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              Biomaterials, Synthetic Synthesis, Fabrication, and Applications                            181

              polymer molecules onto the substrate polymer surface. A  as amides, enamines, enol-ketones, esters, ureas, and ure-
              terminal group reactive to functional groups present on  thaneswhenpresentinpolymersallshowsomebiodegrad-
              the substrate polymer surface is required for the poly-  ability.
              mer chains to be used in the coupling reaction, while  Materials being developed include lactide/glycolide
              the graft polymerization method needs active species on  polymers,  polyorthoesters,  derivatives  of  pseudo-
              the substrate polymer to initiate radical polymerization.  and poly-amino acids such as poly(l-glutamate),
              An apparently grafted surface can also be produced by  polyphosphazenes, poly(∈-caprolactone) and tyrosine–
              physical adsorption of existing polymers. The adsorbed  polycarbonates. Advantages of these materials lies in
              chains are readily desorbed upon immersion in solvents  their ease of processability and their biocompatibility
              or washing with surfactants unless the adsorptive force  with extracellular matrix components present in the body.
              is remarkably strong. Polyethyleneoxide (PEO) has been  They may be made as high surface area, porous devices
              used to modify artificial surfaces by the above chemical  thereby allowing cell movement and adhesion within the
              surface modification methods with the establishment of  device both important for the assimilation of the material
              PEO-surface and PEO-interpenetrating networks. An al-  within the body and in the eventual replacement of the
              ternative simple and cost-effective approach is to use the  biodegradable component with the bodies own tissue.
              meltblendtechniquewheresmallamountsofproteincom-    Future applications of degradable polymers may in-
              patible additives, such as PEO, polyvinyl alcohol (PVA),  volve their use in a foam form as scaffolds for the regen-
              poly(ethyl oxazoline) (PEOX), and poly(vinyl pyrroli-  eration of specific tissues such as liver, bone, cartilage, or
              dine) (PNVP) have been used to modify the substrate  vascular walls.
              polymer. The base polymer could be a single polymer
              or mixture of ethylene–vinyl acetate (EVA), polypropy-  B. Polymers from Natural Sources
              lene (PP), glycol modified poly(ethylene terephthalate)
              (PETG), poly(methylmethacrylate) (PMMA), styrene–  In the search for biocompatible materials scientists
              butadiene copolymer and polyamide-based copolymers.  have taken naturally occurring polymers and modifed the
              Materials modified by these techniques can show en-  structure of the materials for a range of end uses. Materials
              hanced protein adhesion important for general biocompat-  based on collagen and hyaluronic acid are in common
              ibility or show reduced protein adsorption which is useful  use for both dental, ophthalmological and maxillofacial
              in the production of blood-contacting devices, chromato-  reconstructive work where the “natural” polymer phase
              graphic supports, coatings to minimize biofouling, sepa-  is used to fill out defects in the bone thereby providing
              ration membranes, contact lenses, immunoassays, protein  a matrix around which bone will develop. Collagen is
              drug-contacting materials, etc.                   used in film, membrane, solution, gel, and sponge forms.
                                                                It is also used in conjunction with glucosaminoglycans,
                                                                tricalcium phosphate, hydroxyapatite, allogeneic bone,
                3. Biodegradable Polymers
                                                                cells, and with drugs such as tetracycline.
              Although there are many medical applications for poly-  Most implant procedures where collagen has been used
              mers which require materials to be stable over a long time  have required the implant to be a permanent feature in the
              period, there are also devices such as sutures, small bone  human body. The “collagen” used was usually partially
              fixation devices, skin grafts, and drug delivery systems  degraded, enzyme-extracted collagen, or had been stabi-
              where polymers that break down in a controlled fashion  lized by cross-linking it with cytotoxic glutaraldehyde or
              are required. Materials that can be tailored to break down  chromium salts, or else had been assembled into non-
              either unaided or by enzyme-assisted pathways under the  natural polymeric structures such as films and sponges.
              conditions inherent in the location where the implant is  An alternative approach is to maintain as much of the bio-
              found are desired.                                logical and organizational structure of collagen as possible
                Two main factors affect the biodegradability of poly-  using continuous collagen threads to make collagen fibers
              mers. The first is the chemical composition of the ma-  which can then be used to knit and weave fabrics with a
              terial and the presence of hydrolysable and/or oxidizable  structure more akin to that found naturally. Many differ-
              chemical groups in the main chain, suitable substituents in  ent materials have been fabricated each with different bulk
              side chains, stereoconfiguration, balance of hydrophilicity  and extensibility properties.
              andhydrophobicity,andconformationalflexibilityallcon-  Materials derived from hyaluronic acid are convention-
              tribute to the biodegradability of synthetic polymers. The  ally esterified (either 100% or fractional amounts) and
              second aspect is the morphology of the polymer sample  the acid esters so produced have physicochemical prop-
              with amorphous polymer regions degrading prior to crys-  erties which are significantly different from those of the
              talline and cross-linked regions. Functional groups such  parent molecule. Ethylhyaluronic acid ester (HYAFF-07)
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