Synthesis, characterization and ionic conductivity of solid polymer electrolytes based on modified alternating maleic anhydride copolymer with oligo(oxyethylene) side chains

Three comb polymers (CP) based on modified alternating methyl vinyl ether/maleic anhydride copolymer with oligo-oxyethylene side chains of the type -O(CH2CH2O)(n)CH3 were synthesized and characterized, and the ionic conductivity of CP/salt complexes is reported. The conductivity of these complexes was about 10(-5)-10(-6) S cm(-1) at room temperature. The conductivity, which displayed non-Arrhenius behaviour, was analysed using the Vogel-Tammann-Fulcher equation. The conductivity maxima appear at lower salt concentration, when CP has longer side chains. Infrared (i.r.) was used to study the cation-polymer interaction. I.r. results also indicate that the ester in CP might decompose at 140 degrees C and reproduce the maleic anhydride ring. (C) 1997 Elsevier Science Ltd.

Ionic conductivity of solid polymer electrolytes based on modified alternating maleic anhydride copolymer with oligo(oxyethylene) side chains

Comb-like polymers (CP) based on modified alternating methyl vinyl ether/maleic anhydride copolymer with oligo-oxyethylene side chains of the type -O(CH2CH2O)(n)CH3 have been synthesized and characterized, and complexed with lithium salts to form amorphous polymer electrolytes. CP/salt complexes showed conductivity up to 10(-5)Scm(-1) at room temperature. The temperature dependence of ionic conductivity suggests that the ion transport is controlled by segmental motion of the polymer, shown by linear curves obtained in Vogel-Tammann-Fulcher plots. The ionic conductivity maximum moves to a higher salt concentration as the temperature increases. IR results indicate that the ester in CP might decompose at 140 degrees C and reproduce the maleic anhydride ring.

The synthesis and thermotropic liquid crystalline behavior of the novel poly(aryl ether ketone)s containing chloro-side group

The novel poly(aryl ether ketone)s containing chloro-side group were synthesized by nucleophilic substitution reactions of 4,4'-biphenol and chlorohydroquinone with either 4,4'-difluorobenzophenone(BP/CH/DF) or 1,4-bis(p-fluorobenzoyl)benzene (BP/CH/BF) and their thermotropic liquid crystalline properties were characterized by a variety of experimental techniques. The thermotropic liquid crystalline behavior was observed in the copolymers containing 50 and 70% biphenol. Melting transition (Tm) and isotropization transition (Ti) both appeared in the DSC thermograms. A banded texture was formed after shearing the sample in the liquid crystalline state. The novel poly(aryl ether ketone)s had relatively higher glass transition temperature (Tg) in the range of 168 similar to 200 degrees C and lower melting temperature (Tm) in the range of 290 similar to 340 degrees C. The thermal stability (Td) was in the range of 430 similar to 490 degrees C.

Single-chain single crystals of gutta-percha

Single-chain single crystals of gutta-percha have been observed by transmission electron microscopy of atomizer-sprayed particles deposited from a very dilute solution in chloroform onto a carbon film which had a filter paper wetted with ethanol in contact with its under side. Selected-area electron diffraction patterns of crystals having no definite crystal profiles showed that the crystals were of the low-melting crystalline form and that the chain segments in the single crystals were standing up from the substrate during crystallization. In cases of single crystals showing sharply defined crystal profiles, electron diffraction patterns showed that they were neither of the low-melting form nor the high-melting form. The structure of this new crystalline modification needs further studies.

Synthesis and ionic conductivity studies of solid polymer electrolytes based on modified alternating maleic anhydride copolymer with oligo(oxyethylene) side chains

Comb-like polymers (CP) based on modified alternating methyl vinyl ether/maleic anhydride copolymer with oligo-oxyethylene side chains of the type-O(CH2CH2O)(n)CH3 have been synthesized and characterized, and complexed with LiNO3 to form an amorphous polymer electrolyte. CP/salt complexes showed conductivity up to 10(-5) S/cm at room temperature. The temperature dependence of ionic conductivity suggests that the ion transport is controlled by segmental motion of the polymer, shown by linear curves obtained in Vogel-Tammann-Fulcher plots. The ionic conductivity maximum moves to a higher salt concentration as the temperature increases. IR results also indicate that the ester in CP might decompose at 140 degrees C and reproduce the maleic anhydride ring.

Local chain motions in a dilute solution of phenolphthalein poly(ether sulfone)

C-13 and H-1 relaxation times were measured as a function of temperature in two magnetic fields for dilute solutions of phenolphthalein poly(ether sulfone) (PES-C) in deuterated chloroform. The spin-lattice relaxation times were interpreted in terms of segmental motion characterized by the sharp cutoff model of Jones and Stockmayer (J. S. model). The phenyl group rotation is treated as a stochastic diffusion by the J. S. model. The restricted butterfly motion of the phenyl group attached to the cardo ring in PES-C is mentioned but is not discussed in detail in this work. Correlation times for the segmental motion are in the picosecond range which indicates the high flexibility of PES-C chains. The correlation time for the phenyl group internal rotation is similar to that of the segmental motion. The temperature dependence of these motions is weak. The apparent activation energy of the motions considered is less than 10 kJ/mol. The simulating results for PES are also reasonable considering the differences in structure compared with PES-C. The correlation times and the apparent activation energy obtained using the J. S. model for the main chain motion of PES-C are the same as those obtained using the damped orientational diffusion model and the conformational jump model.

Study on the modified electrode of conducting polymers .3. Electron spin resonance characteristic of polypyrrole film electrode doped with heteropolyanions

The ESR of PPy films doped with Co (W2O7)(6)(10-) and CuW12O406- ions were reported and discussed. Results show that heteropolyanions not only play the role of neutralizing electricity in the PPy film, but also interact with the PPy molecular chain to form some adducts. The adducts affect the electronic structure of the PPy film and are unstable at more positive or more negative potentials. Dysonian ESR lineshape was recorded for the dry PPy film with CuW12O406- for the first time.

MOLECULAR-GEOMETRY AND CHAIN ENTANGLEMENT - PARAMETERS FOR THE TUBE MODEL

The tube diameter in the reptation model is the distance between a given chain segment and its nearest segment in adjacent chains. This dimension is thus related to the cross-sectional area of polymer chains and the nearest approach among chains, without effects of thermal fluctuation and steric repulsion. Prior calculated tube diameters are much larger, about 5 times, than the actual chain cross-sectional areas. This is ascribed to the local freedom required for mutual rearrangement among neighboring chain segments. This tube diameter concept seems to us to infer a relationship to the corresponding entanglement spacing. Indeed, we report here that the critical molecular weight, M(c), for the onset of entanglements is found to be M(c) = 28 A/([R2]0/M), where A is the chain cross-sectional area and [R2]0 the mean-square end-to-end distance of a freely jointed chain of molecular weight M. The new, computed relationship between the critical number of backbone atoms for entanglement and the chain cross-sectional area of polymers, N(c) = A0,44, is concordant with the cross-sectional area of polymer chains being the parameter controlling the critical entanglement number of backbone atoms of flexible polymers.

CONFORMATION OF PHENYL RINGS IN THE HELICAL CHAIN POLYMER POLY(TRIPHENYLMETHYL METHACRYLATE)

The conformation of phenyl rings in the side groups of the helical chain polymer poly(tripenyl-methyl methacrylate) (1) in solution was studied by spectroscopic methods. According to the Raman spectrum the phenyl rings of 1 and triphenylmethyl methacrylate in solution have the same depolarization ratio at 1002 cm-1. The electronic spectra (ultraviolet and fluorescence) of 1 are similar to those of model substances, except for the "red shift" of the spectra of about 5 nm. It was concluded that the phenyl rings can rotate around the phenyl-C bond.

A SIMPLE METHOD FOR PREDICTION OF GAS-PERMEABILITY OF POLYMERS FROM THEIR MOLECULAR-STRUCTURE

A method for the prediction of gas permeabilities (P) through polymers from their chemical structure has been developed on the basis of the ratio of molar free volume to molar cohesive energy, V(f)/E(coh). The permeation of small gas molecules through polymer membranes is dependent on the chain packing density measured by V(f) and segmental motion of polymer chains measured by E(coh). But no simple relationship between P and V(f) or E(coh) alone was found. The permeability data of more than 60 polymers covering 7 orders of magnitude for six gases have been treated with linear regression analysis. All plots of log P vs. V(f)/E(coh) gave good straight lines. It is also found that a linear relationship holds when plotting both the intercepts and slopes of log P vs. V(f)/E(coh) lines against square of the diameters of gas molecules. Therefore, the permeabilities of all the non-swelling gases through a great variety of polymers can be estimated using two correlations above. Moreover, this method is more accurate than others in the literature and may found useful for the selection of gas separation or barrier membrane materials.

MOLECULAR CHAIN STRUCTURE OF DOPED POLYANILINE

The chain structure of polyaniline doped with HCl or CF_3COOH has been investigated by FTIR, solid state ~(13)CNMR, resonance laser Raman and UV-VIS spectroscopies. The results show that during the protonic acid doping, a partial redox reaction takes place between the quinone-diimine and benzene-diamine units and it leads to a long conjugate system with a certain charge distribution.

Phase transfer catalysts drive diverse organic solvent solubility of single-walled carbon nanotubes helically wrapped by ionic, semiconducting polymers.

Use of phase transfer catalysts such as 18-crown-6 enables ionic, linear conjugated poly[2,6-{1,5-bis(3-propoxysulfonicacidsodiumsalt)}naphthylene]ethynylene (PNES) to efficiently disperse single-walled carbon nanotubes (SWNTs) in multiple organic solvents under standard ultrasonication methods. Steady-state electronic absorption spectroscopy, atomic force microscopy (AFM), and transmission electron microscopy (TEM) reveal that these SWNT suspensions are composed almost exclusively of individualized tubes. High-resolution TEM and AFM data show that the interaction of PNES with SWNTs in both protic and aprotic organic solvents provides a self-assembled superstructure in which a PNES monolayer helically wraps the nanotube surface with periodic and constant morphology (observed helical pitch length = 10 ± 2 nm); time-dependent examination of these suspensions indicates that these structures persist in solution over periods that span at least several months. Pump-probe transient absorption spectroscopy reveals that the excited state lifetimes and exciton binding energies of these well-defined nanotube-semiconducting polymer hybrid structures remain unchanged relative to analogous benchmark data acquired previously for standard sodium dodecylsulfate (SDS)-SWNT suspensions, regardless of solvent. These results demonstrate that the use of phase transfer catalysts with ionic semiconducting polymers that helically wrap SWNTs provide well-defined structures that solubulize SWNTs in a wide range of organic solvents while preserving critical nanotube semiconducting and conducting properties.

Study of the transamidative ring expansion of N--halogenoalkyl--lactams of alkyl chain lengths 2–12 in liquid ammonia and other liquid amines: syntheses of 7-, 8- and 9-membered 1,5-diaza cyclic ketones, including routes to (±)-dihydroperiphylline and (±)-celabenzine

N-(3-Halogenopropyl)-4-phenylazetidin-2-ones undergo amination in liquid ammonia followed by transamidative ring expansion to give the eight-membered 4-phenyl -1,5-diazacyclooctan-2-one in excellent yield. Ring expansion of the amines in liquid ammonia is found to be much more effective than in hydrocarbon solvents. Formation of 7-, 8-, and 9-membered azalactams from the requisite -halogenoalkyl--lactams is an excellent synthetic process, though it is not applicable to 10membered rings. In the cases of rings of 13-, 15- and 17-members, although amination and apparent expansion takes place, the large rings appear not to be stable to ammonia and the final products are acyclic amides. N-[4-Halogenobut-2(Z)-enyl]-4-phenylazetidin-2-one satisfactorily forms a 9-membered (Z)-olefinic azalactam, but the (E)-isomer gives an acyclic amino amide. By using alkyl-substituted -lactam side-chains, C-substituted medium rings can be obtained; the relative instability of N-acyl -lactams to ammonia, however, leads to acylamino amides rather than expanded rings.Employing ethylamine in place of ammonia, it is shown that N-ethylated azalactams are formed satisfactorily, and using allylamine, N-allyl medium rings capable of further elaboration are obtained. The chemistry of these systems is discussed. Using transamidation in liquid ammonia, a short synthesis of the 9-membered spermidine alkaloid (±)-dihydroperiphylline is reported. Synthesis of key intermediates, whose transformation into the 13-membered alkaloids of the celabenzine group has already been effected, has been carried out.X-Ray single-crystal structure determinations for 4-phenyl-1,5-diazacyclononan-2-one, trans-4-phenyl-8-methyl-1,5-diazacyclooctan-2-one and (Z)-4-phenyl-1,5-diazacyclonon-7-en-2-one are reported, and comment is made on certain conformational features.

Dual functional ionic liquids as plasticisers and antimicrobial agents for medical polymers

Contamination of medical devices with bacteria such as Meticillin resistant Staphylococcus aureus (MRSA) is of great clinical concern. Poly(vinyl chloride) is widely used in the production of medical devices, such as catheters. The flexibility of catheter tubing is derived from the addition of plasticisers. Here, we report the design of two dual functional ionic liquids, 1-ethylpyridinium docusate and tributyl(2-hydroxyethyl)phosphonium docusate, which uniquely provide a plasticising effect, and exhibit antimicrobial and antibiofilm-forming activity to a range of antibiotic resistant bacteria. The plasticisation of poly(vinyl chloride) was tailored as a function of ionic liquid concentration. The effective antimicrobial behaviour of both ionic liquids originates from the chemical structure of the anion or cation and is not limited to the length of the alkyl chain on the anion/cation. The design approach adopted will be useful in developing ionic liquids as multi-functional additives for polymers.

Interplay of the Wzx translocase and the corresponding polymerase and chain length regulator proteins in the translocation and periplasmic assembly of lipopolysaccharide o antigen

Genetic evidence suggests that a family of bacterial and eukaryotic integral membrane proteins (referred to as Wzx and Rft1, respectively) mediates the transbilayer movement of isoprenoid lipid-linked glycans. Recent work in our laboratory has shown that Wzx proteins involved in O-antigen lipopolysaccharide (LPS) assembly have relaxed specificity for the carbohydrate structure of the O-antigen subunit. Furthermore, the proximal sugar bound to the isoprenoid lipid carrier, undecaprenyl-phosphate (Und-P), is the minimal structure required for translocation. In Escherichia coli K-12, N-acetylglucosamine (GlcNAc) is the proximal sugar of the O16 and enterobacterial common antigen (ECA) subunits. Both O16 and ECA systems have their respective translocases, WzxO16 and WzxE, and also corresponding polymerases (WzyO16 and WzyE) and O-antigen chain-length regulators (WzzO16 and WzzE), respectively. In this study, we show that the E. coli wzxE gene can fully complement a wzxO16 translocase deletion mutant only if the majority of the ECA gene cluster is deleted. In addition, we demonstrate that introduction of plasmids expressing either the WzyE polymerase or the WzzE chain-length regulator proteins drastically reduces the O16 LPS-complementing activity of WzxE. We also show that this property is not unique to WzxE, since WzxO16 and WzxO7 can cross-complement translocase defects in the O16 and O7 antigen clusters only in the absence of their corresponding Wzz and Wzy proteins. These genetic data are consistent with the notion that the translocation of O-antigen and ECA subunits across the plasma membrane and the subsequent assembly of periplasmic O-antigen and ECA Und-PP-linked polymers depend on interactions among Wzx, Wzz, and Wzy, which presumably form a multiprotein complex.