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Polymers containing enzymatically degradable bonds V. Hydrophilic polymers degradable by papain.

Copolymers of N-(2-hydroxypropyl)methacrylamide were prepared, in which synthetic polymer chains are joined by crosslinks containing oligopeptidic sequences degradable with papain, with the general structure P-(Gly)n-X-Y-NH-(CH2)6-NH-Y-X-(Gly)n-P (P is the polymer chain, n = 1,2; X...Phe, Val, Gly; Y...Lys, Gly, Tyr, Ala, Phe). The relationship between the structure of these polymeric substrates and their degradability with papain was investigated viscometrically. It was shown that -Phe-Lys- was the most suitable -X-Y- sequence. Extension of the oligopeptidic sequence by one amino acid residue causes a pronounced rise in the rate of cleavage of the polymeric substrates.

Acrylic Resins↗

Enzymatic degradation of atactic poly(R,S-3-hydroxybutyrate) induced by amorphous polymers and the enzymatic degradation temperature window of an amorphous polymer system.

The phase structure and biodegradability were investigated for amorphous blends of chemosynthetic fully amorphous atactic poly(R,S-3-hydroxybutyrate) (a-PHB) with atactic poly(methyl methacrylate) (PMMA) and atactic poly(R,S-lactide) (a-PLA). The differential scanning calorimetry thermal analysis indicated that a-PHB/PMMA blends were partially miscible while a-PHB/a-PLA blends were miscible in the studied composition range. The biodegradations of the blends were carried out in phosphate buffer solution in the presence of bacterial poly(R-3-hydroxybutyrate) extracellular depolymerases purified from Alcaligenes faecalis T1 and P. stutzeri. Although a-PHB in the pure state was not degraded by these depolymerase, it was degraded by blending with PMMA and a-PLA. The results demonstrated that the enzymatic degradation of a-PHB can be induced by amorphous polymers such as PMMA and a-PLA. Also, the biodegradation rate of a-PHB in the blends decreased drastically when the degradation temperature is too much away from the polymer glass transition temperatures. On the basis of these results, a temperature window of the enzymatic degradation was first proposed for the blend and the essence of induced degradation was discussed.

Alcaligenes↗

Polymer catalysts from polymerization catalysts: direct encapsulation of metal catalyst into star polymer core during metal-catalyzed living radical polymerization.

Star polymers containing ruthenium complex in the core were prepared by ruthenium-catalyzed living radical polymerization, where the metal catalysts were directly encapsulated on linking reactions of living poly(MMA) in the presence of ethylene glycol dimethacrylate as a linker and diphenyl-4-styrylphosphine as a ligand incorporated in the core. The products were characterized by SEC/MALLS, UV-vis, NMR, AFM, TEM, and ICP-AES and were employed as polymer catalysts for the oxidation reaction of alcohol.

Journal Article↗

Transfer of photoenergy in pi-conjugated polymers. Two types of photoluminescence that involve energy transfer along a polymer chain.

Two types of energy transfer in pi-conjugated polymers have been investigated using time-resolved photoluminescence (PL) techniques: type i, perpendicular-type energy transfer from the 2,3-di(p-tolyl)quinoxaline unit to the pi-conjugated main chain of poly[2,3-di(p-tolyl)quinoxaline-5,8-diyl], and type ii, parallel-type energy transfer from the oligo(pyridine-2,5-diyl) (O-Py) unit to the oligo(selenophene-2,5-diyl) (O-Se) unit in a block-type copolymer of O-Py and O-Se. Both types of energy transfer were very fast with a time constant shorter than approximately 0.1 ns; in particular, the type ii energy transfer took place with a time constant of approximately 5 ps. Both pi-conjugated polymers were considered to contain segments with various effective pi-conjugation lengths, and the energy transfer to the segment with a larger effective pi-conjugation length and a smaller pi-pi* transition energy required a longer transition time. A polarizing film was obtained by utilizing the perpendicular-type energy transfer.

Journal Article↗

Photoactive additives for cross-linking polymer films: Inhibition of dewetting in thin polymer films.

In this report, we describe a versatile photochemical method for cross-linking polymer films and demonstrate that this method can be used to inhibit thin polymer films from dewetting. A bifunctional photoactive molecule featuring two benzophenone chromophores capable of abstracting hydrogen atoms from various donors, including C-H groups, is mixed into PS films. Upon exposure to UV light, the bis-benzophenone molecule cross-links the chains presumably by hydrogen abstraction followed by radical recombination. Photoinduced cross-linking is characterized by infrared spectroscopy and gel permeation chromatography. Optical and atomic force microscopy images show that photocrosslinked polystyrene (PS) thin films resist dewetting when heated above the glass transition temperature or exposed to solvent vapor. PS films are inhibited from dewetting on both solid and liquid substrates. The effectiveness of the method to inhibit dewetting is studied as a function of the ratio of cross-linker to macromolecule, duration of exposure to UV light, film thickness, the driving force for dewetting, and the thermodynamic nature of the substrate.

Cross-Linking Reagents↗

Self-assembled zinc(II) Schiff base polymers for applications in polymer light-emitting devices.

Thermally stable zinc(II) Schiff base polymers (decomposition temperature up to 461 degrees C; M(n)= 13580 to 20440) formed by self-assembly reactions of zinc(II) salts and salicylaldimine monomers exhibit blue to yellow PL with quantum yields up to 0.34 in DMF; PLEDs employing these polymers as emitters give green or orange EL with turn-on voltage at 5 and 6 V and maximum efficiency of 2.0 and 2.6 cd A(-1) respectively.

Journal Article↗

Critical polymer-polymer phase separation in ternary solutions.

We study polymer-polymer phase separation in a common good solvent by means of Monte Carlo simulations of the bond-fluctuation model. Below a critical, chain-length-dependent concentration, no phase separation occurs. For higher concentrations, the critical demixing temperature scales nonlinearly with the total monomer concentration, with a power law relatively close to a renormalization-group prediction based on "blob" scaling arguments. We point out that earlier simulations and experiments have tested this power-law dependence at concentrations outside the validity regime of the scaling arguments. The critical amplitudes of the order parameter and the zero-angle scattering intensity also exhibit chain-length dependences that differ from the conventional predictions but are in excellent agreement with the renormalization-group results. In addition, we characterize the variation of the average coil shape upon phase separation.

Journal Article↗

Reaction-induced phase separation of pseudo-interpenetrating polymer networks in polydisperse polymer blends: a simulation study.

We develop a minimal model for the process of reaction-induced phase separation in a polydisperse polymer blend. During the reaction, one component undergoes polymerization, leading to phase separation via spinodal decomposition. The effect that changing the final degree of polymerization has on the phase-separation process is studied. Finally an elastic energy term is included mimicking the cross-linking process and the generation of a semi-interpenetrating polymer network. We show that the scaling of the dominant lengthscale with time varies according to the reaction conditions.

Journal Article↗

Bottle-brush polymers as an intermediate between star and cylindrical polymers.

We present a theoretical study of a single bottle-brush molecule, which consists of multiarmed polymer stars grafted densely onto a stiff backbone. Mean-field approximation and a variational approach are used to calculate the dominant trajectories of the grafted chains, the shape of the molecule, and the segment density distribution around the backbone. All these properties are calculated for an arbitrary relationship between the size of the backbone and that of a grafted star. Hence cylindrical comb copolymer brushes and spherically symmetric polymer stars are considered as the limiting cases of the present problem.

Journal Article↗

Influence of bulk nematic orientation on the interface between a liquid crystalline polymer and a flexible polymer.

The structure of the interface between a liquid crystalline polymer (LCP) and a flexible polymer was studied using the three-dimensional bond fluctuation model in Monte Carlo simulations. Orientation in both phases in the neighborhood of the interface is sensitive to the far-field nematic orientation. The more diffuse interface caused by a homeotropic far-field orientation in the LCP results in a substantial reduction in the calculated interfacial tension relative to that for a planar far-field orientation.

Journal Article↗

Voltage-modulated millimeter-wave spectroscopy on a polymer diode: mesoscopic charge transport in conjugated polymers.

We present a new technique to determine the carrier mobility mu in semiconducting, undoped, conjugated polymers in the millimeter-wave frequency range, 10-500 GHz. This method probes charge conduction on mesoscopic length scales, a regime inaccessible to other transport experiments. The experiment is based on the detection of millimeter-wave absorption of field-induced charge in polymer diodes, and is applied to poly( p-phenylene vinylene). We demonstrate that locally mu can be as high as 10(-4) m(2)/V s, and deduce the typical hopping parameters in the mesoscopic high- mu regions in the material.

Journal Article↗

Mesogene-polymer backbone coupling in side-chain polymer liquid crystals, studied by high magnetic-field-induced alignment.

We show that cooling side chain polymer liquid crystals in a magnetic field, from the isotropic to nematic and subsequently to the glass phase, results in a macroscopically ordered, transparent, and strongly birefringent material. The aligned samples retain their properties after the field is removed and can be dealigned only by heating them to the isotropic phase. To induce alignment, a threshold field B(th) is necessary, which strongly depends on the chemical structure details. B(th) reflects the strength of mesogene-polymer backbone coupling, and we will show that this interaction is responsible for the stability of the induced alignment at zero field.

Journal Article↗

Optical limiter with an organic solution sandwiched between a polymer slab and a polymer grating.

An optical limiter was designed and fabricated. The device consists of an organic solution sandwiched between a polymer slab and a transparent relief polymer grating with a triangular groove. At low power the device has a high transmittance because the refractive index of the solution is matched with those of the slab and the grating materials and because the grating does not diffract. However, high power makes the organic solution thermally vaporize and makes the indices of the solution, slab, and grating materials become mismatched, which causes the grating to appear. The incident light is strongly absorbed, scattered, and self-defocused by the organic solution, and the grating suppresses the zero-order diffraction. Thus the transmitted light energy becomes lower than the damage threshold of human eyes or optical sensors. The device is an effective protection for human eyes or optical sensors against broadband pulsed-laser damage.

Journal Article↗

Controlling the growth of polymer trees: concepts and perspectives for hyperbranched polymers.

This article summarizes basic principles and recent progress in the field of cascade-branched polymers. Methods for the preparation of macromolecules with hyperbranched structures are presented and compared concerning the extent of control over molecular weights and polydispersity. Step-growth and recently developed chain-growth strategies as well as enzyme and transition metal catalyzed polymerizations are discussed with respect to mechanism and future potential.

Biopolymers↗

Polymer resin library and the discovery of highly efficient polymer supported reagents and scavengers.

This paper is focused on the preparation of a library of highly efficient, tailor made, macroporous resins as supports for reagents and scavengers. From this library a macroporous resin, prepared with 40% cross-linking and with a porogen level of 300% in toluene gave a material superior to those presently available, and was shown to be highly efficient in the preparation of novel highly reactive polymer supported reagents, including scavengers and oxidants.

Combinatorial Chemistry Techniques↗

Biomembranes as models for polymer surfaces. II. The syntheses of reactive species for covalent coupling of phosphorylcholine to polymer surfaces.

We have proposed previously that the biocompatibility of biomaterial surfaces might be improved by mimicking the phospholipid components which are present on the external faces of cellular plasma membranes. This approach may have particular relevance to the generation of haemocompatible surfaces, since the distributional asymmetry of phospholipids in the plasma membranes of blood cells is critical to the maintenance of haemostasis. The simplest feature common to the external faces of essentially all the mammalian plasma membranes investigated so far is the high content of the electrically neutral, but zwitterionic, phosphorylcholine. The present communication describes the syntheses of a group of novel reactive species capable of covalently linking phosphorylcholine to a variety of polymer surfaces.

Biocompatible Materials↗