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PubMed2004

Charge transport at conjugated polymer-inorganic semiconductor and conjugated polymer-metal interfaces.

Charge transport at conjugated polymer interfaces with metals and inorganic semiconductors is reviewed. Experiments on the equilibrium properties and DC current-voltage behavior of four specific classes of interfaces-metal-doped conjugated polymer, inorganic semiconductor-doped conjugated polymer, metal-intrinsic conjugated polymer, and metal-intrinsic conjugated polymer/electrolyte-are discussed. To facilitate this discussion, classic models of equilibration at ideal interfaces between electronic conductors and free-electron transport are introduced and their limitations discussed. Particular emphasis is placed on the charge distributions and interfacial potential profiles expected at various types of electroactive interfaces.

Journal Article↗

PubMed2005

Planar waveguide-based silica-polymer hybrid variable optical attenuator and its associated polymers.

We have proposed a silica-polymer hybrid variable optical attenuator that we made by creating two trenches along the core of a straight silica planar waveguide and filling the trenches with a polymer. The polymer, which had a superhigh thermo-optic coefficient, was specially designed and developed in this study to lower the power consumption of the device. We achieved a maximum attenuation of -29 dB for the device by changing the polymer's temperature by only 7 degrees C. The device has a very low power consumption at 2-3 mW/channel, making it a good candidate for integration with arrayed waveguide gratings.

Journal Article↗

PubMedDate not supplied

[Allowing for polymer polydispersity--an essential condition for determination of aqueous pore diameters in cell walls and membranes using polymers].

A method of allowing for polydispersion of polyethylene glycol (PEG) preparations was developed for the use of these preparations for the osmometrical evaluation of pore diameters with aqueous pores of Chara corallina cell walls as an example. The mass share of polyethylene glycol preparation fractions gamma p penetrating through the pores was determined using cellular "shadows", fragments of internodal cell walls tied up at the ends and filled with a 25% solution of nonpenetrating PEG 6000. When immersed into water, such "shadow" acquired a turgor (hydrostatic) pressure close to the cellular pressure and persistent over long time. The determination of gamma p for polyethylene glycols with different average molecular weights Mw was performed from the degree of pressure restoration after water was replaced by a 5-10% polymer solution. The kinetics of pressure changes was recorded using a mechanotronic dynamometer, which measures, in the quasi-isometric mode, the force necessary for partial compression of the "shadow" in its small fragment. By utilizing the dependence of the overall share of fractions with molecular weights Mi < Mk on Mk (data of [1]), we found that gamma p, for these polyethylene glycols corresponds to the threshold value of Mk = 800-1100 D (hydrodynamic radius of molecules rh = 0.85-1.05 nm). Thus, the effective diameter of the pores in the cell wall of Chara does not exceed 2.1 nm. It was shown that the smoothness of the sigmoid shape of the dependence of ionic channel conductivity on the Mw value of the polymer in the media is largely due to the polydispersion of polymer preparations, particularly, to the reduction in the share of fractions penetrating the channels as Mw is increased. The method normally used to estimate pore diameters in ionic channels which ignores the dispersion of polymer preparations, results in overestimated values.

Cell Membrane↗

PubMed1997

Histologic and mechanical evaluation for bone bonding of polymer surfaces grafted with a phosphate-containing polymer.

A phosphate-containing polymer was covalently immobilized onto a polyethylene (PE) rod, a poly(ethylene terephthalate) (PET) thread, and a PET film by a surface graft polymerization technique, followed by immersion in calcium phosphate solution to deposit a thin hydroxyapatite (HA) layer on the modified polymer surfaces. The PE rod had a tapered shape, while the PET thread was fixed with clips after implantation, both to minimize the micromovement which may occur in bone. The PE rod was implanted through press-fitting in the femur of rat. Significant enhancement was observed for direct contact of the implant surface with a newly formed bone for both the grafted only and the further HA-deposited PE rods in comparison with the untreated PE at 4, 5, and 6 weeks after implantation. The rats implanted with the modified PET thread in the femur were sacrificed 3 and 6 weeks after implantation. Statistically significant differences were observed for the untreated versus the grafted plus HA-deposited rods at 6 weeks after implantation. To study the resorption of the deposited HA on the methacryloyloxyethylene phosphate-grafted surface, HA-deposited PET films were subcutaneously implanted in the back of rats. The deposited HA was rapidly resorbed within 3 weeks of implantation. These results suggest that the phosphate polymer chains grafted on the PE and PET surfaces effectively induced nucleation and growth of HA crystals. It seems likely that the thin HA layer additionally deposited in vitro onto the grafted PE and PET surfaces was resorbed rapidly and then promoted the growth of HA crystals in vivo.

Animals↗

PubMed1992

Synthesis and nonthrombogenicity of polymer membrane with surface-graft polymers carrying thrombin inhibitor.

An acrylamide derivative of a thrombin inhibitor was synthesized and graft polymerized to the surfaces of polymer membranes. The thrombin-inhibitor activity was unaffected by the introduction of an acryloyl group. The surface-graft membrane deactivated thrombin markedly and suppressed adhesion of platelets, resulting in a high nonthrombogenicity. Immersion of polymer membranes blended with the thrombin inhibitor in phosphate-buffered saline for 10 d resulted in the loss of nonthrombogenicity, while the polymer membranes grafted with the thrombin inhibitor derivative maintained the nonthrombogenicity over a long period.

Acrylamides↗

PubMed1989

Electron diffraction of synthetic polymers: the model compound approach to polymer structure.

X-ray fiber diffraction is a technique most often used to establish the structure of chemically regular crystalline polymers. However, this technique has many shortcomings. Some of them are: ambiguities regarding the choice of the space group, limited intensity data, often large diffraction spots, and overlapping intensities. Microsingle crystals of synthetic polymers, when they can be produced, happen to have dimensions that are well suited to being studied by electron diffraction. Electron diffraction data from microsingle crystals often complement the X-ray fiber data. Strictly speaking, one does not solve the crystal structure of a polymer in the conventional way but rather one chooses from among many potentially acceptable models the one which fits the X-ray and/or the electron diffraction data best. The various steps of model building, its placing within the unit cell, and structure refinement will be discussed.

Microscopy, Electron↗

PubMed2005

Tuning the polymer release from hydrophilic matrix tablets by mixing short and long matrix polymers.

In this work a rotating disc method was developed for studying the dissolution process of "bimodal" polymer tablets, whose dissolution rates have been tuned by mixing low-molecular weight and high-molecular weight samples of poly(ethylene oxide) in various proportions. The tablets were prepared along different routes, by mixing the polymer fractions as powders or by mixing on a molecular level so that the effect of tablet heterogeneity could be assessed, but also by purifying the original powders so the effect of additives could be determined. When the mixed tablet was dominated by the low-molecular weight fraction, a faster dissolution was observed for the tablet mixed at the powder level. In those cases small gel pieces were released from the tablet during the whole dissolution process. As long as no gel piece erosion was observed, it did not matter if the two polymer fractions were blended on the molecular level or on the powder level, the steady-state dissolution rate was the same. The presence of small amounts of additives in the nonpurified commercial samples had no significant effect on the tablet dissolution within the uncertainty of the experiment.

Calorimetry, Differential Scanning↗

PubMed1991

Microcapsules through polymer complexation. II. By complex coacervation of polymers containing a low charge density.

Relationships between ionizable group content, structure and molecular weight, solubility and solution behaviour, and the efficacy of ionic complex formation through complex coacervation, have been established for a range of sparingly soluble synthetic weak polyelectrolyte polymers with low charge content, based on hydroxyalkyl methacrylates. Selected polymers containing methacrylic acid (acidic) and dimethylaminoethyl methacrylate (basic) functionality show promise as capsule-forming pairs for the entrapment of mammalian cells. The solubility of basic polymers and their ability to form microcapsules with structural integrity is enhanced through quaternization of the N-methyl functionality to the quaternary ammonium group. The survival of guinea-pig erythrocytes encapsulated for 4 d in this promising system was shown by the Drabkin's test to be about 41% of the control sample.

Animals↗

PubMed2001

Liquid crystalline polymers as stationary phases. IV. Chemical bonding and immobilization of the polymer on silica characterization by solid-state nuclear magnetic resonance spectroscopy.

Chemical bonding reaction and immobilization through low energy radiation (heating) have been investigated to fix a side-chain liquid crystalline polymer (SC-LCP) on silica particles in order to use the resulting modified silica in normal-phase HPLC. Highly stable chromatographic stationary phases are observed under excellent polymer solvent flow conditions (THF) for both methods and better column efficiencies are also exhibited towards PAHs' separation compared to the classical coated stationary phase. The characterization of these new stationary phases and the rationale for improved column stability have been investigated by solid state 13C and 29Si CP/MAS NMR spectroscopy. It is clearly shown that the chemical bonding is achieved by the classical hydrosilylation reaction between PHMS chains and vinyl modified silica. The bonded polymer is likely a copolymer than a homopolymer. The immobilization of the SC-LCP by heating results in the breaking of Si-O-Si bonds of the polysiloxane chain after the attack of the silica surface silanols. Applications to fullerenes and carotenes separation of these bonded stationary phases are compared to the separation power of a classical monomeric C18 stationary phase in NP-HPLC as n-hexane-toluene or methyl-tertiobutyl ether-methanol mixtures.

Crystallization↗

PubMed2001

Clad polymer buffer rods for polymer process monitoring.

Clad polymer buffer rods consisting of a polyetheretherketone (PEEK) core and a cladding made of a heat resistance epoxy aluminum composite are presented. The core has a uniform diameter or a taper shape. Ultrasonic measurement results indicate that the ultrasonic signal strength and signal to noise ratio of these clad rods are better than those of the non-clad PEEK rods for both longitudinal and shear waves because of the improved ultrasonic wave guidance in the core. Comparisons of these rods with those made of polymide and high-density polyethylene are given. Applications of these buffer rods for ultrasonic monitoring of polymer extrusion at temperatures up to 200 degrees C and pressures up to 180 psi are demonstrated. The monitoring results also reveal that within certain operating temperature and pressure range, clad polymer buffer rods show advantages over clad steel buffer rods.

Benzophenones↗

PubMedDate not supplied

Site-specific conjugation of chain-terminal chelating polymers to Fab' fragments of anti-CEA mAb: effect of linkage type and polymer size on conjugate biodistribution in nude mice bearing human colorectal carcinoma.

Polylysine-based chelating polymers were used for site-specific modification of anti-CEA mAb Fab' fragments via their SH group distal to the antigen-binding site of the antibody molecule. Conjugation was performed using chain-terminal (pyridyldithio)propionate or 4-(p-maleimidophenyl)butyrate moieties to form reducible (S-S) or stable (S-C) bonds between a polymer and Fab' molecule, respectively. One S-S conjugate (S-S9) and two different S-C conjugates (S-C3 and S-C9) were prepared using 3- and 9-kDa molecular weight polymers. No significant loss of immunoreactivity was observed in solid-phase immunoassay, 90-95% of 111In-labeled conjugates being bound to CEA-coated Sepharose beads. After labeling with 111In, the conjugates had a specific radioactivity of 90-120 microCi/micrograms. Injected in nude mice bearing LS 174T carcinoma, the conjugates produced different biodistribution patterns. S-S9 was practically unable to accumulate in tumor and produced very rapid blood clearance of radioactivity and high uptake of radioactivity in liver, spleen, and especially kidneys (225% ID/g 24 h postinjection). S-C3 and S-C9 produced practically the same blood clearances (much slower than that of S-S9) and significant tumor uptake (9-10% ID/g at 24 h). S-C3 gave significantly lower radioactivity in spleen, skin, and bones, and cleared more rapidly from liver and kidneys. Renal uptake for S-C3 and S-C9 was rather high (45% ID/g at 24 h), but much lower than for S-S9.

Adenocarcinoma↗

PubMed2001

Nanoscale clustering of RGD peptides at surfaces using comb polymers. 2. Surface segregation of comb polymers in polylactide.

Part 1 of these studies described poly(methyl methacrylate-r-polyoxyethylene methacrylate) P(MMA-r-POEM) comb polymers that present Arg-Gly-Asp (RGD) peptides at a surface in nanoscale clusters on a protein-resistant background for control of cell adhesion. Here in part 2, we examine surface segregation of these peptide-modified and unmodified comb polymers blended with polylactide (PLA) as a self-assembly approach suitable for surface modification of porous tissue engineering scaffolds. Multiple thermodynamic driving forces for surface enrichment of the comb polymer are exploited by annealing PLA/P(MMA-r-POEM) blends above the glass transition of the blend components but below the melting point of PLA, while in contact with water. Predictions of the interfacial composition profiles of annealed blends were made using a self-consistent field (SCF) lattice model. The calculations predict strong enrichment of the comb in the top approximately 50 A of blends, and organization of comb molecules in quasi-2D conformations at the interface, similar to the apparent structure of pure comb surfaces in contact with water described in part 1. Experimentally, PLA/comb blend surfaces were characterized by contact angle measurements, XPS, quantification of ligand-cluster surface density and stability by AFM and fluorescent nanosphere labeling, and cell attachment assays. These data were consistent with SCF predictions, showing significant enrichment of the comb at water-annealed surfaces and RGD cluster densities consistent with 2D conformations for comb molecules in the surface layer. Bulk miscibility of the blends was verified by dynamic rheometry, small-angle neutron scattering, DSC and X-ray diffraction studies. Surface segregation of combs provided tunable cell adhesion on PLA through surface-localized nanoclusters of RGD atop a cell-resistant background.

Cell Adhesion↗

PubMedDate not supplied

New polymers forming aqueous two-phase polymer systems.

A new type of polymer, starch-modified by acrylamide, has been developed for application in aqueous two-phase systems (ATPS) for protein separation. Partial hydrolysis and acrylamide modification of starch to different degrees make it suitable for forming ATPS with poly(ethylene glycol) in a moderate concentration range. The potential of the polymer to form ATPS with the thermoprecipitating copolymer of 1-vinylimidazole with N-vinylcaprolactam (poly-VI/VCL) has been evaluated. The thermoprecipitation properties of poly-VI/VCL and Cu(II)-loaded poly-VI/VCL have been studied for application in metal affinity partitioning. The formation of ATPS with Cu(II)-loaded thermoprecipitating copolymer was critically achieved for poly-VI/VCL (10/90) copolymer in under-loaded metal concentrations. With the Cu(II)-loaded copolymer, poly-VI/VCL in the top phase and modified starch in the bottom phase, the ATPS formed was used for the purification of alpha-amylase inhibitor from wheat meal. The protein partitioned in the top phase and phase-separated polymer-protein complex could be precipitated by salt. The protein inhibitor was recovered with a yield of 75%.

Acrylamide↗

PubMed1991

Influence of physical aging on mechanical properties of polymer free films: the prediction of long-term aging effects on the water permeability and dissolution rate of polymer film-coated tablets.

The effects of physical aging on the water permeation of cellulose acetate and ethylcellulose, the mechanical properties of ethylcellulose, and the dissolution property of hydroxypropyl methylcellulose phthalate were investigated. The water permeabilities of cellulose acetate and ethylcellulose and the dissolution rate of hydroxypropyl methylcellulose phthalate were found to decrease with physical aging time after being quenched from above the glass transition temperatures to sub-Tg temperatures. The gradual approach toward thermodynamic equilibrium during physical aging decreases the free volume of the polymers. This decrease in free volume is accompanied by a decrease in the transport mobility, with concomitant changes in those properties of the polymer that depend on it. The effects of long-term aging on the dissolution rate and water permeabilities of these polymers can be estimated from a linear double-logarithmic relationship between the mobility properties and physical aging time. The existence of the linear double-logarithmic relationship can be derived from the Williams-Landel-Ferry equation, the Doolittle equation, Struik's model, and Fujita's relationship between diffusion and free volume.

Cellulose↗

PubMed1996

Radiation dose distributions in three dimensions from tomographic optical density scanning of polymer gels: II. Optical properties of the BANG polymer gel.

A newly developed method of radiation dosimetry makes use of the optical properties of polymer gels. The dose-response mechanism relies on the production of light-scattering polymer micro-particles in the gel at each site of radiation absorption. The scattering produces an attenuation of transmitted light intensity that is directly related to the dose and independent of dose rate. For the BANG polymer gel (bis, acrylamide, nitrogen, and gelatin) the shape of the dose-response curve depends on the fraction of the cross-linking monomer in the initial mixture and on the wavelength of light. At 500 nm the attenuation coefficient (mu) increases by approximately 0.7 mm-1 when the dose increases from 0 to 5 Gy. The refractive index of an irradiated gel shows no significant dispersion in the visible region and depends only slightly on the dose. Turbidity difference spectra are compared with theoretical spectra of efficiency factors for total scattering, derived using Mie-Debye theory, and the average sizes of the cross-linked particles produced by radiation, as a function of dose, are established. The particle sizes increase with dose and reach approximately the wavelength of red light. The dependence of the particle sizes on cross-linker fraction parallels a similar dependence of the water proton NMR transverse relaxation rate dose response.

Acrylamide↗

PubMed2002

Influence of polymer-excluded volume on the phase-behavior of colloid-polymer mixtures.

We determine the depletion-induced phase-behavior of hard-sphere colloids and interacting polymers by large-scale Monte Carlo simulations using very accurate coarse-graining techniques. A comparison with standard Asakura-Oosawa model theories and simulations shows that including excluded-volume interactions between polymers leads to qualitative differences in the phase diagrams. These effects become increasingly important for larger relative polymer size. Our simulation results agree quantitatively with recent experiments.

Colloids↗

PubMed1997

Synthetic strategies for the preparation of precursor polymers and of microcapsules suitable for cellular entrapment by polyelectrolyte complexation of those polymers.

The production of microcapsules suitable for the entrapment of mammalian cell by means of polyelectrolyte complexation has, of a necessity, led to the development of novel strategies for the preparation of relatively bioinert polymers which complex efficiently under unique conditions to produce a mechanically resilient membrane with efficient transport properties. In this communication we relate a brief overview of capsule-membrane forming systems for the immunoisolation (or potential immunoisolation) of mammalian cells, which are based upon the complexation of polyelectrolyte (PE) polymers; with emphasis on precursor synthesis and relationships between precursor polymer structure and capsule membrane stability.

Animals↗

PubMedDate not supplied

Gradation of microcapsule wall porosity by deposition of polymer mixtures (Eudragit RL and Eudragit RS). Phase separation of polymer mixtures and effects of external media and conditions on release.

With the aim of increasing flexibility in controlling release from microcapsules, mixtures of wall polymers varying in porosity were investigated by phase separation. Eudragit RL and RS (polymethylmethacrylate linear backbone polymers) mixtures differing in polar substituent content and porosity were used as the wall material and were deposited using a non-solvent addition method. Release rates increased with polar group content of the mixtures, using theophylline, potassium dichromate or sodium chloride as model core materials. Theophylline release rate had the same relationship to polar group content as found earlier for urea permeation of cast mixed-polymer films. Release was generally accelerated in these systems when the external medium contained sodium lauryl sulphate as a wetting agent but not consistently, decreasing unexpectedly for RL-theophylline microcapsules. Localized dissolution of core substance was visible microscopically during release from single microcapsules. The release rate was sensitive to agitation intensity only at low wall to core ratios. Temperature change revealed only a single release mechanism for sodium chloride by Arrhenius equation treatment. Buffer ions penetrated coatings readily, changing theophylline release rates and providing clear evidence of diffusion via a pore-capillary mechanism.

Acrylic Resins↗