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1.
We explore the influence of two solvents, namely water and the ionic liquid 1‐ethyl‐3‐methylimidazolium acetate (EmimAc), on the conformations of two cellulose models (cellobiose and a chain of 40 glucose units) and the solvent impact on glycosidic bond cleavage by acid hydrolysis by using molecular dynamics and metadynamics simulations. We investigate the rotation around the glycosidic bond and ring puckering, as well as the anomeric effect and hydrogen bonds, in order to gauge the effect on the hydrolysis mechanism. We find that EmimAc eases hydrolysis through stronger solvent–cellulose interactions, which break structural and electronic barriers to hydrolysis. Our results indicate that hydrolysis in cellulose chains should start from the ends and not in the centre of the chain, which is less accessible to solvent.  相似文献   
2.
Thin films (monolayer and bilayer) of cylinder forming polystyrene‐block‐polydimethylsiloxane (PS‐b‐PDMS) were shear aligned by the swelling and deswelling of a crosslinked PDMS pad that was physically adhered to the film during solvent vapor annealing. The nanostructures formed by self‐assembly were exposed to ultraviolet‐ozone to partially oxidize the PDMS, followed by calcination in air at 500 °C. In this process, the PS segments were fully decomposed, while the PDMS yielded silica nanostructures. The highly aligned PDMS cylinders were thus deposited as silica nanolines on the silicon substrate. Using a bilayer film, the center‐to‐center distance of these features were effectively halved from 38 to 19 nm. Similarly, by sequential shear‐alignment of two distinct layers, a rhombic array of silica nanolines was fabricated. This methodology provides a facile route to fabricating complex topographically patterned nanostructures. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1058–1064  相似文献   
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4.
Al-pillared clays supported rare earths (RE/Al-PILC) are prepared and used as supports of palladium catalysts for deep oxidation of low concentrations of benzene (130-160 ppm). The supports and catalysts are characterized by X-ray powder diffraction (XRD), FT-IR, BET, transmission electron microscopy (TEM) and temperature-programmed reduction (H2-TPR). The results show that Al-pillaring results in a strong increase in the basal spacing (d0 0 1) from about 1.2 to 1.8 nm, and an increase in the BET surface area from 63.6 (±3.2) to 238.8 (±11.9) m2/g. Activity tests of deep oxidation of low concentration benzene show catalysts supported on Al-PILC and RE/Al-PILC are obviously more active than that on raw clay. Pd/6% Ce/Al-PILC, in particular, can catalyze the complete oxidation of low concentration benzene at a temperature as low as about 290 °C.  相似文献   
5.
We constructed a scanning near-field optical microscope (SNOM) on a commercially available atomic force microscopy (AFM) apparatus (SPM-9500J2; Shimadzu Corp.) to measure the stress distribution in ceramic composite materials. Features of our SNOM system are: (1) a compact SNOM head substituted for the original AFM head; (2) a wide scanning range (125 × 125 μm2) inherited from the original scanner; (3) use of conventional shear-force regulation; (4) an optical system for the illumination-collection (I-C) mode; (5) excitation by a 488 nm line of an Ar-ion laser, and (6) light detection by photon counting or a polychromator equipped with an electronically cooled charge coupled device (CCD). This SNOM system was used to measure the surface structure and stress distribution of an Al2O3/ZrO2 eutectic composite. We simultaneously measured topographic images and fluorescence spectra of an Al2O3/ZrO2 eutectic composite. We estimated its peak intensity, peak position, and peak width from the fluorescence spectrum during scanning, which respectively correspond to the abundance of Al2O3, stress in the grain, and the anisotropy of that stress. Mapping images showed that the stress and its anisotropy were weaker in the center of the Al2O3 grain than its boundary between Al2O3 and ZrO2. That observation suggests that Al2O3 underwent intense anisotropic stress induced by volume expansion in the phase transition of ZrO2 from the cubic phase to the monoclinic phase during preparation.  相似文献   
6.
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.  相似文献   
7.
MicrostructureEvolutioninLaserRSCo-baseMetastableAlloyWANGAnan;CHENGShunqi;GUOZhiyao(KunmingUniversityofScienceandTechnology,...  相似文献   
8.
A series of noncyclic neutral ionophores has been synthesized by the reaction of oligoethylene glycol dihalides with 8-quinolinol. Complexation properties for alkali metal picrates were evaluated from solvent extraction and bulk liquid membrane transport experiments. Complexation profiles of the newly synthesized ionophores with a hexyl chain were similar to those of their homologues without the hexyl chain in the extraction experiments. Among them, the pentaethylene glycol derivatives showed the highest extraction efficiency and selectivity towards potassium ion. From the1H NMR spectra (400 MHz), the change in chemical shifts of the aromatic protons upon the addition of alkali metal thiocyanates suggested the existence of a stabilization effect which is caused by intramolecular stacking conformations between the quinoline rings during complexation. Aryl stacking interactions depend on the size of the cations and on the chain length of the oligoethylene glycol. The relationship between transport ability towards alkali metal cations and lipophilicity of these ionophores is also discussed.  相似文献   
9.
R J Sengwa  Sonu Sankhla 《Pramana》2006,67(2):375-381
Dielectric relaxation study of the binary mixtures of poly(vinyl pyrrolidone) (PVP) (Mw=24000, 40000 and 360000 g mol−1) with ethyl alcohol (EA) and poly(ethylene glycol)s (PEGs) (Mw=200 and 400 g mol−1) in dilute solutions of dioxane were carried out at 10.1 GHz and 35°C. The relaxation time of PVP-EA mixtures was interpreted by the consideration of a wait-and-switch model in the local structure of self-associated ethyl alcohol molecules and also the PVP chain length as a geometric constraint for the reorientational motion of ethyl alcohol molecules. The formation of complexes and effect of PVP chain length on the molecular dynamics, chain flexibility and stretching of PEG molecules in PVP-PEG mixtures were explored from the comparative values of dielectric relaxation time. Further, relaxation time values in dioxane and benzene solvent confirm the viscosity independent molecular dynamics in PVP-EA mixtures but the values vary significantly with the non-polar solvent environment.  相似文献   
10.
完成了19F+27Al深部非弹性碰撞产物的角分布测量.初步分析了反应产B,C,N,O,F,Ne,Na,Mg和Al的实验室系角分布,展现出深部非弹性反应机制的特点,显示了反应系统随时间的演化过程. Angular distributions of fragments produced in the deep inelastic collision of~(19)F+~(27)Al have been measured for incident energy of 114 MeV at θ_(lab)= 9~(o), 24~(o), 40~(o), 55~(o), 70~(o) and 85~(o). Angular distributions of dissipative products B, C, N, O, F, Ne, Na, Mg and Al are analyzed to provide an evolution process of the intermediate dinuclear system formed in the reaction.  相似文献   
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