Controlled Radical Polymerization of Styrene in the Presence of Different Copper Complexes and Organic Halides

ＩｎｔｒｏｄｕｃｔｉｏｎＡｔｏｍｔｒａｎｓｆｅｒｒａｄｉｃａｌｐｏｌｙｍｅｒｉｚａｔｉｏｎ（ＡＴＲＰ）,ｂａｓｅｄｏｎｃｕｐｒｏｕｓｈａｌｉｄｅｓ（ＣｕＸ）／２,２－ｂｙｐｙｒｉｄｉｎｅ（ｂｐｙ）／ａｌｋｙｌｈａｌｉｄｅｓ（ＲＸ）ａｓｃａｔａｌｙｓｔ／ｉｎｉｔｉａｔｏｒｓｙｓｔｅｍ,ｉｓａｎｅｗｍｅｔｈｏｄｔｏｃｏｎｔｒｏｌｔｈｅｒａｄｉｃａｌｐｏｌｙｍｅｒｉｚａｔｉｏｎｏｆｓｔｙｒｅｎｅａｎｄ（ｍｅｔｈｙｌ）ｍｅｔｈａｃｒｙｌａｔｅ（ＭＭＡ）［１,２］．ＢｅｃａｕｓｅｔｈｅＣｕＣｌ／１,１０…     

New Application of bond Function Basis Sets──ab initio Calculations of Nonlinear Optical Properties

ＮｅｗＡｐｐｌｉｃａｔｉｏｎｏｆｂｏｎｄＦｕｎｃｔｉｏｎＢａｓｉｓＳｅｔｓ──ａｂｉｎｉｔｉｏＣａｌｃｕｌａｔｉｏｎｓｏｆＮｏｎｌｉｎｅａｒＯｐｔｉｃａｌＰｒｏｐｅｒｔｉｅｓｏｆＣｈ_（４－ｎ）Ｆ_ｎ（ｎ＝１，２，３）ＬｉＺｈｉ－ｒｕ，ＴＡＯＦｕ－ｍｉ...     

萃取法研究Cu~(2 )-dpx-PCA~-体系配体间的芳环堆积作用及其配合物的组成

用萃取法测定Ｃｕ２＋ｄｐｘＰＣＡ体系中的堆积百分数，其中ｄｐｘ＝２，２′联吡啶胺（ｄｐａ），２，２′联吡啶甲烷（ｄｐｍ）和２，２′联吡啶酮（ｄｐｋ）；ＰＣＡ－＝苯甲酸根（Ｂｚ－），２苯乙酸根（ＰＡｃ－），３苯丙酸根（ＰＰｒ－）和４苯丁酸根（ＰＢｕ－）。结果表明：堆积百分数与羧酸根中亚甲基数有关，其顺序为Ｂｚ－＜ＰＡｃ－＜ＰＰｒ－＜ＰＢｕ，同时还与ｄｐｘ的结构有关，其顺序为ｄｐａ＜ｄｐｍ＜ｄｐｋ。这是堆积作用对配体的结构要求及存在π电子协作效应的缘故。     

A Neutron Diffraction Study for the Crystal Structure of the Deuterium（hydrogen） L－Arginine Phosphate Monohydrate

ＡＮｅｕｔｒｏｎＤｉｆｆｒａｃｔｉｏｎＳｔｕｄｙｆｏｒｔｈｅＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆｔｈｅＤｅｕｔｅｒｉｕｍ（ｈｙｄｒｏｇｅｎ）Ｌ－ＡｒｇｉｎｉｎｅＰｈｏｓｐｈａｔｅＭｏｎｏｈｙｄｒａｔｅＣｈｅｎｇＺｈｉ－Ｘｕ；ＣｈｅｎｇＹｕＦｅｎ；Ｇｕ...     

乳液共聚反应过程与聚合物结构关系及~（13）C－NMR对聚合物结构的表征

用间歇法和半连续法进行了丙烯酸丁酯（ＢｕＡ）与醋酸乙烯酯（ＶＡｃ）乳液共聚合．１３Ｃ－ＮＭＲ对共聚产物分子结构测试表明，在间歇法共聚合中随着反应进行其组成及结构发生很大变化，而半连续法确能制得成份及结构均匀一致的Ｐ（ＢｕＡ－ＶＡｃ）共聚物．由于ＢｕＡ水溶性小于ＶＡｃ，而其竟聚率远大于ＶＡｃ，间歇法共聚合反应初期只有少量ＶＡｃ参加共聚合．通过对间歇法共聚合中不同反应时间聚合物的１３Ｃ－ＮＭＲ测试，表明反应初期聚合的ＶＡｃ以单链节或二元序列形式存在于主要由ＢｕＡ单元构成的分子链中，而并未形成较长ＶＡｃ链段．对上述试样玻璃化转变温度的测试结果与１３Ｃ－ＮＭＲ实验结果颇为一致．     

STUDY ON SYNTHESIS，CHARACTERIZATION AND CATALYSIS OF PILLARED ANION CLAY（Ⅲ）──SYNTHESIS OF ZnAl－BW_（11）O_（39）Z（H_2）~（n－）

ＳＴＵＤＹＯＮＳＹＮＴＨＥＳＩＳ，ＣＨＡＲＡＣＴＥＲＩＺＡＴＩＯＮＡＮＤＣＡＴＡＬＹＳＩＳＯＦＰＩＬＬＡＲＥＤＡＮＩＯＮＣＬＡＹ（Ⅲ）──ＳＹＮＴＨＥＳＩＳＯＦＺｎＡｌ－ＢＷ_（１１）Ｏ_（３９）Ｚ（Ｈ_２）~（ｎ－）ＴｈａｎｋｓｆｏｒｔｈｅｓｕｐｐｏｒｔｏｆＦｏｕｎｄａｔｉｏｎｏｆＣＥＣａｎｄｔｈｅｏｐｅｎｌａｂｏｆＨｙｄｒｏｔｈｅｒｍａｌＳｙｎｔｈｅｓｉｓｉｎＪｉｎｎＵｎｉｖｅｒｓｉｔｙｅｄｄｉｆｆｅｒｅｎｔｋｉｎｄｓｏｆｔｒｉｈｅｔｅｒｏｐｏｌｙｏｘｏｍｅｔａｌａｔｅ（ＴＨ＇ＰＯＭｓ）ｔｏｔｈｅＺｎＡＩｌａｙｅｒｅｄｃｌａｙｓ，ｕｓｉｎｇｔｈｅｅｓｔｅｒｉｆｉｃａｔｉｏｎｏｆｎ－ｂｕｔｙｌａｌｃｏｈｏｌａｎｄａｃｅｔｉｃａｃｉｄａｓｐｒｏｂｅｒｅａｃｔｉｏｎ．ａｎｄｆｏｕｎｄｔｈａｔｔｈｅｐｉｌｌａｒｅｄｃｏｍｐｏｕｎｄｓｗｅｒｅｍｏｒｅａｃｔｉｖｅａｎｄｓｅｌｅｃｔｉｖｅｔｈａｎｔｈｅｓｏｌｉｄａｃｉｄｃａｔａｌｙｓｔｓｓｕｃｈａｓａｃｉｄｉｃｉｏｎ－ｅｘｃｈａｎｇｅｒｅｓｉｎｓｌ４］．Ｏｎｔｈｅｂａｓｉｓｏｆｐｒｅｖｉｏｕｓｗｏｒｋ．ｗｅｎｏｗｅｎｃａｐｓｕｌａｔｅｔｒｉｈｅｔｅｒｏｐｏｌｙｏｘｏｍｅ     

乳液共聚反应过程与聚合物结构关系及13C－NMR对聚合物结构的表征

 用间歇法和半连续法进行了丙烯酸丁酯（ＢｕＡ）与醋酸乙烯酯（ＶＡｃ）乳液共聚合．^１３Ｃ－ＮＭＲ对共聚产物分子结构测试表明，在间歇法共聚合中随着反应进行其组成及结构发生很大变化，而半连续法确能制得成份及结构均匀一致的Ｐ（ＢｕＡ－ＶＡｃ）共聚物．由于ＢｕＡ水溶性小于ＶＡｃ，而其竟聚率远大于ＶＡｃ，间歇法共聚合反应初期只有少量ＶＡｃ参加共聚合．通过对间歇法共聚合中不同反应时间聚合物的^１３Ｃ－ＮＭＲ测试，表明反应初期聚合的ＶＡｃ以单链节或二元序列形式存在于主要由ＢｕＡ单元构成的分子链中，而并未形成较长ＶＡｃ链段．对上述试样玻璃化转变温度的测试结果与^１３Ｃ－ＮＭＲ实验结果颇为一致．     

LaAlO_3衬底上磁控溅射的大面积YBa_2Cu_3O_（7－x）薄膜微观组织

用分析电镜和高分辨电镜对在３０ｍｍ×３０ｍｍＬａＡｌＯ３衬底上，采用中空柱状阴极直流磁控溅射的高ＪｃＹＢａ２Ｃｕ３Ｏ７－ｘ（ＹＢＣＯ）薄膜的微观组织结构进行了研究。薄膜为ｃ轴取向ＹＢＣＯ，含有少量Ｙ２ＢａＣｕＯ５颗粒和纺锤状Ｙ２Ｏ３。膜内主要晶体缺陷为［００１］刃位错和螺位错、堆垛层错、（００１）晶面弯曲带、小于１５ｎｍ的晶格畸变区和阳离子空位。ＬａＡｌＯ３衬底表面呈阶梯状并有小坑。衬底表面第一层膜原子为ＣｕＯ和ＣｕＯ２层，以致在界面形成ＢａＣｕＯ２和ＹａＢａＣｕ２Ｏ５相。ＬａＡｌＯ３衬底表层有较多位错，对薄膜外延生长和缺陷的形成有明显影响。     

Spectroelectrochemical Studies on the Interactions of Complexes of Cu(phen)_2~(2 ) and Cu(bpy)_2~(2 ) with DNA

ＳｐｅｃｔｒｏｅｌｅｃｔｒｏｃｈｅｍｉｃａｌＳｔｕｄｉｅｓｏｎｔｈｅＩｎｔｅｒａｃｔｉｏｎｓｏｆＣｏｍｐｌｅｘｅｓｏｆＣｕ（ｐｈｅｎ）２＋２ａｎｄＣｕ（ｂｐｙ）２＋２ｗｉｔｈＤＮＡＺＨＡＯＧｕａｎｇ－ｃｈａｏ，ＺＨＵＪｕｎ－ｊｉｅａｎｄＣＨＥＮＨｏｎ...     

Novel Highly Branched Polyester Nanoparticles(Ⅱ)──Interactions Between Anionic HBPNP articles and Ca

ＮｏｖｅｌＨｉｇｈｌｙＢｒａｎｃｈｅｄＰｏｌｙｅｓｔｅｒＮａｎｏｐａｒｔｉｃｌｅｓ（Ⅱ）──ＩｎｔｅｒａｃｔｉｏｎｓＢｅｔｗｅｅｎＡｎｉｏｎｉｃＨＢＰＮＰａｒｔｉｃｌｅｓａｎｄＣａｔｉｏｎｉｃＳｕｒｆａｃｔａｎｔ，Ｃｅｔｙｌｔｒｉｍｅｔｈｙｌａｍｍｏ...     

铁钼粉末冶金抗磨材料次表面亚稳相的XRD分析

在一台普通的二圆X射线衍射仪上，利用不对称布拉格反射STD（试样相对于入射线倾斜在某一角度α0，进行2θ扫描）技术与常规CBD（正常的θ/2θ偶合扫描）模式相结合的方法，对铁钼粉末冶金抗磨材料的摩擦表层、次表面层及体相的物相纵向进行了较全面分析，特别揭示了摩擦次表面层Fe-C亚稳相的存在，对材料的摩擦性能有严重影响。     

Effects of gold‐induced crystallization process on the structural and electrical properties of germanium thin films

Gold‐induced (Au‐) crystallization of amorphous germanium (α‐Ge) thin films was investigated by depositing Ge on aluminum‐doped zinc oxide and glass substrates through electron beam evaporation at room temperature. The influence of the postannealing temperatures on the structural properties of the Ge thin films was investigated by employing Raman spectra, X‐ray diffraction, and scanning electron microscopy. The Raman and X‐ray diffraction results indicated that the Au‐induced crystallization of the Ge films yielded crystallization at temperature as low as 300°C for 1 hour. The amount of crystallization fraction and the film quality were improved with increasing the postannealing temperatures. The scanning electron microscopy images show that Au clusters are found on the front surface of the Ge films after the films were annealed at 500°C for 1 hour. This suggests that Au atoms move toward the surface of Ge film during annealing. The effects of annealing temperatures on the electrical conductivity of Ge films were investigated through current‐voltage measurements. The room temperature conductivity was estimated as 0.54 and 0.73 Scm⁻¹ for annealed samples grown on aluminum‐doped zinc oxide and glass substrates, respectively. These findings could be very useful to realize inexpensive Ge‐based electronic and photovoltaic applications.     

Au/ZrLa掺杂 CeO2催化剂在CO氧化反应中优异的催化活性：锆镧协同作用

在过去的25年,纳米金催化剂上 CO氧化反应得到广泛研究,但始终没有一致的结论。这是因为影响纳米金催化活性的因素很多,包括金的价态、载体的性质、氧空位、金属与载体之间的相互作用等,尤其是各影响因素之间相互牵制,增加了催化反应机理的研究难度。氧化铈载体表面氧缺陷的浓度较高,有利于活性金属组分在其表面的稳定和分散,因此氧化铈纳米晶负载的 Au催化剂受到广泛关注。此外,当 CeO2晶格中部分 Ce被化学性质不同的其它元素取代后,可以促进 CeO2晶格氧的活化,提高氧的储放能力,从而有利于催化反应进行。因此,本文采用水热法合成了组成均匀的 CeO2, CeZrOx和 CeZrLaOx三个载体,并通过沉淀-沉积法负载金。利用 X射线衍射(XRD)、拉曼光谱(Raman)、X射线光电子能谱(XPS)、高分辨透射电镜(HRTEM)、X射线吸收精细结构(XAFS)和氢气程序升温还原(H2-TPR)等技术分析了催化剂的物相结构、表面性质、形貌以及金纳米颗粒的大小和价态等性质,并结合其在 CO氧化反应中催化性能的差异,探讨影响金催化剂活性的关键因素。 XRD, TEM, HRTEM和 XAFS结果表明,三个载体上所得金纳米颗粒的平均尺寸都在2–4 nm,且分散较好; XPS结果表明,影响催化剂活性的关键因素不是金的价态,而是载体表面的活性氧物种。从Raman结果可知,掺杂后的氧化铈载体上氧空位浓度明显增加,因而催化剂活性都有所提高。 H2-TPR进一步探讨了三个载体以及负载金后其氧化还原能力的变化,结果表明,金和载体之间的相互作用可以增强载体的氧化还原性能以及表面氧空位浓度,进一步提高了催化剂活性,而负载金催化剂氧化还原性能的变化与载体的组成密切相关。由于锆的掺杂可使金与载体之间相互作用减弱,而镧则增强了二者间相互作用,因此 Au/CeZrLaOx催化剂上锆和镧的协同掺杂作用使其表面活性氧物种浓度最高,低温时表现出最高的催化活性。     

Ag/Au Alloy LSPR Engineering by Co‐deposition of RF‐Sputtering and RF‐PECVD

Silver‐Gold alloy/diamond like carbon (Ag‐Au/DLC) nanocomposite films were prepared by co‐deposition of RF‐sputtering and RF‐PECVD on glass substrates by using acetylene gas and silver‐gold target. The deposition process was carried out at room temperature in one minute with the variable parameters of initial pressures and RF powers. X‐ray diffraction analysis demonstrated the formation of Ag/Au alloy nanoparticles with a face‐centered cubic (FCC) structure. Localized surface plasmon and optical properties of Ag‐Au alloy nanoparticles were studied by UV‐visible spectrophotometry which showed that increasing RF power and initial pressure cause a redshift in all samples. Moreover, the effect of RF power and initial pressure on the size and shape of nanoparticles were studied by 2D Atomic force microscopy images. Energy dispersive X‐ray spectroscopy revealed the formation of Ag‐Au/DLC nanoparticles and the percentages of C, Ag, Au and O in all samples. The applied method for Ag/Au alloy preparation is the one step and low‐cost method which makes the samples ready for sensing application.     

氮化钛的制备及表征

以金红石为原料 ,金属铝作还原剂合成氮化钛 ,以X射线衍射、热分析等方法进行测定 ,结果表明该法合成得到的氮化钛纯度较高 ,经济可行。     

Structure‐activity relationship of supported Au catalysts with high catalytic activity by modifying the inactive supports

Three supported Au catalysts have been prepared by the deposition‐precipitation method by using the active carbon (AC), SiO₂‐AC, and SiO₂‐AC‐hollowed. The 3 supports were characterized by Brunauer‐Emmett‐Teller and scanning electron microscopy. Meanwhile, the supported Au nanoparticles were also characterized in detail by X‐ray powder diffraction, transmission electron microscopy, H₂‐TRP, and X‐ray photoelectron spectroscopy, and their catalytic activity and stability in CO oxidation was evaluated. The results demonstrated that Au supported on SiO₂‐AC‐hollowed exhibited much higher catalytic activity with acceptable stability for 72 hours than the other 2. We attributed to finer supported Au nanoparticles with abundant low‐coordinated Au atoms on the surfaces of hollowed supports with large special surface area and abundant pore structure. In summary, we successfully found an efficient and cheap method to prepare catalysts with high catalytic activity and acceptable stability by modifying the inactive supports.     

The fabrication of layer‐by‐layer mode LaCoO3 film by pulsed laser deposition

The relationship between strain and growth conditions in LaCoO₃ thin film was obtained to control the magnetic‐electric characteristics. The LaCoO₃ thin films on the SrTiO₃ substrates have been achieved by the pulsed laser deposition method, and the reflection high‐energy electron diffraction method (RHEED) was applied to monitor the growth process in situ; the layer‐by‐layer growth mode was discovered. The X‐ray diffraction and atomic force microscopy were applied to the phase analysis, and the layer thickness and the layer‐by‐layer growth mode were uncovered. Compared with the 100‐nm LaCoO₃ thin films, the strain in the layer‐by‐layer ultra thin film was more controllable. The enhanced magnetic properties of the layer‐by‐layer mode ultra‐thin films could be tested in future work.     

Growth of Textured Adenine Thin Films to Exhibit only Chiral Faces

The growth of adenine on Au(111) from the submonolayer up to several microns film thickness is studied by combining STM and surface X‐ray diffraction techniques. The study shows that adenine thin films are composed of highly textured crystallites with the reported α‐adenine crystal structure in such a way that they only exhibit (001)‐faces. Such faces, with chiral p2 symmetry planes, have an average size of 15 nm. Thus, the formed adenine films reported herein, which expose only chiral and biocompatible faces, might find applications such as enantioselective heterogeneous catalysts for the chemical and pharmaceutical industries.     

The influence of initial surface conditions on field crystallization of anodic aluminum oxide films determined by synchrotron X‐ray diffraction

X‐ray diffraction measurements were performed using synchrotron radiation at the SPring‐8 facility and electrochemical techniques to investigate the effect of polishing methods and storage conditions on the crystal structure of air‐formed oxide films and anodic oxide films formed on highly pure aluminum. Storage in an N₂ environment hinders local film breakdown during anodizing, and it was established that the X‐ray diffraction measurements showed the presence of a γ‐Al₂O₃ in the anodic oxide film formed on mechanically polished (MP) specimens. Formation of γ‐Al₂O₃ during anodizing was inhibited by electropolishing because of the removal of the work‐hardened layer that was formed on the MP by electro‐polishing. The X‐ray diffraction results do not show clear differences in the influence of the polishing method on the crystal structure of air formed oxide film. This is due to the very fast oxidation rate of the air‐formed oxide film and very long storage times for the X‐ray measurements. The anodic oxide film formed on aluminum, which has a very flat surface, shows color and the color depended on grain orientation. The electrochemical impedance of the MP specimen is slightly lower than that of the mechanically and then electrochemically polished specimen at the middle frequency range. This impedance difference may be due to formation of γ‐Al₂O₃ in the amorphous anodic oxide film and the thickness of the film. Copyright © 2010 John Wiley & Sons, Ltd.     

Rietveld法在半结晶聚酯二相共存结构分析中的应用

用Rietveld法对试样的BaF2的实测X射线衍射全谱图(XDWP)数据进行精修，获得正确的结晶相结构参数，重点讨论了如何正确选择衍射峰型函数和评价精修结构参数的可靠性；特别指出，当把Rietveld法和Fourier过滤技术及径向分布函数(radial distribution function，RDF)联用来研究半结晶聚酯(PET)的两相结构参数时，除需用R因子判断结晶相之精修结构参数的可靠性外，还要判断由非品相散射强度数据计算的RDF是否合理；如果忽视后一判据，则有可能导致错误的计算结果。