Medical applications degradation

There are two principal ways by which polymer chains can be hydrolyzed, passively by chemical hydrolysis or actively by enzymatic reaction. The latter method is most important for naturally occurring polymers such as polysaccharides and polyfhydroxy alkanoate)s, e.g., polyhydroxybutyrate and polyhydroxyvaler-ate [121,125]. Many synthetic aliphatic polyesters utilized in medical applications degrade mainly by pure hydrolysis [121]. 

Engelberg I and Kohn J. Physio-mechanical properties of degradable pol3miers used in medical applications A comparative study. Biomaterials, 1991, 12, 292-304. 

Biodegradable polyurethanes have been proposed and studied before (9-72). The difference in our study is the inclusion of a phosphoester linkage instead of the commonly used polyester component. This seems to provide more flexibility as the side chain of the phosphate or phosphonate can be varied. For controlled drug delivery applications, drugs can be linked to this site to form a pendant delivery system. Moreover, for certain medical applications, fast degradation rate is obtainable by the introduction of these hydrolyzable phosphoester bonds. With the LDI based polyurethanes, drugs or other compounds of interest can also be coupled to the ester side chain of the lysine portion. 

In situations where inappropriate clot formation results in the blockage of a blood vessel, the tissue damage that ensues depends, to a point, upon how long the clot blocks blood flow. Rapid removal of the clot can often minimize the severity of tissue damage. Thus, several thrombolytic (clot-degrading) agents have found medical application (Table 12.5). The market for an effective thrombolytic agent is substantial. In the USA alone, it is estimated that 1.5 million people suffer acute myocardial infarction each year, and there are another 0.5 million suffer strokes. 

In dentistry, silicones are primarily used as dental-impression materials where chemical- and bioinertness are critical, and, thus, thoroughly evaluated.546 The development of a method for the detection of antibodies to silicones has been reviewed,547 as the search for novel silicone biomaterials continues. Thus, aromatic polyamide-silicone resins have been reviewed as a new class of biomaterials.548 In a short review, the comparison of silicones with their major competitor in biomaterials, polyurethanes, has been conducted.549 But silicones are also used in the modification of polyurethanes and other polymers via co-polymerization, formation of IPNs, blending, or functionalization by grafting, affecting both bulk and surface characteristics of the materials, as discussed in the recent reviews.550-552 A number of papers deal specifically with surface modification of silicones for medical applications, as described in a recent reference.555 The role of silicones in biodegradable polyurethane co-polymers,554 and in other hydrolytically degradable co-polymers,555 was recently studied. 

More recently, polyesters with beneficial degradation products (salicylic acid) have been produced to promote healing through enhanced regeneration of tissue [10]. Degradation mechanisms relevant to medical applications include... 

Polyethylene oxide) (PEO) is a semicrystalline water-soluble polymer [64, 65], with a crystallinity that is very sensitive to the thermal history of the sample, making this property interesting as an indicator of degradation. Because it is biodegradable and biocompatible, PEO is a good candidate for environmental and medical applications [66-68]. The mechanisms of thermo- and photo-oxidation of PEO have already been investigated [69, 70] on the basis of IR identification of the oxidation products and are summarized in Scheme 10.1. 

Engelberg, I., and Kohn, J. "Physicomechanical properties of degradable polymers used in medical applications - a comparative-study". Biomaterials 12(3), 292-304 (1991). 

The second method is azeotropic condensation polymerization of lactic acid, which produces high-molecular weight PLA without using chain-extenders or esterification-promoting adjuvants. This type of polymerization needs high reaction rates and thus uses catalysts however, due to the use of catalysts, the PLA produced by this method is not suitable for some applications, such as medical, since any residual catalyst offers toxicity within the polymer, which is harmful for medical applications. In addition to toxicity, residual catalyst degrades PLA in further processing (39). On the other hand, the level of residual catalyst can be reduced with the use of sulphuric acid (55,56). 

Biodegradable polymers have some - however very few - useful applications wherever the degradation is an essential part of the products function (e.g. in certain medical applications, as collection bags for humid biowaste, whereever used plastic bags and bottles end up in the sea, etc.). 

At the time of writing, the applications of biodegradable polymers are confined mostly to the field of agriculture, where they are used in products with limited lifetimes, such as mulch films and pellets for the controlled release of herbicides. The synthetic polyesters used in medical applications, principally polylactide and poly(lactide-co-glycolide), while claimed to be biodegradable, are degraded in the body mainly, if not entirely, by chemical hydrolysis. There is little evidence that the hydrolysis of these polyesters of a-hydroxyacids can be catalyzed by hydrolase or depolymerase enzymes. 

Among the many classes of polymeric materials now available for use as biomaterials, non-degradable, hydrophobic polymers are the most widely used. Silicone, polyethylene, polyurethanes, PMMA, and EVAc account for the majority of polymeric materials currently used in clinical applications. Consider, for example, the medical applications listed in Table A.l most of these applications require a polymer that does not change substantially during the period of use. This chapter describes some of the most commonly used non-degradable polymers that are used as biomaterials, with an emphasis on their use in drug delivery systems. 

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