Tetrahydrofuran (co)polymers as potential materials for vascular prostheses

Polyethers were studied as potential materials for vascular prostheses. By crosslinking poly(tetramethylene oxide) (PTMO) with poly(ethylene oxide) (PEO), hydrophilic networks were obtained containing PTMO as well as PEO. Attempts were made to reduce the crystallinity and melting point of PTMO because of the required elastomeric behaviour at body temperature. Compared to non-crosslinked PTMO, crosslinking in the melt resulted in a decrease in the melting point from 43·7 to 38·7°C and a decrease of the crystallinity from 46 to 28%. By copolymerizing tetrahydrofuran with oxetane or dimethyloxetane, melting points below 38°C were obtained, together with crystallinities lower than 20%

Iron(III)-chelating resins X. Iron detoxification of human plasma with iron(III)-chelating resins

Iron detoxification of human blood plasma was studied with resins containing desferrioxamine B (DFO) or 3-hydroxy-2-methyl-4(1H)-pyridinone (HMP) as iron(III)-chelating groups. The behaviour of four resins was investigated: DFO-Sepharose, HMP-Sepharose and crosslinked copolymers of 1-(ß-acrylamidoethyl)-3-hydroxy-2-methyl-4(1H)-pyridinone (AHMP) with 2-hydroxyethyl methacrylate (HEMA) and of AHMP with N,N-dimethylacrylamide (DMAA). The efficiency of iron detoxification of plasma of the resins was mainly dependent on the affinity of the ligands and the hydrophilicity of the resins. The results of a stability study in phosphate-buffered saline at a physiological pH indicated that AHMP-DMAA was the most stable resin, whereas the Sepharose gels had a relatively lower stability. Experiments with the AHMP-DMAA resin showed that the resin was able to remove iron from plasma with different iron contents, and from plasma poisoned with FeCl3, iron(III) citrate or transferrin. A rapid removal from free serum iron was observed, whereas iron from transferrin was removed slowly afterwards. Only the overload iron was removed since in all cases the normal serum iron level of ca. 1 ppm was obtained

Platelet deposition studies on copolyether urethanes modified with poly(ethylene oxide)

Pellethane ® 2363 80A films and tubings were chemically modified and the effect of these modifications on platelet deposition was studied. Grafting of high molecular weight poly(ethylene oxide) and graft polymerization of methoxy poly(ethylene glycol) 400 methacrylate resulted in surfaces with a good water wettability. The increased hydrophilicity of these modified surfaces could be demonstrated by contact angle measurements. The platelet deposition was investigated with tubings in a capillary flow system, using different types of perfusates. Platelet deposition from a buffer-containing perfusate on surfaces modified with either high molecular weight poly(ethylene oxide) or methoxy poly(ethylene glycol) 400 methacrylate was almost absent and less than on Pellethane 2363 80A. Using a citrated plasmacontaining perfusate the amount of deposited platelets on Pellethane 2363 80A modified with high molecular weight poly(ethylene oxide) was low and about the same as on unmodified surfaces. However, a marked reduced platelet deposition compared to unmodified Pellethane 2363 80A was found when the platelets were activated by Ca2+ ionophore. The improved blood compatibility of the modified Pellethane 2363 80A tubings obviously indicates the favourable effect of the presence of grafted PEO on the surface

In vivo testing of crosslinked polyethers. II. Weight loss, IR analysis, and swelling behavior after implantation

As reported in Part I (In vivo testing of crosslinked polyethers. I. Tissue reactions and biodegradation, J. Biomed. Mater. Res., this issue, pp. 307-320), microscopical evaluation after implantation of crosslinked (co)polyethers in rats showed differences in the rate of biodegradation, depending on the presence of tertiary hydrogen atoms in the main chain and the hydrophilicity of the polyether system. In this article (Part II) the biostability will be discussed in terms of weight loss, the swelling behavior, and changes in the chemical structure of the crosslinked polyethers after implantation. The biostability increased in the order poly(POx) < poly(THF-co-OX) < poly(THF) for the relatively hydrophobic polyethers. This confirmed our hypothesis that the absence of tertiary hydrogen atoms would improve the biostability. On the other hand, signs of biodegradation were observed for all polyether system studied. Infrared surface analysis showed that biodegradation was triggered by oxidative attack on the polymeric chain, leading to the formation of carboxylic ester and acid groups. It also was found that in the THF-based (co)polyethers, α-methylene groups were more sensitive than β-methylene groups. For a hydrophilic poly(THF)/PEO blend, an increase in surface PEO content was found, which might be due to preferential degradation of the PEO domains

Iron(III) chelating resins-IV. Crosslinked copolymer beads of 1-(B-acrylamidoethyl)-3-hydroxy-2-methyl-4(1H)-pyridinone (AHMP) with 2-hydroxyethyl methacrylate (HEMA)

Iron(III) chelating beads have been synthesized by copolymerization of 1-(ß-acrylamidoethyl)-3-hydroxy-2-methyl-4(IH)-pyridinone (AHMP) with 2-hydroxyethyl methacrylate (HEMA), and ethyleneglycol dimethacrylate (EGDMA) as the crosslinking agent. The synthesis of the AHMP-HEMA beads was performed by suspension polymerization of AHMP, HEMA and EGDMA in benzyl alchol¿20% aqueous NaCl solution using 2,2¿-azobisisobutyronitrile (AIBN) as the initiator and polyvinylalcohol (40¿88) as a suspending agent.\ud \ud The crosslinked copolymer beads were characterized by IR, and the AHMP content was determined by elemental analysis. The AHMP-HEMA beads were not too hydrophilic, and the copolymers absorbed at equilibrium only 40¿50% water. It was found that the copolymer beads were very stable at 25°, but some degradation was observed at 121°.\ud \ud The AHMP-HEMA copolymers were able to chelate iron(III) and the chelation was dependent on the conditions such as pH and temperature. However, the capacities towards iron(III) chelation were always found to be much lower than the calculated values. The influence of the polymeric matrix on the iron(III) chelating ability was studied with iron(III) chelating resins containing various polymeric matrices. It was found that the iron(III) chelating efficiencies of the resins were strongly affected by their hydrophilicities. The low chelating efficiency of the AHMP-HEMA beads (0¿40%) is probably due to their poor swelling in water

Synthetic polymers with anticoagulant activity

Polymers with C=C bonds have been modified by reaction with chlorosulfonyl isocyanate (CSI). Addition products were obtained in yields varying from 60% to 75%. Reaction of these products with NaOH yielded polyelectrolytes with sulfamate and carboxylate groups, whereas from the reaction with NH4OH polyelectrolytes with sulfamate and carbonamide groups, were obtained. The polyelectrolytes showed anticoagulant activity depending on the structure and on the presence of both sulfamate and carboxylate groups. These groups are essential for the anticoagulant activity, because N-S bond cleavage in the sulfamate groups as well as substitution of carboxylate by carbonamide groups resulted in loss of activity. From the recalcification times of bovine plasma, it could be concluded that the most active polyelectrolyte had an activity of 6-7% compared with heparin. However, determination of the activated clotting time of blood from rabbits showed that this compound had an in vivo activity of 50% in comparison with heparin

Mechanical properties and chemical stability of pivalolactone-based poly(ether ester)s

The processing, mechanical and chemical properties of poly(ether ester)s, prepared from pivalolactone (PVL), 1,4-butanediol (4G) and dimethyl terephthalate (DMT), were studied. The poly(ether ester)s could easily be processed by injection moulding, owing to their favourable rheological and thermal properties. The tensile response of a poly(ether ester) with a butylene terephthalate (4GT) content of 72 mol%, which exhibited the phenomena of necking and strain-hardening, was related to the morphology of these copolymers. The influence of the short 4G-PVL segments was reflected in a high Young's modulus and yield stress, and resulted in a tough behaviour for the poly(ether ester), with an ultimate elongation of 500%. The poly(ether ester)s were stable towards treatment at room temperature with water or weakly acidic or alkaline solutions. Conditioning at 90°C in water for 264 h resulted in a water uptake of 1 wt%, whereas the rate of hydrolysis was 0.0003 (expressed in An rel h-1) for the poly(ether ester) with a 4GT content of 72 mol%. Although a decay in the mechanical properties for the PVL-based poly(ether ester) after exposure to water at 90°C was observed, these materials were assumed to have a higher hydrolytical stability than other poly(ether ester)

Antithrombin activity of a polyelectrolyte synthesized from cis-1,4-polyisoprene

A polyelectrolyte synthesized from cis-1,4-polyisoprene, containing aminosulfonate and carboxylate groups was shown to have an anticoagulant activity of about 1/30 compared with heparin. Because the substance prevents the coagulation of plasma in the presence of thrombin it is assumed that it acts as an antithrombin

Synthetic heparinoids labelled with 125I and 35S

The labelling of a water-soluble synthetic polyelectrolyte, having anticoagulant activity, has been studied. The polyelectrolyte is derived from cis-1,4-polyisoprene and contains N-sulfate and carboxylate groups. [125I]-Iodination of the polyelectrolyte, using the Chloramine-T method and an electrolytic method, resulted in a [125I]-labelled polyelectrolyte from which release of the label occurred. Resulfation of a partially desulfated polyelectrolyte with a [35S]-sulfur trioxide trimethylamine complex resulted in a [35S]-labelled polyelectrolyte which showed no release of the label