氢气对铬系催化剂催化乙烯四聚制1-辛烯的影响

以Ph2PN(i-Pr)PPh2/Cr Cl3(THF)3(THF为四氢呋喃)为催化剂进行了乙烯四聚制1-辛烯反应,用GC,GPC,1H NMR,13C NMR等方法研究了H2对聚合活性和选择性、聚合物的生成量和相对分子质量及其分布的影响,推测了乙烯四聚反应过程中H2可能的作用机理。表征结果显示,随H2分压的增大,聚合活性先升高后降低,1-辛烯和1-己烯的总体选择性略降低;当H2分压为1.0 MPa时,只有微量的丝状聚合物生成。在保证较高催化活性和1-辛烯选择性的前提下,H2的加入可有效减少丝状聚合物的生成,有利于乙烯四聚制1-辛烯反应的连续长周期稳定运行。乙烯四聚制1-辛烯反应中得到的丝状聚合物主要为线型聚乙烯,蜡状聚合物主要为线型α-烯烃。前者反应原理为"Cossee"增长反应机理,后者反应原理为成环机理。

Syntheses and catalytic performances of three coordination polymers with tetracarboxylate ligands

Three zincand cobaltcoordination polymers,namely{[Zn_(2)(μ_(6)-adip)(phen)_(2)]·4H_(2)O}_(n)(1),{[Co_(2)(μ_(6)-adip)(bipy)_(2)]·4H_(2)O}_(n)(2),and[Co_(2)(μ4-adip)(μ-bpa)_(2)]_(n)(3)have been constructed hydrothermally using H4adip(H4adip=5,5′-azanediyldiisophthalic acid),phen(phen=1,10-phenanthroline),bipy(bipy=2,2′-bipyridine),bpa(bpa=bis(4-pyridyl)amine),and zinc and cobalt chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and single-crystal X-ray diffrac-tion analyses.Single-crystal X-ray diffraction analyses revealed that three compounds crystallize in the orthorhom-bic system Pnna(1 and 2)or P21212(3)space groups.All compounds exhibit 3D frameworks.The catalytic perfor-mances in the Henry reaction of these compounds were investigated.Compound 3 exhibited an effective catalytic activity in the Henry reaction at 70℃.CCDC:2339391,1;2339392,2;2339393,3.

分子筛超笼中酞菁钴的原位合成与表征

以NaY分子筛为载体 ,利用其晶胞直径约为 1.2～ 1.3nm的八面沸石超笼结构 ,通过邻苯二甲腈的四聚反应将酞菁钴在Co2 +交换的NaY分子筛超笼里进行了原位合成 ,用紫外可见光谱分析、傅立叶变换红外可见光谱分析、比表面积分析和热分析技术对合成的催化剂进行了表征 ,并对CoNaY分子筛中酞菁钴的原位合成过程与机理进行了初步探讨。实验结果表明 ,合成的催化剂与纯酞菁钴有相似的紫外和红外吸收谱峰 ,这表明分子筛超笼中确实生成了酞菁钴。差热分析结果表明 ,超笼中生成的酞菁钴比纯化合物热稳定性好。

YKL40 expression in CD14^+ liver cells in acute and chronic injury

AIM:To demonstrate that CD14 + cells are an important source of the growth factor YKL40 in acute and chronic liver damage.METHODS:Rats were inoculated with one dose of CCl4 to induce acute damage.Liver biopsies were obtained at 0,6,12,24,48 and 72 h.For chronic damage,CCl4 was administered three days per week for 6 or 8 wk.Tissue samples were collected,and cellular populations were isolated by liver digestion and purified by cell sorting.YKL40 mRNA and protein expression were evaluated by realtime polymerase chain reaction and western blot.RESULTS:Acute liver damage induced a rapid increase of YKL40 mRNA beginning at 12 h.Expression peaked at 24 h,with a 26fold increase over basal levels.By 72 h however,YKL40 expression levels had nearly returned to control levels.On the other hand,chronic damage induced a sustained increase in YKL40 expression,with 7and 9fold higher levels at 6 and 8 wk,respectively.The pattern of YKL40 expression in different subpopulations showed that CD14+cells,which include Kupffer cells,are a source of YKL40 after acute damage at 72 h[0.09 relative expression units(REU)]as well as after chronic injury at 6 wk(0.11 REU).Hepatocytes,in turn,accounted for 0.06 and 0.01 REU after 72 h(acute)or 6 wk(chronic),respectively.The rest of the CD14cells(including T lymphocytes,B lymphocytes,natural killer and natural killer T cells) yielded 0.07 and 0.15 REU at 72 h and 6 wk,respectively.YKL40 protein expression in liver was detected at 72 h as well as 6 and 8 wk,with the highest expression relative to controls(11fold;P≤0.05)seen at 6 wk.Macrophages were stimulated by lipopolysaccharide.We demonstrate that under these conditions,these cells showed maximum expression of YKL40 at 12 h,with P<0.05 compared with controls.CONCLUSION:Hepatic CD14 + cells are an YKL40 mRNA and protein source in acute and chronic liver injury,with expression patterns similar to growth factors implicated in inflammationfibrogenesis.

Architecture of PtFe/C catalyst with high activity and durability for oxygen reduction reaction

A PtFe/C catalyst has been synthesized by impregnation and high-temperature reduction followed by acid-leaching. X-ray diffraction, X-ray photoelectron spectroscopy and X-ray atomic near edge spectroscopy characterization reveal that PtgFe alloy formation occurs during high-temperature reduction and that unstable Fe species are dissolved into acid solution. The difference in Fe concentration from the core region to the surface and strong O-Fe bonding may drive the outward diffusion of Fe to the highly corrugated Pt-skeleton, and the resulting highly dispersed surface FeOx is stable in acidic medium, leading to the construction of a PtBFe@Pt-FeOx architecture. The as prepared PtFe/C catalyst demonstrates a higher activity and comparable durability for the oxygen reduction reaction compared with a Pt/C catalyst, which might be due to the synergetic effect of surface and subsurface Fe species in the PtFe/C catalyst.

Theoretical study of fusion reactions ^(32)S + ^(94,96)Zr and ^(40)Ca + ^(94,96)Zr and quadrupole deformation of ^(94)Zr

The dynamic coupling effects on fusion cross sections for reactions^(32)S + ^(94,96)Zr and ^(40)Ca + ^(94,96)Zr are studied with the universal fusion function formalism and an empirical coupled channel(ECC) model. An examination of the reduced fusion functions shows that the total effect of couplings to inelastic excitations and neutron transfer channels on fusion in ^(32)S +^(94)Zr(^(40)Ca +^(94)Zr) is almost the same as that in ^(32)S +^(96)Zr(^(40)Ca +^(96)Zr). The enhancements of the fusion cross section at sub-barrier energies due to inelastic channel coupling and neutron transfer channel coupling are evaluated separately by using the ECC model. The results show that effect of couplings to inelastic excitations channels in the reactions with94 Zr as target should be similar as that in the reactions with ^(96) Zr as target. This implies that the quadrupole deformation parameters β_2of ^(94)Zr and^(96) Zr should be similar to each other.However, β_2 's predicted from the finite-range droplet model, which are used in the ECC model, are quite different. Experiments on^(48) Ca +^(94)Zr or^(36) S +^(94)Zr are suggested to solve the puzzling issue concerning β_2for^(94)Zr.