Oxyanion-encapsulated caged supramolecular frameworks of a tris(urea) receptor: evidence of hydroxide- and fluoride-ion-induced fixation of atmospheric CO2 as a trapped CO3(2-) anion

A tris(2-aminoethyl)amine-based tris(urea) receptor, L, with electron-withdrawing m-nitrophenyl terminals has been established as a potential system that can efficiently capture and fix atmospheric CO(2) as air-stable crystals of a CO(3)(2-)-encapsulated molecular capsule (complex 1), triggered by the presence of n-tetrabutylammonium hydroxide/fluoride in a dimethyl sulfoxide solution of L. Additionally, L in the presence of excess HSO(4)(-) has been found to encapsulate a divalent sulfate anion (SO(4)(2-)) within a dimeric capsular assembly of the receptor (complex 2) via hydrogen-bonding-activated proton transfer between the free and bound HSO(4)(-) anions. Crystallographic results show proof of oxyanion encapsulation within the centrosymmetric cage of L via multiple N-H···O hydrogen bonds to the six urea functions of two inversion-symmetric molecules. The solution-state binding and encapsulation of oxyanions by N-H···O hydrogen bonding has also been confirmed by quantitative (1)H NMR titration experiments, 2D NOESY NMR experiments, and Fourier transform IR analyses of the isolated crystals of the complexes that show huge spectral changes relative to the free receptor.     

Temperature- and magnetic field-dependent electrical transport studies of poly(-3,4 ethylenedioxythiophene) nanoparticles

Large-scale silver nanowires (AgNWs) with a width of 50–60 nm and a typical length of 10 ± 5 μm were synthesized conveniently through a simple polyol reduction method, and the weight of obtained AgNWs was close to 10 g in this one-pot reaction with 500 ml of solution. The as-prepared AgNWs were incorporated into polyvinylidene fluoride matrix (PVDF) to fabricate the AgNWs/PVDF composites, and dielectric behaviors of the composites were investigated. The results revealed that a low percolation threshold of 1.8 vol% was observed in the AgNWs/PVDF composites, which was due to the large aspect ratio of one-dimension structured AgNWs. A giant dielectric constant of 80,000 at 1 kHz was obtained with 1.8 vol% of AgNWs mainly caused by the percolation effect. Besides, the large micro-capacitor networks and strong interfacial polarization at percolation threshold contributed to the enhanced dielectric constant.     

Effects of POSS nanoparticles on glass transition temperatures of ultrathin poly(t‐butyl acrylate) films and bulk blends

As a model system, thin films of trisilanolphenyl‐POSS (TPP) and two different number average molar mass (5 and 23 kg mol^?1) poly(t‐butyl acrylate) (PtBA) were prepared as blends by Langmuir–Blodgett film deposition. Films were characterized by ellipsometry. For comparison, bulk blends are prepared by solution casting and the samples are characterized via differential scanning calorimetry. The increase in T_g as a function of TPP content for bulk high and low molar mass samples are in the order of ～10 °C. Whereas bulk T_g shows comparable increases for both molar masses (～10 °C), the increase in surface T_g for higher molar mass PtBA is greater than for low molar mass (～22 °C vs. ～10 °C). Nonetheless, the total enhancement of T_g is complete by the time 20 wt % TPP is added without further benefit at higher nanofiller loads. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 175–182     

Coupling effects of resonant and discretized non-resonant continuum states in4He +6Li scattering at 10 MeV/A

Alpha- particle scattering from the resonant (3 ₁ ⁺ ) and non-resonant continuum states of⁶Li is studied at incident energy 10 MeV/A. Theα+d breakup continuum part within the excitation energyE _ex=1.475–2.475 MeV is discretized in two energy bins. Unlike the results at higher incident energies, here the coupled-channel calculations show significant breakup continuum coupling effects on the elastic and inelastic scattering. It is shown that even when the continuum-continuum coupling effects are strong, the experimental data of the ground state and the resonant as well as discretized non-resonant continuum states impose stringent constraint on the coupling strengths of the non-resonant continuum states.     

Hybrid organic-inorganic inhibitors of a PDZ interaction that regulates the endocytic fate of CFTR

Together strong: Cooperative binding of organic (see picture, red) and inorganic fragments provides a strategy for the potent inhibition of protein-protein interactions. By targeting specific Lewis basic side chains in peripheral regions of the binding site for coordination to a rhodium(II) center, the affinity of otherwise weak ligands is improved.     

The importance of an additional water bridge in making the exchange coupling of bis(μ-phenoxo) dinickel(II) complexes ferromagnetic

Two new nickel(II) complexes [Ni(2)L(2)(PhCOO)(2)(H(2)O)] (1), [Ni(2)L(2)(PhCH(2)COO)(2)(H(2)O)] (2) have been synthesized using a tridentate Schiff base ligand, HL (2-[(3-dimethylamino-propylimino)-methyl]-phenol) and the carboxylate monoanions, benzoate and phenylacetate, respectively. The complexes have been characterized by spectral analysis, variable temperature magnetic susceptibility measurement and crystal structure analysis. The structural analyses reveal that both complexes are dinuclear in which the distorted octahedral Ni(2+) ions share a face, bridged by one water molecule and two μ(2)-phenoxo oxygen atoms. A monodentate benzoate or phenylacetate anion and two nitrogen atoms of the chelating deprotonated Schiff base (L) complete the hexa-coordination around the metal ion. Variable-temperature magnetic susceptibility studies indicate the presence of dominant ferromagnetic exchange coupling in complexes 1 and 2 with J values of 11.1(2) and 10.9(2) cm(-1) respectively. An attempt has been made to rationalize the observed magneto-structural behavior considering the importance of the additional water bridge in the present two complexes and also in other similar species.     

Electrical and electrochemical properties of poly (methyl methacrylate) based nanocomposite gel electrolytes dispersed with dedoped (insulating) polyaniline nanofibers

In this work, we have investigated the effect of dedoped (insulating) polyaniline (PAni) nanofibers on the electrical and electrochemical properties of poly(methyl methacrylate) (PMMA)-based gel electrolytes. PAni nanofibers have been synthesized using interfacial polymerization technique. By analysis of X-ray diffraction (XRD) and impedance spectroscopy results, it has been demonstrated that the incorporation of dedoped PAni nanofibers up to a moderate concentration (4 wt%) to PMMA–(PC?+?DEC)–LiClO₄ gel polymer electrolyte system significantly enhances the ionic conductivity of the electrolyte system, which can be attributed to the inhibition of polymer chain reorganization upon dispersion of high aspect ratio nanofibers in PMMA matrix resulting in reduction in polymer crystallinity, which gives rise to an increase in ionic conductivity. At higher concentration, dedoped nanofibers appear to get phase separated and form insulating clusters, which impede ionic transport. The phase separation phenomena at higher fraction of nanofibers are confirmed by XRD. Studies on electrochemical behavior reveal that electrochemical potential window increases with the increase of nanofibers loading.     

Dopant size dependent variable range hopping conduction in polyaniline nanorods

The present work investigates the electrical transport and dielectric relaxation of polyaniline (PAni) nanorods doped with organic camphorsulfonic acid (CSA) and inorganic hydrochloric acid (HCl) synthesized by interfacial polymerization technique. High resolution transmission electron micrographs (HRTEM) depict that initially spherical nuclei directionally grow into nanorods and CSA doped PAni produces more uniform and aligned structures. The electrical transport studies reveal that the CSA doped nanorods follow 1D Mott variable-range hopping (VRH), whereas the HCl doped nanorods exhibit 2D VRH conduction mechanism. The value of interchain charge transfer integral is found to be higher for smaller size HCl doped PAni than that for larger size CSA doped PAni. The resistivity measurements exhibit semiconducting behavior for both organic and inorganic dopants and the resistivity of the CSA doped nanorods is found to be smaller than that of the HCl doped nanorods. The dielectric relaxation studies suggest Debye type relaxation with a single relaxation peak for both the dopants and the relaxation time of the carriers of the CSA doped PAni nanorods is smaller than that of the HCl doped nanorods.     

Effect of Radiofrequency Plasma Assisted Grafting of Polypropylene on the Properties of Muga Silk Yarn

Radiofrequency (RF) Ar/propylene glow discharge is utilized for grafting polypropylene onto muga silk yarn at working pressure of 1.2?×?10^?1 mbar and in the of RF power range of 20?C80?W. The plasma discharge is diagnosed using self-compensated emissive probe to study the variation of ion energy impinging on the substrates with RF power. From chemical compositional analysis, a possible grafting mechanism between propylene and muga yarn is proposed by considering the charge-transfer initiation through the formation of electron-donor?Cacceptor (EDA) complex. X-ray photoelectron spectroscopy reveals that at RF power values of 60?C80?W, the ion sputtering effect becomes dominant over plasma grafting thereby leading to severe destruction in chemical structure of the polypropylene grafted (PP-grafted) muga yarns. The experimental results show that PP-grafted muga yarns exhibit improved mechanical strength and hydrophobic behavior as compared to the virgin yarn. The properties of the PP-grafted muga yarns are observed to be dependent on atomic concentration, surface morphology as well as the results obtained from plasma discharge characteristics.