Side‐chain crystallization behavior of graft copolymers consisting of an amorphous main chain and crystalline side chains. II. Poly(n‐hexyl methacrylate)‐graft‐poly(ethylene glycol)

The phase behavior and crystallization of graft copolymers consisting of poly(n‐hexyl methacrylate) (PHMA) as an amorphous main chain and poly(ethylene glycol) (PEG) as crystallizable side chains (HMAx with 15 ≤ x ≤ 73, where x represents the weight percentage of PEG) were investigated. Small‐angle X‐ray scattering profiles measured above the melting temperature of PEG suggested that a microdomain structure with segregated PHMA and PEG domains was formed in HMA40 and HMA46. This phase behavior was qualitatively described by a calculated phase diagram based on the mean‐field theory. Because of the segregation of PEG into microdomains, the crystallization temperature of the PEG side chains in HMAx was higher than that in poly(methyl acrylate)‐graft‐poly(ethylene glycol) having a similar value of x, which was considered to be in a disordered state above the melting temperature. In HMAx with x ≤ 40, PEG crystallization was strongly restricted, probably because the PEG microdomains were isolated in the PHMA matrix. As a result, the growth of PEG spherulite was not observed because the PEG crystallization occurred after vitrification of the PHMA segregated domains. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 129–137, 2007     

Gradient- and Sensitivity-Enhanced TOCSY Experiments

A pulsed field gradient version of the sensitivity-enhanced 2D TOCSY experiment is proposed which yields high-quality spectra with improved sensitivity and a minimum of two scans pert₁increment. For rapid acquisition of 1D TOCSY spectra, the 1D DPFGSE–TOCSY experiment was modified to include phase-encoded multiple-selective excitation followed by a simple spectral editing. Combination of these two building blocks is used in a sensitivity-enhanced 2D analog of the 3D TOCSY–TOCSY experiment which provides an efficient tool for resolving severely overlapped signals of oligomers in short experimental time.     

超重元素(新核素)合成研究进展情况分析和展望

本文在介绍和分析国际、国内在超重元素（新核素）合成实验研究与理论研究进展情况的基础上对我国今后如何从理论与实验的结合上开展超重元素（核）合成研究工作提出一些看法和建议，提供讨论。     

Synthesis of silicon nitride based ceramic nanoparticles by the pyrolysis of silazane block copolymer micelles

Diblock copolymer poly(1,1,3,N,N′‐pentamethyl‐3‐vinylcyclodisilazane)‐block‐polystyrene (polyVSA‐b‐polySt) and triblock copolymer poly(1,1,3,N,N′‐pentamethyl‐3‐vinylcyclodisilazane)‐block‐polystyrene‐block‐poly(1,1,3,N,N′‐pentamethyl‐3‐vinylcyclodisilazane) (polyVSA‐b‐polySt‐b‐polyVSA), consisting of silazane and nonsilazane segments, were prepared by the living anionic polymerization of 1,1,3,N,N′‐pentamethyl‐3‐vinylcyclodisilazane and styrene. PolyVSA‐b‐polySt formed micelles having a poly(1,1,3,N,N′‐pentamethyl‐3‐vinylcyclodisilazane) (polyVSA) core in N,N‐dimethylformamide, whereas polyVSA‐b‐polySt and polyVSA‐b‐polySt‐b‐polyVSA formed micelles having a polyVSA shell in n‐heptane. The micelles with a polyVSA core were core‐crosslinked by UV irradiation in the presence of diethoxyacetophenone as a photosensitizer, and the micelles with a polyVSA shell were shell‐crosslinked by UV irradiation in the presence of diethoxyacetophenone and 1,6‐hexanedithiol. These crosslinked micelles were pyrolyzed at 600 °C in N₂ to give spherical ceramic particles. The pyrolysis process was examined by thermogravimetry and thermogravimetry/mass spectrometry. The morphologies of the particles were analyzed by atomic force microscopy and transmission electron microscopy. The chemical composition of the pyrolysis products was analyzed by X‐ray fluorescence spectroscopy and Raman scattering spectroscopy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4696–4707, 2006     

A new on-line sample preparation system for the liquid chromatography/time-of-flight mass spectrometry simultaneous analysis of pesticides in river water.

Current on-line solid-phase extraction methods combined with HPLC for shortening the clean-up operation are not suitable for simultaneously detecting compounds that have a wide variety of hydrophobicities. To solve these problems, we designed a new on-line sample preparation system. The system consists of an eluting pump, a mixing TEE connector, a 10-port 2-position valve and a solid-phase extraction precolumn. The eluate from the precolumn is diluted with a weak solvent from the HPLC at the TEE connection to load low hydrophobic compounds onto the analytical column. The proposed on-line sample preparation system was successfully applied to the simultaneous analysis of 21 pesticides in river water using LC/TOF-MS. In this method, the recoveries from river water samples were 67 to 126% (mean 83%), the reproducibility (CV%) was in the range from 1.1 to 11% (mean 5.6%), the calibration curve was linear in the range from 1 ppb to 500 ppb (r > 0.999) and the detection limits (S/N = 3) were in the range from 0.0034 ppb (daimuron) to 3.3 ppb (oxine-copper).     

Gold ultra-microelectrode arrays: application to the steady-state voltammetry of hydroxide ion in aqueous solution.

Gold ultra-microelectrode arrays are used to explore the electrochemical oxidation of hydroxide ions and are shown to be analytical useful. Two types of ultra-microelectrode arrays are used; the first consist of 256 individual electrodes of 5 microm in radius, 170 of which are electrochemically active in a cubic arrangement which are separated from their nearest neighbour by a distance of 100 microm. The second array compromises 2597 electrodes of 2.5 microm in radius and of which 1550 of which are electrochemically active in a hexagonal arrangement separated by the nearest neighbour by 55 microm. Well defined voltammetric waves are found with peak currents proportional to the concentration of hydroxide ions in the range 50 microM to 1 mM. Detection limits of 20 microM using the 170 ultra-microelectrode and 10 microM with the 1550 ultra-microelectrode array are shown to be possible but with a higher sensitivity of 4 mA M(-1) observed using the 1550 ultra-microelectrode array compared to 1.2 mA M(-1) with the 170 ultra-microelectrode array.     

Benzenoid Molecules with Uniform Distribution of π-Electrons within Rings

In a recent work it was demonstrated that in linear hexagonal chains the distribution of π-electrons into rings (as computed by means of the Randić–Balaban method) is uniform, irrespective of the nature of the terminal fragments. We now establish that an analogous, yet somewhat more complex, uniformity in the π-electron distribution exists also in double linear hexagonal chains, as well as in some other benzenoid systems.     

XRR and GISAXS study of silicon oxynitride films

Thin films of silicon oxynitride have largely replaced pure silicon oxide films as gate and tunnel oxide films in modern technology due to their superior properties in terms of efficiency as boron barrier, resistance to electrical stress and high dielectric strength. A single chamber system for plasma enhanced chemical vapor deposition was employed to deposit different films of SiO_xN_yH_z with 0.85 < x < 1.91. All films were previously characterized by Rutherford back-scattering and infrared spectroscopy to determine the stoichiometry and the presence of various bonding configurations of constituent atoms. We used X-ray reflectivity to determine the electron density profile across the depth, and we showed that the top layer is densified. Moreover, grazing incidence small-angle X-ray scattering was used to study inhomogeneities (clustering) in the films, and it is shown that plate-like inhomogeneities exist in the top and sphere-like particles at the bottom part of the film. Their shape and size depend on the stoichiometry of the films.     

Establishment of hybrid-derived offspring populations in the Ohomopterus ground beetles through unidirectional hybridization

An approach to deduce the mechanism of stabilization of the hybrid-derived populations in the Ohomopterus ground beetles has been made by comparative studies on the phylogenetic trees of the mitochondrial and nuclear DNA. A phylogenetic tree based on the internal transcribed spacer (ITS) of nuclear ribosomal gene roughly reflects the relations of morphological species group, while mitochondrial NADH dehydrogenase subunit 5 (ND5) gene shows a considerable different topology on the tree; there exist several geographically-linked lineages, most of which consist of more than one species. These results suggest that the replacement of mitochondria has occurred widely in the Ohomopterus species. In most cases, hybridization is unidirectional, i.e., the species A (♂) hybridized with another species B (♀) and not vice versa, with accompanied replacement of mitochondria of A by those of B. The results also suggest that partial or complete occupation of the distribution territory by a hybrid-derived morphological species. The morphological appearance of the resultant hybrid-derivatives are recognized as that of the original species A. Emergence of a morphological new species from a hybrid-derived population has been exemplified.