Preparation, patterning and luminescent properties of oxyapatite La-9.33(SiO6)(4)O-2 : A (A = Eu3+, Tb3+, Ce3+) phosphor films by sol-gel soft lithography

Silicate oxyapatite La-9.33 (SiO6)(4)O-2:A (A = Eu3+, Tb3+ and/or Ce3+) phosphor films and their patterning were fabricated by a sol-gel process combined with soft lithography. X-ray diffraction (XRD), Fourier transform infrared spectroscopy, atomic force microscopy, optical microscopy and photoluminescence spectra, as well as lifetimes, were used to characterize the resulting films. The results of XRD indicated that the films began to crystallize at 800degreesC and the crystallinity increased with the increase in annealing temperatures. Transparent nonpatterned phosphor films were uniform and crack-free, which mainly consisted of rodlike grains with a size between 150 and 210 nm. Patterned thin films with different bandwidths (20, 50 mum) were obtained by the micromoulding in capillaries technique. The doped rare earth ions (Eu3+, Tb3+ and Ce3+) showed their characteristic emission in crystalline La-9.33(SiO6)(4)O-2 phosphor films, i.e. Eu3+ D-5(0)-F-7(J) (J = 0, 1, 2, 3, 4), Tb3+ D-5(3,4)-F-7(J) (J = 3, 4, 5, 6) and Ce3+ 5d (D-2)-4f (F-2(2/5), F-2(2/7)) emissions, respectively. Both the lifetimes and PL intensity of the Eu3+, Tb3+ ions increased with increasing annealing temperature from 800 to 1100 degreesC, and the optimum concentrations for Eu3+, Tb3+ were determined to be 9 and 7 mol% of La3+ in La-9.33(SiO6)(4)O-2 films, respectively. An energy transfer from Ce3+ to Tb3+ was observed in the La-9.33(SiO6)(4)O-2:Ce, Tb phosphor films, and the energy transfer efficiency was estimated as a function of Tb3+ concentration.

Hydrothermal synthesis and structural characterization of a novel organic-inorganic hybrid compound {[Cu(2, 2 '-bpy)(2)](2)-Mo8O26}

A novel organic-inorganic hybrid compound {[Cu (2, 2'-bpy)(2)](2)Mo8O26} has been hydrothermally Synthesized and structurally characterized by single-crystal X-ray diffraction. The compound crystallizes in the orthorhombic space group, Pna2(1), with a=2.4164 (5), b=1.8281 (4), c=1.1877 (2) nm, V=5.247(2) nm(3), Z=4, and final R-1=0.0331, wR(2)=0.0727. The structure consists of discrete {[Cu(2,2'-bpy)(2)](2)Mo8O26} clusters, constructed from a beta -octamolybdate subunit[Mo8O26](4-) covalently bonded to two [Cu(2,2'-bpy)(2)](2+) coordination complex cations via bridging oxo groups. In addition, the spectroscopic properties and thermal behavior of this compound have been investigated by spectroscopic techniques (UV-vis, IR, Raman and EPR spectra) and TG analysis.

Synthesis and crystal structure of [Nd(eta(6)-1,3,5-C6H3Me3)(AlCl4)(3)]( C6H6) and structural comparison of Ln(eta(6)-arene)(AlCl4)(3)

Reaction of NdCl3, with AlCl3 and mesitylene in benzene gives complex [Nd(eta (6)-1,3,5-C6H3Me3) (AlCl4)(3)] (C6H6) (1) which was characterized by elemental analysis, IR spectra, MS and X-lay diffractions. The X-ray determination indicates that 1 has a distorted pentagonal bipyramidal geometry and crystallizes in the monoclinic, space group P2(1)/n with a = 0.9586(2), b = 1.1717(5), c = 2.8966(7) nm, beta = 90.85 (2)degrees, V = 3.2529(6) nm(3), D-c = 1.573 g/cm(3), Z = 4. A comparison of bond parameters for all the reported Ln(eta (6)-Ar) (AlCl4)(3) complexes indicates that the bond distance of Ln-C is shortened with the increasing of methyl group on benzene and with the decreasing of radius of lanthanide ions.

4-羟基偶氮苯与6-氯-5,12-萘并萘醌反应产物的NMR分析

无水碳酸钾存在下6-氯-5,12-萘并萘醌与4-羟基偶氮苯在干燥DMF中反应的主要产物在某些反应条件下不是6[4-(苯基偶氮基)苯氧基]-5,12-萘并萘醌(1)。该未知反应产物2经核磁共振方法研究证实是6-(N,N-二甲氨基)-5,12-萘并萘醌。本文对化合物2的~1H-和~(13)C化学位移、偶合信息和结构作了详细归属,并推测其反应进程,实验结果表明,化合物2是由化合物1与溶剂DMF反应生成。

Synthesis and crystal structure of (eta(8)-C8H8)Gd(eta(5)-C6H5CH2C5H4)center dot DME

LnCl(3) reacted with C6H5CH2C5H4Na in THF (tetrahydrofuran) in the ratio 1.1 at room temperature for 1 h giving C(6)H(5)CH(2)C(6)H(4)LnCl(2) . nTHF, which reacted with C8H8K2/THF and the crystals obtained were recrystallized in DME to yield the title complex. The crystal structure of (C8H8) Ln (C6H5CH2C5H4). DME was determined revealing that the Gd complex has one conformation. One benzylcyclopentadienyl (eta(5)), one cyclooctatetraenyl (eta(8)) and the two oxygen atoms of DME (dimethoxyethane) are coordinated to Gd with the effective coordination number of 10.

La_(2-x)Sr_xNiO_(4-λ)系列催化剂结构与氨氧化活性的关系

本文报道了La_(2-x)Sr_xNiO_(4-λ)(O≤x≤1)系列复合氧化物的固体结构性质和用于氨的氧化制硝酸的催化性能.La_(2-x)Sr_xNiO_(4-λ)的晶胞体积Ⅴ随x的增大而逐渐减小;c轴在x≤0.5前逐渐增大,在x≥0.5后逐渐减小.a轴在x≤0.5前逐渐减小,在x≥0.5后基本保持恒定.在x≤0.5前,La_(2-x)Sr_xNiO_(4-λ)中存在氧过剩,在x≥0.5后存在氧缺陷.TPD表明,a氧(吸附在氧缺陷上的氧)在x=0.6时出现极大,β氧(晶格氧)随x增大而逐渐增大.La_(2-x)Sr_xNiO_(4-λ)的氧化还原能力,Ni~(3+)的量,氨氧化的NO选择性都随x增大而增加.由此得出,Ni~(3+)是催化剂的活性离子,β氧是氨的氧化的活性氧种,在La_(2-x)Sr_xNiO_(4-λ)上的氨的氧化遵循氧化还原(Redox)机理.

水溶性聚合物和两亲聚合物18．2－丙烯酰胺基烷磺酸类两亲单体

２－丙烯酰胺基烷磺酸的溶解行为和胶体化学性质明显随烷基长短而异。由于手性碳原子的存在，与其相邻亚甲基的质子峰在~１ＨＮＭＲ谱上清楚地发生分裂。研究了２－丙烯酰胺基十六烷磺酸（ＡＭＣ１６Ｓ）在水／二氧六环混合溶剂中的聚合动力学和胶体化学性质。发现聚合速度和所得聚合物分子量均在水／二氧六环体积比为１～１／２时出现最小值，临界胶束浓度随混合溶剂中二氧六环含量的增加而增加，当水／二氧六环体积比为１／２～１／４时，观察不到胶束化现象。

SYNTHESIS AND MOLECULAR-STRUCTURE OF NBU2[(MEO)3C6H2C(O)N2CHC6H4O]SN FORMED IN THE REACTION OF DI-N-BUTYLTIN(IV) OXIDE WITH 3,4,5-TRIMETHOXY-BENZOYL SALICYLAHYDRAZONE

The title complex was synthesized and characterized by H-1, C-13, Sn-119 NMR and IR spectra. A single crystal X-ray diffraction study confirmed its molecular structure and revealed that 3,4,5-trimethoxy-benzoyl salicylahydrazone was a tridentate and approximately planar ligand. The complex crystallizes in the triclinic space group P1BAR with a = 9.208(3), b = 12.536(2), c = 12.187(4) angstrom, alpha = 113.12(2), beta = 90.58(2), gamma = 81.42(2), V = 1277.5(6) angstrom, Z = 2. The structure was refined to R = 0.033 and R(w) = 0.041 for 3944 observed independent reflections. The tin atom has a distorted trigonal bipyramidal coordination. The Sn-C bond lengths are 2.129(5) and 2.113(5) angstrom (av. 2.121(5) angstrom), the C-Sn-C angle is 123.3(2); the bond length between the tin atom and the chelating nitrogen is 2.173(3) angstrom. Two chain carbon atoms and the chelating nitrogen atom occupy the basal plane. The skeleton of two erect oxygen atoms and the tin atom is bent (O-Sn-O angle = 153.5(1)). In the complex, the ligand exists in the enol-form.

粉状巯基棉富集——水中痕量CH_3Hg~+及Hg~(2+)的冷原子荧光测定

本文提出了一种新的高巯基粉状巯基棉的合成方法,按此法合成的流基棉含量在2.2%～2.5%之间.在盐酸介质中,用溴水在室温下快速分解甲基汞,冷原子荧光测定的新方法.将粉状巯基棉与稀释剂按一定比例混合装柱,用于富集水体中溶解态痕量Hg~(2+)和CH_3Hg~+,富集流速100ml/min.检出限CH_3Hg~+为4.2×10~(-5)μg/l,Hg~(2+)为6.6×10~(-5)μg/l.

α-羰基烯酮环二硫代缩醛化学(Ⅹ)——β,β-1,5-亚丙二硫基-α,β-不饱和酮与烯丙基Grignard试剂加成物的酸催化反应取向研究

β,β-1,5-亚丙二硫基-α,β-不饱和酮2b和2-甲基烯丙基氯化镁加成可得醇3b.在BF_3·Et_2O催化下,3b经分子内环合芳构化生成芳硫醚5b.2和烯丙基溴化镁反应得醇4,4在BF_3·Et_2O催化下经β-消除脱水生成共轭多烯类化合物6.二硫缩醛基以环和非环结构及环的大小对2与烯丙基Grignard试剂加成物在酸催化下的反应取向有重要影响.

(η~5-C_9H_7)_2Yb(THF)_2的晶体结构

双(茚基)镱(Ⅱ)四氢呋喃配合物(η~5-C_9H_7)_2Yb(THF)_2的晶体属单斜晶系,C_c空间群,晶体学参数a=13.506(4),b=11.081(2),c=15.577(5),β=92.68(3)°,V=2329(1),D_c=1.56g/cm~3,Z=4,μ=42.4cm~(-1),F(000)=1088,最终编离因子R=0.029,R_w=0.031。中心离子Yb~(2+)与两个茚基以η~5形式成键且与两个四氢呋喃中的氧成键,茚基的两个质心和四氢呋喃中的两个氧形成扭曲的四面体,Yb~(2+)在四面体的中心。Yb~(2+)的配位数为8。Yb~(2+)到质心In1的距离为2.52,到质心In2的距离为2.40。Yb~(2+)到O(1)的键长为2.356(7),到O(2)的键长为2.417(5)。

THE ALGEBRAIC-METHOD ESTIMATING +/-PI/2 TYPE OF PHASES OF STRUCTURE FACTORS

The algebraic formulas of 1.5 and 2.5 rank which can be applied to estimating +/- pi/2 type of phases for P2(1)2(1)2(1) space group were derived using the method of structure factor algebra. Both types of the formulas are satisfactory for two known crystal structures in estimating their +/- pi/2 type of phases.

杂多酸盐K_4H[SiMO_(11)VO_(40)]·18H_2O 1和K_4H_2[PMo_9V_3O_(40)]·18H_2O 2的晶体结构

杂多酸是种类多,应用广的重要的无机化合物。其中有一类是12-系列化合物Z,(XM_(12-n)M_n′O_(40))·mH_2O,中心离子X可以是过渡元素或非过渡元素;M常是Mo、W;M′为V_(5+)、Mn_(2+)、CO_(2+)等;n=0,1,2…;Z为H~+或一价阳离子;y=1,2,…。它们同其相应氧化型化合物比较具有引人注目的特性,但迄今尚未见到还原型化合物晶体结构文章,只是

稀土硝酸盐15-冠-5络合物的一些性质

稀土冠醚络合物的组成和稳定性不但与稀土离子直径和冠醚孔径是否匹配,而且也和阴离子及合成用的溶剂有关.因15-冠-5(简写15C5)的孔径(2.2?)和大部分稀土离子直径相近.因此它们的络合物是研究孔径匹配关系的理想模型. Bunzli在乙腈中合成了大部分镧系硝酸盐15C5络合物,轻镧系(La-Gd)生成1:1无水络合物,重镧系(Tb-Lu)为含1—3分子水的1:1络合物.我们在无水丙酮中制备

近2千万年以来东亚季风演化的南海沉积矿物学记录

本论文通过对南海南部ODP1143站和北部ODP1146站两个长柱状沉积物的陆源矿物组成和堆积速率、生物硅含量和堆积速率、粘土矿物组成、结晶学特征、微形貌和化学成分、陆源物质粒度和元素地球化学的综合研究，分析了1143站和1146站的陆源物质来源的演变，分别建立了南海南部和北部的季风演化代用指标，并与黄土、深海风尘沉积、海洋微体古生物记录对比，重建了东亚季风在近20 Ma以来的长期演化，并探讨了青藏高原隆升在季风长期演化中的驱动作用。 地质背景和元素地球化学分析表明ODP1143站的陆源物质主要来自于湄公河的输入。但陆源物质堆积速率、中值粒径、粘土矿物组合、蒙脱石结晶度指数和生物硅含量和堆积速率在5.2 Ma前后的变化表明ODP1143站的湄公河物源在10–5.2 Ma可能受到了越南区域性地壳隆升和玄武岩喷发的影响。而自~5.2 Ma以来，到达ODP1143站的沉积物受湄公河流域内部物源通量所控制。 ODP1146站的陆源物质为多物源、多传输方式供应，并且近20 Ma以来各个物源/传输方式的强度发生了改变。粒度端员组分模拟揭示出，近20 Ma以来风尘平均贡献了20%物质到1146站，河流输入贡献80%。河流输入中，75%来自珠江和台湾，25%来自吕宋岛。1146站的沉积环境、粘土矿物、地球化学分析表明河流输入的石英、长石来自珠江、台湾；蒙脱石主要来自于吕宋岛，高岭石主要来自于珠江，伊利石和绿泥石来自于珠江、台湾、长江。 ODP1146站17–15 Ma间异常高的陆源物质(石英、长石、蒙脱石、高岭石)、生物硅和碳酸盐的堆积速率暗示了在17–15 Ma南海周围地区发生了强烈的构造活动，这可能与南海扩张停止有关。而ODP1146站稀土元素地球化学、粘土矿物结晶学特征在3 Ma以来的明显变化显示近3 Ma以来台湾物质的输入强度显著加强，这可能与3 Ma以来台湾造山活动加强有关。 ODP1143站粘土矿物/长石、高岭石/绿泥石比值和生物硅含量和堆积速率、陆源物质堆积速率的指标组合被用来建立了一个简单的东亚夏季风演化模型。结果显示8.5–7.6 Ma和 7.1–6.2 Ma分别为两个较强的夏季风阶段，在6.2–3.5 Ma为一相对稳定的阶段，然后在3.5–2.5 Ma不断加强，随后从2.5 Ma以来又不断减弱，直到1.0 Ma夏季风强度又再次加强，并且变化幅度和频率加大。 ODP1146站风尘含量、风尘堆积速率、(伊利石+绿泥石)/蒙脱石、(石英+长石)%、陆源物质的平均粒径被用来作为南海北部季风演化的代用指标。研究表明，近20 Ma以来东亚冬季风强度、亚洲内陆干旱程度和冬季风相对夏季风强度在12−9 Ma、8−4 Ma有所加强，在3 Ma以来显著加强。相比而言，夏季风强度在15−3 Ma间比较稳定，在3 Ma可能与冬季风同步加强。 ODP1143站、1146站、1148站的线性沉积速率，以及1143、1146站的总陆源物质、石英、长石和粘土矿物的物质堆积速率在3.5–2.5 Ma的几乎同时增加，代表着对3.5 Ma以来全球气候恶化和东亚夏季风加强的侵蚀响应。青藏高原的阶段性隆升可能促进了东亚季风在8 Ma和3 Ma左右的加强，但两极冰川扩展和全球变冷也是一个可能因素，也可能季风演化是二者共同作用的结果。我们的研究结果倾向于支持青藏高原阶段性隆升在东亚季风长期演化中的驱动作用。