Phase transition and conformational variation of N-alkylated branched poly(ethyleneimine) comblike polymer

A series of branched poly(ethyleneimine) (PEI) derived polymers with different lengths of n-alkyl side chains, denoted as PEI(n)Cs (n = 12, 14, 16, 18, 20, number of carbon atoms in alkyl side group), have been prepared by a N-alkylation method, and systematically characterized by differential scanning calorimertry (DSC) and wide-angle X-ray diffraction (WARD) as well as Fourier transform infrared spectroscopy (FTIR). The side chains grafted on these comblike polymers are long enough to form crystalline phase composed of paraffin-like crystallites. The crystallization of the side chains forces the branched poly(ethyleneimine) molecules to pack into layered structure, between which the crystallites are located. The melting temperatures of the side chain crystallites increase from -12.36 to +51.49 degreesC with increasing the length of the side chains from n. = 12 to n = 20, which are a little bit lower than the corresponding pristine n-alkanes. PEI18C was taken as an example in this work for the investigation of phase transition and conformational variation of the side chains with temperature changing.

Polyhedral oligomeric silsesquioxane nanocomposite thin films via layer-by-layer electrostatic self-assembly

Fabrication of ultrathin polymer composite films with low dielectric constants has been demonstrated. Octa( aminophenyl) silsesquioxane (OAPS) was synthesized and assembled with poly( acrylic acid) (PAA) and poly( styrene sulfonate) (PSS) via a layer-by-layer electrostatic self-assembly technique to yield nanoporous ultrathin films. The OAPS was soluble in water at pH 3 or lower, and suitable pH conditions for the OAPS/PAA and OAPS/PSS assemblies were determined. The multilayer formation process was studied by contact angle analysis, X-ray photoelectron spectroscopy, atomic force microscopy, quartz crystal microgravimetry, UV-vis spectroscopy, and ellipsometry. The multilayer growth was found to be steady and uniform, and the analysis of the film surface revealed a rough topography due to OAPS aggregates. The incorporation of porous OAPS molecules into the thin films significantly lowered their dielectric constants. The OAPS/PAA multilayer thin film thus prepared exhibited a dielectric constant of 2.06 compared to 2.58 for pure PAA film. The OAPS/PAA multilayer film was heated to effect cross-linking between the OAPS and the PAA layers, and the transformation was verified by reflection-absorption Fourier transform infrared spectroscopy.

Multiple morphologies and their transformation of a polystyrene-block-poly(4-vinylpyridine) block copolymer

We report the multiple morphologies and their transformation of polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) in low-alkanol solvents. In order to improve the solubility of polystyrene block in alcohol solvents, the solution of block copolymer sample was treated at a higher temperature, and then the influence of rate of decreasing temperature on multiple morphologies (including spheres, rods, vesicles, porous vesicles, large compound vesicles, and large compound micelles) was observed. The transformation of spheres to rods, to tyre-shaped large compound micelles, and to sphere-shaped large compound micelles was also realized. The formation mechanisms of the multiple morphologies and their transformation are discussed briefly.

Analysis of strychnos alkaloids using electrospray ionization Fourier transform ion cyclotron resonance multi-stage tandem mass spectrometry

The fragmentations of four strychnos alkaloids have been investigated by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) in the positive ion mode. Experiments using multi-stage tandem mass spectrometry (ESI-FT-ICR-MSn) allowed us to obtain precise elemental compositions of product ions at high mass resolution. The experimental data demonstrated that the nitrogen bridge and the coordinated oxygen atom on the nitrogen bridge in the alkaloid compounds were the active sites in the MS2 fragmentations. The loss of CH3 or the OCH3 group in those alkaloids, which have an OCH3 substituent, was the dominant fragmentation mode in the MS3 fragmentations. Logical fragmentation schemes for strychnos alkaloids have been proposed and these should be useful for the identification of these compounds.

Self-assembled monolayer growth of octanol on mica: Atomic force microscopy and Fourier-transform infrared spectroscopy studies

The growth kinetics of self-assembled monolayers formed by exposing freshly cleaved mica to octanol solution has been studied by atomic force microscopy (AFM) and Fourier-transform infrared spectroscopy (FTIR). AFM images of samples immersed in octanol for varying exposure times showed that before forming a complete monolayer the octanol molecules aggregated in the form of small islands on the mica surface. With the proceeding of immersion, these islands gradually grew and merged into larger patches. Finally, a close-packed film with uniform appearance and few defects was formed. The thickness of the final film showed 0.8 nm in height, which corresponded to the 40degrees tilt molecular conformation of the octanol monolayer. The growth mechanisms consisted of nucleation, growth, and coalescence of the submonolayer films. The growth process was also confirmed by FTIR. And the surface coverage of the submonolayer islands estimated from AFM images and FTIR spectra as a function of immersion time was quite consistent.

Mechanism of phase transformation and formation of barium hexaferrite doped with rare-earths in sol-gel process

The phase-transformation in sol-gel preparation of barium hexaferrite and the formation of barium hexaferrite doped with La3+ Were studied by chemical phase analysis, X-ray diffraction and infrared spectrometry analysis. The experimental results show that phase transformation reactions of FeCO3, Fe2O3 and BaFe2O4, barium hexaferrite and gamma-Fe2O3 take place in the heat treatment of gel. While the doping lanthanide ion replace barium ion, an equivalent quantity of Fe3+ are reduced to Fe2+ to maintain the charge equilibrium.

Crystal transformation of Nylon 11 using in situ WAXD

alpha Form Nylon 11 films were found to exist a non-linear transformation at 70 degrees C during the heating process using in situ WAXD. The alpha Form disappeared but delta Form appeared when the temperature was higher 70 degrees C.

Investigation of thermal unfolding process of cyanic adduct of horseradish peroxidase by Fourier transform infrared and circular dichroism spectrometry

Detailed circular dichroism(CD) and Fourier transform infrared (FTIR) studies have been carried out to monitor thermal unfolding of horseradish peroxidase isoenzyme C(HRP) inhibited by CN(HRP-CN). The results suggest that HRP-CN is quite different from native HRP with different spin states of Fe of heme and different coordinated states. Cyanide becomes the sixth ligand of Fe(I) of heme and the hydrogen-binding network is destroyed partly at the same time, which cause the drastic decrease of thermal stability of HRP. The FTIR and Soret-CD spectra analysis demonstrate that during the heating process there is an intermediate state(I') which has both partly destroyed secondary and tertiary structures of native HRP, then it is the appearance of protein aggregation state(A) after fully unfolding. The unfolding pathway thus can be shown as follows: I -->I'-->U -->A.