Modified conformation and physical properties in conducting polymers due to varying conjugation and solvent interactions

Small angle X-ray scattering (SAXS) studies of poly2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) with varying conjugation, and polyethylene dioxythiophene complexed with polystyrene sulfonate (PEDOT-PSS) in different solvents have shown the importance of the role of pi-electron conjugation and solvent-chain interactions in controlling the chain conformation and assembly. In MEH-PPV, by increasing the extent of conjugation from 30 to 100%, the persistence length (l(p)) increases from 20 to 66 angstrom. Moreover, a pronounced second peak in the pair distribution function has been observed in the fully conjugated chain, at larger length scales. This feature indicates that the chain segments tend to self-assemble as the conjugation along the chain increases. In the case of PEDOT-PSS, the chains undergo solvent induced expansion and enhanced chain organization. The clusters formed by chains are better correlated in dimethyl sulfoxide (DMSO) solution than water, as observed in the scattered intensity profiles. The values of radius of gyration and the exponent (water: 2.6, DMSO: 2.31) of power-law decay, obtained from the unified scattering function (Beaucage) analysis, give evidence for chain expansion from compact (in water) to an extended coil in DMSO solutions, which is consistent with the Kratky plot analysis. The mechanism of this transition and the increase in dc conductivity of PEDOT-PSS in DMSO solution are discussed. The onset frequency for the increase in ac conduction, as well as its temperature dependence, probes the extent of the connectivity in the PEDOT-PSS system. The enhanced charge transport in PEDOT-PSS in DMSO is attributed to the extended chain conformation, as observed in the SAXS results.

Colloidal dispersions in a liquid crystalline medium

We have prepared stable colloidal suspensions in a lyotropic liquid crystal exhibiting an isotropic-nematic-lamellar phase sequence. Small angle neutron scattering (SANS) and dynamic light scattering (DLS) studies show the existence of attractive interparticle interactions in the nematic phase, which lead to a gas-liquid transition of the particles. The resulting liquid phase is weakly anisotropic. Further, the nematic-lamellar transition of the liquid crystal is found to be accompanied by a liquid-solid transition of the particles.

Correlated conformation and charge transport in multiwall carbon nanotube-conducting polymer nanocomposites

The strikingly different charge transport behaviours in nanocomposites of multiwall carbon nanotubes (MWNTs) and conducting polymer polyethylenedioxythiophene-polystyrene-sulfonic-acid (PEDOT-PSS) at low temperatures are explained by probing their conformational properties using small-angle x-ray scattering (SAXS). The SAXS studies indicate the assembly of elongated PEDOT-PSS globules on the walls of nanotubes, coating them partially, thereby limiting the interaction between the nanotubes in the polymer matrix. This results in a charge transport governed mainly by small polarons in the conducting polymer despite the presence of metallic MWNTs. At T > 4 K, hopping of the charge carriers following one-dimensional variable range hopping is evident which also gives rise to a positive magnetoresistance (MR) with an enhanced localization length (similar to 5 nm) due to the presence of MWNTs. However, at T < 4 K, the observation of an unconventional positive temperature coefficient of resistivity is attributed to small polaron tunnelling. The exceptionally large negative MR observed in this temperature regime is conjectured to be due to the presence of quasi-1D MWNTs that can aid in lowering the tunnelling barrier across the nanotube-polymer boundary resulting in large delocalization.

Phase Characterization and Study of Molecular Order of a Three-Ring Mesogen by (13)C NMR in Smectic C and Nematic Phases

Molecules exhibiting a thermotropic liquid-crystalline property have acquired significant importance due to their sensitivity to external stimuli such as temperature, mechanical forces, and electric and magnetic fields. As a result, several novel mesogens have been synthesized by the introduction of various functional groups in the vicinity of the aromatic core as well as in the side chains and their properties have been studied. In the present study, we report three-ring mesogens with hydroxyl groups at one terminal. These mesogens were synthesized by a multistep route, and structural characterization was accomplished by spectral techniques. The mesophase properties were studied by hot-stage optical polarizing microscopy, differential scanning calorimetry, and small-angle X-ray scattering. An enantiotropic nematic phase was noticed for lower homologues, while an additional smectic C phase was found for higher homologues. Solid-state high-resolution natural abundance (13)C NMR studies of a typical mesogen in the solid phase and in the mesophases have been carried out. The (13)C NMR spectrum of the mesogen in the smectic C and nematic phases indicated spontaneous alignment of the molecule in the magnetic field. By utilizing the two-dimensional separated local field (SLF) NMR experiment known as SAMPI4, (13)C-(1)H dipolar couplings have been obtained, which were utilized to determine the orientational order parameters of the mesogen.

Studies towards synthesis, evolution and alignment characteristics of dense, millimeter long multiwalled carbon nanotube arrays

We report the synthesis of aligned arrays of millimeter long carbon nanotubes (CNTs), from benzene and ferrocene as the molecular precursor and catalyst respectively, by a one-step chemical vapor deposition technique. The length of the grown CNTs depends on the reaction temperature and increases from similar to 85 mu m to similar to 1.4 mm when the synthesis temperature is raised from 650 to 1100 degrees C, while the tube diameter is almost independent of the preparation temperature and is similar to 80 nm. The parallel arrangement of the CNTs, as well as their tube diameter can be verified spectroscopically by small angle X-ray scattering (SAXS) studies. Based on electron diffraction scattering (EDS) studies of the top and the base of the CNT films, a root growth process can be deduced.

Deviation from 3-D Ising critical behaviour in aqueous electrolyte solutions

The near-critical behaviour in complex fluids, comprising electrolyte solutions, polymer solutions and amphiphilic systems, reveals a marked departure from the 3-D Ising behaviour. This departure manifests itself either in terms of a crossover from Ising to mean-field (or classical) critical behaviour, when moving away from a given critical point (Tc), or by the persistence of only mean-field region in the surprisingly close vicinity of Tc. The ilo,non-Ising features of the osmotic compressibility (chi(T,p)) in solutions of electrolytes, that exhibit orle or many liquid-liquid transitions, will be presented. The underlying cause of the breakdown of the anticipated 3-D Ising behaviour in aqueous electrolyte solutions is traced to the structuring induced by the electrolytes. New evidence constituting, measurements of small-angle X-ray scattering (SAXS) and the excess molar volume, is advanced to support the thesis of the close relationship, between the structuring and the deviation from the 3-D Ising critical behaviour in aqueous electrolyte solutions.

Dendrimer building toolkit: Model building and characterization of various dendrimer architectures

We have developed a graphical user interface based dendrimer builder toolkit (DBT) which can be used to generate the dendrimer configuration of desired generation for various dendrimer architectures. The validation of structures generated by this tool was carried out by studying the structural properties of two well known classes of dendrimers: ethylenediamine cored poly(amidoamine) (PAMAM) dendrimer, diaminobutyl cored poly(propylene imine) (PPI) dendrimer. Using full atomistic molecular dynamics (MD) simulation we have calculated the radius of gyration, shape tensor and monomer density distribution for PAMAM and PPI dendrimer at neutral and high pH. A good agreement between the available simulation and experimental (small angle X-ray and neutron scattering; SAXS, SANS) results and calculated radius of gyration was observed. With this validation we have used DBT to build another new class of nitrogen cored poly(propyl ether imine) dendrimer and study it's structural features using all atomistic MD simulation. DBT is a versatile tool and can be easily used to generate other dendrimer structures with different chemistry and topology. The use of general amber force field to describe the intra-molecular interactions allows us to integrate this tool easily with the widely used molecular dynamics software AMBER. This makes our tool a very useful utility which can help to facilitate the study of dendrimer interaction with nucleic acids, protein and lipid bilayer for various biological applications. © 2012 Wiley Periodicals, Inc.

Dendrimer building toolkit: Model building and characterization of various dendrimer architectures

We have developed a graphical user interface based dendrimer builder toolkit (DBT) which can be used to generate the dendrimer configuration of desired generation for various dendrimer architectures. The validation of structures generated by this tool was carried out by studying the structural properties of two well known classes of dendrimers: ethylenediamine cored poly(amidoamine) (PAMAM) dendrimer, diaminobutyl cored poly(propylene imine) (PPI) dendrimer. Using full atomistic molecular dynamics (MD) simulation we have calculated the radius of gyration, shape tensor and monomer density distribution for PAMAM and PPI dendrimer at neutral and high pH. A good agreement between the available simulation and experimental (small angle X-ray and neutron scattering; SAXS, SANS) results and calculated radius of gyration was observed. With this validation we have used DBT to build another new class of nitrogen cored poly(propyl ether imine) dendrimer and study it's structural features using all atomistic MD simulation. DBT is a versatile tool and can be easily used to generate other dendrimer structures with different chemistry and topology. The use of general amber force field to describe the intra-molecular interactions allows us to integrate this tool easily with the widely used molecular dynamics software AMBER. This makes our tool a very useful utility which can help to facilitate the study of dendrimer interaction with nucleic acids, protein and lipid bilayer for various biological applications. (c) 2012 Wiley Periodicals, Inc.

How Does the Spacer Length of Cationic Gemini Lipids Influence the Lipoplex Formation with Plasmid DNA? Physicochemical and Biochemical Characterizations and their Relevance in Gene Therapy

Lipoplexes formed by the pEGFP-C3 plasmid DNA (pDNA) and lipid mixtures containing cationic gemini surfactant of the 1,2-bis(hexadecyl dimethyl ammonium) Acmes family referred to as C16CnC16, where n = 2 3, 5, or 12, and the zwitterionic helper lipid, 1,2-dioleoyl-sn-glycero-3-phosphatidylethanolamine (DOPE) have been studied from a wide variety of physical, chemical, and biological standpoints. The study has been carried out using several experimental methods, such as zeta potential, gel electrophoresis, small-angle X-ray scattering (SAXS), cryo-TEM, gene transfection, cell viability/cytotoxicity, and confocal fluorescence microscopy. As reported recently in a communication (J. Am. Chem. Soc. 2011, 133, 18014), the detailed physicochemical and biological studies confirm that, in the presence of the studied series lipid mixtures, plasmid DNA is compacted with a large number of its associated Na+ counterions. This in turn yields a much lower effective negative charge, q(pDNA)(-), a value that has been experimentally obtained for each mixed lipid mixture. Consequently, the cationic lipid (CL) complexes prepared with pDNA and CL/DOPE mixtures to be used in gene transfection require significantly less amount of CL than the one estimated assuming a value of q(DNA)(-) = -2. This drives to a considerably lower cytotoxicity of the gene vector. Depending on the CL molar composition, alpha, of the lipid mixture, and the effective charge ratio of the lipoplex, rho(eff), the reported SAXS data indicate the presence of two or three structures in the same lipoplex, one in the DOPE-rich region, other in the CL-rich region, and another one present at any CL composition. Cryo-TEM and SAXS studies with C16CnC16/DOPE-pDNA lipoplexes indicate that pDNA is localized between the mixed lipid bilayers of lamellar structures within a monolayer of similar to 2 nm. This is consistent with a highly compacted supercoiled pDNA conformation compared with that of linear DNA. Transfection studies were carried out with HEK293T, HeLa, CHO, U343, and H460 cells. The alpha and rho(eff) values for each lipid mixture were optimized on HEK293T cells for transfection, and using these values, the remaining cells were also transfected in absence (-FBS-FBS) and presence (-FBS+FBS) of serum. The transfection efficiency was higher with the CLs of shorter gemini spacers (n = 2 or 3). Each formulation expressed GFP on pDNA transfection and confocal fluorescence microscopy corroborated the results. C16C2C16/DOPE mixtures were the most efficient toward transfection among all the lipid mixtures and, in presence of serum, even better than the Lipofectamine2000, a commercial transfecting agent Each lipid combination was safe and did not show any significant levels of toxicity. Probably, the presence of two coexisting lamellar structures in lipoplexes synergizes the transfection efficiency of the lipid mixtures which are plentiful in the lipoplexes formed by CLs with short spacer (n = 2, 3) than those with the long spacer (n = 5, 12).

Self-Adapting Peripherally Heterofunctionalized Hyperbranched Polymers: Formation of Janus and Tripodal Structures

A peripherally clickable hyperbranched polyester carrying numerous propargyl terminal groups was prepared by a simple melt transesterification polycondensation of a suitably designed AB(2) monomer; this clickable hyperscaffold was then transformed into a variety of different derivatives by using the Cu-catalyzed azide-yne click reaction. Functionalization of the periphery with equimolar quantities of mutually immiscible segments, such as hydrocarbon, fluorocarbon, and PEG, yielded frustrated molecular systems that readapt and form structures wherein the immiscible segments appear to self-segregate to generate either Janus structures (when two immiscible segments are present) or tripodal structures (when three immiscible segments are present). Evidence for such self-segregation was obtained from a variety of studies, such as differential scanning calorimetry, Langmuir isotherms, AFM imaging, and small-angle X-ray scattering measurements. Crystallization of one or more of the peripheral segments reinforced this self-segregation; the weight-fraction-normalized enthalpies of melting associated with the different domains revealed a competition between the segments to optimize their crystalline organization. When one or more of the segments are amorphous, the remaining segments crystallize more effectively and consequently exhibit a higher melting enthalpy. AFM images of monolayers, transferred from the Langmuir trough, revealed that the thickness matches the expected values; furthermore, contact angle measurements clearly demonstrated that the monolayer films are fairly hydrophobic, and in the case of the tripodal hybramers, the presence of domains of hydrocarbon and fluorocarbon appears to impart nanoscale chemical heterogeneity that is reflected in the strong hysteresis in the advancing and receding contact angles.

Probing hemoglobin confinement inside submicron silica tubes using synchrotron SAXS and electrochemical response

The configuration of hemoglobin in solution and confined inside silica nanotubes has been studied using synchrotron small angle X-ray scattering and electrochemical activity. Confinement inside submicron tubes of silica aid in preventing protein aggregation, which is vividly observed for unconfined protein in solution. The radius of gyration (R-g) and size polydispersity (p) of confined hemoglobin was found to be lower than that in solution. This was also recently demonstrated in case of confined hemoglobin inside layered polymer capsules. The confined hemoglobin displayed a higher thermal stability with Rg and p showing negligible changes in the temperature range 25-75 degrees C. The differences in configuration between the confined and unconfined protein were reflected in their electrochemical activity. Reversible electrochemical response (from cyclic voltammograms) obtained in case of the confined hemoglobin, in contrary to the observance of only a cathodic response for the unconfined protein, gave direct indication of the differences between the residences of the electroactive heme center in a different orientation compared to that in solution state. The confined Hb showed loss of reversibility only at higher temperatures. The electron transfer coefficient (alpha) and electron transfer rate constant (k(s)) were also different, providing additional evidence regarding structural differences between the unconfined and confined states of hemoglobin. Thus, absence of any adverse effects due to confinement of proteins inside the inorganic matrices such as silica nanotubes opens up new prospects for utilizing inorganic matrices as protein ``encapsulators'', as well as sensors at varying temperatures.

On the Mechanism of Phase Transfer Catalysis in Brust-Schiffrin Synthesis of Metal Nanoparticles

The two-phase Brust-Schiffrin method (BSM) is used to synthesize highly stable nanoparticles of noble metals. A phase transfer catalyst (PTC) is used to bring in aqueous phase soluble precursors into the organic phase to enable particle synthesis there. Two different mechanisms for phase transfer are advanced in the literature. The first mechanism considers PTC to bring in an aqueous phase soluble precursor by complexing with it. The second mechanism considers the ionic species to be contained in inverse micelles of PTC, with a water core inside. A comprehensive experimental study involving measurement of interfacial tension, viscosity, water content by Karl-Fischer titration, static light scattering, H-1 NMR, and small-angle X-ray scattering is reported in this work to establish that the phase transfer catalyst tetraoctylammonium bromide transfers ions by complexing with them, instead of encapsulating them in inverse micelles. The findings have implications for particle synthesis in two-phase methods such as BSM and their modification to produce more monodispersed particles.

Biased PN based impact angle constrained guidance using a nonlinear engagement model

Impact angle constrained guidance laws are important in many applications such as guidance of torpedoes, anti-ballistic missiles and reentry vehicles. In this paper, we design a guidance law which is capable of achieving a wide range of impact angles. Biased proportional navigation guidance uses a bias term in addition to the basic PN command to satisfy additional constraints. Angle constrained BPNG (ACBPNG) uses small angle approximations to derive the bias term for impact angle requirement. We design a modified ACBPNG (MACBPNG) where the required bias term is derived in a closed form considering non-linear equations of motion. Simulations are carried out for a wide range of impact angle requirements. We also analyze capturability from different initial positions and also the launch angles possible at each initial position. The performance of the proposed law is compared with an existing law.

Anomalous structural relaxations in PVDF rich blends with PMMA in the presence of surface functionalized CNTs

The structural relaxations in PVDF rich blends with PMMA can be quite interesting in understanding the origin of the different molecular relaxations associated with the crystalline and amorphous phases, crystal-amorphous interphase and the segmental motions. In light of our recent findings, we understood that the origin of these molecular relaxations were strongly contingent on the concentration of PMMA in the blend, crystalline morphology and the surface functional moieties on multiwall carbon nanotubes (CNTs). In addition, for the blends with concentration of PMMA >= 25 wt%, the structural relaxations often merge and are dielectrically indistinguishable. In this study, we attempted to determine the critical width in composition where the structural relaxations can be distinctly realized both in the control as well as blends with amine functionalized CNTs (NH2-CNTs). Intriguingly, we observed that in a narrow zone in composition (with PMMA concentration >= 10 wt% and <= 25 wt%), the molecular relaxations can be dielectrically distinguished and they often merge for all other compositions. Furthermore, we attempted to understand how this critical width in composition is related to the crystalline morphology using small angle X-ray scattering and polarizing optical microscopy and the crystal structure using FTIR and Raman spectroscopy. We now understand that although the formation of beta crystals in the blends has no direct correlation with the observed molecular relaxations, the amorphous miscibility and the interphase regions seem to be dictating the origin of different molecular relaxations in the blends. The latter was observed to be strongly contingent on the concentration of PMMA in the blends.

Enhanced Efficacy of Pluronic Copolymer Micelle Encapsulated SCR7 against Cancer Cell Proliferation(a)

5,6-Bis(benzylideneamino)-2-mercaptopyrimidin-4-ol (SCR7) is a new anti cancer molecule having capability to selectively inhibit non-homologous end joining (NHEJ), one of the DNA double strand break (DSB) repair pathways inside the cells. In spite of the promising potential as an anticancer agent, hydrophobicity of SCR7 decreases its bioavailability. Herein the entrapment of SCR7 in Pluronic copolymer is reported. The size of the aggregates was determined by transmission electron microscopy (TEM) and dynamic light scattering (DLS) which yields an average diameter of 23 nm. SCR7 encapsulated micelles (ES) were also characterized by small-angle neutron scattering (SANS). Evaluation of its biological properties by using a variety of techniques, including Trypan blue, MTT and Live-dead cell assays, reveal that encapsulated SCR7 can induce cytotoxicity in cancer cell lines, being more effective in breast cancer cell line. Encapsulated SCR7 treatment resulted in accumulation of DNA breaks within the cells, resulting in cell cycle arrest at G1 phase and activation of apoptosis. More importantly, we found approximate to 5 fold increase in cell death, when encapsulated SCR7 was used in comparison with SCR7 alone.