Surface chemical studies on the competitive adsorption of poly(acrylic acid) and poly(vinyl alcohol) onto alumina

The adsorption of poly(acrylic acid) (PAA) and poly(vinyl alcohol) (PVA) onto alumina has been studied as a function of pH, both individually and in the presence of each other. The adsorption density of PAA is found to decrease with an increase of pH while that of PVA shows the opposite trend. In a binary system containing PAA and PVA, the presence of PVA does not affect the adsorption of PAA onto alumina, but the addition of PAA diminishes the adsorption of PVA in the pH range investigated. The adsorption isotherm of PAA at acidic pH exhibits high-affinity Langmuirian behavior. The isotherms for PVA appear rounded and are of the low-affinity type, Once again the adsorption isotherms of PAA remain unaltered in the presence of PVA whereas those of PVA are significantly affected resulting in a lowering of the adsorption density consequent to PAA addition. A variation in the sequence of addition of PAA and PVA does not affect the adsorption behavior of either of the polymers, The electrokinetic behavior of alumina with PAA is hardly influenced by the addition of PVA, On the other hand, the electrophoretic mobility of alumina in the presence of PVA is significantly altered in the presence of PAA and closely resembles the trend observed with PAA alone. Desorption studies reveal that over 80% of PVA could be desorbed in the pH range 3-9 whereas in the case of PAA, the percent desorption increases from 20 to about 70% as the pH is increased from about 3 to 8. Solution conductivity tests confirm interaction of aluminum species and PAA in the bulk solution. FTIR spectroscopic data provide evidence in support of hydrogen bonding and chemical interaction in the case of the PAA-alumina system and hydrogen bonding with respect to the PVA-alumina interaction. (C) 1999 Academic Press.

Structural and dielectric studies on poly(l-lithocholic acid)

In this paper, we report the results pretaining to the study of the structural, microstructural and the dielectric properties of poly(I-lithocholic acid) (PL), and the composite of PL dispersed in PMMA. The density of the composites was measured using Archimedes principle. The microstructural properties of the composities were studied using XRD and SEM techniques, which give an idea about the dispersion of the polymer PL in the PMMA matrix. The dielectric constants er of the composites were measured with a HP 4194A Impedance/Gain-Phase Analyzer in the frequency range 100 Hz-40 MHz at room temperature. The dielectric constants of the composites at different frequencies were predicted using Clasius-Mossotti and Maxwell's models.

Thermal degradation studies of para-substituted poly(styrene peroxide)s

The thermal degradation of a series of para-substituted poly(styrene peroxide)s with electron-donating [CH3, C(CH3)(3)] and electron-attracting (Br) substitutents are investigated by thermogravimetric analysis (TGA). The results indicate that the Hammett relationship can describe quantitatively the trends in maximum rate of polymer decomposition (T-max) observed in TGA and thus thermostability of substituted poly(styrene peroxide)s depends only on the electronic nature of substituents and their ability to stabilize macroradicals formed during chain scission. The experimental results are also substantiated by thermochemical calculations. (C) 2002 Elsevier Science Ltd. All rights reserved.

Poly(lactic-co-glycolic acid): Carbon nanofiber composites for myocardial tissue engineering applications

The objective of the present in vitro research was to investigate cardiac tissue cell functions (specifically cardiomyocytes and neurons) on poly(lactic-co-glycolic acid) (PLGA) (50:50 wt.%)-carbon nanofiber (CNF) composites to ascertain their potential for myocardial tissue engineering applications. CNF were added to biodegradable PLGA to increase the conductivity and cytocompatibility of pure PLGA. For this reason, different PLGA:CNF ratios (100:0, 75:25, 50:50,25:75, and 0:100 wt.%) were used and the conductivity as well as cytocompatibility of cardiomyocytes and neurons were assessed. Scanning electron microscopy, X-ray diffraction and Raman spectroscopy analysis characterized the microstructure, chemistry, and crystallinity of the materials of interest to this study. The results show that PLGA:CNF materials are conductive and that the conductivity increases as greater amounts of CNF are added to PLGA, from OS m(-1) for pure PLGA (100:0 wt.%) to 5.5 x 10(-3) S m(-1) for pure CNF (0:100 wt.%). The results also indicate that cardiomyocyte density increases with greater amounts of CNF in PLGA (up to 25:75 wt.% PLGA:CNF) for up to 5 days. For neurons a similar trend to cardiomyocytes was observed, indicating that these conductive materials promoted the adhesion and proliferation of two cell types important for myocardial tissue engineering applications. This study thus provides, for the first time, an alternative conductive scaffold using nanotechnology which should be further explored for cardiovascular applications. (C) 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Anisotropic electrical transport properties of poly(methyl methacrylate) infiltrated aligned carbon nanotube mats

We report the electrical anisotropic transport properties of poly(methyl methacrylate) infiltrated aligned carbon nanotube mats. The anisotropy in the resistivity increases with decreasing temperature and the conduction mechanism in the parallel and perpendicular direction is different. Magnetoresistance (MR) studies also suggest anisotropic behavior of the infiltrated mats. Though MR is negative, an upturn is observed when the magnetic field is increased. This is due to the interplay of electron weak localization and electron-electron interactions mechanisms. Overall, infiltrated carbon nanotube mat is a good candidate for anisotropically conductive polymer composite and a simple fabrication method has been reported. (C) 2012 American Institute of Physics. [doi: 10.1063/1.3675873]

Efficacies of multivalent vs monovalent poly(ether imine) dendritic catalysts within a generation in multiple C-C bond forming reactions

Dendrimers are ideal platforms to study multivalent effects due to the presence of uniform end groups at their peripheries. This report concerns with a study of multivalent dendritic catalysts, both within and across dendrimer generations, and their effects to mediate C-C bond forming reactions on multivalent substrates that have two and three acrylate reactive sites. As many as fourteen multivalent dendritic catalysts were prepared using 0-3 generations of poly(propyl ether imine) dendrimers, incorporated with Pd(II) catalytic sites, both within and across the dendrimer generations. C-C Bond forming reactions of these substrates with iodobenzene, mediated by uniform concentration of the metal across all catalysts, showed formation of partially and fully functionalized cinnamates in varying ratios, depending on the extent of clustering of catalytic moieties at the peripheries of dendrimers within a dendrimer generation. In a given generation, higher clustering of catalytic moieties greatly assisted multiple C-C bond formations than presenting the same in lesser number. The studies demonstrate true benefits of clustering catalytic moieties within a dendrimer generation and the beneficial effects applicable to catalysis of substrates presenting more than one reactive center. (C) 2011 Elsevier B.V. All rights reserved.

Symmetrized DMRG studies of low-energy electronic states of poly-para-phenylene (PPP) and poly-para-phenylenevinylene (PPV) systems

Symmetrized DMRG calculations on long oligomers of poly- para-phenylene (PPP) and poly-para-phenylene vinylene (PPV) systems within a `U-V' model have been carried out to obtain the one-photon, two-photon and singlet-triplet gaps in these systems. The extrapolated gaps (in eV) are 2.89, 3.76 and 2.72 in PPP and 3.01, 3.61 and 2.23 in PPV for the one- photon, two-photon and spin gaps respectively. By studying doped systems, we have obtained the exciton binding energies. The larger exciton binding energies, compared to strongly dimerized linear chains emphasizes the role of topology in these polymers. Bond orders, charge and spin correlations in the low-lying states bring out the similarities between the lowest one-photon, the lowest triplet and the lowest bipolaronic states in these systems. The two-photon state bond orders show evidence for strong localization of this excitation in both PPP and PPV systems.

Dynamic Internal Cavities of Dendrimers as Constrained Media. A Study of Photochemical Isomerizations of Stilbene and Azobenzene Using Poly(alkyl aryl ether) Dendrimers

Dendritic rnicroenvironments defined by dynamic internal cavities of a dendrimer were probed through geometric isomerization of stilbene and azobenzene. A third-generation poly(alkyl aryl ether) dendrimer with hydrophilic exterior and hydrophobic interior was used as a reaction cavity in aqueous medium. The dynamic inner cavity sizes were varied by utilizing alkyl linkers that connect the branch junctures from ethyl to n-pentyl moiety (C(2)G(3)-C(5)G(3)). Dendrimers constituted with n-pentyl linker were found to afford higher solubilities of stilbene and azobenzene. Direct irradiation of trans-stilbene showed that C(5)G(3) and C(4)G(3) dendrimers afforded considerable phenanthrene formation, in addition to cis-stilbene, whereas C(3)G(3) and C(2)G(3) gave only cis-stilbene. An electron-transfer sensitized trans-cis isomerization, using cresyl violet perchlorate as the sensitizer, also led to similar results. Thermal isomerization of cis-azobenzene to trans-azobenzene within dendritic microenvironments revealed that the activation energy of the cis- to trans-isomer was increasing in the series C(5)G(3) < C(4)G(3) < C(3)G(3)

Ionic conductivity of bis(2-cyanoethyl) ether-lithium salt and poly(propylether imine)-lithium salt liquid electrolytes

We report here a multiple-nitrile based lithium-salt liquid electrolyte. The ionic conductivity of poly (propyl ether imine) (abbreviated as PETIM) lithium salt dendrimer liquid electrolyte was observed to be a function of dendrimer generation number, n=0 (monomer)-3. While the highest room temperature ionic conductivity value (similar to 10(-1) Sm-1) was recorded for the bis-2cyanoethyl ether monomer (i.e. zeroth generation; G(0)-CN), conductivity decreased progressively to lower values (similar to 10(-3) Sm-1) with increase in generation number (G(1)-CN -> G(3)-CN). The G(0)-CN and higher dendrimer generations showed high thermal stability (approximate to 150 to 200 degrees C), low moisture sensitivity and tunable viscosity (similar to 10(-2) (G(0)-CN) to 3 (G(3)-CN) Pa s). The linker ether group was found to be crucial for ion transport and also eliminated a large number of detrimental features, chiefly moisture sensitivity, chemical instability associated typically with prevalent molecular liquid solvents. Based on the combination of several beneficial physicochemical properties, we presently envisage that the PETIM dendrimers especially the G(0)-CN electrolytes hold promise as electrolytes in electrochemical devices such as lithium-ion batteries.

Photophysical behavior of poly(propyl ether imine) dendrimer in the presence of nitroaromatic compounds

This paper deals with a study of the photophysical property of poly(ether imine) (PETIM) dendritic macromolecule in the presence of aromatic compounds. The inherent photoluminescence property of the dendrimer undergoes quenching in the presence of guest aromatic nitro-compounds. From life-time measurements study, it is inferred that the lifetimes of luminescent species of the dendrimer are not affected with nitrophenols as guest molecules, whereas nitrobenzenes show a marginal change in the lifetimes of the species. Raman spectral characteristic of the macromolecular host-guest complex is conducted in order to identify conformational change of the dendrimer and a significant change in the stretching frequencies of methylene moieties of the dendrimer is observed for the complex with 1,3,5-trinitrobenzene, when compared to other complexes, free host and guest molecules. The photophysical behavior of electron-rich, aliphatic, neutral dendritic macromolecule in the presence of electron-deficient aromatic molecules is illustrated in the present study. (C) 2012 Elsevier B.V. All rights reserved.

A Novel Anticancer Agent, 8-Methoxypyrimido4 `,5 `: 4,5]thieno(2,3-b) Quinoline-4(3H)-One Induces Neuro 2a Neuroblastoma Cell Death through p53-Dependent, Caspase-Dependent and Independent Apoptotic Pathways

Neuroblastoma is the most common cancer in infants and fourth most common cancer in children. Despite recent advances in cancer treatments, the prognosis of stage-IV neuroblastoma patients continues to be dismal which warrant new pharmacotherapy. A novel tetracyclic condensed quinoline compound, 8-methoxypyrimido 4 `,5 `: 4,5] thieno(2,3-b) quinoline-4(3H)-one (MPTQ) is a structural analogue of an anticancer drug ellipticine and has been reported to posses anticancer property. Study on MPTQ on neuroblastoma cells is very limited and mechanisms related to its cytotoxicity on neuroblastoma cells are completely unknown. Here, we evaluated the anticancer property of MPTQ on mouse neuro 2a and human SH-SY5Y neuroblastoma cells and investigated the mechanisms underlying MPTQ-mediated neuro 2a cell death. MPTQ-mediated neuro 2a and SH-SY5Y cell deaths were found to be dose and time dependent. Moreover, MPTQ induced cell death reached approximately 99.8% and 90% in neuro 2a and SH-SY5Y cells respectively. Nuclear oligonucleosomal DNA fragmentation and Terminal dUTP Nick End Labelling assays indicated MPTQ-mediated neuro 2a cell death involved apoptosis. MPTQ-mediated apoptosis is associated with increased phosphorylation of p53 at Ser15 and Ser20 which correlates with the hyperphosphorylation of Ataxia-Telangiectasia mutated protein (ATM). Immunocytochemical analysis demonstrated the increased level of Bax protein in MPTQ treated neuro 2a cells. MPTQ-mediated apoptosis is also associated with increased activation of caspase-9, -3 and -7 but not caspase-2 and -8. Furthermore, increased level of caspase-3 and cleaved Poly ( ADP Ribose) polymerase were observed in the nucleus of MPTQ treated neuro 2a cells, suggesting the involvement of caspase-dependent intrinsic but not extrinsic apoptotic pathway. Increased nuclear translocation of apoptosis inducing factor suggests additional involvement of caspase-independent apoptosis pathway in MPTQ treated neuro 2a cells. Collectively, MPTQ-induced neuro 2a cell death is mediated by ATM and p53 activation, and Bax-mediated activation of caspase-dependent and caspase-independent mitochondrial apoptosis pathways.

Flexible poly(vinyl alcohol-co-ethylene)/modified MMT moisture barrier composite for encapsulating organic devices

Flexible, nano-composite moisture barrier films of poly(vinyl alcohol-co-ethylene) with surface modified montmorillonite fabricated by solution casting were used to encapsulate organic devices. The composite films were characterized by FTIR, UV-visible spectroscopy and SEM imaging. Thermal and mechanical properties of the composite films were studied by DSC and UTM. Calcium degradation test was used to determine the transmission rate of water vapour through the composite films, which showed a gradual reduction from similar to 0.1 g m(-2) day(-1) to 0.0001 g m(-2) day(-1) with increasing modified montmorillonite loading in the neat copolymer. The increase in moisture barrier performance is attributed to the decreased water vapour diffusivity due to matrix-filler interactions in the composite. The accelerated aging test was carried out for non-encapsulated and encapsulated devices to evaluate the efficiency of the encapsulants. The encapsulated devices exhibited longer lifetimes indicating the efficacy of the encapsulant.

Efficient Dendrimer-DNA Complexation and Gene Delivery Vector Properties of Nitrogen-Core Poly(propyl ether imine) Dendrimer in Mammalian Cells

Dendrimers as vectors for gene delivery were established, primarily by utilizing few prominent dendrimer types so far. We report herein studies of DNA complexation efficacies and gene delivery vector properties of a nitrogen-core poly(propyl ether imine) (PETIM) dendrimer, constituted with 22 tertiary amine internal branches and 24 primary amines at the periphery. The interaction of the dendrimer with pEGFPDNA was evaluated through UV-vis, circular dichroism (CD) spectral studies, ethidium bromide fluorescence emission quenching, thermal melting, and gel retardation assays, from which most changes to DNA structure during complexation was found to occur at a weight ratio of dendrimer:DNA similar to 2:1. The zeta potential measurements further confirmed this stoichiometry at electroneutrality. The structure of a DNA oligomer upon dendrimer complexation was simulated through molecular modeling and the simulation showed that the dendrimer enfolded DNA oligomer along both major and minor grooves, without causing DNA deformation, in 1:1 and 2:1 dendrimer-to-DNA complexes. Atomic force microscopy (AFM) studies on dendrimer-pEGFP DNA complex showed an increase in the average z-height as a result of dendrimers decorating the DNA, without causing a distortion of the DNA structure. Cytotoxicity studies involving five different mammalian cell lines, using 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-tetrazolium bromide] (MTT) assay, reveal the dendrimer toxicity profile (IC50) values of similar to 400-1000 mu g mL(-1), depending on the cell line tested. Quantitative estimation, using luciferase assay, showed that the gene transfection was at least 100 times higher when compared to poly(ethylene imine) branched polymer, having similar number of cationic sites as the dendrimer. The present study establishes the physicochemical behavior of new nitrogen-core PETIM dendrimer-DNA complexes, their lower toxicities, and efficient gene delivery vector properties.

Fabrication and characterization of poly(methyl methacrylate)/CaCu3Ti4O12 composites

Composites comprising Poly(Methyl Methacrylate) (PMMA) and CaCu3Ti4O12 (CCTO) via melt mixing followed by hot pressing were fabricated. These were characterized using X-ray diffraction, thermo gravimetric, scanning electron microscopy, and Impedance analyzer for their structural, morphology, and dielectric properties. Composites were found to have better thermal stability than that of pure PMMA. The composite, with 38 Vol % of CCTO (in PMMA), exhibited remarkably low dielectric loss at high frequencies and the low frequency relaxation is attributed to the space charge polarization/MWS effect. Theoretical models were employed to rationalize the dielectric behavior of these composites. At higher temperatures, the relaxation peak shifts to higher frequencies, due to the merging of both beta and alpha relaxations into a single dielectric dispersion peak. The AC conductivity in the high frequency region was attributed to the electronic polarization. POLYM. ENG. SCI., 54:551-558, 2014. (c) 2013 Society of Plastics Engineers

A composition-dependent ``re-entrant'' crystallographic phase transition in the substitutional metal acetylacetonate complex (Cr1-xGax)(acac)(3)

The formation of a complete solid solution between acetylacetonate (acac) complexes of chromium and gallium, (Cr1-x,Ga-x)(acac)(3) for 0.1