Synthesis and characterization of molybdenum incorporated mesoporous aluminophosphate

A synthesis of molybdenum incorporated mesoporous aluminophosphate with long-chain n-alkylamine as template material had been prepared under non-aqueous condition. These materials were extensively characterized by using X-ray diffraction (XRD), nitrogen sorption isotherms, nuclear magnetic resonance of ²⁷Al and ³¹P (NMR), inductive coupled plasma (ICP), electron spin resonance (ESR), Fourier transform infrared (FTIR) and thermogravimetric-differential thermal analysis (TG-DTA). Morphology of the materials had been observed by using transmission electron microscope (TEM) that revealed the mesoporous materials possessed wormhole-like structures. Alkaline solvent extraction using n-butylamine/ethanol had been efficiently removed the n-alkylamine from the mesoporous samples which yielded BET surface areas around 550-730 m²/g. BJH analysis showed a narrow pore size distribution which increased with increasing of the carbon chain length of alkylamine (template). Valence state and coordination of the molybdenum in the obtained samples were investigated by using ESR and FTIR where it was found that Mo⁴⁺ and Mo⁶⁺ molybdenum species existed in the molybdenum incorporated mesoporous aluminophosphate in tetrahedral coordination.     

FT-IR study on solvent effects in building blocks of bioactive compounds. V

3-Hydroxy-4-hydroxymethyl pyrrolidin-2-ones, easily prepared from the Baylis–Hillman adduct 1-ethyl-4-methyl-2-hydroxy-3-methylenebutanedioate, are useful intermediates in the synthesis of bioactive compounds. In order to understand the mechanism involved in this reaction, vibrational and Montecarlo molecular mechanics conformational analysis on 1-ethyl-4-methyl-2-hydroxy-3-methylenebutanedioate were carried out, confirming the existence of a low energy intramolecular H-bonded five-member ring.     

Optimization of the synthesis of non-symmetrical alkyl dimethyl sulfonium halides

This work is aimed at the optimization of the yield and purity of non-symmetrical trialkyl sulfonium halide salts. The effects of parameters such as solvent, temperature and concentration were studied. The products were carefully analyzed and the crystal structure of [{n-CH₃(CH₂)₁₅}(CH₃)₂S]Br determined. The overall aim of the present study is future syntheses of low-dimensional magnetic materials.     

Molecular dynamics simulations on the structures and properties of ε-CL-20-based PBXs ——Primary theoretical studies on HEDM formulation design

Five polymer bonded explosives (PBXs) with the base explosive ε-CL-20 (hexanitrohexaazaisowurtzi- tane), the most important high energy density compound (HEDC), and five polymer binders (Estane 5703, GAP, HTPB, PEG, and F2314) were constructed. Molecular dynamics (MD) method was employed to investigate their binding energies (Ebind), compatibility, safety, mechanical properties, and energetic properties. The information and rules were reported for choosing better binders and guiding formula- tion design of high energy density material (HEDM). According to the calculated binding energies, the ordering of compatibility and stability of the five PBXs was predicted as ε-CL-20/PEG > ε-CL-20/ Estane5703 ≈ε-CL-20/GAP > ε-CL-20/HTPB > ε-CL-20/F2314. By pair correlation function g(r) analyses, hydrogen bonds and vdw are found to be the main interactions between the two components. The elasticity and isotropy of PBXs based ε-CL-20 can be obviously improved more than pure ε-CL-20 crystal. It is not by changing the molecular structures of ε-CL-20 for each binder to affect the sensitivity. The safety and energetic properties of these PBXs are mainly influenced by the thermal capability (C°p) and density (ρ) of binders, respectively.     

Memory effects in gas chromatographic detection with a microwave-induced plasma

Capillary gas chromatography coupled to microwave-inducedplasma detection furnishes sensitivity adequate for trace analysis when the signal is monitored at a carbon emission line. Work performed with one of these systems at high electronic gain for the carbon signal has revealed solvent band widths in excess of four minutes; these impeded quantification of peaks eluting after the solvent. This report discusses two phenomena which could be related to the unexpected intensity of this solvent response: photomultiplier tube saturation and carbon deposits in the quartz plasma discharge tube.     

红外光谱中溶剂效应机理初探——配位机制的提出

本文就红外光谱中溶剂效应机理提出了溶质和溶剂分子间的瞬时配位作用机制，认为同－溶质在不同溶剂中的振动波数不同，是由于这种瞬时配位作用改变了溶质价电子运动状态所致。据此提出了溶剂效砂的定量关系式，测定了七种溶剂配位效应常数。用这一套经验参数处理了几种取代苯甲酸的羰基伸缩振动的溶剂效应，得较好的线性关系。还发现羰基的振动波数与取代基的Ｈａｍｍｅｔｔ常数σ之间，羰基伸缩振动对溶剂效应的敏感度与σ之间，Ｈ     

Deposition conditions in tailoring the morphology of highly porous reticular films prepared by electrostatic spray deposition (ESD) technique

Spongy-like reticular structure is a unique morphology fabricated by electrostatic spray deposition (ESD) technique. The effects of solvent, substrate temperature, precursor feeding rate, static electric field strength, and deposition time on tailoring the reticular structure were investigated. Scanning electron microscopy was used to observe the film morphology. MnO_x or LiMn₂O₄ were selected as the model materials. It is found that in addition to the conventional solvent butyl carbitol, other kinds of solvents such as ethylene glycol and propylene glycol can also be used to obtain reticular films at a suitable substrate temperature. Porous films with a low cross-linking degree pore structure can be prepared by increasing precursor feeding rate or decreasing substrate temperature. Increasing the deposition time or the electric field strength helps to obtain reticular films with more homogeneous pore size distribution. In addition, the addition of a high boiling-point solvent in mixed alcohol solvent results in the increase of proper substrate temperature. It is concluded that the fluidity of the spray droplets on the surface of a hot substrate is an important factor to form a reticular film.     

Time-resolved fluorescence spectra of a bichromophoric molecule, 2-methyl-1,2,3,4-tetrahydroisoquinoline in various media

Time-resolved fluorescence spectra of a title molecule (with benzene and aliphatic amine parts) in various media, after excitation by several lasers were observed to complement the previous work by conventional spectroscopy [N. Kanamaru, J. Tanaka, J. Phys. Chem. 95 (1991) 6441]. Though complex with many new features, the results were roughly consistent with the previous ones. The significant conclusions are as follows: (1) The emission to be ascribed to the amine (N) part, with more than one component (of nN and aN types) is observed not only for the acetonitrile solution (as previously reported) but also for all the other media. (2) Contrary to the case of a nonpolar hexane solution, both of N fluorescences in the other media reveal unusually long-lived decay components. This can be interpreted by assuming the so-called charge-transfer-to-solvent (CTTS) state that is nonfluorescent and lies just below the fluorescent state. (3) This observation in the protic media can also be taken as another evidence of the peculiar hydrogen bonding between this amine and the protic solvent molecules [N. Kanamaru, J. Tanaka, J. Phys. Chem. 95 (1991) 6441]. (4) Thus, the unexpectedly large quantum yields of N fluorescences in the polar media are now interpreted as arising due to the slow S₁^N→(CTTS)→S₀ internal conversions.     

Physical properties and phase separation structure of Antheraea pernyi/Bombyx mori silk fibroin blend films

The physical structure and compatibility of solution-cast Antheraea pernyi/Bombyx mori silk fibroin blend films were stuided by differential scanning calorimetry (DSC), thermomechanical (TMA) and thermogravimetric (TGA) analysis, dynamic viscoelastic measurement, infrared spectroscopy, and x-ray diffractometry. The DSC curves of the blend films showed independent endotherms at 280 and 358°C, corresponding to the thermal decomposition of B. mori and A. pernyi silk fibroins with random coil conformation. The intensity was roughly proportionate to the amount of each component in the blend. The thermal behavior corresponding to the conformational transitions induced by heating on A. pernyi and B. mori silk fibroins overlapped in the temperature range 190–230°C. Thermal expansion and contraction properties, as well as weight retention behavior of the blend films were intermediate between the pure components, as shown by the TMA and TGA curves. The onset temperature of the storage modulus curve decreased markedly, approaching that of B. mori silk fibroin film when the amount of this component in the blend increased. The loss modulus curve of the blend films showed two peaks at ca. 190 and 210°C, the former corresponding to B. mori, and the latter to A. pernyi silk fibroin. Infrared spectra of the blends exhibited absorption bands characteristic of the pure components overlapping in the spectral region 2000–400 cm^?1. The x-ray diffraction peaks at 23 and 21.5°, attributed to the crystalline spacings of A. pernyi and B. mori fibroins, respectively, overlapped in the diffraction curves of the blends, while the peak at 11.4°, of A. pernyi, increased as the content of this fibroin in the blend increased. The degree of crystallinity, calculated from the x-ray diffraction curves, diminished as the amount of B. mori silk fibroin decreased. A low degree of compatibility exists between the two fibroins when they are cast from aqueous solution in the experimental conditions adopted in this work. © 1994 John Wiley & Sons, Inc.