Novel pyridyl-stabilised rigid-rod organometallic polymers and their monomeric precursors

Reaction of trans-[Pt(NC5H4CHBu2n)(2)Cl-2] 1 with an excess of HC=CR (R = Ph, C6H4Me, C6H4NO2) affords the monomeric complex trans-[Pt(NC5H4CHBu2n)(2)(C=CR)(2)] (R = Ph 2a, C6H4Me 2b, C6H4NO2 2c), the trans arrangement of the alkynyl ligands being confirmed from spectroscopic data and by an X-ray analysis of 2c;when 1 is treated with 1 equiv, of HC=CC6H2(Me)(2)C=CH the polymer [Pt(NC5H4CHBu2n)(2)C=CC6H2Me2C=C](n) is formed, which is soluble in a range of organic solvents.

Synthesis and characterization of rigid-rod sulfonated polyimides bearing sulfobenzoyl side groups as proton exchange membranes

A novel wholly aromatic diamine, 2,2 '-bis(3-sulfobenzoyl)benzidine (2,2 '-BSBB), was successfully prepared by the reaction of 2,2 '-dibenzoylbenzidine (2,2 '-DBB) with fuming sulfuric acid. Copolymerization of 1,4,5,8-naphathlenetetracarboxylic dianhydride with 2,2 '-BSBB and 2,2 '-DBB generated a series of rigid-rod sulfonated polyimides. The synthesized copolymers with the -SO3H group on the side chain of polymers possessed high molecular weights revealed by their high viscosity and the formation of tough and flexible membranes. The copolymer membranes exhibited excellent oxidative stability and mechanical properties due to their fully aromatic structure extending through the backbone and pendent groups. They displayed clear anisotropic membrane swelling in water with negligibly small dimensional changes in the plane direction of the membrane. The proton conductivities of copolymer membranes increased with increasing IEC and temperature, reaching value above 1.25 x 10(-1) S/cm at 20 degrees C, which is higher than that of Nafion (R) 117 at the same measurement condition. They displayed reasonably high proton conductivity due to the higher acidity of benzoyl sulfonic acid group, the larger interchain spacing, which is available for water to occupy, taking their lower water uptake (WU) into account. Consequently, these materials proved to be promising as proton exchange membrane.

Morphology of polyimide fibers derived from 3,3 ',4,4 '-biphenyltetracarboxylic dianhydride and 4,4 '-oxydianiline

As one member of high performance fibers, aromatic polyimide fibers possess many advantages, such as high strength, high modulus, high and low temperature resistance, and radiation resistance. However, the preparation of the high performance fibers is so difficult that the commercial fibers have not been produced except P84 with good flame retardancy. In this report, a polyimide was synthesized from 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and 4,4'-oxydianiline (ODA) and the fibers were prepared from its solution by a dry-jet wet-spinning process. The formation of the as-spun fibers in different coagulation bath composition was discussed. Scanning electron microscope (SEMI) was employed to study the morphology of the as-spun fibers. As a result, the remnant solvent existed in the as-spun fibers generated from coagulation bath of alcohol and water. There were many fibrils and microvoids with the dimension of tens of nanometers in the fibers. One could observe the obvious fibrillation and the drawn fibers.

Phase transition and conformational variation of N-alkylated branched poly(ethyleneimine) comblike polymer

A series of branched poly(ethyleneimine) (PEI) derived polymers with different lengths of n-alkyl side chains, denoted as PEI(n)Cs (n = 12, 14, 16, 18, 20, number of carbon atoms in alkyl side group), have been prepared by a N-alkylation method, and systematically characterized by differential scanning calorimertry (DSC) and wide-angle X-ray diffraction (WARD) as well as Fourier transform infrared spectroscopy (FTIR). The side chains grafted on these comblike polymers are long enough to form crystalline phase composed of paraffin-like crystallites. The crystallization of the side chains forces the branched poly(ethyleneimine) molecules to pack into layered structure, between which the crystallites are located. The melting temperatures of the side chain crystallites increase from -12.36 to +51.49 degreesC with increasing the length of the side chains from n. = 12 to n = 20, which are a little bit lower than the corresponding pristine n-alkanes. PEI18C was taken as an example in this work for the investigation of phase transition and conformational variation of the side chains with temperature changing.

Phosphonate-Functionalized Polyfluorene as a Highly Water-Soluble Iron(III) Chemosensor

An anionic, phosphonate-functionalized polyfluorene, i.e., poly(9,9-bis(3'-phosphatepropyl)fluorene-alt-1,4-phenylene) sodium salt (PFPNa), has been synthesized by copolymerization of phosphonic acid-substituted 2,7-dibromofluorene and phenyldiboronic ester via direct Suzuki polycondensation reaction in DMF/water. Polymer PFPNa is highly soluble and emissive in water with a solubility of 60 mg/mL and a photoluminescence quantum yield of 75%. The absorption and fluorescence spectra of PFPNa are strongly dependent on pH value owing to the partial protonation of phosphate groups and the aggregation of the polymer chains.

Synthesis and properties of novel regioirregular polyimides from easily synthesized asymmetrical dichlorophthalimide monomers

New asymmetrical aromatic dichlorophthalimide monomers containing pendant groups (trifluoromethyl or methyl) were conveniently prepared from inexpensive and commercially available compounds. With these monomers, a new class of soluble polyimides with a regioirregular structure within the polymer backbone was obtained by the Ni(0)-catalyzed polymerization method. The structures of the polymers were confirmed by various spectroscopic techniques. The polyimides displayed better solubility and higher thermal stability than the corresponding regular polyimides. In addition, fluorinated polyimides in this study had low dielectric constants ranging from 2.52 to 2.78, low moisture absorptions of less than 0.59%, and low thermal expansion coefficients between 10.6 and 19.7 ppm/degrees C. The oxygen permeability coefficients and permeability selectivity of oxygen to nitrogen of the films were in the ranges of 2.99-4.20 barrer and 5.55-7.50, respectively. We have demonstrated that the synthetic pathway for polyimides provides a successful approach to increasing the solubility and processability of polyimides without sacrificing their thermal stability.

Synthesis and characterization of soluble poly(amideimide)s bearing triethylamine sulfonate groups as gas dehumidification membrane material

A series of soluble poly(amide-imide)s (PAIs) bearing triethylammonium sulfonate groups were synthesized directly using trimellitic anhydride chloride (TMAC) polycondensation with sulfonated diamine such as 2,2'-benzidinedisulfonic acid (BDSA), 4,4'-diaminodiphenyl ether-2,2'-disulfonic acid (ODADS), and nonsulfonated diamine 4,4-diaminodiphenyl methane in the presence of triethylamine. The resulting copolymers exhibited high molecular weights (high inherent viscosity), and a combination of desirable properties such as good solubility in dipolar aprotic solvents, film-forming capability, and good mechanical properties. Wide-angle X-ray diffraction revealed that the polymers were amorphous. These copolymers showed high permeability coefficients of water vapor because of the presence of the hydrophilic triethylammonium sulfonate groups. The water vapor permeability coefficients (P-w) and permselectivity coefficients of water vapor to nitrogen and methane [alpha(H2O/N-2) and (alpha(H2O/CH4)] Of the films increased with increasing the amount of the triethylammonium sulfonated groups.

Synthesis and properties of soluble polyimides based on isomeric ditrifluoromethyl substituted 1,4-bis(4-aminophenoxy)benzene

A new fluorinated diamine monomer, [1,4-bis(4-amino-3-trifluoromethylphenoxy)benzene (2)], and a known isomeric analog 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene (3) were synthesized. A series of organosoluble polyimides Ia-d and IIa were prepared from the diamines (2, 3) and dianhydrides (a-d) by a high-temperature one-step method. The effects of the trifluoromethyl substituents on the properties of polyimides were evaluated through the study of their soluble, thermal, optical, and gas permeability properties. Polyimides (Ia-d) had glass transition temperatures between 229 and 279 degrees C, and the temperatures at 5% weight loss ranged from 510 to 533 degrees C under nitrogen. These polyimides could be cast into flexible and tough membranes from DMAc solutions. The membranes had tensile strengths in the range of 137-169 MPa, tensile modulus in the range of 1.6-2.2 GPa and elongations at break from 11% to 14%. The polyimide la with trifluoromethyl groups ortho to the imide nitrogen exhibited enhanced gas permeability, solubility, transparency, and thermal stability compared with the isomeric polyimide IIa with the CF3 group meta to the imide nitrogen.

Tailored conductivity in ion implanted polyetheretherketone

Ion implantation can be used to confer electrical conductivity upon conventional insulating polymers such as polyetheretherketone (PEEK). We have implanted PEEK films using three different types of ion implantation: conventional inert gas and metal ion implantation, and ion beam mixing. We have applied a number of analytical techniques to compare the chemical, structural and electrical properties of these films. The most effective means of increasing electrical conductivity appears to be via ion beam mixing of metals into the polymer, followed by metal ion implantation and finally, inert gas ion implantation. Our results suggest that in all cases, the conducting region corresponds to the implanted layer in the near surface to a depth of similar to750 Angstrom (ion beam mixed) to similar to5000 Angstrom (metal ion). This latter value is significantly higher than would be expected from a purely ballistic standpoint, and can only be attributed to thermal inter-diffusion. Our data also indicates that graphitic carbon is formed within the implant region by chain scission and subsequent cross-linking. All ion implanted samples retained their bulk mechanical properties, i.e. they remained flexible. The implant layers showed no signs of de-lamination. We believe this to be the first comparative study between different implantation techniques, and our results support the proposition that soft electronic circuitry and devices can be created by conductivity engineering with ion beams. (C) 2004 Elsevier B.V. All rights reserved.

A biomechanical investigation of dual growing rods used for fusionless scoliosis correction

Background The use of dual growing rods is a fusionless surgical approach to the treatment of early onset scoliosis (EOS), which aims of harness potential growth in order to correct spinal deformity. The purpose of this study was to compare the in-vitro biomechanical response of two different dual rod designs under axial rotation loading. Methods Six porcine spines were dissected into seven level thoracolumbar multi-segmental units. Each specimen was mounted and tested in a biaxial Instron machine, undergoing nondestructive left/right axial rotation to peak moments of 4Nm at a constant rotation rate of 8deg.s-1. A motion tracking system (Optotrak) measured 3D displacements of individual vertebrae. Each spine was tested in an un-instrumented state first and then with appropriately sized semi-constrained growing rods and ‘rigid’ rods in alternating sequence. Range of motion, neutral zone size and stiffness were calculated from the moment-rotation curves and intervertebral ranges of motion were calculated from Optotrak data. Findings Irrespective of test sequence, rigid rods showed significantly reduction of total rotation across all instrumented levels (with increased stiffness) whilst semi-constrained rods exhibited similar rotation behavior to the un-instrumented (P<0.05). An 11% and 8% increase in stiffness for left and right axial rotation respectively and 15% reduction in total range of motion was recorded with dual rigid rods compared with semi-constrained rods. Interpretation Based on these findings, the semi-constrained growing rods do not increase axial rotation stiffness compared with un-instrumented spines. This is thought to provide a more physiological environment for the growing spine compared to dual rigid rod constructs.

Spin and relativistic motion of bound states

The wave functions of moving bound states may be expected to contract in the direction of motion, in analogy to a rigid rod in classical special relativity, when the constituents are at equal (ordinary) time. Indeed, the Lorentz contraction of wave functions is often appealed to in qualitative discussions. However, only few field theory studies exist of equal-time wave functions in motion. In this thesis I use the Bethe-Salpeter formalism to study the wave function of a weakly bound state such as a hydrogen atom or positronium in a general frame. The wave function of the e^-e^+ component of positronium indeed turns out to Lorentz contract both in 1+1 and in 3+1 dimensional quantum electrodynamics, whereas the next-to-leading e^-e^+\gamma Fock component of the 3+1 dimensional theory deviates from classical contraction. The second topic of this thesis concerns single spin asymmetries measured in scattering on polarized bound states. Such spin asymmetries have so far mainly been analyzed using the twist expansion of perturbative QCD. I note that QCD vacuum effects may give rise to a helicity flip in the soft rescattering of the struck quark, and that this would cause a nonvanishing spin asymmetry in \ell p^\uparrow -> \ell' + \pi + X in the Bjorken limit. An analogous asymmetry may arise in p p^\uparrow -> \pi + X from Pomeron-Odderon interference, if the Odderon has a helicity-flip coupling. Finally, I study the possibility that the large single spin asymmetry observed in p p^\uparrow -> \pi(x_F,k_\perp) + X when the pion carries a high momentum fraction x_F of the polarized proton momentum arises from coherent effects involving the entire polarized bound state.

DNA Compaction by a Dendrimer

At physiological pH, a PAMAM dendrimer is positively charged and can effectively bind negatively charged DNA. Currently, there has been great interest in understanding this complexation reaction both for fundamental (as a model for complex biological reactions) as well as for practical (as a gene delivery material and probe for sensing DNA sequence) reasons. Here, we have studied the complexation between double-stranded DNA (dsDNA) and various generations of PAMAM dendrimers (G3-05) through atomistic molecular dynamics simulations in the presence of water and ions. We report the compaction of DNA on a nanosecond time scale. This is remarkable, given the fact that such a short DNA duplex with a length close to 13 nm is otherwise thought to be a rigid rod. Using several nanoseconds long MD simulations, we have observed various binding modes of dsDNA and dendrimers for various generations of PAMAM dendrimers at varying charge ratios, and it confirms some of the binding modes proposed earlier. The binding is driven by the electrostatic interaction, and the larger the dendrimer charge, the stronger the binding affinity. As DNA wraps/binds to the dendrimer, counterions originally condensed onto DNA (Na+) and the dendrimer (Cl-) get released. We calculate the entropy of counterions and show that there is gain in entropy due to counterion release during the complexation. MD simulations demonstrate that, when the charge ratio is greater than 1 (as in the case of the G5 dendrimer), the optimal wrapping of DNA is observed. Calculated binding energies of the complexation follow the trend G5 > 04 > 03, in accordance with the experimental data. For a lower-generation dendrimer, such as G3, and, to some extent, for G4 also, we see considerable deformation in the dendrimer structure due to their flexible nature. We have also calculated the various helicoidal parameters of DNA to study the effect of dendrimer binding on the structure of DNA. The B form of the DNA is well preserved in the complex, as is evident from various helical parameters, justifying the use of the PAMAM dendrimer as a suitable delivery vehicle.

Synthesis and properties of polyquinolines and polyanthrazolines containing pyrrole units in the main chain

A series of eight new polyquinolines and polyanthrazolines with pyrrole isomeric units in main chain were synthesized and characterized. The new polymers showed high glass transition temperatures (T-g = 242-339 degreesC) and excellent thermal stability (T-5% = 398-536 degreesC in air, TGA). Compared to the series of polyanthrazolines, the series of polyquinolines exhibited higher thermal stability, better solubility in common organic solvents, and lower maximum absorption wavelengths (lambda(max)(a)). Polyanthrazolines with 2,5-pyrrole linkage showed an unusually high lambda(max)(a) (565 nm) and small band gap (2.02 eV). All polymers in solution had low photoluminescence quantum yields between 10(-2%) and 10(-5%) and excited-state lifetimes of 0.28-1.29 ns. The effects of molecular structure, especially pyrrole linkage structures, on the electronic structure, thermodynamics, and some of the optical properties of the polymers were explored. A model of hydrogen bonds in the main chain of the polymers was suggested to explain the difference in the properties of the isomer polymers. In addition, a polyquinoline (PBM) was chosen to examine the proton conductivity; the result indicated that the PBM/H3PO4 complex exhibited a high conductivity of 1.5 x 10(-3) S cm(-1) at 157 degreesC.

The effect of chain flexibility and chain mobility on radiation crosslinking of polymers

Radiation crosslinking of polymers mainly depends on the structure of polymer chain. The flexibility and mobility of chain directly influence the possibility of the reactive radicals recombination. Flexible chain is easier to crosslink than rigid-chain polymer. The latter must be crosslinked at high temperature, as most polymers can only crosslink above their melting point. Structural effect also influences the mechanism of radiation crosslinking of polymers. We find from the results in literature and in our laboratory that, the flexibility chain polymer mainly crosslinked with H type, but the rigid chain polymer mainly crosslinked with Y type. (C) 2001 Published by Elsevier Science Ltd.

HREM IMAGING OF POLY(ARYL-ETHER-KETONE) CRYSTAL

High resolution transmission electron microscope (HREM) was used to observe the rigid chain polymer poly(aryl-ether-ketone) (PEK), so as to study the morphology of the crystals and molecular arrangement within a crystal.Many kinds of material crystal structures have been studied with HREM in recent years. So far as polymeric materials are concerned, the application of HREM