用蛇纹石提镁残渣直接合成六配位有机硅化物

以蛇纹石提镁残渣为原料,采用常压蒸馏法直接合成了六配位有机硅化物。用红外光谱法和X射线衍射法分析了合成产物的结构。结果表明:合成的产物为有机硅化合物。实验确定的最佳合成条件为:氮气通入量50 ml/min,反应时间2.5 h,乙二醇相对馏出量为75％。在此条件下,钡盐和钙盐的收率分别为86.5％和54.6％。

环氧树脂/含磷有机硅杂化物固化体系的耐热性与阻燃性研究

利用γ(2,3-环氧丙氧基)丙基三甲氧基硅烷与磷酸反应制备了一种含磷有机硅杂化物,并利用红外光谱对这种含磷有机硅杂化物进行了结构表征。将这种含磷有机硅杂化物加入到双酚A环氧树脂/4,4′-二氨基二苯基甲烷体系制备了环氧树脂/含磷有机硅杂化物固化体系,对这种固化体系进行了热失重分析,并测试了其玻璃化转变温度(Tg)和极限氧指数。结果表明,该固化体系的Tg比纯环氧树脂固化体系有所提高,初始分解温度比纯环氧树脂低,而高温残炭率有大幅提高;当含磷有机硅杂化物含量为30份时,固化体系的Tg提高9℃,极限氧指数达到27.3%,700℃残炭率达到34.1%,比纯环氧树脂分别提高28%和77.8%。

麦秆皮层硅化物的XPS研究(Ⅱ)

用X射线光电子能谱法(XPS)研究了麦秆节间不同部位皮层的硅化物组成及含量,探索皮层硅化物的碱稳定性。结果表明,在实验条件下,节间所有部位皮层中的硅化物均是由有机硅化物和无机硅化物组成;无机硅化物的含量约为有机硅化物的3倍,且种类更复杂;节间上部皮层的硅化物含量最高,下部皮层的硅化物含量最低;自外至里,上部皮层中硅化物的含量、分布具有与其他禾本科原料皮层相似的规律性,下部皮层的规律性较差。不同硅化物的碱稳定性有差别;部分无机硅化物微块由于其连接机构的碱溶解而脱落,完好地存在于黑液之中。在皮层生物结构中,硅化物的堆砌、连接方式及其碱溶机理有待进一步研究。

Li_(1.02)Cr_(0.1)Mn_(1.9)O_4表面包覆的热稳定性研究

Improvement of elevated-temperature performance of Li1.02Cr0.1Mn1.9O4 cathode material by silicious surface modification was studied. The Li1.02Cr0.1Mn1.9O4 cathode material was treated by silanes coupling agent and then heated at 580 ℃ to remove organic material. The structures of the modified and unmodified Li1.02Cr0.1Mn1.9O4 were characterized by SpectraPlus, SEM and XRD. The results show that the surface layer of Li1.02Cr0.1Mn1.9O4 material is found to be rich in silicious compound. X-ray diffraction show that all the samples have perfect spinel structure. The electrochemical characterization of modified Li1.02Cr0.1Mn1.9O4 cathode material was tested. The cycle stability of charge/discharge at 55℃ is improved. The results of the charge/discharge curves show that the modified Li1.02Cr0.1Mn1.9O4 has better performance than those unmodified according to the inhibition of decline of reversible capacity of spinel Li1.02Cr0.1Mn1.9O4. Therefore, cycle performance is improved so obviously that 86.03% of the initial capacity is preserved after 100 cycles.

Fabrication and characterization of tungsten-containing mesoporous silica for heterogeneous oxidative desulfurization

A series of functional,tungsten-containing mesoporous silica materials（W-SiO2） have been fabricated directly from an ionic liquid that contained imidazole and polyoxometalate,which acted as mesoporous template and metal source respectively.These materials were then characterized through X-ray diffraction（XRD）,transmission electron microscopy（TEM）,Raman spectroscopy,Fourier transform infrared spectra（FTIR）,diffuse reflectance spectra（DRS）,and N2 adsorption-desorption,which were found to contain tungsten species that were effectively dispersed throughout the structure.The as-prepared materials W-SiO2 were also found to possess a mesoporous structure.The pore diameters of the respective sample W-SiO2-20 determined from the TEM images ranged from 2 to 4 nm,which was close to the average pore size determined from the nitrogen desorption isotherm（2.9 nm）.The materials were evaluated as catalysts for the heterogeneous oxidative desulfurization of dibenzothiophene（DBT）,which is able to achieve deep desulfurization within 40 min under the optimal conditions（Catalyst（W-SiO2-20）= 0.01 g,temperature = 60℃,oxidant（H2O2）= 20 μL）.For the removal of different organic sulfur compounds within oil,the ability of the catalyst（W-SiO2-20） under the same conditions to remove sulfur compounds decreased in the order：4,6-dimethyldibenzothiophene Dibenzothiophene Benzothiophene 1-dodecanethiol.Additionally,they did not require organic solvents as an extractant in the heterogeneous oxidative desulfurization process.After seven separate catalytic cycles,the desulfurization efficiency was still as high as 90.3%.From the gas chromatography-mass spectrometer analysis,DBT was entirely oxidized to its corresponding sulfone DBTO2 after reaction.A mechanism for the heterogeneous desulfurization reaction was proposed.

Selenium Distribution Pattern, Antineoplastic and Immunostimulatory Activities of a Novel Organoselenium Compound Eb

Aim To study the distribution pattern, antineoplastic activity and immunocompetence of a novel organoselenium compound Eb and investigate its in vivo antineoplastic potential. Methods Eb was administered to Kunming mice (dosage, 0.1 g·kg^(-1)·d^(-1)) intragastrically for 7 successive days. The contents of selenium in heart, liver, spleen, kidneys, lungs, stomach, brain, muscle, and bone were determined by fluorometric method on the eighth day. MTT assay was used to study tumor growth inhibition of Eb in vitro, and lymphocyte transformation, hemolysin formation and phagocytosis assay were used to study its immunocompetence. Results After 7 days′ administration of Eb, the tissue contents of sele-(nium) in liver, spleen, lungs, kidneys, and bone of mice increased, especially those in liver and spleen increased significan-tly, compared with controls; but no significant changes of such contents were found in muscle, heart, brain, and stomach. Eb demonstrated inhibitory effects on human Bel-7402, BGC-823, and Calu-3 cancer cell lines in vitro. Eb also showed ability to enhance lymphocyte transformation and serum hemolysin formation in vitro and increase the phagocytosis of macrophages. Conclusion The validated antitumor and immunostimulatory activities of Eb suggest a hypothesis that Eb may behave as a biological response modifier when used as an antitumor agent. Eb is worthy of further study in developing a new antineoplastic and immunity enhancing agent in the light of its antitumor activity, immunocompetence and specific distribution in liver, lungs, kidneys, bone, and spleen.

Research Progress of Interfacial Chemism of High Efficiency Organic Grinding Fluid for Si_3N_4 Ceramics

Grinding is a most important machining method for Si3N4 ceramics. Utilizing interracial chemistry reaction membrane between grinding fluid and Si3N4 ceramics can reduce friction factor, soften surface layer and meanwhile improve the grinding efficiency, which is a bran-new research direction. This article, based on high efficiency grinding of Si3N4 ceramics by the way of half plasticity removal, descanted on the assistant function of interface chemistry reaction to improve the removal rate of Si3N4 ceramics in the application of organic grinding fluids represented by alcohols grinding fluid. To target action mechanism research, it applies the methods of classification, comparison and induction, and advanced test equipments to explore the effects of long, short carbochain alcohol and their water solutions acting as grinding fluids. In addition, it also discusses the effective function of three groups of organic matters such as perhalogeno hydrocarbon, cationic surfactant and tetra ethoxysilane acting as grinding fluid components from different angles, reveals their mechanisms of action, and supplies theoretical basis for the development of machining ceramic grinding fluid of high efficiency, low cost.

Effects of 4 Types of Remediation Agents on Reducing Cd Contents in Soil and Rice on Cd-contaminated Farmland

A field experiment was carried out in Cd-contaminated rice fields in a county of Hengyang to explore the effects of different types of remediation agents on the contents of soil available Cd and rice Cd,and rice yield by using one rice variety Longliangyouhuazhan,and 4 kinds of remediation agents:DG foliar control agent,SMA microbial inoculant,XFJ organic fertilizer and LXM calcium-and silicon-based passivator as test materials.The results showed that compared with CK,after applying DG foliar control agent,soil available Cd content increased rather than decreased,whereas rice Cd content decreased,not reaching a significant level.When applied with SMA microbial inoculant,soil pH value,soil available Cd and rice Cd contents showed a downward then upward trend with the increase of its application rates.Between 3 levels of SMA treatments,the content of soil available Cd in SMA2 was the lowest,decreased by 8.59%in comparison with CK,contrarily,two other SMA treatments were increasing instead of decreasing in the content of soil available Cd.The application of XFJ organic fertilizer and LXM calcium-and silicon-based passivator increased soil pH value,and reduced soil available Cd and rice Cd contents;the contents of soil available Cd and rice Cd decreased with their application rates increasing.Compared with CK,XFJ3 reduced soil available Cd content by 9.40%,and significantly reduced rice Cd content by 57.28%.In LXM3 treatment,soil available Cd content reduced by 14.57%,rice Cd content was 71.57%lower than CK,reaching the lowest level.In general,LXM calcium-and silicon-based passivator had the best Cd reduction effect,with the optimal application amount of 6000 kg/hm^(2).

One-pot synthesis of mesosilica/nano covalent organic polymer composites and their synergistic effect in photocatalysis

Organic-inorganic hybrid materials provide a desirable platform for the development of novel functional materials.Here,we report the one-pot synthesis of mesoporous hybrid nanospheres by the in-situ sol-gel condensation of tetraethoxysilane around surfactant micelle-confined nano covalent organic polymer(nanoCOP)colloids.The hybrid nanospheres containing nanoCOPs uniformly distributed in the mesosilica network,inherited the visible light responsive properties of the nanoCOPs.The turnover frequency of the hybrid nanospheres is almost 12 times that of its corresponding bulk COP counterpart for the photocatalytic reductive dehalogenation of a-bromoacetophenone,which is attributed to activation of the Hantzsch ester reductant by the hydroxyl group.The existence of a volcano relationship between the activity and nano COP/mesosilica ratio confirmed the synergistic effect between nano COP and mesosilica.Our preliminary results suggest that hybridization of semiconductors and reactant-activating materials is an efficient strategy for enhancing the activity of a catalyst for photocatalysis.

Direct silylation reactions of inert C-H bonds via transition metal catalysis

In the past thirty years,transition metal catalyzed silylation of inert C–H bonds has attracted intensive attention due to the importance and wide use of organosilicon compounds.In this review,the silylation reactions of inert C–H bonds catalyzed by transition metal complexes of Ir,Rh,Ru,Pt,Pd,Ni,and Sc,and the strategies utilized to access the site-selective C–H silylation products have been summarized.Furthermore,the mechanisms of C–H silylation reactions have been discussed briefly.

Nanostructuring gold wires as highly durable nano- catalysts for selective reduction of nitro compounds and azides with organosilanes

A general method is developed to prepare durable hybrid nanocatalysts by nanostructuring the surface of gold wires via simple alloying and dealloying. The resulting nanoporous gold/Au （NPG/Au） wire catalysts possess nanoporous skins with their thicknesses on robust metal wires specified in a highly controllable manner. As a demonstration, the as-obtained NPG/Au was shown to be a highly active, chemo-selective, and recyclable catalyst for the reduction of nitro com- pounds and azides using organosilanes as reducing agents.

Synergistic Ni/Cu catalyzed migratory arylsilylation of terminal olefins

Synthesis of organosilanes from alkenes is a very important topic owing to their wide applications.A Ni/Cu dual metal-catalyzed arylsilylation of terminal alkenes,featuring migratory selectivity,has been developed.A wide diversity of aliphatic silanes have been prepared from terminal alkenes,aryl halides and Suginome’s reagent.This protocol is highlighted by excellent regioselectivity,mild reaction conditions and good functional group tolerance.In addition to benzylic positions,carbon–carbon bonds can also be constructed at allylic positions.Preliminary mechanistic studies suggest that the copper cocatalyst promotes the transmetalation of Suginome’s reagent,and the addition of a Pyr Ox ligand inhibits the formation of side-products from the carbon-Heck pathway.Moreover,studies toward the nature of the Pyr Ox ligand revealed that the steric hindrance of the oxazoline moiety greatly affects the chain–walking process,but not the arylation step.