Hybrid organogels and aerogels from co-assembly of structurally different low molecular weight gelators

The blending of perfluorinated bile ester derivatives with the gelator 2,3-didecyloxyanthracene (DDOA) yields a new class of hybrid organo- and aerogels displaying a combination of optical and mechanical properties that differ from those of pure gels. Indeed, the nanofibers constituting the hybrid organogels emit polarized blue light and display dichroic near-UV absorption via the achiral DDOA molecules, thanks to their association with a chiral bile ester. Moreover, the thermal stability and the mechanical yield stress of the mixed organogels in DMSO are enhanced for blends of DDOA with the deoxycholic gelator (DC11) having a C-11 chain, as compared to the pure components' gels. When the chain length of the ester is increased to C-13 (DC13) a novel compound for aerogel formation directly in scCO(2) is obtained under the studied conditions. A mixture of this compound with DDOA is also able to gelate scCO(2) leading to novel composite aerogel materials. As revealed by SAXS measurements, the hybrid and the pure DDOA and DC13 aerogels display cell parameters that are very similar. These SAXS experiments suggest that crystallographic conditions are very favorable for the growth of hybrid molecular arrangements in which DDOA and DC13 units could be interchanged. Specific molecular interactions between two components are not always a pre-requisite condition for the formation of a hybrid nanostructured material in which the components mutually induce properties.

Buckling in polymer monolayers: Molecular-weight dependence

We present systematic investigations of buckling in Langmuir monolayers of polyvinyl acetate formed at the air-water interface. On compression the polymer monolayers are converted to a continuous membrane with a thickness of ~2–3 nm of well-defined periodicity, lambdab. Above a certain surface concentration the membrane undergoes a morphological transition buckling, leading to the formation of striped patterns. The periodicity seems to depend on molecular weight as per the predictions of the gravity-bending buckling formalism of Milner et al. for fluidlike films on water. However anomalously low values of bending rigidity and Young's modulus are obtained using this formalism. Hence we have considered an alternative model of buckling-based solidlike films on viscoelastic substrates. The values of bending rigidity and Young's modulus obtained by this method, although lower than expected, are closer to the bulk values. Remarkably, no buckling is found to occur above a certain molecular weight. We have tried to explain the observed molecular-weight dependence in terms of the variation in isothermal compressive modulus of the monolayers with surface concentration as well as provided possible explanations for the obtained low values of mechanical properties similar to that observed for ultrathin polymer films.

Effect of Molecular Weight on the Thermal and Impact Sensitivity of Polymers in Propellants

Abstract is not available.

A possible role for a low molecular weight peptide in regulation of testosterone production by rat Leydig cells

Sodium dodecyl sulphate-polyacrylamide gel electrophoresis of Percoll purified Leydig cell proteins from 20- and 120-day-old rats revealed a significant decrease in a low molecular weight peptide in the adult rats. Administration of human chorionic gonadotropin to immature rats resulted in a decrease in the low molecular weight peptide along with increase in testosterone production. Modulation of the peptide by human chorionic gonadotropin could be confirmed by Western blotting. The presence of a similar peptide could be detected by Western blotting in testes of immature mouse, hamster, guinea pig but not in adrenal, placenta and corpus luteum. Administration of testosterone propionate which is known to inhibit the pituitary luteinizing hormone levels in adult rats resulted in an increase in the low molecular weight peptide, as checked by Western blotting. It is suggested that this peptide may have a role in regulation of acquisition of responsiveness to luteinizing hormone by immature rat Leydig cells.

Structural effects on the vaporization of high molecular weight esters

To understand the effect of molecular weight and branching on the heats of vaporization (AH,) and their flow behavior, AH, and viscosity (7) were measured at different temperatures in the high molecular weight ester series: linear flexible di-n-alkyl sebacates and compact branched triglycerides with molecular weight ranging from 300 to 900. AHv" values (AHv corrected to 298 K) have been obtained with experimental AH, and also computed according to the group additivity method; a smaller-CH,- group value of 3.8 kJ mol-' compared to the normal value of 5.0 kJ mol-' is found to give good agreement with the experimental data (within 2-5% error). Both ester series have the same AH," irrespective of their molecular features, namely,shape, flexibility, and polarity, suggesting the coiling of the molecules during vaporization. The segmental motion of these ester series during their flow and its dependence on their molecular features unlike AH,' are demonstrated by the correlation of the enthalpy of activation for viscous flow (AH*) and the ratio AE,/AH* = n (AE, is the energy of vaporization) with molecular weight.

Structural dependence of density in high molecular weight esters

The effect of molecular structure on density has been examined in high molecular weight esters (molecular weight 300-900), having varying degrees of branching. Densities were calculated from an empirical equation, which agrees well with the experimental values (error +/-1.5%), irrespective of branching. Since density is related to molecular packing and hence to the molecular rotation, in n-alkanes, the glass transition temperature (T(g)) and density both increase with molecular weight, and hence T(g) is directly related to the density. The esters exhibit a complex behavior. In linear esters the T(g) decreases with molecular weight which is explained from group contribution and molecular interactions. In the +-branched esters, however, T(g) decreases with molecular weight until the molecular weight reaches 600 and increases sharply thereafter. The Y-branched esters show an intermediate behavior. The dependence of T(g) on molecular weight has been explained from the segmental motion.

Control of Molecular Weight and Polydispersity of Hyperbranched Polymers Using a Reactive B(3) Core: A Single-Step Route to Orthogonally Functionalizable Hyperbranched Polymers

Molecular weight and polydispersity are two structural features of hyperbranched polymers that are difficult to control because of the statistical nature of the step-growth polycondensation of AB(2) type monomers; the statistical growth also causes the polydispersity index to increase with percent conversion (or molecular weight). We demonstrate that using controlled amounts of a specifically designed B(3) core, containing B-type functionality that are more reactive than those present in the AB(2) monomer, both the molecular weight and the polydispersity can be readily controlled; the PDI was shown to improve with increasing mole-fraction of the B(3) core while the polymer molecular weight showed an expected decrease. Incorporation of a ``clickable'' propargyl group in the B(3) core unit permitted the generation of a core-functionalizable hyperbranched polymer. Importantly, this clickable core, in combination with a recently developed AB(2) monomer, wherein the B-type groups are allyl ethers and A is an hydroxyl group, led to the generation of a hyperbranched polymer carrying orthogonally functionalizable core and peripheral groups, via a single-step melt polycondensation. Selective functionalization of the core and periphery using two different types of chromophores was achieved, and the occurrence of fluorescence resonance energy transfer (FRET) between the donor and acceptor chromophores was demonstrated.

Control of Molecular Weight and Polydispersity of Hyperbranched Polymers Using a Reactive B(3) Core: A Single-Step Route to Orthogonally Functionalizable Hyperbranched Polymers

Molecular weight and polydispersity are two structural features of hyperbranched polymers that are difficult to control because of the statistical nature of the step-growth polycondensation of AB(2) type monomers; the statistical growth also causes the polydispersity index to increase with percent conversion (or molecular weight). We demonstrate that using controlled amounts of a specifically designed B(3) core, containing B-type functionality that are more reactive than those present in the AB(2) monomer, both the molecular weight and the polydispersity can be readily controlled; the PDI was shown to improve with increasing mole-fraction of the B(3) core while the polymer molecular weight showed an expected decrease. Incorporation of a ``clickable'' propargyl group in the B(3) core unit permitted the generation of a core-functionalizable hyperbranched polymer. Importantly, this clickable core, in combination with a recently developed AB(2) monomer, wherein the B-type groups are allyl ethers and A is an hydroxyl group, led to the generation of a hyperbranched polymer carrying orthogonally functionalizable core and peripheral groups, via a single-step melt polycondensation. Selective functionalization of the core and periphery using two different types of chromophores was achieved, and the occurrence of fluorescence resonance energy transfer (FRET) between the donor and acceptor chromophores was demonstrated.

Synthesis and characterization of high molecular weight polyaniline for organic electronic applications

High molecular weight polyaniline (PANI) was synthesized by a combined procedure incorporating various synthesis methods. Temperature and open circuit potential of the reaction mixture were collected to monitor the reaction progress. The polymer is characterized by various techniques including gel permeation chromatography, dynamic light scattering, infrared spectroscopy, solid-state nuclear magnetic resonance, and differential scanning calorimetry for elucidating the molecular architecture obtained by this method. As-synthesized PANI was found to possess high molecular weight, reduced branching, reduced cross-linking, and to predominantly consist of linear polymer chains. This polymer was also found to be more stable in solution form. JV characteristics of as-synthesized PANI films indicate a high current density which is due to increased free pathways and less traps for the charge transport to occur in PANI films. POLYM. ENG. SCI., 2012. (C) 2012 Society of Plastics Engineers

Combinatorial effect of rolling and carbonaceous nanoparticles on the evolution of crystallographic texture and structural properties of ultra high molecular weight polyethylene

Ultra high molecular weight polyethylene (PE) is a structural polymer widely used in biomedical implants. The mechanical properties of PE can be improved either by controlled crystalline orientation (texture) or by the addition of reinforcing agents. However, the combinatorial effect has not received much attention. The objective of this study was to characterize the structure and mechanical properties of PE composites incorporating multiwall carbon nanotubes (MWCNT) and reduced graphene oxide (RGO) subjected to hot rolling. The wide angle X-ray diffraction studies revealed that mechanical deformation resulted in a mixture of orthorhombic and monoclinic crystals. Furthermore, the presence of nanoparticles resulted in lower crystallinity in PE with smaller crystallite size, more so in RGO than in MWCNT composites. Rolling strengthened the texture of both orthorhombic and the monoclinic phases in PE. Presence of RGO weakened the texture of both phases of PE after rolling whereas MWCNT only mildly weakened the texture. This resulted in a reduction in the elastic modulus of RGO composites whereas moduli of neat polymer and the MWCNT composite increased after rolling. This study provides new insight into the role of nanoparticles in texture evolution during polymer processing with implications for processing of structural polymer composites.

Antipyrine complexes of titanium(IV), zirconium(iv), thorium(IV) and uranium(VI) perchlorates

Antipyrine complexes of TiO2+, ZrO2+, Zr4+, Th4+ and UO2+2 perchlorates with molecular formulae TiO(Apy)4(ClO4)2, ZrO(Apy)3(ClO4)2, Zr(Apy)6(ClO4)4, Th(Apy)7(ClO4)4 and UO2(Apy)5(ClO4)2 have been prepared and characterized. The complexes are stable in air at room temperature and decompose exothermally at ~3OO °C. The i.r. study indicates the bonding of the antipyrine to the metal ion through its carbonyl oxygen. The nature of the bonding of the perchlorate and the stereochemistry of the complexes are discussed in the light of infrared spectra, conductivity in solvents of different polarity, and molecular weight measurements. From the UO2+2 group frequencies, the force constant K and rU-o are found to be 6.29 × 105 dynes/ cm-1 and 1.74 Å, respectively.

Light scattering studies on solutions of chlorinated rubber

Measurements have been made of the depolarisation factors \sigma u ,\sigma v ,\sigma h, and the intensity of scattering in the horizontal transverse direction, in the case of solutions of four different samples of chlorinated rubber in carbon tetrachloride. The size, shape and molecular weight of the micelles have been deduced by the application of the light scattering theories of Gans, Vrklajan and Katalinic and Debye. The extent to which the degradation of the rubber molecule occurs on chlorination has also been assessed.

Curing Reactions in Elastomers. 11. Carboxy- Terminated Polybutadiene

Attempts have been made to understand the curing reactions in carboxy-terminated polybutadiene (CTPB), which happens to be the most practical binder in advanced solid composite propellants. The curing of CTPB has been studied for different ratios of curing agents (MAPO and Epoxide) by gel content, molecular weight, crosslink density, and penetration temperature measurements, and the optimum composition of curators for effective curing of CTPB has been determined. Activation energy calculations on the curing of CTPB with 9.5% epoxide and 0.5% MAPO in the temperature range 75100°C gave 14.1 kcal/mol for which a diffusion-controlled or acid-catalyzed epoxide ring opening mechanism has been suggested for the curing process in CTPB.

Absence of reptation in highly confined polymers

We present results of mechanical stress relaxation measurements on polymers confined at the air-water interface in the form of a monolayer. Systematic measurements allow, to our knowledge, for the first time, observation of the scaling of the stress relaxation time of the highly confined polymers as a function of both surface concentration and molecular weight. The observed scaling is found to be very close to that expected for motion of unentangled polymer solutions with hydrodynamic interactions. Our experimental observations thus clearly rule out the possibility of entanglement and hence reptation as a mode of relaxation in such highly confined polymeric systems.

Nucleosome core protein: Asymmetric dissociation of the octamer

The octameric nucleosomal core-histone complex, (H2A)2-(H2B)2-(H3)2-(H4)2, isolated from rat liver, undergoes dissociation during gel exclusion chromatography as a result of dilution occurring in the columns. The elution pattern at pH 7.0 and 4°C showed a sharp leading peak containing all four histones but predominantly H3 and H4, and a trailing peak containing equal amounts of histones H2A and H2B. As column length was increased the area under the leading peak decreased and that under the trailing peak increased. In addition the relative positions of the two peaks varied with column length. From an analysis of the data on increase in elution volume of the leading peak in relation to column length an apparent molecular weight of 86 000 was calculated for the undissociated molecule. Its apparent molecular weight, histone composition and pattern of further dissociation in relation to column length suggest that this species is the hexamer, (H2A-H2B)-(H3)2-(H4)2. At pH 7.0 and 4°C the dissociation of the core complex appears to be as follows: (H2A)2-(H2B)2-(H3)2-(H4)2 → (H2A-H2B) + (H2A-H2B)-(H3)2-(H4)2 → 2(H2A-H2B) + (H3)2-(H4)2 This dissociation was accelerated by an increase in temperature or decrease in pH and was accompanied by marked conformational changes as judged by circular dichroism measurements.