Solid phase synthesis of azapeptides using an automatic synthesizer

Peptides containing azaglycine located terminally or within the backbone have been prepared in the solid phase by means of an automatic synthesizer.     

脂肪乳剂Intralipid代谢产物的高效液相色谱测定

本文介绍了利用ＨＰＬＣ色谱柱前衍生化技术简便，正确和灵敏地测定血清中游离脂肪酸的方法。在最佳条件下，一些脂肪酸的最低检知量为０．０４μｇ。方法已用于脂肪乳剂Ｉｎｔｒａｌｉｐｉｄ在诱发急性坏死性胰腺炎动物体内代谢产物测定。     

Chemical reactivity of hypervalent silicon compounds: The local hard and soft acids and bases principle viewpoint

The silicon atom may increase its coordination number to values greater than four, to form pentacoordinated compounds. It has been observed experimentally that, in general, pentacoordinated compounds show greater reactivity than tetracoordinated compounds. In this work, density functional theory is used to calculate the global softness and the condensed softness of the silicon atom for SiH _n F_4−n and SiH _n F _5−n ¹⁻ . The values obtained show that the global and condensed softness are greater in the pentacoordinated compounds than in the tetracoordinated compounds, a result that explains the enhanced reactivity. If the results are analysed through a local version of the hard and soft acids and bases principle, it is possible to suggest that in nucleophilic substitution reactions, soft nucleophiles preferably react with SiH _n F _5−n ¹⁻ , and hard nucleophiles with SiH _n F_4−n .     

Surface and interfacial properties of PVDF/acrylic copolymer blends before and after UV exposure

Morphological and chemical properties of both the surface and interface of poly(vinylidene fluoride)/poly(methyl methacrylate)-co-poly(ethyl acrylate) (PVDF/PMMA-co-PEA) blend films have been investigated before and after the samples were exposed to ultraviolet (UV) irradiation using a xenon arc lamp at 50 °C and 9% relative humidity (RH) for 7 months. Surface and interfacial morphologies were studied by atomic force microscopy (AFM). Chemical composition information was obtained by confocal Raman microscopy, attenuated total reflection-FTIR spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), and contact angle measurements. Results show an enrichment of the PVDF material at the air surface, while the acrylic copolymer enriches the interface. Blends having greater than 50% mass fraction of PVDF show little change in the surface morphology after UV exposure for 7 months. However, for a lower PVDF content, blends exhibit significant degradation of PMMA-co-PEA copolymer and a much rougher surface after UV exposure. Microstructural changes in the PVDF spherulites are also observed after UV degradation. It is found that the surface and interfacial morphologies are correlated with the chemical properties.     

Quantitative Comparison of REAPDOR and TRAPDOR Experiments by Numerical Simulations and Determination of H–Al Distances in Zeolites

Quantitative H–Al distances in acid sites of two zeolites with MFI and IFR framework topology were obtained by numerical simulation of ¹H{²⁷Al} rotational echo adiabatic passage double resonance (REAPDOR) experiments. A ²⁷Al offset-dependent data set yields for each resolved ¹H NMR line a corresponding nuclear electric quadrupole coupling constant of the neighboring ²⁷Al site. This information is used for analyzing a second data set for on-resonance irradiation, where the dipolar evolution time (number of rotor cycles) was varied, to yield the ¹H–²⁷Al dipolar coupling constant. Numerical simulations indicate that the REAPDOR method does not depend significantly on the polar angles, defining the orientation of the electric field gradient tensor of ²⁷Al with respect to the Al–H dipolar vector. In contrast, the transfer of populations in double resonance sequence is sensitive to these angles, and it can be thus used to measure them.     

过氧聚钨酸薄膜上光栅的制备

用过氧聚钨酸（PPTA）水溶液，通过离心涂膜法在显微镜载玻片上制备了具有光滑表面且厚度为100nm的PPTA薄膜，利用PPTA薄膜在紫外光照下可研制光栅以及其它光学元件的薄膜材料，具有很高的利用价值。     

Microwave synthesis of magnetic Fe3O4 nanoparticles used as a precursor of nanocomposites and ferrofluids

Methods to synthesize magnetic Fe₃O₄ nanoparticles and to modify the surface of particles are presented in the present investigation. Fe₃O₄ magnetic nanoparticles were prepared by the co-precipitation of Fe³⁺ and Fe²⁺, NH₃·H₂O was used as the precipitating agent to adjust the pH value, and the aging of Fe₃O₄ magnetic nanoparticles was accelerated by microwave (MW) irradiation. The obtained Fe₃O₄ magnetic nanoparticles were characterized by Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), X-ray powder diffraction (XRD) and vibrating sample magnetometer (VSM). The average size of Fe₃O₄ crystallites was found to be around 8–9 nm. Thereafter, the surface of Fe₃O₄ magnetic nanoparticles was modified by stearic acid. The resultant sample was characterized by FT-IR, scanning electron microscopy (SEM), XRD, lipophilic degree (LD) and sedimentation test. The FT-IR results indicated that a covalent bond was formed by chemical reaction between the hydroxyl groups on the surface of Fe₃O₄ nanoparticles and carboxyl groups of stearic acid, which changed the polarity of Fe₃O₄ nanoparticles. The dispersion of Fe₃O₄ in organic solvent was greatly improved. Effects of reaction time, reaction temperature and concentration of stearic acid on particle surface modification were investigated. In addition, Fe₃O₄/polystyrene (PS) nanocomposite was synthesized by adding surface modified Fe₃O₄ magnetic nanoparticles into styrene monomer, followed by the radical polymerization. The obtained nanocomposite was tested by thermogravimetry (TG), differential scanning calorimetry (DSC) and XRD. Results revealed that the thermal stability of PS was not significantly changed after adding Fe₃O₄ nanoparticles. The Fe₃O₄ magnetic fluid was characterized using UV–vis spectrophotometer, Gouy magnetic balance and laser particle-size analyzer. The testing results showed that the magnetic fluid had excellent stability, and had susceptibility of 4.46×10⁻⁸ and saturated magnetization of 6.56 emu/g. In addition, the mean size d (0.99) of magnetic Fe₃O₄ nanoparticles in the fluid was 36.19 nm.     

高固体分羟基丙烯酸树脂的合成

以过氧化二苯甲酰（BPO）／过氧化二异丙苯（DCP）（质量比为2：3）为复合引发剂，二甲苯为溶剂，选用适量含羟基单体和分子量调节剂，以减缓树脂合成聚合反应中的自动加速现象，合成了分子量为3000-4000，多分散性指数d〈2的高固体分羟基丙烯酸树脂．该树脂与缩二脲多异氰酸酯（HDI）的配漆实验证明，所得漆膜鲜映性好、丰满度高、色泽好、雾影值低、综合性能较好．     

Vibrational EELS and DFT study of propionic acid and pyruvic acid on Ni(1 0 0): Effects of keto group substitution on room-temperature adsorption and thermal chemistry

The room-temperature adsorption and thermally induced processes of propionic acid and pyruvic acid on Ni(1 0 0) have been investigated by electron energy loss spectroscopy (EELS). Computational vibrational analysis of the optimized bidentate structures for acid-Ni model complexes (involving the organic acid and a Ni atom) has been performed by using the two-layer ONIOM method with the Density Functional Theory and used to interpret the vibrational EELS data. Dehydrogenation of the hydroxyl group is found to result in bonding of the carboxylate group in the propionate and pyruvate adspecies to either a single Ni surface atom in a bidentate configuration or two neighbouring Ni atoms in a bridge configuration. Given the similarities in the total energies and related vibrational frequencies obtained by the calculations in the case of pyruvate adspecies, it is difficult to differentiate the alternate adsorption structure, in which the keto O and hydroxyl O atoms are bonded to a Ni atom in a five-member chelate ring configuration. Furthermore, temperature-dependent EELS studies show that both the propionate and pyruvate adspecies could decompose upon annealing to above 400 K and further dissociate to CO adspecies above 550 K and to C and/or O above 600 K.     

功能性丙烯酸/MBAM体系共聚产物的研制

以丙烯酸和MBAM为主要原料，经聚合，合成了一种高性能的具有良好保水性能的聚合产物，其保水量达到750～1000倍．50℃以下有良好的保水性能，28℃以下有极好的保水性能，并研究了工艺条件对该产品性能的影响因素．