Layer-by-layer electrodeposition of redox polymers and enzymes on screen-printed carbon electrodes for the preparation of reagentless biosensors

Layer-by-layer electrodeposition of redox polymer/enzyme composition films on screen-printed carbon electrodes for fabrication of reagentless enzyme biosensors has been proposed and the resulting films were found to be very stable and rigid.

Brittle-ductile transition of polymers and its percolation model

The brittle-ductile transition (BDT) of particle toughened polymers was extensively studied in terms of morphology, strain rate, and temperature. The calculation results showed that both the critical interparticle distance (IDc) and the brittle-ductile transition temperature (T-BD) of polymers were a function of strain rate. The IDc reduced nonlinearly with increasing strain rate, whereas T-BD increased considerably with increasing strain rate. The effects of temperature and plasticizer concentration on BDT were discussed using a percolation model. The results were in agreement with the experiments.

MECHANISM OF RADIATION CROSS-LINKING OF POLYMERS AND ITS RELATIONSHIP WITH STRUCTURAL MULTIPLICITY

In an attempt to explore the effect of structural multiplicity of polymers on the mechanism of radiation crosslinking, the adaptability of the Charlesby-Pinner's equation and its various modified versions are examined. It is recognized that both chemical and morphological multiplicity of polymer structure results in the multiplicity of crosslinking mechanism, and that any single equation can only be applicable to a certain step of the whole radiation process.

Synthesis of novel star-like hyperbranched polymers with poly(amido amine) core and poly(L-lysine) shell

Hyperbranched poly(amido amine)s containing vinyl and hydroxyl groups were successfully synthesized via Michael addition polymerization of triacrylamide (TT) and 3-amino-1,2-propanediol (APD) with equal molar ratio in feed. H-1, C-13 and HSQC NMR techniques were used to clarify the structure of hyperbranched polymers and polymerization mechanism.

Synthesis and catalytic application of chiral 1, 1 '-binaphthyl polymers

The synthesis of a new type of polymers with main chain chirality based on BINOL skeleton is described. Titanium-BINOLate catalysts are easily generated from these polymers and applied to the asymmetric reaction of Et2Zn with benzaldehyde. The products are obtained in good yields with moderate enantioselectivities.

Electrodeposition of platinum nanoclusters on type I collagen modified electrode and its electrocatalytic activity for methanol oxidation

We firstly reported a novel polymer matrix fabricated by type I collagen and polymers, and this matrix can be used as nanoreactors for electrodepositing platinum nanoclusters (PNCs). The type I collagen film has a significant effect on the growth of PNCs. The size of the platinum nanoparticles could be readily tuned by adjusting deposition time, potential and the concentration of electrolyte, which have been verified by field-emitted scanning electron microscopy (FE-SEM). Furthermore, cyclic voltammetry (CV) has demonstrated that the as-prepared PNCs can catalyze methanol directly with higher activity than that prepared on PSS/PDDA film, and with better tolerance to poisoning than the commercial E-TEK catalyst. The collagen-polymer matrix can be used as a general reactor to electrodeposit other metal nanostructures.

Novel NIR-absorbing conjugated polymers for efficient polymer solar cells: effect of alkyl chain length on device performance

Three low bandgap conjugated polymers, i.e., PDTPBT-C8, PDTPBT-C6 and PDTPBT-C5, which consist of alternating N-alkyl dithieno[3,2-b: 2',3'-d] pyrrole and 2,1,3-benzothiadiazole units and carry 1-octylnonyl, 1-hexylheptyl and 1-pentylhexyl as side chains, respectively, were synthesized. These polymers show strong absorption in the wavelength range of 600-900 nm with enhanced absorption coefficient as the length of alkyl chain decreases. The film morphology of the polymers and 1-(3-methoxycarbonyl) propyl-1-phenyl-[6,6]-C-61 (PCBM) blends is also dependent on the alkyl chain length. As the length decreases, the film becomes more uniform and the domian size decreases from 400-900 nm for PDTPBT-C8 to similar to 50 nm for PDTPBT-C5.

Full View of Single-Molecule Force Spectroscopy of Polyaniline in Oxidized, Reduced, and Doped States

The macroscopic mechanical properties of polyaniline (PANI) lie mainly on two factors, the structure of molecular aggregations of polymers and the mechanical properties of a single polymer chain. The former factor is swell revealed; however, the latter is rarely studied. In this article, we have employed atomic force microscopy-based single-molecule force spectroscopy to investigate the mechanical properties of a kind of water-soluble PANI at a single-molecular level. We have carried out the study comparatively on single-chain-stretching experiments of oxidized, reduced, and doped PANI and obtained a full view of the single-chain elasticity of PANI in all these states. It is found that oxidized and reduced PANI chains are rigid, and the oxidized PANI is more rigid than the reduced PANI. Such a difference in single-chain elasticity can be rationalized by the molecular structures that are composed of benzenoid diamine and quinoid diimine its different proportions. The doped PANI has been found to be more flexible than the oxidized and reduced PANI, and the modified freely jointed chain parameters of doped PANI are similar with those of a common flexible-chain polymer.

CNT Templated Regioselective Enzymatic Polymerization of Phenol in Water and Modification of Surface of MWNT Thereby

Carbon nanotubes (CNTs) are used as templates to synthesize regioselective polymers from enzymatic polymerization of phenol in water. About 90% of total polymeric units in the obtained polymers are the highly thermally stable oxyphenylene units. The polymer-yields are dependent on the quantities of CNTs used. On the basis of MWNT-templated enzymatic polymerization of phenol, covalent attachment of polyphenol chains to the surface of MWNT by way of a linking molecule, hydroquinone, is achieved. This approach supplies a novel way for producing high-performance polymers and for functionalization of the surface of CNT.

Relaxation time and conductivity of comb-like gel polymer electrolytes

Using the copolymer of acrylonitrile (AN), methyl methacrylate (MMA), and poly(ethylene glycol) methyl ether methacrylate as a backbone and poly(ethylene glycol) methyl ether (PEGME) with 1100 molecular weight as side chains, comb-like gel polymers and their Li salt complexes were synthesized. The dynamic mechanical properties and conductivities were investigated. Results showed that the gel copolymer electrolytes possess two glass transitions: alpha-transition and beta-transition. Based on the time-temperature equivalence principle, a master curve was constructed by selecting T. as reference temperature. By reference to T-0 = 50 degrees C, the relation between log c, and c was found to be linear. The master curves are displaced progressively to higher frequencies as the content of plasticizer is increased. The relation between log tau(p) and the content of plasticizer is also linear.

Rheological properties in blends of poly(aryl ether ether ketone) and liquid crystalline poly(aryl ether ketone)

Rheological properties of the blends of poly(aryl ether ether ketone) (PEEK) with liquid crystalline poly(aryl ether ketone) containing substituted 3-trifluoro-methylbenzene side group (F-PAEK), prepared by solution precipitation, have been investigated by rheometer. Dynamic rheological behaviors of the blends under the oscillatory shear mode are strongly dependent on blend composition. For PEEK-rich blends, the systems show flow curves similar to those of the pure PEEK, i.e., dynamic storage modulus G' is larger than dynamic loss modulus G", showing the feature of elastic fluid. For F-PAEK-rich systems, the rheological behavior of the blends has a resemblance to pure F-PAEK, i.e., G" is greater than G', showing the characteristic of viscous fluid. When the PEEK content is in the range of 50-70%, the blends exhibit an unusual rheological behavior, which is the result of phase inversion between the two components. Moreover, as a whole, the complex viscosity values of the blends are between those of two pure polymers and decrease with increasing F-PAEK content. However, at 50% weight fraction of PEEK, the viscosity-composition curves exhibit a local maximum, which may be mainly attributed to the phase separation of two components at such a composition.

Controlling dispersed state and exfoliation process of clay in polymer matrix

In the present review, the authors do not try to provide a comprehensive review of researches on polymer/clay nanocomposites (PCNs), but some examples to demonstrate different exfoliation processes of the clay in various polymer matrixes and the dispersed state of clay. Interaction between polymers and layered silicates plays an important role in adjusting the exfoliation process of layered silicates and the microstructure of polymer nanocomposites. Properties of polymer/layered silicate nanocomposites mainly depend on the dispersed state of layered silicates. The authors will also address the outline of the present research in the direction of PCNs including the discussion of technical problems and their possible solutions.

Shear induced mixing/demixing: Blends of homopolymers, of homopolymers plus copolymers, and blends in solution

Shear may shift the phase boundary towards the homogeneous state (shear induced mixing, SIM), or in the opposite direction (shear induced demixing, SID). SIM is the typical behavior of mixtures of components of low molar mass and polymer solutions, SID can be observed with solutions of high molar mass polymers and polymer blends at higher shear rates. The typical sequence with increasing shear rate is SIM, then occurrence of an isolated additional immiscible area (SLD), melting of this island into the main miscibility gap, and finally SIM again. A three phase line originates and ends in two critical end points. Raising pressure increases the shear effects. For copolymer containing systems SID is sometimes observed at very low shear rates, preceding the just mentioned sequence of shear influences.

Influence of intermolecular entanglements on the glass transition and structural relaxation behaviors of macromolecules. 2. Polystyrene and phenolphthalein poly(ether sulfone)

The effect of entanglements on the glass transition and structural relaxation behaviors has been studied for polystyrene (PS) and phenolphthalein poly(ether sulfone) (PES-C) samples by fast evaporation of the solution of concentrations varying from above the overlapping concentration to far below it, and compared to the results we have studied previously in PC. It has been found that for all the polymers we have studied, in the concentrated solution region, the T-g of the samples obtained from solution are independent of the change of concentration and are very close to that of normal bulk samples, whereas in the dilute solution region the T-g of the samples decrease with the logarithm of decreasing concentration. The critical concentrations that divide the two distinct regions for the three polymers are 0.9% g/mL for PC, 0.1% g/mL for PS, and 1% g/mL for PES-C. The decrease of T-g of the samples is interpreted by the decrease of intermolecular entanglements as the isolation of polymer chains, and the entanglement of polymer chains restrained the mobility of the segments. The structural relaxation behavior of the polymers is also found to be different from that of normal bulk samples. The enthalpies of single-chain samples are lower than that of the bulk ones, which correspond to the lower glass transition temperature; the peaks are lower and broader, and the relaxed enthalpy is much lower as compared to that of bulk samples. In the three polymers we have studied, the influence of change of entanglements on both the decrease in glass transition temperature and relaxed enthalpy is the most significant for PS and the least for PES-C. It is indicated that the interactions in the flexible polymers are weak; thus, the restraint of the entanglements on the mobility of the segments plays a more important role in the flexible polymers, and the change of entanglement in the flexible polymers has a more significant influence on the physical properties.

Study of the conductivity and side chain mobility of a comb-like polymer electrolyte using the dynamic mechanical method

Using poly(styrene-co-maleic anhydride) as a backbone and poly(ethylene glycol) methyl ether (PEGME) with different molecular weights as side chains, three comb-like polymers and their Li salt complexes were synthesized. The dynamic mechanical properties and conductivities were investigated. Results showed that the polymer electrolytes possess two glass transitions: alpha -transition and beta -transition, and the temperature dependence of the ionic conductivity shows WLF (Williams-Landel-Ferry) behavior. Based on the time-temperature equivalence principle, a master curve was constructed by selecting T-beta as reference temperature. The values of the WLF parameters (C-1 and C-2) were obtained and were found to be almost independent of the length of the PEGME side chain and the content of Li salt. By reference to T-0 = 50 degreesC. the relation between log tau (c) and c was found to be linear. The master curves are displaced progressively to higher frequencies as the molecular weight of the side chain is increased. The relation between log tau (n) and the molecular weight of the side chain is also linear. (C) 2001 Elsevier Science B.V. All rights reserved.