Clotting Phenomena at the Blood-Polymer Interface and Development of Blood Compatible Polymeric Surfaces

In the past two decades many attempts have been made to relate surface and interfacial parameters with the blood compatibility of polymeric surfaces. It is however doubtful if by a single parameter the behaviour of blood on a surface can be predicted. Two major aspects of blood compatibility - the prevention of platelet adhesion and the deactivation of the intrinsic coagulation system are determined by the measure and nature of competitive blood protein adsorption on the foreign surface. The adhesion of blood platelets is promoted by adsorbed fibrinogen and gamma globulin, while adsorbed albumin inhibits platelet adhesion. Heparinised surfaces do not adsorb fibrin and consequently no adhesion of platelets takes place. Other surfaces with low platelet adhesion are the hydrogels, certain block copolyetherurethanes, polyelectrolyte complexes and biolised proteins. Heparinised surfaces of the cationically bonded type inhibit the intrinsic coagulation as well, however this may be due to unstable coatings and heparin leakage. \ud In the authors laboratory a synthetic heparinoid was prepared with the structure - [CH2 - C(CH3 NHSO3 Na - C(H) COONa - CH2 -]x with Mw = (7.5 /pm 1.0) × 105 and an in vivo anticoagulant activity of 50% of heparin. Its coatings on PVC, using tridodecylmethyl-ammonium chloride as a coupling agent, are stable in plasma and salt solutions and provide surfaces which show negligible platelet adhesion and a strong inhibition of the intrinsic coagulation on contact with blood. Similar results were found with polydimethylsiloxane surfaces coated with this heparinoid

A route to anionic hydrophilic films of copolymers of l-leucine, l-aspartic acid and l-aspartic acid esters

A series of copolymers of l-leucine and β-benzyl-l-aspartate [Leu/Asp(OBz)] covering the range 30–70 mol % of l-leucine, was synthesized by the N-carboxyanhydride (NCA) method. The copolymers were characterized by elemental analysis, infra-red spectroscopy and viscometry. For all compositions high molecular weight copolymers were prepared with excellent film-forming properties. Tercopolymers of l-leucine, β-benzyl-l-aspartate and β-methyl-l-aspartate [Leu/Asp(OBz)/Asp(OMe)] were obtained after an ester interchange reaction (conversion 85–95%) with the original copolymer systems. These tercopolymers were characterized by elemental analysis and i.r. spectroscopy. Films of the tercopolymers, cast from organic solvents, could be converted into hydrophilic films by saponification of the methyl ester groups using alkaline water/organic solvent media. The hydrophilic films, which will be further investigated for their use as haemodialysis membranes were characterized by potentiometric titration and i.r. spectroscopy

Uptake of tridodecylmethylammonium chloride by PVC

The uptake of tridodecylmethylammonium chloride (TDMAC) by poly(vinyl chloride) has been investigated to provide a more quantitative basis for the preparation of blood-compatible surfaces based on TDMAC-heparin coatings. Sorption isotherms of TDMAC from toluene-cyclohexane and toluene-methanol mixtures have been measured. In toluene-cyclohexane mixtures, the TDMAC uptake is proportional to the degree of swelling of the polymer. From ion-exchange experiments with 36Cl-, it appears that only a small fraction of the TDMAC remains near the PVC surface to provide the heparin binding capacity. Methanol forms a strong H-bonded complex with TDMAC in toluence and prevents its sorption by PVC

Investigations on vinylene carbonate. IV. Radiation induced graft copolymerization of vinylene carbonate and N-vinyl-N-methylacetamide onto polyethylene films

Graft copolymerization of binary mixtures of vinylene carbonate (VCA) and N-vinyl-N-methylacetamide (VIMA) onto low density polyethylene (LDPE) films was studied by the mutual γ-irradiation technique. Sufficient amounts of functionally active VCA groups could be grafted onto the surface and the hydrophilicity of the surface was also improved. The grafting of VCA onto polyethylene films in the binary solutions was found to be promoted by the presence of VIMA, thus showing a positive synergism. The VCA content in the graft copolymers was always higher than in the copolymers obtained by homogeneous copolymerization using the same monomer feed composition. The monomer reactivity ratios, as well as a preferential partitioning of the monomers surrounding the polymeric substrate, were considered to explain the grafting reactions in the binary systems

Investigations on vinylene carbonate. V. Immobilization of alkaline phosphatase onto LDPE films cografted with vinylene carbonate and N-vinyl-N-methylacetamide

Low-density polyethylene (LDPE) films cografted with vinylene carbonate (VCA) and N-vinyl-N-methylacetamide (VIMA) were studied as a matrix for the immobilization of the enzyme alkaline phosphatase (ALP) either by direct fixation or by inserting spacers. When water-soluble alkyldiamines such as diaminoethylene, diaminobutane, diethylenetriamine, and diaminohexane were used as spacers between the matrix and the enzyme, the surface concentration (SC) of the active ALP coupled on the matrix was increased, whereas the effect of the spacer on the SC was dependent on the length of the spacer. Bovine serum albumin (BSA) was preimmobilized onto the LDPE films to provide a better simulation of the biological environment for the enzyme, and the SC of ALP on the matrix was significantly increased by coupling ALP onto the BSA preimmobilized surfaces. Compared to native ALP, some physicochemical properties of ALP could be improved by the covalent immobilization

Adsorption of a synthetic heparinoid polyelectrolyte on an ion-exchanging surface

The adsorption of a synthetic heparinoid polyelectrolyte on poly(vinylchloride) previously treated with tridodecylmethylammonium chloride (TDMAC) was studied using radiotracer techniques to provide a more quantitative picture of antithrombogenic surface coatings. 125I-labeled polyelectrolyte was used for overall adsorption measurements. Experiments with 36Cl-labeled TDMAC yielded information on actually adsorbed polyelectrolyte segments in good agreement with existing theory. A large excess of free dangling segments was found. In the presence of NaCl the total adsorption was diminished, although no desorption occurred on treatment of adsorbates with 0.15 M NaCl or blood plasma

Hacking Stereoscopic Vision: the Nineteenth-Century Culture of Critical Inquiry in Stereoscope Use

While recent scholarship has emphasised the narratives of immersive realism that surrounded the parlour stereoscope, my aim in this paper is to better understand the counter-currents of nineteenth century stereoscopic culture – the artefacts, practices and discourses that powerfully undermined realist assumptions about spatial perception and the “truth” of stereoscopic representation. Wheatstone’s original stereoscopes were designed to “hack” spatial perception and subject each of its component principles to artificial manipulation. What Wheatstone uncovered were glaring anomalies in the prevailing theories of veridical sight, which had relied upon the principle of binocular convergence (understood as a precise trigonometric measure of depth). Following a popular tradition of critical inquiry known as “rational recreation,” amateurs too used their stereoscopes to reflect on the perplexities of binocular spatial perception. Analytic line drawings highlighted the inexplicable binocular suture of strikingly disparate images. Stereograms with their images transposed revealed the capacity of the mind to constitute volumetric objects irrespective of binocular cues. Hyper-stereo images (taken from a wide separation and therefore at an increased angle of binocular convergence) sparked debate and perceptual uncertainty as to whether their 3D effects, or indeed all stereograms, were distorted – elongated along the z axis and/or miniaturised. Realists, including some astronomers hoping to use hyper-stereo photographs as visual evidence of the shape of the moon’s surface, sought unsuccessfully to solve the problem of elongation by ensuring that the angles at which stereo photographs were taken were reproduced in the angles at which the eyes viewed them in the stereoscope. Astronomers were forced to quietly abandon the stereoscope as a reliable witness of spatial form. Others, artists in particular, revelled in the anti-realist implications of a spatial imagination which constructed the perceptual world in a sometimes capricious fashion

Elastic modulus in the crystalline region of poly(p-phenylene terephthalamide)

Fibres from aromatic polyamides have a much higher Young's modulus than fibres from aliphatic polyamides. In order to contribute to the explanation of this observed difference we looked at one of the ultimate properties, the elastic modulus in the crystalline region in the chain direction (Ecr). We carried out measurements on a bundle of filaments of PRD 49 fibre, which we identified by i.r. and X-ray analyses as poly(p-phenylene terephthalamide). With the X-ray technique we determined the lattice extensions under loading and from these data the Ecr was calculated. The Ecr was found to be 20 × 1011 dyne/cm2 which is in good agreement with the calculated Ecr, but not very different from that of nylon-6,6. The Young's modulus was found to be 11 × 1011 dyne/cm2

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%

Detection of surface-adsorbed (lipo)proteins by means of a two-step enzyme-immunoassay: a study on the Vroman effect

In view of reports on the involvement of high-molecular-weight (HMW) kininogen and high-density lipoprotein (HDL) in the Vroman effect, we studied the adsorption of fibrinogen, HMW kininogen, HDL and several other proteins from pooled human plasma and congenitally HMW kininogen-deficient plasma onto glass and low-density polyethylene, both as a function of the plasma concentration and the contact time. Mixtures of purified (lipo)proteins were also included in the study. Protein adsorption was determined by means of a two-step enzyme-immunoassay. Our results support the hypothesis that HMW kininogen is involved in the displacement of fibrinogen, which is almost instantly adsorbed from normal plasma onto glass. On hydrophobic polymers like polyethylene, the low amounts of adsorbed fibrinogen and HMW kininogen from plasma and concentrated plasma solutions may be due to a preferential adsorption of HDL