Synthesis and Crystal Structure of a Zinc(II) Complex Salt with the Schiff Base of Picolinaldehyde N-oxide and Semicarbazone

The title zinc（Ⅱ） complex salt [Zn（H2O）6]（ClO4）2-（PNOS）4, where PNOS is derived from picolinaldehyde N-oxide with semicarbazone, has been prepared and structurally characterized by X-ray single-crystal analysis. It crystallizes in triclinic, space group PI with a = 7.529（3）, b = 10.206（4）, c = 14.678（6）A, a = 86.293（6）, β= 87.686（7）, γ= 81.382（6）°, C28H44Cl2N16O22Zn, Mr = 1093.06, V = 1112.3（8） ,A^3 Z = 1, Dc = 1.632 g/cm^3, S = 1.089, μ（MoKa） = 0.773 mm^-1, F（000） = 564, the final R = 0.0438 and wR = 0.1076 for 3888 independent reflections with Rint = 0.0224. The crystal structure possesses a [Zn（H2O）6]^2＋ cation, two ClO4^- anions and four PNOSs. In the crystal structure, Zn^2＋ cation is located at the symcenter and coordinated by six water molecules. In [Zn（H2O）6]^2＋, an elongate octahedral complex cation, the average Zn-O bond length is 2.087（2） A. There exist a lot of H bonds in the structure, linking the cation [Zn（H2O）6]^2＋, anion ClO4^- and PNOS to form a 3D network.

Synthesis, Structural Characterization and DFT Studies of Silver(I) Complex Salt of Bis(4,5-dihydro-1<i>H</i>-benzo[g]indazole)

A new silver complex salt [Ag(N2C11H10)2]NO3 (where N2C11H10 = 4,5-dihydro-1H-benzo[g]indazole), has been synthesized and characterized by elemental and thermal analyses, IR and 1HNMR spectroscopies, single crystal X-ray structure determination and DFT studies. Its molecular structure comprises of a silver center coordinated to two nitrogen atoms from two 4,5-dihydro-1H-benzo[g]indazole molecule giving rise to a cationic complex entity, [Ag(N2C11H10)2]+ with as counter ion. The bulk structure is consolidated by N–H…O, C–H…π, Ag…π and Ag…O intermolecular interactions, thus generating a pseudo-helical network. The optimized structure, frontier molecular orbitals (HOMO and LUMO) and global reactivity descriptors were investigated by performing DFT calculations.

Synthesis, Rietveld Refinement and DFT Studies of Bis(4,5-dihydro-1<i>H</i>-benzo[g]indazole)silver(I) Hexafluorophosphate Complex Salt

The new salt bis(4,5-dihydro-1H-benzo[g]indazole)silver(I) hexafluorophosphate, [Ag(N2H10C11)2]PF6, has been synthesized in methanol at ambient temperature and characterized by elemental and thermal analyses, FTIR and 1HNMR spectroscopies, Rietveld refinement from powder diffraction data and DFT studies. The salt crystallizes in the triclinic space group P-1 with the parameters: a = 7.776 ?, b = 8.676 ?, c = 9.226 ?, α = 69.27° β = 89.86°, γ = 74.50°, V = 558.02 ?3, Z = 1. In the structure, the silver center is coordinated to two nitrogen atoms from two 4,5-dihydro-1H-benzo[g]indazole ligands, forming a centrosymmetric complex cation, [Ag(N2H10C11)2]+, with a linear coordination geometry around the silver center. The hexafluorophosphate ion, , acts as counter anion. The crystal packing is governed by N-H···F and C-H···F hydrogen bonds that interconnect the ionic constituents and Ag···F and Ag···π interactions help for the stabilization of the packing. The optimized structure was obtained at B3LYP/LanL2DZ level in the gas phase. The stability and reactivity of the structure were studied using respectively HOMO-LUMO gap and electronic global quantities (ionization potential (I) and electron affinity (A)) as descriptors.

Application of the Reactions of Ferrocene（Ⅰ） Salts with Bis［dicarbonyl（η￣5－cyclopentadienyl）iron］ and Bis［dicarbonyl（η￣4－butadiene）cobalt］ Complexesto Organic Synthesis

omplexes[(η￣5-C_5H_5)Fe (CO)_2L]￣+BF(Ⅰ)[L=PPh_3,P(OPH)_3,P(OC_2H_5)_3,pyridine, 3-acetyl-pyridine, 4-methyl-pyridine, phenyl cyanide, quinoline] and[(η￣4-C_4H_6)Co(CO)_2L]￣+BF(Ⅱ)[L=PPh_3,P(OPH)_3,P(OC_2H_5)_3],were respec-tively produced in the reactions of[(η￣5-C_5H_5)Fe (CO)_2 ]_2 and [ (η￣4-C_4H_5 )Co (CO)_2]_2with Cp_2FeBF_4 in the presence of the ligands. Some characteristics of these reac-tions were discussed and all the complexes were identified by iR and ￣1H NMR spec-troscopy. These complexes are air-stable and the preparative metliods are simple.

RADICAL PHOTOPOLYMERIZATION USING ARYLIODONIUM SALT/TERTIARY AMINE COMPLEX SYSTEM AS THE PHOTOINITIATOR

The diphenyliodonium salt (DPIOC)/triethylamine (TEA) is used as photoinitiator for radical photopolymerization. It was found that a ground state CT complex formed between DPIOC as electron acceptor and TEA as electron donor, which results in extending the photosensitivity range of DPIOC/TEA system up to above 500nm compared with DPIOC alone. The kinetic studies on photopolymerization of methyl methacrylate (MMA) were carried out in CH_3CN: H_2O (14: 1, v/v) mixture solution at 30℃ by dilatometer. The results obtained show that the polymerization rate (R_p) increases with increasing concentrations of DPIOC and TEA with exponent 0. 65 and 0. 62 respectively. The activation energy E_a and k_p/k_^(1/2) value were determined to be 4.1 Kcal mol^(-1) and 0.045 respectively. The other influence factors and reaction mechanism were also discussed.

Preparation of Heteropoly Molybdoselenite Complex and Its Lanthanide Salts and Their Catalysis for Hydroxylation of Phenol

A heteropoly molybdoselenite complex （NH4）6[ Se2Mo8O31 ]·5H2O and its lanthanide salts Ln2 [Se2Mo8O31]-XH2O（Ln = La^3＋, Ce^3＋, Nd^3＋ Sm^3＋） were synthesized and characterized with elemental analysis, IR, UV, XRD and TG-DTA. Their reactivity for hydroxylation of phenol was investigated. The results show that catalytic activity of （ NH4 ）6 [Se2Mo8O31 ]·5H2O is higher than that of its lanthanide salts. The reaction temperatures, the reaction time. the catalvst amount, the ratio of phenol and H2O2 have influence on the phenol conversation, H2O2 selectivity and product distribution. The optimum reaction condition was obtained with orthogonal method. At optimum reaction condition which the ratio of phenol and H2O2 = 1 ： 1, reaction time is 4 h, reaction temperatures is 70℃ and catalyst is 10 g·mol^-1, and the conversation of phenol reaches as high as 29.65 %, the product selectivity can reach 77.2 % for catalyst （NH4）6[ Se2Mo8O31 ]·5H2O.

Crystal Structures of Co(Ⅱ) and Cu(Ⅱ) Complexes and Ammonium Salt Involving Ethylenediamine

The Co（II） complex I and ammonium salt II were synthesized from the direct reaction of 1,2-ethylenediamine and cobaltous acetate tetrahydrate and manganese acetate tetrahydrate in anhydrous ethanol. Treatment of N,N＇-bis（salicylidene）ethylenediamine with Cu（OAc）2·H2O results in the formation of Cu（II） complex III. C14H37CoNaO8 （I）： triclinic, space group P1, a = 8.6296（12）, b = 12.0291（17）, c = 12.1108（17） A, α = 75.335（2）, β = 69.991（2）, γ = 72.248（2）°, V= 1109.4（3） A3, Z = 2, ρcaloa = 1.342 g/cm3, the final R= 0.0342 for 4817 observed reflections with I 〉 2σ（I） and Rw = 0.1263 for all data. C6H16N204 （II）： space group P1, a = 5.5513（10）, b = 5.5589（11）, c = 7.4437（14） A, α = 94.332（4）, β = 104.497（4）, γ = 103.487（4）°,V= 214.06（7） A3, Z = 1, ρcalcd = 1.398 g/cm3, the final R = 0.0431 for 829 observed reflections with I〉 2σ（I） and Rw = 0.1263 for all data. C14H37CuN40 （III）, space group P21/n, a = 9.050（9）, b = 18.434（17）, c = 11.659（11） A, β = 107.134（19）°, V= 1859（3） A3, Z = 4, ρcalcd =1.443 g/cm3, the final R = 0.0616 for 3308 observed reflections （O 〉 2σ（I）） and Rw = 0.1229 for all data. Their structures were all determined by X-ray diffraction, elemental analysis and IR.

Reaction of Arylselenium Titanocene Complexes with Diaryl Iodonium Salts——a Convenient Synthesis of Unsymmetrical Diarylselenides

The diaryldiselenides reacted with titanocene hydried （Cp2TiH） generted from Cp2TiCl2/i-BuMgBr to give arylselenium complexes of titanocene. They reacted readily with diaryliodoiums salt to give unsymmetical diarylselenides.

Synthesis and Crystal Structure of a Complex Bimetallic Salt [Ni(trans_[14]diene)] [Ni (mnt)_2]

The title compound has been synthesized by the reaction of [Ni(trans[14]diene)]I2 with Na[Ni(mnt)2] in water and THF, where [trans[14]diene]= 5, 7,7, 12, 14, 14-hexamethyl-1, 4, 8, 11-tetraazacyclotetradeca-4, 11-diene and mnt2- = cis-1, 2-dicyano-1,2-ethylenedithiolato. Its crystal structure has been determined by X-raycrystallography analysis with 4827 independent reflections (Fo>4σ(F0). The bimetallic complex salt [Ni (trans [14] diene )] [Ni (mnt )2] (C24 H32N8Ni2S4, Mr = 678. 24 )crystallizes in the triclinic system with space group P1, a = 9. 2911 (9), b= 11. 7075(12), c=15. 799(2) A, α=68. 384(7), β=79. 324(7), γ=67. 581(6)°, V=1474. 9(3) A3, Dc=1. 527 Mg/m3, Z=2, λ=0. 71073 A, μ=1. 589mm-1, F(000) =704,R=0. 0367. The structure consists of slightly distorted Square planar units [Ni(trans[14]diene)]2+ and [Ni(mnt)2]2-.

一种植物蛋白复合肽盐的工艺研究

食盐与我们的日常生活密切相关,但如果摄入过多食盐,会导致体内钠离子积累过多,进而引发一系列的疾病。该研究在以谷朊粉为原料制得咸味肽的基础上,以感官评分、色差值、水分、乳化性和乳化稳定性为指标,对氯化钾、酵母提取物和柠檬粉的添加量进行单因素试验,并利用响应面试验优化肽盐的配方。结果表明,在氯化钾为0.4 g、酵母提取物为0.2 g、柠檬粉为0.3 g的条件下,复合肽盐中多肽含量为11.4 mg/g,钠离子含量为0.35 g/100 g,钾离子含量为1.181 g/100 g,且添加酵母提取物和柠檬粉掩盖了肽盐的不良气味,外观呈浅黄色;减少了生活中钠的摄入量,得到低钠、减盐不减咸的调味品。

不同金属盐体系对锦纶66纤维结构与性能的影响

选用氯化钙、氯化锂、氯化铜及氯化锌四种金属盐,分别以去离子水和无水乙醇为溶剂配置成溶液,对锦纶66纤维进行络合改性处理,采用FTIR、DSC、XRD、SEM、单纤维拉伸研究不同金属盐及其溶剂种类对锦纶66纤维结构性能的影响。结果表明,经四种金属盐处理后,氯化铜对锦纶66纤维的结构性能影响最大、对纤维的络合作用最强,氯化锌对锦纶66纤维的结构、性能影响最小,氯化钙和氯化锂的影响程度居中,具体表现为红外光谱图中N-H振动峰向低波数移动,熔融温度下降、结晶度减小、拉伸断裂强度降低。选择氯化钙为金属盐络合剂时,以乙醇作为溶剂时对锦纶66纤维的结构、性能的影响作用大于以水为溶剂时,说明乙醇有利于金属离子与纤维之间形成络合作用。

光诱导基于EDA机理构建S-芳基黄原酸酯新策略

黄原酸酯类化合物作为药物化学、农业化学、材料化学中重要的组成部分,一直备受化学家们的关注.寻找简单、高效合成S-芳基取代黄原酸酯的方法引起了研究者广泛的关注.报道了一种可见光诱导下基于硫负离子与噻蒽盐间的EDA(电子供体受体)过程实现C-S键构建的新策略.在温和无金属的条件下,以中等至优良的收率得到了一系列S-芳基黄原酸酯,克级实验与日光实验证明了反应的应用潜力,为黄原酸酯类化合物的合成提供了一种新思路.

废盐无害化处理工艺研究

为了解决制备精四氯化锆过程中产出废盐的处理难题,根据废盐微观形貌分析结果,将废盐加水溶解,利用强酸性体系使废盐中的金属离子溶出进入溶液,通过采用不同搅拌方式、浸出时间、压滤方式以及浸出试剂等实验,研究金属元素的分配及迁移规律。通过实验室条件摸索试验、放大试验以及条件优化试验,使处理后废盐中锆平均收率大于80%,不同阶段废盐锆收率基本稳定,处理每吨废盐用水量在10 t以下,中和渣及水溶渣pH值达到国家《危险废物鉴别标准腐蚀性鉴别》(GB 5085.1-2007)标准要求。

四种方法消毒视力检查遮眼板效果比较

目的比较四种消毒方法清洁消毒视力检查遮眼板的效果。方法选取患者使用过的遮眼板120件,设置为A、B、C、D四组(各30件),分别采用500 mg/L含氯消毒剂、75%乙醇、复合醇消毒湿巾、湿热消毒法进行消毒。在消毒前、消毒后5 min,消毒后4 h及8 h分别采用微生物培养法和三磷酸腺苷(ATP)生物荧光检测法比较消毒合格率,并比较四种消毒方法的消毒成本。结果消毒后5 min,四组微生物培养和ATP生物荧光检测的消毒不合格率均为0;消毒后4 h,B组消毒不合格率显著高于D组(P<0.008),消毒后8 h,A组、B组和C组消毒不合格率显著高于D组(均P<0.008)。结论湿热消毒法消毒效果明显优于500 mg/L含氯消毒剂、75%乙醇及复合醇消毒湿巾,简便易行。

仿生细胞膜介导的白藜芦醇包合物的制备与表征

以磺丁基-β-环糊精(SBE-β-CD)为壁材,同时复配具有仿生细胞膜结构的聚季铵盐-51(PQ-51),制备白藜芦醇/磺丁基-β-环糊精/PQ-51(RES-SBE-β-CD-PQ-51)包合物。通过红外光谱、扫描电子显微镜对包合物的微观构象进行表征,以高效液相色谱法进行测定。结果表明,白藜芦醇(resveratrol,RES)被成功包合于SBE-β-CD-PQ-51中,包合后RES的溶解度、变色情况及热稳定性均得到改善。相较于RES-SBE-β-CD,PQ-51的加入使RES的包封率由90.0%提高至99.2%,负载量由6.8%提高至7.9%,溶解度由2267倍提高至3160倍,变色情况进一步减缓,同时提高了细胞安全性。

下川东震旦系气井复杂处理技术实践与认识——以YT1井为例

为了安全有效开发四川盆地下川东地区震旦系气藏,保障川渝地区天然气能源的有效接替,需对震旦系气井的开发难点进行研究,解决易发生的故障复杂。以中国石油西南油气田公司重点探井YT1井为研究对象,分析了该井面临的地层多压力系统、压力系统窗口大、井漏严重、井壁易缩径等地质难点,从井身结构、堵漏技术、防溢流技术、防塌技术等方面开展复杂处理技术研究。研究结果表明:①优化井身结构为五开非标结构,能有效封隔必封点;②大井眼段下侏罗统自流井组—上二叠统龙潭组综合应用随钻堵漏、复合堵漏、水泥堵漏技术,可有效提升堵漏成功率,降低复杂时率;③241.3 mm井眼奥陶系十字铺组—上寒武统洗象池组优化钻具组合,综合治理溢、漏、塌等复杂,可有效提升作业效率。结论认为:①沙溪庙—凉高山地层采用空气/雾化钻进未发生故障复杂,防漏、提速效果显著;②龙潭组—下寒武统筇竹寺组地层优选“水力振荡器+复合钻头+MWD定向”技术,23趟钻完成3150.94 m长段膏盐层井段定向作业;③190 mm井眼开展185 mm双向微扩眼器试验,解决了长段膏盐层缩径问题,三次扩眼后下套管顺利到位;④通过复杂防控技术集成应用,YT1井复杂时率降低至17.47%,避免了恶性卡钻;⑤推广应用下川东地区震旦系气藏复杂防控技术对川渝地区后续震旦系气藏深井技术研究具有指导意义。

Influence of Molten Salt on Luminescent Intensity and Particle Size of Y_2O_3:Eu^(3+) Phosphor

The Y-Eu oxalate precursor was prepared with a homogeneous precipitation method. And the additives, Na2CO3, S, NaCl or their combination, were introduced into the precursor to prepare Y2O3 ：Eu^3＋ red phosphors at 1000 1300 ℃ for 2 h. The effect of molten salts on particle size and luminescent intensity was studied. The experimental results showed that the complex molten salt （Na：CO3 ＋ S ＋ NaCl） was conductive to enhance the luminescent intensity of Y2O3 ：Eu^3＋. The emission intensity of the phosphor prepared with these additives at 1300 ℃ was about 45% higher than that of the one prepared without molten salt, and about 11% higher than that of the corresponding commercial phosphor. Meanwhile, the particle size of Y2O3 ：Eu^3＋ phosphor was controlled effectively with the molten salt.