Synthesis and characterization of organic–inorganic hybrid materials prepared by sol–gel and containing CdS nanoparticles prepared by a colloidal method using poly(N-vinyl-2-pyrrolidone)

This paper describes the synthesis and characterization of CdS nanoparticles (NPs) stabilized with poly(N-vinyl-2-pyrrolidone) and their further immobilization on a hybrid organic–inorganic matrix produced by the sol–gel process. The production of the hybrid matrix doped with CdS NPs was carried out in two steps. In the first step a precursor, designated diureasil precursor, was synthesized from the reaction between the terminal amine groups of α,ω-diamine-poly(oxyethylene-co-oxypropylene) and the isocyanate group of 3-isocyanatopropyltriethoxysilane. The next step involved the hydrolysis and condensation reactions of ethoxy groups attached to silicon, this step resulting in the formation of a crosslinked siliceous network linked through urea bonds to a poly(oxyethylene)/poly(oxypropylene) chain. The NPs were added to the diureasil precursor before the gelation process to allow a homogeneous dispersion of the NPs within the matrix. The developed method allowed the transfer of colloidal NPs to a solid matrix without the need of exchange the capping agents or the solvent. The materials were characterized by absorption, steady-state photoluminescence spectroscopy and by TEM. The results obtained showed the presence of CdS NPs with quantum size effect dispersed within the diureasil matrix. The obtained nanocomposites show a high transparency in the visible range accounting for the good dispersion of the NPs within the matrix. The TEM analysis confirmed that the NPs are uniformly dispersed within the diureasil matrix.     

Structure of Amido Pyridinium Betaines: Persistent Intermolecular C−H⋅⋅⋅N Hydrogen Bonding in Solution

A hydrogen bond of the type C?H???X (X=O or N) is known to influence the structure and function of chemical and biological systems in solution. C?H???O hydrogen bonding in solution has been extensively studied, both experimentally and computationally, whereas the equivalent thermodynamic parameters have not been enumerated experimentally for C?H???N hydrogen bonds. This is, in part, due to the lack of systems that exhibit persistent C?H???N hydrogen bonds in solution. Herein, a class of molecule based on a biologically active norharman motif that exhibits unsupported intermolecular C?H???N hydrogen bonds in solution has been described. A pairwise interaction leads to dimerisation to give bond strengths of about 7 kJ mol^?1 per hydrogen bond, which is similar to chemically and biologically relevant C?H???O hydrogen bonding. The experimental data is supported by computational work, which provides additional insight into the hydrogen bonding by consideration of electrostatic and orbital interactions and allowed a comparison between calculated and extrapolated NMR chemical shifts.     

Multi-Scale Jacobi Method for Anderson Localization

We prove that the fluctuations of mesoscopic linear statistics for orthogonal polynomial ensembles are universal in the sense that two measures with asymptotic recurrence coefficients have the same asymptotic mesoscopic fluctuations (under an additional assumption on the local regularity of one of the measures). The convergence rate of the recurrence coefficients determines the range of scales on which the limiting fluctuations are identical. Our main tool is an analysis of the Green’s function for the associated Jacobi matrices.As a particular consequencewe obtain a central limit theorem for the modified Jacobi Unitary Ensembles on all mesoscopic scales.     

Reactive blends derived from modified soybean oil and silicone

Reactive blends prepared from methoxysilane terminated silicone polymers and silylated soybean oil are described and characterized. Although simple mixing of soy and silicones results in gross phase separation, homogeneous polymeric products are obtained by introducing reactive sites. These products can be used as protective coatings, additives to adhesives and new sealants. Exposure of the mixtures to moisture leads to hydrolysis of the methoxysilanes and subsequent condensation of the resulting silanols that yields stable siloxane linkages between the two immiscible phases. FTIR, TGA, and swell‐gel analyses indicate effective formation of these siloxane crosslinks. Reactive blends containing less than 20% silylated oil appeared completely transparent but increasing the soy content decreased the optical transparency. SEM micrographs reveal the silicone polymer as the continuous phase with individual spherical silylated soy oil particles distributed in it. The properties of these reactive blends vary from high elongation elastomers to high modulus resins depending on the composition. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3086–3093     

Synthesis,Characterization, and Electronic Structures of Porphyrins Fused with Polycyclic Aromatic Ring Systems

A series of porphyrins fused with acenaphthylene, phenanthroline, and benzofluoranthene polycyclic aromatic rings were prepared by means of a 3+1 porphyrin synthesis approach and subsequent retro‐Diels–Alder reaction of bicyclo[2.2.2]octadiene‐fused precursors. Analysis of the magnetic circular dichroism spectra and the results of time‐dependent DFT calculations are used to identify the reasons for the trends observed in the wavelengths and relative intensities of the Q bands of the products. Michl's perimeter model is used as a conceptual framework to explain the changes in the relative energies of the frontier π‐molecular orbitals.