce
synthetic polymers. If natural polymers possess a hierarchi- crosslinks in collagen fibrils [67]. However this crosslinking
cal native structure it may happen that during mixing with is complicated by peptide bond scission events that may
a synthetic polymer the natural polymers native structure also occur through free radical mechanisms. The photo-
is altered. chemical reactions may be attributed to direct absorption
by tyrosine/phenylalanine or to peptide bonds. The fine-
3. Collagen as a biopolymer tuning of irradiation processes may therefore allow either
degradation or crosslinking. The efficiency of these two
Collagen is the most abundant protein in animals, where types of reaction depends mainly on the sample prepara-
it provides the principal structural and mechanical support tion and irradiation dose [67].
[60]. It is a major structural protein, forming molecular In the collagen molecule, atoms in the individual chains
strands that strengthen the tendons, and vast, resilient are held together with covalent bonds, while the three
sheets that support the skin and internal organs. Bones chains are held in the triple-helical structure by weaker
and teeth are made of collagen with the addition of min- bonds [68–70]. These weak bonds are: hydrogen bonds,
eral crystals, mainly hydroxyapatites. Collagen provides dipole–dipole bonds, ionic bonds, van der Waals inter-
structure to all animal bodies, protecting and supporting actions. When the protein is heat-denatured, these weak
the softer tissues and connecting them with the skeleton. bonds are broken but the covalent bonds stay intact and
There are 20 genetically distinct members of the collagen the three chains separate from one another and collapse
family. The major ones are fibril forming collagens: type into random coils [71,72]. Collagen fibers in vivo must be
I (skin, tendon and bone), type II (cartilage) and type III stable enough to withstand the disruptive influence of ther-
(skin and vasculature). These collagen types can be found mal agitation, but capable of assembly and disassembly of
as part of fibrillar structures that form an essential part the component molecules. In solution, the unfolding tem-
of tissue architecture and integrity [60–65]. Each chain of peratures of a wide range of fibrous collagens are within
collagen contains 1000 amino acids. A sturdy structure is only a few degrees of the animal’s body temperature, but
formed by a repeated sequence of three amino acids. Every when the molecules are aggregated to form fibers there
third amino acid is glycine, a small amino acid that fits per- is an increase in the transition temperature of ∼27 ◦ C
fectly inside the helix. Many of the remaining positions [73–75]. Stability of the triple helix in collagen depends on
in the chain are filled by two unexpected amino acids: hydrogen bonds. The temperature of thermal denaturation
proline and a modified version of proline, hydroxyproline. (so-called melting temperature) of collagen depends on
Hydroxyproline, which is responsible for collagen stabil- water content, pH of environmental medium, and degree
ity, is formed by modifying regular proline amino acids of cross-linking [73–77]. One can say, that collagen, as most
after the collagen chain is built. Collagen within a fibril proteins, loses all of its structure during heating. The triple
is stabilized by the numerous intra- and intermolecular helix unwinds and the chains separate. Then, when this
forces. The main role in the stabilization of the collagen denatured mass of tangled chains cools down, it absorbs
triple helix is carried out by hydrogen bonds [61]. The all of the surrounding water like a sponge, forming gelatin.
alignment of charged groups between collagen molecules Gelatin itself is a mixture of water-soluble proteins derived
contributes to electrostatic interactions and is important primarily from collagen. Gelatin usually binds more water
in defining the intra-molecular structure. Each collagen than collagen as it is partially degraded collagen and more
molecule undergoes a strong molecular connection with active groups are exposed to interactions with water via
neighboring collagen molecules and an applied force can hydrogen bonds. Based on their structural roles and com-
be transmitted through a fibril to each collagen molecule. patibility within the body, collagen and gelatin are the most
The role of naturally occurring collagen crosslinks is also commonly used biomaterials in the medical, pharmaceuti-
important in the formation of a stable fibrillar structure. cal and cosmetic industries. As collagen is a very expensive
Tendon collagen exhibits a crystalline lateral packing order biopolymer and exhibits low thermal stability there is a
whereas fibrils from tissues such as skin exhibit a close need to combine this natural polymer with a synthetic one
packed structure with liquid like disorder. The suprafib- with good thermal properties.
rillar packing geometry makes a tendon or a ligament Collagen-based materials are widely used in
extremely strong along the axis of the tissue, where there reconstructive medicine, pharmacy and cosmetics
is preferential alignment of fibrils. Skin, which comprises [5,14,16,22,36,38,44,46,49,51,56–59,67,78,79]. The prop-
a two dimensional network of randomly oriented collagen erties of collagen-based materials are influenced by the
source of collagen and by the method of preparation advancement in the field of advanced wound-care has
involving purification, fibril formation or casting and arisen with breakthroughs in the area of tissue engineering.
subsequent crosslinking. This has enabled the development of, for example, tempo-
rary skin substitutes, that is, synthetic skin products that
4. Collagen blends with synthetic polymers can be used to treat seriously injured patients.
The applications of collagen in tissue regenera-
The process of blending of collagen with synthetic tion/engineering may include: artificial skin, bone graft
polymers depends on many factors. The main problem substitutes, dental implants, implants for incontinence,
is the solubility of the polymeric components in a com- artificial tendons and blood vessels, corneal implants, nerve
mon solvent. The solubility of collagen strongly depends regeneration, regeneration of cartilage, skin and organs
on the age of the tissue from which it is derived [66]. [78,79]. However, the application of animal-derived mate-
For soluble collagen it is possible to obtain the blend rials in the preparation of tissue-engineered products is
with synthetic polymers and form the blend in a solvent. generally viewed as a problem. For these reasons we can
From the blends one acquires films and sponges for poten- expect that the use of hybrid polymer systems composed
tial biomedical applications. Blends of collagen with other of natural and synthetic macromolecules may be useful for
hydrophilic polymers can be used as good quality hydro- various applications in the science of biomaterials.
gels [15,16,31,36,51,57] and as biodegradable polymeric The use of blends of collagen and synthetic polymers
scaffolds, which are widely used in medical applications is not restricted to applications in medical products. New
[6,11,14,22,28,35–37,45,48–50,53,56,58]. A basic advan- materials based on the blends of collagen and other poly-
tage is the avoidance of surgery to remove the polymer mers could result in a new generation of biodegradable
from the body, when the implanted device is no longer polymeric packaging material. The majority of current
needed. Highly porous structures of scaffolds maintain packaging material is composed of non-biodegradable
large areas for the cells to attach and proliferate. plastic. As a consequence, plastic waste accumulating in
Drug delivery devices offer another application for the environment has a negative influence on the biological
blends of collagen and synthetic polymers [16,36,42,44,57]. system. The combination of natural polymers, which are
Drugs formulated in polymeric devices are released either biodegradable with synthetic ones may lead to biodegrad-
by diffusion through the polymer barrier, by erosion of the able composites. Collagen as a biopolymer extracted from
polymer material, or as a result of the combination of both. animal tissues is very expensive, so its usage for packaging
Biodegradable polymers provide flexibility in the design of materials is not feasible from an economic point of view.
delivery systems of large molecular weight drugs such as However, after enzymatic hydrolysis of collagen waste it is
peptides and proteins, which are not suitable for diffusion possible to use collagen hydrolysate for a diverse range of
controlled release through non-biodegradable polymeric applications (fertilizer, adhesives, concrete mixtures, etc.),
matrices. These systems release the bioactive substances as as well as an additive to plastics, consequently increasing
they degrade to the desired area with an effective dose, for their sustainability. Therefore, synthetic polymers mod-
a predetermined rate and duration. The polymers selected ified with collagen hydrolysate can form a sustainable
as delivery devices must meet several requirements such as plastic material workable to films for use in agriculture,
biocompatibility, drug compatibility, the possibility of their forestry, packaging, etc. By blending collagen hydrolysate
processing, suitable biodegradation kinetics and mechan- with synthetic polymers, biodegradable and water-soluble
ical properties. A wide variety of natural and synthetic polymeric products can be obtained using waste from the
biodegradable polymers have been investigated for drug leather industry [42]. The main problem in the application
targeting or prolonged drug release. However, only a few of of waste derived from the leather industry is the chromium
them are biocompatible. Natural biodegradable polymers content of the waste material.
like bovine serum albumin (BSA), human serum albumin Several properties have to be studied to develop new
(HSA), collagen, gelatin, and haemoglobin have been stud- materials based on blends of two or more polymers. The
ied for drug delivery [4,57,58]. The use of these natural properties of new polymeric blends that have regularly
polymers is limited due to their high cost and questionable been evaluated are the mechanical properties, such as
purity. Biodegradable polymeric systems can be designed ultimate tensile strength and the percentage of elonga-
in various shapes such as membranes, pellets, sponges, tion at breaking point. For packaging materials, the barrier
micro- or nanospheres, depending on the purpose of appli- properties, for example, water vapor and oxygen perme-
cation. ability are very important. Sometimes the developed films
Collagen and its blends with synthetic polymers are show desirable oxygen permeability, but their moisture
also widely studied for their application in the wound barrier and mechanical properties are poor in compari-
healing process. In addition to its involvement in the son to the synthetic polymeric films. Another key factor
healing process within the wound, collagen can also be for biopolymeric blends is their surface, as many pro-
formed into matrices that adhere well to wounds. Such cesses including material–tissue interactions start just at
a matrix can therefore act as a template for new tis- the surface. The surface plays a crucial role in biology and
sue growth, absorbing many times its weight in fluids, medicine because most biological reactions occur at sur-
and effectively supporting new tissue growth. This is the faces and interfaces. It is also important for most tissue
basis behind occlusive dressings, which keep the wound engineering approaches aiming at the repair or regen-
moist, and the prospective development of artificial skin eration of living tissues, the interactions of cells and
[4,6,14,19,22,28,31,36,43,49,50]. A further and more recent polymeric biomaterial. Surface modifications that directly
Table 1
b Parameter for binary blends containing collagen and synthetic polymer. Reprinted from [34] with permission from Elsevier.
X2 (collagen) X3 (synthetic) b coll/PVP b coll/PVA b coll/PEO b coll/PEG
0.00 1.00
0.20 0.80 0.0867 1.9811 −0.2189 −0.2901
0.50 0.50 0.3942 0.0839 0.0765 −0.3811
0.80 0.20 1.2901 1.2691 1.4131 3.7500
1.00 0.00
affect the biological function can be performed in sev- CH2 CH CH CH 2

eral ways: producing specific surface functional groups,
N C
adsorption–adhesion of specific bio-molecules and atoms,
C O.......... HO O
or by deposition of microparticles such as functional inor-
ganic species, catalysts, microcapsules to deliver a specific
reagents depends on environmental conditions. For the Fig. 1. An example of hydrogen bonding in collagen/PVP blend.
tissue engineering approach the surface can be also modi-
fied by UV-irradiation [80]. Both, medical devices and their
as side groups. Therefore, a hydrogen-bonding interaction
packaging need to be sterilized before usage. However, the
may take place between these two chemical moieties in
medical device and its packaging can be degraded irre-
a blend of collagen and PVP. The formation of hydrogen
versibly by the sterilization process. Frequently the earliest
bonds between two different macromolecules competes
evidence of material degradation will appear in the surface
with the formation of hydrogen bonds between molecules
layers of the product or its package.
of the same polymer.
In many laboratories water-soluble synthetic polymers
FTIR spectra of collagen and collagen/PVA blends
have been blended with natural polymers such as collagen,
showed that the positions of amide bands were at the same
elastin, keratin, silk, chitosan and gelatin. The following
wave numbers for the blends with different compositions
synthetic polymers can be used for blends: poly(vinyl
and only slightly different than for pure collagen film. The
pyrrolidone) PVP, poly(vinyl alcohol) PVA, poly(ethylene
comparison of the position of amide bands in FTIR spectra
glycol) PEG and poly(ethylene oxide) PEO. From the blends
of collagen and its blends with synthetic polymers is shown
thin films, hydrogels, and sponges may be obtained. Colla-
in Table 2.
gen films may be prepared by solvent evaporation from
In these studies, carbonyl stretching regions together
collagen solution and by treating collagen gel solutions
with hydroxyl stretching regions of the FTIR spectra of the
with different concentrations of glutaraldehyde and/or
components and the blends reveals a significant amount
other cross-linking agents. Polymeric films based on the
of information about the specific bonding interactions in
blends of natural polymers and synthetic polymers were
the systems. On the other hand, in a polymer mixture
obtained by solvent evaporation from a collagen solu-
of two components where both components have multi-
tion in acetic acid [8,9,11–13,34]. Miscibility between the
ple hydroxyl groups (as in the case of PVA), the analysis
two components has been studied by viscometry meth-
would be more complex. It suggests only a minor interac-
ods, Fourier transform infrared spectroscopy (FTIR) and
tion between collagen and PVA in the solid state. It seems
differential scanning calorimetry (DSC) methods [34]. Vis-
that hydrogen bond formation between collagen molecules
cometric data for binary blends containing collagen and
competes with the formation of hydrogen bonds between
PVP showed that collagen and PVP are miscible [7]. Sim-
molecules of PVA and collagen in thin film [12,34].
ilar results have been obtained for collagen/PVA blends
Viscometric data for binary blends containing col-
[12,34]. The comparison between b parameters which
lagen/PEO (poly ethylene oxide) and collagen/PEG
shows miscibility of two polymers is presented in Table 1;
(polyethylene glycol) showed that collagen and those
b is obtained by the use of Eqs. (1)–(10).
polymers are immiscible (Table 1). However, from the
Miscibility of polymers mentioned above in thin films
mixture it was possible to prepare films which have the
has been confirmed by FTIR spectra of collagen and
potential for future applications. FTIR spectra revealed
collagen/synthetic polymer blend. FTIR is a very power-
some minor interactions between collagen and PEO and/or
ful technique to detect the inter-molecular interactions
PEG in a solid state (thin film). The positions of amide
between two polymers. The inter-molecular interaction
through hydrogen bonding can be characterized by FTIR,
because the specific interaction affects the local electron Table 2
Amide band position of collagen before and after blending with synthetic
density and the corresponding frequency shift can be
polymers. Reprinted from [34] with permission from Elsevier.
observed. The example of hydrogen bonding between a col-
lagen molecule and PVP is shown in Fig. 1. The shift of amide Sample Amide band position [cm−1 ]
bands in FTIR spectra of the blend suggests an interaction A B I II
between collagen and PVP by hydrogen bonds (Table 2).
Collagen 3326 3094 1654 1557
Collagen, which is a hydrogen donor, forms a hydro- Collagen/PVP blend 3330 3088 1658 1557
gen bond with carbonyl group from PVP. The pyrrolidone Collagen/PEO blend 3328 3082 1656 1557
rings in PVP contain a proton-accepting carbonyl moi- Collagen/PVA blend 3325 – 1654 1559
ety, while collagen presents hydroxyl and amino groups Collagen/PEG blend 3228 3090 1656 1557
Table 3 Table 4
Atomic ratio deduced from XPS survey spectra and the percentage of car- The surface free energy for collagen, PVP and collagen/PVP films before
bonyl band on the surface. Reprinted from [83] with permission from and after UV-irradiation. Reprinted from [11] with permission from
Elsevier. Elsevier.
Collagen PVP Collagen/PVP Irradiation time [h] Surface free energy [mN/m]
a
% C O/surface Collagen PVP Collagen/PVP
Non irradiated 12.4 ± 0.1 10.3 ± 2.1 12.4 ± 0.9
Irradiated 10.9 ± 0.5 9.3 ± 0.6 11.6 ± 0.4 0 35.44 47.38 35.55
4 35.45 44.23 36.77
O/C 8 37.63 51.64 34.28
Non irradiated 0.254 0.150 0.222
Irradiated 0.280 0.162 0.235
N/C The contact angle and the surface free energy were
Non irradiated 0.186 0.100 0.167 altered by UV-irradiation for both collagen and PVP films,
Irradiated 0.138 0.106 0.141 however, the changes of these parameters were much
a
Calculated from the survey and HR of C spectra: %C = O on the surface = (% smaller for the film of the collagen/PVP blend. We found
of the band at 288 keV in HR) × (%C in survey)/100. that the blends were more photo-resistant than the pure
components. The values of surface free energy for colla-
gen/PVP blends before and after UV-irradiation are shown
bands for collagen in blends were similar to those for pure in Table 4.
collagen, as shown in Table 2 [34]. The AFM images showed that collagen surface morphol-
The surface properties and biocompatibility of materi- ogy is somehow ordered in an opposing way to that of PVP
als based on blends of collagen and synthetic polymers or (the surface of a PVP film is flat). The blend surface was
other natural polymers have been studied [11,13,34,83,89]. similar to that of pure collagen. UV-irradiation caused only
It was found that the surface of a collagen/PVP blend is small changes in the surface morphology of collagen/PVP
enriched in the low surface energy component, i.e., col- films (Fig. 2).
lagen. In Table 3 one can see that the percentage of C O In Fig. 3 the biocompatibility of newly developed poly-
group on the surface of the collagen/PVP blend is similar to meric materials based on the blends of collagen and
the percentage of C O groups on the surface of a collagen synthetic polymers is compared with that of pure colla-
film [83]. In Table 4 one can see that surface free energy of gen film. The biocompatibility test of collagen–polymer
the collagen/PVP blend is similar to the surface free energy blend sheets was carried out as follows: polymeric films
of collagen. The value of surface free energy of PVP is larger were soaked in ethyl alcohol for 15 min to sterilize,
than collagen or collagen/PVP films. then an appropriate medium was added and incubated
Fig. 2. AFM images of collagen, PVP and collagen/PVP blends before and after irradiation.
Reprinted from [11] with permission from Elsevier.
1000
900
800
700
Fluorescence
600
500
400
300
200
100
0
Control Collagen Collagen- Collagen- Collagen- Collagen-
surface PEG PEO PVP PVA
(petri dish)
Film Type
Fig. 3. Fluorescence of resazurine after 3.25 h reaction-fibroblast growth time of 5 days (gain = 60).
H O OH
1
O2
CH3+ H3C CH3
O OH O
O
CH3 H3C +
CH3 HO H3C + CH
H
OH
CH CH3 + HO H3C CH3
Fig. 4. General scheme of photooxidation process on the polymer surface and a formation of new polar groups.
until cells proliferate. When cells have spread adequately of blends based on collagen usually occurs in two steps (in
the Resazurin assay test was performed [34]. After the nitrogen). The first stage is connected with water bounded
Resazurin test the fluorescence of each sample was to the blend, whereas the second stage is connected with
measured with a spectrofluorometer. Fig. 3 shows that thermal destruction and reduction of the molecular weight
fibroblasts grow with the fastest rate on collagen films. of the polymer.
However, the biocompatibility of new polymeric materi- Recently it has been shown that collagen fibrils can be
als based on the blends of collagen, PEG and PVA seems to formed in the synthetic polymer matrix [91]. AFM images
be sufficient for biomedical applications [84,90]. showed the fibrils formation in PVP films containing col-
It is commonly known that living cells tend to attach to lagen. The amount of collagen in the PVP matrix has an
polar chemical groups at the material surface [186]. Dur- important effect on the structure and size of collagen fib-
ing UV-irradiation, the photo-oxidation process takes place ril formed. The size of fibrils formed in the PVP matrix is
and new polar groups can be formed. The example of the presented in Table 6.
formation of this polar group is shown in Fig. 4. The size of fibrils formed in the PVP matrix can be mod-
The interaction of UV radiation with the blends is impor- ified by UV-irradiation [92]. The size of collagen fibrils in
tant, as the behavior of the blends needs to be understood irradiated PVP films is larger than in nonirradiated ones
under potentially harsh conditions. UV radiation may be (Table 6). A small amount of collagen (1-5%) in a synthetic
used to refine the blend preparation process to produce polymer matrix may change several properties of the main
blends of specific structural and chemical characteris- polymer [87,92–94]. The values of polar and dispersive
tics. After different doses of UV-irradiation the mechanical
and surface properties of the film should be investigated.
Table 5
During UV-irradiation of polymers, excited molecules are Thermal parameters of collagen, collagen/PVP and collagen/PVA blends.
formed in the first step and then, the secondary pro- Reprinted from [34] with permission from Elsevier.
cesses such as chain scission, crosslinking and oxidation
Specimen Peak 1 Peak 2
take place. In the presence of thermally stable synthetic
polymers collagen is usually more stable and undergoes T1 [◦ C] H1 [J/g] T2 [◦ C] H2 [J/g]
thermal degradation in a higher temperature than pure col- Collagen 80.3 222.3 212.8 3.6
lagen [34]. The thermal stability of collagen blends with Collagen/PVP 87.1 119.5 206.8 2.4
PVP or PVA is shown in Table 5. The thermal degradation Collagen/PVA 85.1 129.5 216.8 122.4
Table 6 Table 8
Size of collagen fibers in PVP films containing 1%, 3% and 5% of collagen Thermal parameters of thermal decomposition of collagen films after
before and after 12 h of UV irradiation of PVP. Reprinted from [92] with chemical cross-linking with EDC/NHS and DEPE: the temperature of the
permission from Elsevier. maximum speed of the process (Tmax ) and the mass decrement during the
heating process (m).
Specimen Diameter of fibril [nm] irradiation
time [h] Specimen Thermal parameter
0 12 Tmax [◦ C] m [%]
PVP + 1% collagen 39,1 58,6 Collagen not cross-linked 308.99 62.43

PVP + 3% collagen 41,0 44,9 Collagen EDC/NHS 1:10 311.23 67.85
PVP + 5% collagen 58,6 80,1 Collagen EDC/NHS 1:19 309.85 80.82
Collagen DEPE 1:20 303.52 70.36
Collagen + 10% elastin 314.85 69.27
components of surface free energy show that PVP films are

more polar when collagen is added (Table 7). Moreover,
in a 1,1,1,3,3,3-hexafluoroisopropanol/trifluoroacetic acid
the increase of polarity of PVP containing collagen after
(v/v, 90/10) mixture was investigated for the fabrication
UV-irradiation indicates an efficient photooxidation on the
of a biocompatible and biomimetic nanostructure scaf-
surface of thin film.
fold in tissue engineering [97]. The morphology of the
Water soluble natural polymers as well as polypep-
electrospun collagen–chitosan nanofibers has been stabi-
tides derived from natural polymers are sometimes not
lized by glutaraldehyde (GTA) vapor via crosslinking. It was
stable enough for biomedical applications. Chemical and
found that both endothelial cells and smooth muscle cells
physical crosslinking can enhance properties such as
proliferated well on or within the nanofiber, making it a
biodegradability, mechanical properties and thermal prop-
candidate for tissue engineering in biomedical applications
erties. Polymeric materials can be cross-linked by chemical
such as scaffolds [97]. XRD analysis implied that neither
cross-linking using 1-ethyl-3(3-dimethyl aminopropyl)
collagen nor chitosan crystallized in the course of electro-
carbodiimide (EDC) and N-hydroxysuccinimide (NHS).
spinning and cross-linking, and gave amorphous structure
Moreover, diepoxypropylether (DEPE) can be used as a
in nanofibers. The collagen–chitosan nanofibrous matri-
cross-linking agent [95]. Chemical cross-linking of collagen
ces, especially with a chitosan content of 20% or 50%, have
materials leads to a loss of water bounded to the macro-
the advantages of similar components and the nanometer-
molecule. Collagen films cross-linked by EDC/NHS become
scale architecture of ECM [97].
fragile with poor mechanical properties. Thermally cross-
Blends based on collagen and chitosan have been stud-
linked collagen films possess slightly better mechanical
ied quite frequently [8,9,39,43,49,58,98]. The ultimate
properties. Collagen films cross-linked by DEPE are ther-
properties and applications of these films depend on the
mally less stable and contain much less bonded water than
concentration of the individual components. However,
collagen films before cross-linking. Elastin hydrolysates
since this review is focused on the blends of natural and
can work as a good cross-linking agent for collagen
synthetic polymers, blends composed of collagen and chi-
Table 8 [95].
tosan are not discussed in detail in this review.
Appropriate new materials obtained from the blend
Blends using three different polymers have received
of collagen with a synthetic polymer may be turned to
attention recently. For example, tertiary blends composed
fibers by electrospinning. Aligned nanofibrous blends of
of poly(caprolactone) (PCL), elastin and collagen have been
poly (dl-lactide-co-glycolide) (PLGA) and collagen with
prepared to mimic the structure of native artery [99,100].
various PLGA/collagen compositions were fabricated by
By electrospinning of such blends the nano- to micro-
electrospinning to obtain new materials for bone tissue
fibrous three-layered small diameter vascular grafts with
engineering [96]. Crosslinking with EDC resulted in an
distinct material properties for each layer can be produced.
increase in mechanical properties of the materials. The
most promising properties for bone tissue engineering
among the PLGA/collagen blends were found for the com-
position 80/20 [96]. Electrospinning has also been used to 5. Chitosan as a biopolymer
fabricate collagen and chitosan blends. To mimic a natu-
ral extracellular matrix (ECM), collagen–chitosan complex Chitosan is a natural cationic polyelectrolyte copolymer
nanofibrous scaffolds were obtained by electrospinning. derived from chitin. Chitin is a homopolymer compris-
Electrospinning of collagen and chitosan blend solutions ing 2-acetamido-2-deoxy-␤-d-glucopyranose units. The
Table 7
p
Dispersive components ( sd ) and polar ( s ) components of surface free energy for PVP films containing 1%, 3% and 5% of collagen before and after 2 h, 8 h
or 24 h UV-irradiation (calculated by Owens–Wendt method).
Time of UV [h] PVP PVP + 1% coll PVP + 3% coll PVP + 5% coll

d p d p d p d p
s s s s s s s s
0 40.44 5.87 32.74 4.92 29.60 5.27 31.99 3.97

2 31.31 7.07 32.49 2.56 29.13 7.40 29.00 5.88
8 32.24 8.16 28.92 4.91 30.21 12.63 31.08 13.96
24 29.01 19.40 32.14 19.87 30.22 19.19 30.24 21.51
Fig. 5. Structure of chitin and chitosan. Scheme of deacetylation process of chitin.
majority of units in chitosan chains exist in the deacety- of chitosan can be stiff as well as having the ability to stabi-
lated form as 2-amino-2-deoxy-␤-d-glucopyranose. When lize a liquid crystalline phase in acetic acid solution [105].
chitin is deacetylated to at least 50%, it becomes soluble in However, the stiffness of the macromolecular chain of chi-
dilute acids and is referred to as chitosan. The structures of tosan is very sensitive to pH condition and even a small
chitin and chitosan are shown in Fig. 5. perturbation in pH can change the properties of the chains.
Chitosan is a biodegradable natural polymer with great Many papers examine the advances in the application of
potential for pharmaceutical and cosmetic applications due chitosan and chitosan derivatives to non-viral gene deliv-
to its biocompatibility, high charge density, non-toxicity ery, and give an overview of transfection studies which
and mucoadhesion. Recently chitosan has attracted atten- have been performed recently using chitosans as trans-
tion because the range of its applications has been extended fection agents [106]. Many laboratories have attempted
to medical, wastewater treatment, biomembranes and to modify the properties of chitosan. The novel properties
hydrogel development [101–104]. For this reason it can be of chitosan make it a versatile biomaterial for cell ther-
used in many applications in the formulations employed apy, tissue engineering and gene therapy. It is believed
in drug delivery. Furthermore the macromolecular chain that these diverse approaches for regenerative medicine
Fig. 6. Example of covalent crosslinking of chitosan using glutaraldehyde.
will produce materials with the required properties for the Chitosan derivatives can also be applied in various tis-
future [107]. For biomedical applications chitosan hydro- sue engineering applications namely, skin, bone, cartilage,
gels and networks (for instance interpenetrating polymer liver, nerve and blood vessel [115,116]. Injectable chitosan
networks) formed by aggregation or complexation have hydrogels can be used in cancer treatment. In literature,
been developed [108]. In farming applications chitosan is formulation protocols for in situ hydrogel systems, their
widely used in veterinary drug delivery. Chitosan based cytotoxic properties, loading and in vitro release of drugs,
products can be used for the delivery of chemotherapeutics their effect on cell growth in vitro and inhibition of tumour
such as antibiotics, antiparasitics, anaesthetics, painkillers growth in vivo using mouse models are often discussed
and growth promotants to mucosal epithelium for absorp-
tion for local or systemic activity [109]. However, it is
not clear whether these applications are really commer-
cialized. Chitosan based products are widely applied in
cosmetic formulations and there they are highly commer-
cialized.
Interesting characteristics that render chitosan suitable
for biomedical applications are a minimal foreign body
reaction, an intrinsic antibacterial nature, and the ability
to be molded into various geometries and forms such as
porous structures, suitable for cell ingrowth and osteocon-
duction. Due to its favorable gelling properties chitosan can
deliver morphogenic factors and pharmaceutical agents in
a controlled fashion. Its cationic nature allows it to form a
complex with DNA molecules making it an ideal candidate
for gene delivery strategies [110–113]. Covalent crosslink-
ing of chitosan leads to the formation of hydrogels with
a permanent network structure, since irreversible chemi-
cal links are formed. This type of linkage allows absorption
of water and/or bioactive compounds without dissolution,
and permits drug release by diffusion under pH-controlled
conditions. Ionically crosslinked chitosan hydrogels exhibit
a higher swelling sensitivity to pH changes than cova-
lently crosslinked chitosan hydrogels. This fact extends
the potential application of ionically crosslinked chitosan,
since dissolution can occur in extreme acidic or basic pH
conditions [114]. An example of covalent and ionic cross-
linking of chitosan is shown in Figs. 6 and 7. Fig. 7. Example of ionic crosslinking of chitosan.
Fig. 8. The influence of UV irradiation on ultimate tensile strength of chitosan (1) and chitosan/PVP films (2, 80:20; 3, 60:40; 4, 40:60; 5, 20:80). Each value
is reported with its standard deviation.
[117–119]. The future enhancement of this technology can than 50% chitosan [122]. The miscibility of chitosan and
be predicted. PVP has been studied in many research groups [123,124].
The properties of the blends obtained have also been
6. Chitosan blends with synthetic polymers studied in the context of their biomedical applications. The
mechanical and surface properties of chitosan, poly(vinyl
The existing methods of preparing polymer blends of pyrrolidone) (PVP) and chitosan/PVP blends have been
cellulose, chitin and chitosan with natural and synthetic studied and the influence of UV irradiation on these
polymers and their applications have been reviewed by properties has been compared [125–129].
Rogovina and Vikhoreva [120], discussing the methods of New materials based on blends of chitosan and PVP
solid-phase blending of these polymers under conditions were submitted to treatment with UV irradiation with
of high pressure and shear deformation. The advantages wavelength 254 nm for different lengths of time as this
of this method compared to the conventional techniques radiation is usually used for the sterilization of biomedi-
of polysaccharide mixture production have been shown cal materials. Some mechanical properties of chitosan/PVP
[120]. Chitosan blends with hydrophilic polymers includ- blends in Fig. 8 show that the mechanical properties of the
ing poly(vinyl alcohol) (PVA), poly(ethylene oxide) (PEO) blends were affected by UV irradiation. After 4 h of UV-
and poly(vinyl pyrrolidone) (PVP) were investigated as irradiation with 254 nm wavelength the value of ultimate
candidates for oral gingival delivery systems [121,122]. tensile strength for the blends with composition 60:40,
Chitosan/PVP blends can be used as a drug release system 40:60 and 20:80 was smaller than for irradiated pure chi-
and to control the release profile of a drug with poor tosan films. The level of the changes of the mechanical
water solubility. Several research groups have shown properties was smaller in the blend than in pure chitosan
miscibility of chitosan and PVP and the possibility of and strongly dependent on the dose of irradiation and the
using the blend material. Poly(vinyl alcohol) (PVA) is composition of the samples. The contact angle and the
another synthetic polymer appropriate for blending with surface free energy were altered by UV irradiation. The
chitosan. Chitosan and PVA form an immiscible system, influence of UV-irradiation on surface properties is shown
as the interactions between macromolecules of PVA are in Table 9. The values of the polar component of surface free
stronger than between PVA and chitosan [122]. However, energy indicate photooxidation and an increase in polarity
even in a phase separated system the blend may show of the surface. The range of these changes points to greater
interesting and exploitable properties. The study indicated sensitivity of chitosan to photooxidation in comparison
that chitosan/PVA blends were superior in other proper- with PVP and chitosan/PVP blends [125].
ties compared to chitosan alone and could be promising The interaction between chitosan and PVP is mainly due
candidates for formulation in drug delivery systems [122]. to hydrogen bonding. An example of such an interaction is
Several methods have been employed to study the inter- shown in Fig. 9.
action of chitosan with the synthetic polymers mentioned Chemical crosslinking of chitosan and PVP blend using
above. Results from differential scanning calorimetry and crosslinking agents leads to a highly crosslinked material.
dynamic mechanical thermal analysis, Fourier transform A pH-sensitive chitosan/poly(vinyl pyrrolidone) blend can
infrared spectroscopy and tensile testing, indicated that be synthesised by crosslinking chitosan/PVP blend with
the chitosan/PEO and chitosan/PVP blends showed evi- glutaraldehyde to form a semi-interpenetrating polymer
dence of miscibility, while only the chitosan/PVA blend network (semi-IPN). Such materials can be used as a con-
showed evidence of interaction in blends containing more trolled drug release system for antibiotic delivery [126].
Table 9
Surface energy calculated by Owens–Wendt method of the chitosan, PVP, chitosan/PVP blend after UV irradiation. Reprinted from [125] with permission
from Elsevier.
Sample Irradiation time [h] Surface energy (total) [mN/m] Disperse part Polar part
Chitosan 0 27.2 21.8 5.4

4 39.3 22.8 16.5
8 50.0 20.0 30.0
Chitosan/PVP 0 27.7 22.4 5.3
80:20 4 38.7 21.4 17.3
8 47.4 21.7 25.7
Chitosan/PVP 0 28.4 25.3 3.1
60:40 4 34.7 26.8 7.9
8 43.1 23.4 19.7
Chitosan/PVP 0 28.6 26.1 2.5
50:50 4 34.3 26.6 7.7
8 39.9 24.5 15.4
Chitosan/PVP 0 29.0 25.1 3.9
40:60 4 34.2 26.6 7.6
8 43.0 22.3 20.7
Chitosan/PVP 0 31.8 24.2 7.6
20:80 4 35.3 30.6 4.6
8 49.5 18.8 30.7
CH2OH In several research papers it is shown that chitosan and

O PVA form an immiscible system. Several attempts have
H been made to enhance the miscibility of these two com-
OH H H O ponents. To increase the physicochemical compatibility
between chitosan and PVA, the blends have been prepared
H N H in a two-step reaction. In the first step, chitosan–g-
poly(vinyl acetate)/poly(vinyl acetate) (CS-g-PVAc/PVAc)
H blends were produced in situ by adding sufficient amounts
...............
of vinyl acetate to acetic aqueous solutions with different

amounts of chitosan, using a ceric ion as the initia-
CH2 CH tor. The results showed that the cellular compatibility
of PVA was improved due to the incorporation of chi-
N tosan [130]. Blends of PVA and chitosan may also be used
C O for hydrogel preparation. Electron spectroscopy for the
chemical analysis of the resulting hydrogel membranes
showed that the chitosan component was concentrated
Fig. 9. The example of hydrogen bonding between chitosan and synthetic
polymer. on the top-surface side of cast membranes. The hydrogel
with 40%wt. chitosan content was superior to collagen,
which is widely used for cell attachment and growth.
This cell attachment/growth behavior appears to be due
Hydrogels with a porous structure can be obtained using not only to the interaction between chitosan molecules
the freeze-drying method. It was found that porous freeze- and cells, but also to the nature of the two-dimensional
dried hydrogels exhibited superior pH-dependent swelling distribution of chitosan components on the surface of
properties over non-porous air-dried hydrogels. The pro- the hydrogels [122,131]. Solutions of PVA and chitosan
tonation of a primary amino group on chitosan leads to were homogeneously mixed and electrospun to result
an increase in swelling properties. A nontoxic, biocompati- in blend nanofibers. Microporous PVA/chitosan scaffolds
ble, pH-sensitive hydrogel system with the potential ability were fabricated from nanofibers using a cryogenic grind-
to immobilize and absorb proteins can be obtained from ing method with subsequent compaction. Such multiscale
the blend of poly(N-vinylpyrrolidone) and carboxymethy- porous structures can be considered as matrices for tissue
lated chitosan. Blends can be prepared with electron beam engineering applications [132].
irradiation at room temperature [127]. The capacity of Chitosan can be blended with poly(ethylene oxide)
these gel membranes to adsorb bovine serum albumin (PEO). A chitosan/PEO blend was used to develop novel
was studied by varying the content of modified chitosan drug delivery systems with pH-sensitive swelling and drug
by static adsorption experiment at pH 7.4. It has been release properties for localized antibiotic delivery in the
shown that the carboxymethylated-chitosan molecules stomach [122,133]. It was found that freeze-dried chi-
were more hydrophilic than PVP molecules, and a large tosan/PEO semi-interpenetrating polymer network with
polar component of surface free energy was found [127]. a porous matrix has better swelling properties than the
Chitosan/PVP blends may possess high ion exchange capac- air-dried hydrogel. The blend could be useful for local-
ity and their applicability in direct methanol fuel cells has ized delivery of antibiotics in the acidic environment of
been highlighted in the literature [128]. the gastric fluid [133]. Blend membranes of chitosan/PEO
were developed for improved permeability and blood Chitosan can be blended with polymers which pos-
compatibility [134]. The equilibrium of hydration was sess electrical properties, such as conductivity. To meet
higher for chitosan/PEO blend membranes than for chi- electrical properties chitosan has been blended with a
tosan itself. An increase in the hydration of PEO highly polyaniline and as well as poly(acrylic acid) and the blends
porous blend membranes was due to intermolecular asso- have been studied as polyelectrolyte complexes [148,149].
ciations between PEO and chitosan chains. Membranes The conductivity of chitosan/PVA and chitosan/PVP has
based on the blends of chitosan/PEO appear to be bene- been studied by Abou-Aiad et al. [150]. The blends of
ficial in improving the permeability of toxic metabolites chitosan, polyvinyl alcohol and chitosan polyvinyl pyrroli-
and in reducing the thrombogenicity for haemodialysis done in dilute acetic acid were found to be compatible
[134]. by viscosity measurements. The dielectric behavior of
Chitosan can be blended with nylon 11 and thin films the investigated blends were studied using a frequency
can be prepared by the solution casting method [135]. response analyzer covering a frequency range from 102 to
Such blends can be used as a pervaporation membrane 106 Hz and in a wide range of temperatures. The permit-
for the separation of ethanol–water mixtures [136]. Chi- tivity ε′ was found to decrease with increasing frequency,
tosan can also be blended with polyacrylamide (PAAm) and showing an anomalous dispersion. The biological activi-
the formation of non-woven fibers without bead defects ties of chitosan/PVA and chitosan/PVP were tested against
by electrospinning of the above blend solutions has been a representative number of pathogenic organisms using
reported [137]. Another polymer which could be blended minimum inhibitory concentration method. The minimum
with chitosan is poly(lactic acid) PLA, a biodegradable and inhibitory concentration for both systems decreased on
resorbable polymer used widely in biomedical applica- increasing the amount of chitosan in the blends, i.e.,
tions. Biodegradable film blends can mainly be prepared increase in the biological activity. The conductive materials
by mixing the components in solution and film cast- based on the blends of chitosan with other polymers can be
ing [138]. The water vapor barrier of chitosan has been used in biomedical devices.
improved by blending it with a hydrophobic biodegradable Thermal properties of chitosan can be modified by
polymer. However, the mechanical properties of such blending it with thermally stable polymers. For this reason
blends are inferior to those of chitosan. The tensile chitosan and natural rubber latex blends were prepared
strength and elastic modulus of chitosan decreased with and thermal properties were studied [151]. The ther-
the addition of PLA. Interesting membranes can also mal behavior of chitosan/natural rubber latex blends has
be obtained from the blend of chitosan and polyhe- been studied by thermogravimetry and differential scan-
dral oligomeric silsesquioxane derivatives [139], as well ning calorimetry. The decomposition behavior of chitosan
as poly(caprolactone) [140,141]. Poly(caprolactone) PCL, changed with the addition of natural rubber latex. Although
a synthetic polymer, can be used together with chi- DSC studies revealed that the chitosan/rubber blends are
tosan for the preparation of several materials for medical thermodynamically incompatible, their thermal stability is
applications. The blends of chitosan with PCL have not better than chitosan. For the blend containing 15% chitosan
only been studied as a membrane but also as particles and 85% of a natural rubber latex the thermal stability was
[140,141]. Poly-(␧-caprolactone) particles were obtained better than for other compositions.
by an emulsion-diffusion-evaporation method using a Several papers have been published regarding the inter-
blend of poly(vinyl alcohol) and chitosan derivatives as sta- actions for both chitosan/collagen and chitosan/gelatine
bilizers. Chitosan hydrochloride and trimethyl chitosans blends [8,9,152–162]. However, as was mentioned earlier,
with varying degrees of quaternization have been used this review paper is focused on the blends of natural poly-
as chitosan derivatives [140]. Such cationic nanopar- mers with synthetic ones, so collagen/chitosan blends are
ticles can form stable complexes with DNA. It was not discussed here in detail except to note that the blending
found that the membrane of the blends of chitosan of collagen with chitosan gives the possibility of produc-
and poly(caprolactone) (50:50) showed better mechanical ing new “made to order” materials for potential biomedical
properties and support for cellular activity than chitosan applications [153,154].
[141]. Sometimes chitosan is blended not only with a syn- Attempts have also been made to study the ternary
thetic polymer but also with a third component. By mixing blends of chitosan/PVA/gelatin [163]. However, the inves-
chitosan and poly(caprolactone) with a third component (a tigations have been focused uniquely on the surface
whey-protein-isolate) an increase in the water vapor resis- properties of these blends. Chitosan has been blended
tivity of chitosan is observed [142]. Poly(ethylene glycol) with other proteins, such as soy protein and silk fibroin
is also a good synthetic polymer for blending with chi- [164–168]. However, again as blends of two natural poly-
tosan. A microporous chitosan membrane may be prepared mers these are not discussed in detail here. New materials
from such a blend [143]. Usually, the chitosan membrane is for potential biomedical applications can also be obtained
obtained by a solution casting technique using a common based on the blends of chitosan and starch [169,170].
solvent. Blends of chitosan with polyamide 6 and polylac- Starch/chitosan blend films have been prepared by electron
tide have been prepared by the solution casting technique beam irradiation of compression-molded starch-based
[144,145]. However, no significant interaction between mixture in a physical gel state at room temperature. The
chitosan and polylactide molecules has been found. These tensile strength and the flexibility of the starch film were
two components could be blended into a solid construct at improved after incorporation of 20% chitosan. After irra-
a partially miscible level depending on the blend composi- diation of such blends, antibacterial activity was induced,
tion [146,147]. even when the content of chitosan was only 5%, due to the
degradation of chitosan in blend films under the action mers have been published [190–209]. Polymer scaffolds
of irradiation [169]. Fibers of chitosan and starch, with can be made from blends of silk fibroin with synthetic poly-
salicylic acid as a model drug incorporated in different mers and/or another natural polymer. Materials made from
concentrations, were obtained by spinning the solution silk aimed at mimicking the structure and/or function of
through a viscose-type spinneret into a coagulating bath the native extracellular matrix, can be used as a compo-
containing aqueous tripolyphosphate and ethanol [170]. nent of biosensors, mainly sensors for glucose [190,191].
The diameter of the fibers was around 15 ␮m. The chi- Boschi et al. studied silk fibers coated by polypyrrole by
tosan/starch fiber can be potentially useful in drug delivery in situ oxidative polymerization from an aqueous solution
systems. The chitosan/starch fibers are sensitive to pH and of pyrrole [192]. They found that polypyrrole can com-
ionic strength [170]. pletely coat the surface of individual silk fibers. However,
Chitosan has been blended with several other polysac- the polymerization process occurred only at the fiber sur-
charides derived from plants such as cellulose [171,172], face (not in the bulk). The mechanical properties of silk
alginates [173–176], pullulan [177], dextran [178], and fibers were not altered upon polymerization of pyrrole
phosphatidylcholine [179]. [192]. Blends of silk fibroin and wool keratose have been
studied for nanofiber preparation [193]. The electrospun
7. Other natural polymers for potential blending wool keratose/silk fibroin blend nanofiber was prepared
with man-made polymers and evaluated as a heavy metal ion adsorbent which can
be used in the water purification field [193]. Some physical
Elastin is an extracellular matrix protein in mammals, interaction between silk fibroin and wool keratose has been
where it is the main component of skin, blood vessels, such identified. Silk fibroin has also been blended with Nylon-6
as the aorta, and lung tissues. The main amino acids in [194]. A strong interaction between Nylon-6 and silk fibroin
elastin are glycine, proline and alanine. Elastin has specific chains was observed, possibly as a result of the formation of
cross-linkages – desmosine and isodesmosine, which are hydrogen bonds between Nylon-6 and silk fibroin chains.
responsible for the formation of a three-dimensional net- The blends possessed improved thermal stability in com-
work with 60–70 amino acids between two cross-linking parison to single components. Another blend was obtained
points [180,181]. The presence of cross-linking ensures the from silk and polyurethane. Silk powders were blended
stability, elasticity and flexibility of elastin [132]. Elastin with a solution of commercially available biomedical grade
can provide an excellent basis for biomaterials, such as arte- segmented polyurethane (PU) to prepare elastic biofibers
rial prosthesis, dermal substitute and hydrogels [183–186]. by a wet-spinning process [195]. Superfine silk fibroin pow-
It is extremely difficult to blend elastin with synthetic poly- ders and PU were dispersed in dimethyl formamide and the
mers as it is a highly insoluble structural protein. To avoid dope solution exhibited good fiber formation in a warm dis-
the problem with solubility, elastin can be hydrolysed into tilled water coagulation bath. The superfine silk powder/PU
smaller chains (peptides, polypeptides) which are soluble blend fiber had a smooth surface, dense structure, and con-
in water making them more useful for biomedical applica- siderably high strength with a circular cross-section. The
tions. Elastin hydrolysates contain the same amino acids structure and morphology of such fibers has not been inves-
as elastin, with similar properties to the native protein, tigated. The silk-inspired biomedical polyurethane biofiber
and improve the biocompatibility of materials [187–189]. showed potential as a biomaterial for small-diameter arti-
The material made from only elastin hydrolysates is very ficial vascular scaffolds [195]. Fibers can also be made of
elastic, but low in strength. A good method for obtain- cellulose and silk fibroin at different compositions by alter-
ing new materials is a preparation of a blend containing ing the spinning conditions [196]. However, researchers
elastin hydrolysates and collagen [186,189]. It was shown experienced a phase separation in the whole blend compo-
that an elastin/collagen blend is less sensitive to UV irra- sitions. The mechanical properties of pure cellulose fibers
diation than elastin hydrolysates alone, and also that have been improved after blending with silk fibroin. Cel-
the surface of a collagen/elastin film is enriched in the lulose derivatives can also be mixed with silk fibroin.
less polar component – collagen. There is a lack of pub- Solutions of silk fibroin–sodium cellulose xanthate (vis-
lished work regarding blends of elastin and/or elastin cose) in aqueous NaOH, and silk fibroin–viscose–sodium
hydrolysates with synthetic polymers. The presence of N-acetylchitosan salt (alkaline chitin) in aqueous NaOH
elastin hydrolysates in a blend with synthetic polymers can were spun at room temperature to obtain cellulose–silk
lead to an increase of biocompatibility and can improve fibroin filaments [197]. A membrane can be obtained by
elasticity. It can be anticipated that research on the blends coagulating the solution of cellulose and silk fibroin in
of elastin with man-made polymers will develop in near cuoxam with acetone–acetic acid in basic aqueous solu-
future. tion [198]. A strong hydrogen bond interaction between
Silk fibroin has been used as biomaterial for decades. cellulose and silk fibroin in such a membrane has been
Natural fibroin comprises repeat sequences of alanine and found [199]. Silk can be blended with carboxymethyl ker-
glycine that readily form the ␤-sheet crystals responsi- ateine [200]. The physical state of water, absorbed in silk
ble for the mechanical properties of silk. Silk fibroin can fibroin/S-carboxymethyl kerateine blend films was stud-
be processed into films and scaffolds to improve tissue ied by differential scanning calorimetry and it was shown
regeneration in skin, nerve, bone and cartilage. Blending that the amount of non-freezing bound water in the blend
the natural fibroin with the less expensive synthetic poly- film was decreased with the addition of carboxymethyl ker-
mers is one approach to reduce the cost of materials, and ateine because of the change in the secondary structure of
many papers regarding blends of silk with synthetic poly- silk fibroin from random coil to a ␤-structure form. The
maximum change of the secondary structure was observed films; one film was dissolved in formic acid and recast as a
at a blend ratio of 50/50 (w/w). film [212]. Turbidity measurements showed that the ker-
The electrospinning technique uses several different atin, dissolved in formic acid formed transparent and stable
solvents, for example, to fabricate biomimetic nanostruc- solutions and that flocculation did not develop. Keratins
tured scaffolds for tissue engineering the electrospinning of are the major structural proteins of vertebrate epidermis,
chitin/silk fibroin blend solutions in 1,1,1,3,3,3-hexafluoro- constituting up to 85% of fully differentiated keratinocytes.
2-propanol was investigated [201]. Chitin and silk fibroin Keratins form keratin intermediate filaments, heteropoly-
were immiscible in this solvent. The average diameters of mers comprised of two types of keratin species, type I
chitin/silk fibroin blend fibers decreased with the increase keratins and type II keratin. Keratin like many other pro-
in chitin content in the blend compositions. The nanofi- teins can be damaged by the exposition to ultraviolet and
brous matrix made from a chitin/silk fibroin blend can visible radiation [213,214]. It has been found that chronic
be considered as a potential candidate for tissue engi- UVB exposure significantly reduced the elasticity of epi-
neering scaffolds with excellent cell attachment properties dermis, induced the formation of wrinkles and disrupted
[201,202]. Another material for biomedical application the ultrastructure of keratin. A possible mechanism for the
can be produced as a film by mixing chitosan and silk formation of cysteine, cysteic acid and partially oxidized
fibroin [203]. Attempts have been made to produce a blend cysteine species in keratin following exposure to UVC radi-
membrane of PVA and regenerated silk fibroin [204]. The ation at 254 nm was proposed [213]. In wool keratin after
addition of poly(ethylene glycol) in the blend solution exposure to UV radiation both a change in color and weak-
increases the porosity of the membranes. Such blends are ening of the fiber were observed [214].
considered for immobilization of enzymes. A series of blend Tanabe et al. found that one can obtain chemically
films of silk fibroin with nylon 66 can be obtained by the crosslinked films from keratin [215]. Keratin can be
common solution cast method [205]. However, the mis- blended with synthetic polymers, such as poly(ethylene
cibility of these components was not clearly evaluated. oxide) [216,217], or with biopolymers such as silk fibroin
Filaments can be prepared by the wet spinning process and chitosan [193,218]. A keratin/chitosan composite film
from a silk fibroin/PVA blend [206]. Due to the miscibility of was prepared by casting from an acetic acid solution of
the components in formic acid, the filament had a smooth these biopolymers. The mechanical properties of keratin
surface and dense structure with a circular cross-section. film are adjustable by appropriately adding chitosan and
Porous gels can be obtained from silk fibroin/PVA aqueous glycerol. Although keratin film is very fragile without any
mixtures by freeze- or air-drying [207]. The freeze-dried additive, the addition of 10–30 wt% of chitosan gave a
gels had a characteristic porous structure potentially useful strong, flexible film. The composite film supported fibro-
as a cell culture substrate. Silk fibroin blended with polox- blast attachment and proliferation, demonstrating this to
amer 407 macromer has been considered as a matrix for be a good substrate for mammalian cell culture [218].
wound dressing [208]. Soluble keratin and/or keratin hydrolysates can be easily
Chitosan/silk fibroin blend films containing nanoparti- blended in the same solvent and then thin films can be
cles of methoxy poly(ethylene glycol)-b-poly(dl-lactide) prepared by evaporating the solvent. Such thin films can be
were prepared by film casting of nanoparticle used as a biomaterial as well as a material for the covering
suspension–chitosan/silk blend solution [209]. Inter- of other materials made of synthetic polymers. Keratin as a
molecular bonds between nanoparticles and chitosan/silk waste material is relatively inexpensive and the application
fibroin film matrices were observed in the nanocomposite of this biopolymer in the medical field may reduce the cost
obtained. An increase in film strength and a decrease in of new biomedical materials. However, purification of ker-
film flexibility and wettability were observed. Nanocom- atin waste to meet biomedical requirements may generate
posites based on the blends of silk with other polymers additional costs, which in fact could add to the cost of final
have been developed recently and further developments products. Nevertheless, given the abundance of keratin, an
in such materials may be anticipated. increasing interest in using keratin in the preparation of
Keratin is one of the most abundant proteins in the blends with synthetic polymers may be anticipated in near
animal population. It is the major component of hair, feath- future.
ers, nails and horns of mammals, reptiles and birds. As a
waste material keratin should be very cheap source for 8. Blends of natural and synthetic polymers as a
many applications. This fibrous protein is composed of sev- matrix for micro- and nanoparticles incorporation
eral repeating sequences of amino acids along its chain.
The sequence of amino acids defines the possibility of Biological materials very often contain inorganic
intermolecular links and the access of amino acids to the nanoparticles. The ‘hard’ phases are strengthened primar-
chemical reaction. The presence of cysteine (amino acid ily by minerals, which nucleate and grow in a biomediated
containing sulfur) in the keratin chain leads to charac- environment that determines the size, shape and distri-
teristic inter and intramolecular disulphide bonds which bution of individual crystals. The most important mineral
determine the properties of keratin. From the point of view phases include hydroxyapatite, silica, and aragonite [220].
of polymer science, keratin is a biopolymer that is insoluble Although characteristic of materials in the living body, it is
in water and common solvent [210,211]. Many attempts not easy to mimic this self-organization in the laboratory.
have been made to produce soluble keratin. In one such However, several laboratories are working on the devel-
study a solution of keratin in an alkaline solution contain- opment of new materials based on the blends of two or
ing urea was dialyzed against water, and then cast into more polymers and inorganic nanoparticles. New materi-
als based on the blends of two polymers or biopolymers eral papers report consistent conclusions that collagen and
which contain nanoparticles can be used as an implant in chitosan form miscible blends [8,9,15,39,58,152,154,157].
the context of both hard and soft tissues. Nano-structured In the Scopus® database one can find that about 800
materials can be achieved by the intercalation of inor- papers have been published up to this time regarding mate-
ganic nanoparticles in a polymeric matrix. However, it is rials based on the blends of chitosan with other polymers.
extremely difficult to connect nanoparticles with natu- About 50% of those papers concern blends of chitosan
ral polymers, as many of them are insoluble [221,222]. with synthetic polymers. It seems that it is much eas-
As noted above, in many projects insoluble natural poly- ier to compare results obtained in the field of chitosan
mers such as collagen, elastin, chitosan, keratin and silk blends with synthetic polymers than collagen blends, as
have been converted to soluble derivatives by chemical and many research groups work with polysaccharide blends.
enzymatic hydrolysis. The hydrolysed proteins, after char- The results reported by Naveen Kumar et al. [231] showed,
acterization, can be used to design polymeric matrix for the that chitosan and PVA were miscible in both diluted solu-
incorporation of an inorganic phase. tion as well as in solid state. Similar results were obtained
Several papers have been published so far in the area by He et al. [232] and by Wanchoo et al. [233]. How-
of biomaterials based on the blends of natural polymers ever, detailed results reported by Lewandowska reported
and synthetic polymers containing inorganic nanoparticles that chitosan and PVA are poorly miscible in the solid
[222–229]. It was found that the biocomposites of HAp state [234]. Jawalkar et al. [235] used molecular modeling
with PVA and collagen exhibited relatively high elastic- strategies to understand interaction between chitosan and
ity especially upon cryogenic treatment. The incorporation PVA. Molecular dynamic simulations showed that inter-
of the collagen into the PVA/HAp biocomposite provided action between these two polymers are very probable
internal porosity to the biocomposite with the pores in and tentatively identified the atoms and groups involved
the 50–100 nm range for collagen/HAp and 50–500 nm in these interactions. The discrepancies between research
for the collagen/HAp/PVA [228]. For bone repair and groups are probably caused by a differences in the polymer
replacement, novel hydroxyapatite/chitosan/silk fibroin molecular weight and the deacetylation degree of chitosan.
composites were prepared by a coprecipitation method. Interaction between chitosan and PVP has been studied by
The HAp crystallites were found to be needle-like in shape many research groups. The miscibility between chitosan
with a typical size of 20–50 nm in length and around 10 nm and PVP was reported by Sakurai et al. in a thin film [123]
in width. The composite exhibited a higher compressive and by Wanchoo et al. in dilute solution [233]. Marsano
strength than the precipitated HAp without any organic et al. reported that the interaction between chitosan and
source involved, which was closely related to the perfect PVP in the solid state was evident, but in solution it was
incorporation of chitosan and silk fibroin macromolecules too small to allow a prediction of miscibility to be made
into the composite [229]. [10]. Similar results were reported by Nikonovich et al.
We can expect that in the near future several new mate- [236]. Yilmaz et al. [237] reported that miscibility between
rials will be designed based on nanoparticles in blends of chitosan and PVP depended on the molecular weight of
natural and synthetic polymers. PVP. This is probably the main reason why results reported
by different research groups are sometimes inconsistent.
9. Critical comparison of the existing knowledge in Yin et al. [238] reported that molecular dynamic simula-
the field of bioartificial blends tion using Flory–Huggins theory had shown miscibility of
chitosan and PVP for blends containing more than 50% of
Although there are many papers regarding blends of chitosan.
collagen, chitosan, silk, keratin with synthetic polymers, it Although starch blends with synthetic polymers are not
is hard to compare results obtained by different research a specific aim of this review it is worth mentioning that
groups. According to the Scopus® database about 300 there are several papers regarding such materials. There
papers have been published so far regarding materials are also several research groups working on bioartificial
based on the blends of collagen with other polymers. blends of this kind. According to the Scopus® database
However, only about 25% of these papers concern blends about 1600 papers have been published so far regarding
of collagen with synthetic polymers. Existing knowledge materials based on blends of starch with other polymers.
on the blending of collagen with synthetic polymers is More than 50% of these papers concern blends of starch
rather consistent, and several research groups report simi- with synthetic polymers. Miscibility between starch and
lar results concerning the interaction between these two synthetic polymers depends on the type of starch used and
polymers. Immiscibility of PVA and collagen has been on many other parameters [239–241]. Starch based bioar-
shown by Sarti et al. [54], Sionkowska et al. [12,34,153] and tificial blends and their potential applications have been
Barbani et al. [33]. However, the interaction and miscibility widely studied by Reis et al. [242–244]. The large number of
between PVA and hydrolysed collagen as well as compat- papers regarding starch based bioartificial blends may sug-
ibility were reported by Crovoi and Vasile [230]. The lack gest that another review paper regarding miscibility and
of interaction and immiscibility for collagen/poly(ethylene properties of starch based bioartificial blend would be nec-
glycol) as well as collagen/poly(ethylene oxide) was essary. A review article concerning advances in polymer
reported by Sionkowska [81,82]. For collagen/PVP blends blends and composites from renewable resources and their
interactions on the molecular level in solution and mis- potential applications was published by Yu et al. [245]; this
cibility were reported by Sionkowska et al. [7,34,83], but review did not include blends based on collagen and syn-
there are no further scientific reports on this matter. Sev- thetic polymers. The authors reported that various blends
and composites have been developed over the last decade [10] Marsano E, Vicini S, Skopinska J, Sionkowska A. Chitosan and
in order to overcome disadvantages such as poor mechan- poly(vinyl pyrrolidone): compatibility and miscibility of blends.
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Current Research On The Blends of Natura

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Progress in Polymer Science 36 (2011) 1254–1276

Contents lists available at ScienceDirect

Progress in Polymer Science

Current research on the blends of natural and synthetic polymers

Polymeric materials are widely applied in the biomed-

synthetic polymers. After preparing the two component is:

X2 (collagen) X3 (synthetic) b coll/PVP b coll/PVA b coll/PEO b coll/PEG

affect the biological function can be performed in sev- CH2 CH CH CH 2

PVP + 1% collagen 39,1 58,6 Collagen not cross-linked 308.99 62.43

components of surface free energy show that PVP films are

Time of UV [h] PVP PVP + 1% coll PVP + 3% coll PVP + 5% coll

0 40.44 5.87 32.74 4.92 29.60 5.27 31.99 3.97

Fig. 5. Structure of chitin and chitosan. Scheme of deacetylation process of chitin.

Fig. 6. Example of covalent crosslinking of chitosan using glutaraldehyde.

Chitosan 0 27.2 21.8 5.4

CH2OH In several research papers it is shown that chitosan and

of vinyl acetate to acetic aqueous solutions with different

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