B(C6F5)3催化Si-H/Si-OR缩聚反应机理及产物结构

根据DFT理论,用量子化学的方法对B(C₆F₅)₃催化Si—H/Si—OR缩聚反应的机理进行了研究,用²⁹Si NMR对1,4-双（二甲基硅基）苯（BDSB）与二甲基二甲氧基硅烷、甲基乙烯基二甲氧基硅烷、二苯基二甲氧基硅烷缩聚产物的微观结构进行了表征,结合反应机理,对单体的结构与缩聚产物的微观结构的关系进行了讨论。B(C₆F₅)₃先与Si—H形成弱加合物,然后Si—OR进攻Si—H/B(C₆F₅)₃加合物使Si—H断裂,形成氧钅翁离子中间体,最后H^-向正电中心迁移形成产物。H^-迁移方向的不同将导致3种反应：缩合、交换、逆反应。烷氧基硅烷中的乙烯基、苯基可以增加烷氧基C的正电性,并使C—O键伸长,减少Si—H/Si—OR交换反应的发生,使得缩聚产物具有更为交替的结构。     

Col4a3-/- Mice on Balb/C Background Have Less Severe Cardiorespiratory Phenotype and SGLT2 Over-Expression Compared to 129x1/SvJ and C57Bl/6 Backgrounds

Alport syndrome (AS) is a hereditary renal disorder with no etiological therapy. In the preclinical Col4a3^-/- model of AS, disease progression and severity vary depending on mouse strain. The sodium-glucose cotransporter 2 (SGLT2) is emerging as an attractive therapeutic target in cardiac/renal pathologies, but its application to AS remains untested. This study investigates cardiorespiratory function and SGLT2 renal expression in Col4a3^-/- mice from three different genetic backgrounds, 129x1/SvJ, C57Bl/6 and Balb/C. male Col4a3^-/- 129x1/SvJ mice displayed alterations consistent with heart failure with preserved ejection fraction (HFpEF). Female, but not male, C57Bl/6 and Balb/C Col4a3^-/- mice exhibited mild changes in systolic and diastolic function of the heart by echocardiography. Male C57Bl/6 Col4a3^-/- mice presented systolic dysfunction by invasive hemodynamic analysis. All strains except Balb/C males demonstrated alterations in respiratory function. SGLT2 expression was significantly increased in AS compared to WT mice from all strains. However, cardiorespiratory abnormalities and SGLT2 over-expression were significantly less in AS Balb/C mice compared to the other two strains. Systolic blood pressure was significantly elevated only in mutant 129x1/SvJ mice. The results provide further evidence for strain-dependent cardiorespiratory and hypertensive phenotype variations in mouse AS models, corroborated by renal SGLT2 expression, and support ongoing initiatives to develop SGLT2 inhibitors for the treatment of AS.     

Catalytic Deoxygenative Reduction of Hydrazides to Hydrazines via B(C6F5)3-Catalyzed Hydrosilylation

The catalytic deoxygenative reduction of hydrazides to the corresponding alkyl hydrazine with PhSiH₃ via B(C₆F₅)₃-catalyzed hydrosilylation is reported. This metal-free protocol is compatible with various acylhydrazides and diacylhydrazides, giving rise to a variety of structurally diverse alkyl hydrazine products in 63–95% yields. The proper selection of borane catalyst and hydrosilane reductant is essential for catalysis. Mechanistic investigations reveal that the reaction involves a hydrazone intermediate.     

Effects of feedingCuphea oil to three generations of CBA/2 and C57B1/6 mice

Three generations of CBA/2 and C57B1/6 mice were reared on semipurified diets containing either 17.2% beef tallow and 3.5% corn oil or 8.6% beef tallow, 8.6% crudeCuphea oil and 3.5% corn oil. TheCuphea oil contained 76% decanoic acid; therefore, health effects of long-term feeding of moderate amounts of medium-chain triacylglycerols were evaluated. The reproductive performance of both strains of mice varied little with diet but, compared with the F1 generation, survival of F2 and F3 pups was diminished. At several time points during 13 wk,Cuphea feeding suppressed body weights and food intakes of males of three generations of both strains. But during long-term feeding of males (5–12 mon),Cuphea did not suppress body weight or food intake. Mice of both strains developed fatty livers. Mice of the CBA/2 strain had hepatic nodular hyperplasia.Cuphea oil feeding caused no specific pathological changes. Although medium-chain triacylglycerols have been reported to be hypocholesterolemic, the substitution ofCuphea for half of the dietary beef tallow did not suppress serum cholesterol concentrations in males aged 4–13 mon. The effects of long-term substitution of medium-chain triacylglycerols for beef tallow do not differ from feeding the beef tallow diet. Long-term and multigenerational feeding of crudeCuphea oil does not cause any specific toxic effect in mice.     

Lewis Pair Polymerization of Acrylic Monomers by N-Heterocyclic Carbenes and B(C6F5)3

This work has uncovered the first highly active and efficient Lewis pair polymerization (LPP) system based on N-heterocyclic carbene (NHC)/B(C₆F₅)₃ pairs for converting acrylic monomers into medium- to high-molecular weight polymers. The study has systematically examined steric and electronic effects of three 1,3-dialkyl(Me, ⁱPr, ^tBu)imidazol-2-ylidene NHCs on the LPP of three classes of acrylic monomers, including linear methyl methacrylate (MMA), cyclic biorenewable γ-methyl-α-methylene-γ-butyrolactone (_γMMBL), and difunctional allyl methacrylate (AMA). For MMA polymerization, IⁱPr is not only the most active (∼3× and ∼120× more active than IMe and I^tBu, respectively), but also the most effective NHC, especially under low NHC loading conditions. Kinetic results are consistent with a bimolecular, activated monomer propagation mechanism. In the case of the more reactive _γMMBL, the polymerization by NHC/B(C₆F₅)₃ in CH₂Cl₂ is extremely rapid, with all three NHCs achieving quantitative monomer conversion in 1 min and thus reaching a high turnover frequency of≥48,000 h⁻¹. The molecular weight (MW) of P_γMMBL can be tuned by adjusting the [_γMMBL]/[NHC] ratio, and thus high MW polymers with relatively narrow MW distributions can be readily synthesized (e.g., from M_n=1.41×10⁵ g mol⁻¹, Đ=1.08 to M_n=4.89×10⁵ g mol⁻¹, Đ=1.20). The LPP by NHC/B(C₆F₅)₃ is completely chemoselective, as demonstrated by the polymerization of AMA, which selectively polymerizes the conjugated vinyl group while leaving the non-conjugated vinyl group in the allyl moiety intact, thanks to its activated monomer propagation mechanism. The resulting PAMA is syndiotactic (rr=83 %), uncross-linked, and soluble in common solvents, thus suitable for further functionalization. This quantitatively chemoselective polymerization by NHC/B(C₆F₅)₃ should provide a facile, yet powerful, approach to functional acrylic polymers.     

Ethylene/α‐olefin copolymerization using diphenylcyclopentadienyl‐phenoxytitanium dichloride/Al(iBu)3/[Ph3C][B(C6F5)4] catalyst systems

Copolymerization of ethylene with 1‐octene and 1‐octadecene using constrained geometry catalysts 2‐(3,4‐diphenylcyclopentadienyl)‐4,6‐di‐tert‐butylphenoxytitanium dichloride (1), 2‐(3,4‐diphenylcyclopentadienyl)‐6‐tert‐butylphenoxytitanium dichloride (2), 2‐(3,4‐diphenylcyclopentadienyl)‐6‐methylphenoxytitanium dichloride (3), and 2‐(3,4‐diphenylcyclopentadienyl)‐6‐phenylphenoxytitanium dichloride (4) was studied in the presence of Al(ⁱBu)₃ and [Ph₃C][B(C₆F₅)₄](TIBA/B). The effect of the catalyst structure, comonomer, and reaction conditions on the catalytic activity, comonomer incorporation, and molecular weight of the produced copolymers was also examined. The 1 /TIBA/B catalyst system exhibits high catalytic activity and produces high molecular weight copolymers. The melting temperature and the degree of crystallinity of the copolymers show a decrease with the increase in the comonomer incorporation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Polymerization of ethylene by zirconocene—B(C6F5)3catalysts with aluminum compounds

Ethylene polymerization by zirconocene—B(C₆F₅)₃ catalysts with various aluminum compounds has been investigated. It is found that the catalytic activity depended on zirconocenes used, and especially on the type of aluminum compounds. For Et(H₄Ind)₂ZrCl₂ (H₄Ind: tetrahydroindenyl), the activity decreases in the following order: Me₃Al > i-Bu₃Al > Et₃Al ≫ Et₂AlCl. While for Cp₂ZrCl₂(Cp : cyclopentadienyl), it varies as follows: i-Bu₃Al > Me₃Al ≫ Et₃Al. Furthermore, the activity is significantly affected by the addition mode of the catalytic components, which may imply that the formation of active centers is associated with an existing concentration of catalytic components. Results of thermal behavior of polyethylene (PE) studied by differential scanning calorimetry (DSC) show that crystallinity of the polymer prepared with Et₃Al is higher than that with Me₃Al or i-Bu₃Al. It is also found that the number-average molecular weight (M ) of the polymers prepared with Me₃Al or i-Bu₃Al is much higher than that with Et₃Al. ¹H-NMR studies substantiate that i-Bu₃Al is a more efficient alkylation agent of Cp₂ZrCl₂ in comparison with Me₃Al. © 1997 John Wiley & Sons, Inc. JAppl Polym Sci 66: 1715–1720, 1997     

工艺温度对F2604/HMX复合粒子包覆效果及撞击感度的影响

为了解工艺温度对PBX炸药性能的影响,采用相分离法将氟橡胶(F2604)包覆在奥克托今(HMX)表面,制备了F2604/HMX复合粒子;通过扫描电镜(SEM)和X射线光电子能谱(XPS)对复合粒子的微观形貌和元素含量变化进行表征;采用分子动力学模拟不同工艺温度下F2604对HMX包覆效果的影响;采用特性落高法测试了F2604/HMX复合粒子的撞击感度。结果表明,随着温度的升高,样品中的N元素含量先降低后升高,包覆度先升高再降低;当工艺温度为50℃时,复合粒子的表面平滑、规整,N元素含量最低,包覆度为58.25%,包覆效果最好;分子动力学模拟结果表明,50℃时F2604/HMX复合体系结合能最高,为197.24 kJ/mol,形成的F2604/HMX体系最稳定;随着温度的升高,撞击感度特性落高H 50先升高后降低,50℃时样品的特性落高最高,为81.7 cm,与20℃时相比提高了78.8%;50℃时,F2604和HMX之间的相互作用力最强,形成的复合体系稳定性最好,使得包覆和粘结效果增强,从而降低了撞击感度。     

全氟三乙胺和全氟己酮混合气体的灭火效果研究

全氟己酮是一种新型的哈龙替代灭火介质,但是研究人员发现全氟己酮在低浓度时具有助燃效果,未通过美国联邦航空局气溶胶爆炸实验(FAA-ACT)。为抑制全氟己酮的助燃效果,采用混合气体的方法,引入全氟三乙胺作为全氟己酮的协同灭火介质。首先利用杯式燃烧器研究不同浓度全氟己酮作用下的火焰高度、火焰宽度,并获取其临界灭火浓度;以火焰高度和火焰宽度作为助燃现象的判据,实验结果表明全氟己酮浓度为3.00%(占氧化剂体积分数,下同)左右时助燃现象最为显著,临界灭火浓度为5.80%。为研究全氟三乙胺抑制全氟己酮助燃现象的效果,在保持全氟己酮浓度3.00%不变的条件下,逐渐增加全氟三乙胺的浓度,获取火焰高度、火焰脉动频率和混合气体的临界灭火浓度变化趋势;结果表明全氟三乙胺对全氟己酮的助燃现象有抑制作用,且预测全氟三乙胺单独作用下的临界灭火浓度约为4.86%。全氟己酮和全氟三乙胺的混合灭火气体中,全氟三乙胺占灭火剂体积分数超过10.00%后,全氟己酮和全氟三乙胺具有较好的协同灭火效果。     

Inductively coupled plasma etching of Pb(ZrxTi1-x)O3 thin films in Cl2/C2F6/Ar and HBr/Ar plasmas

Pb(Zr_xTi_1-x)O₃ thin films were etched in an inductively coupled plasma by using various etch gases such as Cl₂/Ar, C₂F₆/Ar, Cl₂/C₂F₆/Ar and HBr/Ar. The etch rates and etch profiles for each etch gas were investigated. Fast etch rates were obtained in chlorine-containing etch gases (e.g., Cl₂/Ar and Cl₂/C₂F₆/Ar), and clean and steep etch profiles were achieved in Cl₂/Cv₂F₆/Ar or HBr/Ar gases. The gas mixture of Cl₂ and C₂F₆ was proposed to give a fast etch rate and a steep sidewall angle of etched patterns. The optimum gas mixture of Cl₂C₂F₆/Ar was found by varying the gas ratio of Cl₂ to C₂F₆. On the other hand, HBr/Ar gas as an alternative for etching of the Pb(Zr_xTi_1-x)O₃ films was examined. Cl₂/C₂F₆/Ar and HBr/Ar etch gases were compared with respect to etch rate, etch profile and electrical properties.     

Evaluation of Benzo[c]Chrysene Dihydrodiols in the Morphological Cell Transformation of Mouse Embryo Fibroblast C3H10T1/2CL8 Cells

The morphological cell transforming activities of three dihydrodiols of benzo[c]chrysene (B[c]C), trans?B[c]C-7,8-diol, trans?B[c]C-9,10-diol, and trans?B[c]C-1,2-diol were compared to those of B[c]C in order to study the possible routes of metabolic activation in transformable C3H10T1/2 mouse embryo fibroblasts. B[c]C-treated C3H10T1/2 cells exhibited a concentration-related increase in morphologically transformed foci over a concentration range of 0–3 μg/ml. At 3 μg/ml, B[c]C induced 1.23 Type II & III foci/dish, with 73% of the dishes exhibiting Type II or Type III foci, and a survival of 87%. trans?B[c]C-7,8-diol produced concentration-related responses over a range of 0–5 μg/ml. At 3 μg/ml, trans?B[c]C-7,8-diol produced 1.13 Type II & III foci/dish with 72% of the dishes exhibiting foci, and a survival of 76%. trans?B[c]C-9,10-diol was inactive as a morphological cell transforming agent over a concentration range of 0–3 μg/ml. trans?B[c]C-1,2-diol was also inactive as a morphological cell transforming agent over a concentration range of 0–3 μg/ml. These results suggest that a K-region dihydrodiol of B[c]C, trans?B[cC-7,8-diol, may play a role in the ability of B[c]C to morphologically transform C3H10T1/2 cells.     

Interactions among indicators of B1, B2, B6 and vitamin C status in university students

In 209 young university students (109 males and 80 females) with body mass index within the normal range, the activation coefficient of the erythrocyte transketolase (ETKAC) glutathione reductase (EGRAC) and aspartate amino transferase (EASTAC) as well as the circulating levels of vitamin C were determined. Using the usual cutoff points for ETKAC and serum vitamin C and higher than usual cutoff points for EASTAC and EGRAC 99, 95, 92, and 87% of the study subjects exhibited activation coefficients which were compatible with an acceptable status for vitamin B2, B6, C and B1 respectively. A correlation analysis showed a high correlation (r = 0.81) between erythrocyte indicators of B1 and B2 status a lower correlation between indicators of the status of these vitamins and B6 and no correlation between the indicators of B1, B2, and B6 status and serum vitamin C. This study indicated that in this largely nutritionally adequate population, the activation coefficient of the erythrocyte enzymes used here as markers of the nutritional status of B1, B2, and B6 were related between themselves and varied in the same direction. These changes, however, were not associated with circulating levels of vitamin C.     

Synthesis and characterization of (Zr1/3Nb1/3Ti1/3)C metal carbide solid-solution ceramic

(Zr_1/3Nb_1/3Ti_1/3)C metal carbide solid-solution ceramic has been successfully fabricated by hot pressing sintering at 2473 K using ZrC, NbC, and TiC powders as raw materials. The results show that the as-prepared solid-solution ceramic possesses a single rock-salt crystal structure of metal carbides and simultaneously exhibits high compositional uniformity from nanoscale to microscale. By taking advantage of these unique features, it shows relatively high hardness of 38.8 ± 4.4 Gpa and elastic modulus of 481.8 ± 31.0 Gpa and relatively low thermal conductivity of 17.1 ± 0.3 W/(m·K) and thermal diffusivity of 6.1 ± 0.1 mm²/s, which may attribute primarily to the presence of solid solution effects.     

1H, 19F and 11B nuclear magnetic resonance characterization of BF3: amine catalysts used in the cure of C fibre-epoxy prepregs

¹H, ¹⁹F and ¹¹B nuclear magnetic resonance studies are reported which characterize the complexes of boron trifluoride with monoethylamine and with piperidine, BF₃:NH₂C₂H₅ and BF₃:NHC₅H₁₀, respectively. These complexes are used as catalysts for the cure of high performance C fibre-epoxy composities from prepregs. The chemical compositions of commercial BF₃:amine complexes are variable and contain BF₄^? and BF₃(OH)^? salts together with other unidentified highly reactive species. The BF₃:amine complexes, which are susceptible to hydrolysis, also partially convert to the BF₄^? salt (i.e. BF₄^?NH₃⁺C₂H₅) upon heating. This salt formation is accelerated in dimethyl sulphoxide solution and in the presence of the epoxides that are present in commercial prepregs. Commercial C fibre-epoxy prepregs are shown to contain either BF₃:NH₂C₂H₅ or BF₃:NHC₅H₁₀ species together with their BF₄^? salts and a variety of boron-fluorine or carbon-fluorine prepreg species. Considerable variation in the relative quantities of BF₃:amine to its BF₄^? salt was observed from prepreg lot to lot, which will cause variable viscosity-time-temperature prepreg cure profiles. It is concluded that the chemically stable and mobile BF₄^? salt is the predominant catalytic species, acting as a cationic catalyst for the prepreg cure reactions. During the early stages of cure the BF₃:amine catalysts convert to the BF₄^? salts in the presence of epoxides, whereas the BF₃-prepreg species are susceptible to catalytic deactivation and immobilization.     

Predicting drug metabolism by cytochrome P450 2C9: comparison with the 2D6 and 3A4 isoforms

By the use of knowledge gained through modeling of drug metabolism mediated by the cytochrome P450 2D6 and 3A4 isoforms, we constructed a 2D-based model for site-of-metabolism prediction for the cytochrome P450 2C9 isoform. The similarities and differences between the models for the 2C9 and 2D6 isoforms are discussed through structural knowledge from the X-ray crystal structures and trends in experimental data. The final model was validated on an independent test set, resulting in an area under the curve value of 0.92, and a site of metabolism was found among the top two ranked atoms for 77% of the compounds.     

浅谈3C1B涂装技术在塑料件涂装中的应用

3C1B涂装技术指底漆、色漆和罩光清漆三涂层湿态连续涂装后一起进行烘干的涂装方式。介绍此方式应用于塑料件涂装的技术难点和解决方法