在聚乙烯醇-124存在下钌-二氯化锡-乙基紫离子缔合体系测定钌的研究

本文对钌(Ⅲ)SnCl_2-EV高灵敏显色体系测定钌进行了研究。摩尔吸光系数ε_(640nm)高达1.5×10~5L.mol~(-1)·cm~(-1),钌含量在0.2～1.4和1.4～2.2μg/25ml范围内符合比尔定律.对外来离子的干扰进行了研究,并对纯金属镍中痕量钌的含量进行了测定。     

STUDIES ON STRUCTURES OF SOME PLATINUM COMPLEXES WITH 1, 1-CYCLOPROPANEDICAR BOXYLATE

The crystal structure, of [Pt(NH_3)_2CPrDCA]. H_2O (Ⅰ), [Pt(CH_3NH_2)_2CPrDCA] (Ⅱ), and [Pt(dmbn) CPrDCA]·2.5H_2O(Ⅲ) (where CPrDCA is 1, 1-cyclopropanedicarboxylate; dmbn is 2, 3-dimethyl-2, 3-butyldiamine) are determined. Compound Ⅰ crystallizes in the orthorhombic space group P_(nma) with the cell dimensions: a=6.517(2), b=9.709(3), c=14.205(5), Z=4, R=0.058. Compound Ⅱ is monoclinic with space group P2_1/n, a=9.648(3), b=8.720(2), c=12.770(4), β=107.12(2), Z=4, R=0.059. Compound Ⅲ belongs to the monoclinic system space group P2_1/m with the cell dimensions: a=6.494(1), b=19.638(3), c=6.606(1), β=94.44(1), Z=2, R=0.038.Electronic structures of the complexes are studied and the correlstion between structure of the amine ligands and biological activity of the complexes is explored.     

ZnTi_(0.6)Fe_(1.4)O_4/膨胀石墨复合物对污染物的吸附-光催化降解活性

用化学共沉淀法制备了Zn Ti0.6Fe1.4O4/膨胀石墨(ZT0.6F1.4/EG)复合物.通过现代分析技术表征了样品的组成、微观结构、磁性能、吸附性能和光催化活性.结果表明,ZT0.6F1.4/EG不仅保持了膨胀石墨原有的特殊结构和吸附性能,并且具有良好的ZT0.6F1.4负载率、磁性能和光催化活性;样品对罗丹明B(Rh B)的去除率取决于EG的吸附作用和ZT0.6F1.4的光催化降解作用;ZT0.6F1.4和EG质量比(mZTF/mEG)为1:1的ZT0.6F1.4/EG复合物对Rh B的最大吸附量(qm)为5.102mg g?1,且吸附行为与Langmuir等温吸附模型相一致.ZT0.6F1.4/EG对工业染料废水、柴油/水混合溶液也具有良好的去污效果.此外,ZT0.6F1.4/EG回收方便、活化处理简便、循环使用性能良好.     

Fabrication,adsorption and photocatalytic properties of ZnTi0.6Fe1.4O4/Carbon nanotubes composites

ZnTi_xFe_(2–x)O_4 and ZnTi_(0.6)Fe_(1.4)O_4/Carbon nanotubes(ZT_(0.6)F_(1.4)/CNTs) composites were prepared by chemical co-precipitation method. The composition, microstructure, magnetic property, adsorption and photocatalytic activity of the prepared samples were characterized by means of modern analytical techniques. The results indicated that ZT_(0.6)F_(1.4)/CNTs composites not only held the original special structure and excellent adsorption properties of CNTs, but also had suitable magnetic property and excellent photocatalytic activity. The removal rate of the samples on Rhodamine B(RhB) depended on the adsorption of CNTs and the photocatalytic degradation of ZT_(0.6)F_(1.4) in the composites. The maximum adsorption amount(q_m) of ZT_(0.6)F_(1.4)/CNTs with the mass ratios of ZT_(0.6)F_(1.4) to CNTs(mZ/C)=1 was up to 17.153 mg g~(–1) for RhB, its adsorption behavior was in accord with Langmuir model, and its photocatalytic degradation activity on RhB had a positive correlation with the content of ZT_(0.6)F_(1.4) in the sample. The experimental results indicate that the total removal rate of composite with mZ/C=1 on RhB was more than 95% and the composite had good decontamination capability on industrial dye wastewater. In addition, the samples can be recovered conveniently, activated easily and had good performance for recycling.     

Synthesis, Crystal Structure and Ferromagnetic Properties of a New Dicyanamide Bridged Dicopper(Ⅱ) Complex with IM-1'-MeBzIm-κ2 N, O Mode

A new dinuclear copper(Ⅱ) complex with imino nitroxide radicals [Cu2(NO3)2(IM-1'-MeBzlm)2(dca)2] (IM-1'-MeBzlm = 2-{2'-[(1'-methyl)benzimidazolyl]}-4,4,5,5-tetramethylimi-dazoline-1-oxyl, dca = dicyanamide anion) has been prepared and structurally characterized by single-crystal X-ray diffraction. The complex crystallizes in triclinie, space group P1, with a =9.440(5), b = 10.124(6), c = 11.603(7)(A°), α= 102.904(7),β = 94.033(6), γ= 104.299(7)°,C34H40Cu2N16O8, Mr= 927.90, V= 1038.2(10) (A°)3, Z = 1, Dc=1.484 g/cm3,μ(MoKα) = 1.093 mm-1,F(000) = 478, R = 0.0609 and wR = 0.1512 for 2889 observed reflections with I > 2σ(I). X-ray analysis reveals that two Cu(Ⅱ) atoms are bridged by two dicyanamides to form a centrosymmetric Cu(Ⅱ)-Cu(Ⅱ) dinuclear entity. Every Cu(Ⅱ) ion is five-coordinated with a distorted square pyramidal coordination geometry and IM-1'-MeBzlm ligand coordinates to the metal ion with the κ2 N(1'-MeBzlm), O(IM) mode to avoid steric hindrance with the methyl group in the complex. Meanwhile, the molecules are linked by intermolecular hydrogen bonds, leading to a 1-D chain structure. Moreover, such chains are further linked by π-π stacking interactions to form a 2-D network structure. Magnetic measurement demonstrates that the intramolecular exchange couplings between Cu(Ⅱ) ion and the IM-1'-MeBzlm are ferromagnetic with J = 12.46 cm-1, where the spin Hamitonian is defined as H= -2JS1S2 within the complex.     

Cyclopropanation of 1, 1-Dichloro-4-methyl-1,3-pentadiene with Diazoacetate

DuetoitswideappIicationasakeyintermediateofvariouskindsofeffectivepyrethroids,thesynthesisof3(2,2-dichlorovinyl)-2,2-dimethy(III)hasattractedmuchattentionI1-3J.Severalsyntheticmethodshavebeenreportedandsomehavebeenindustrialized.However-comparedwiththegreatamountofliteratUtreusingothermethodstosynthesizelll.onlyafewworkswerereportedaboutcyclopropanationofl,l-dichloro-4-methyl-l-3-pentadiene(I)withdiazoacetate(II),andtheirchemicaIyieldswererelativel}Io.l'~leventhoughthiskindofreactiOI1wasv…     

1H NMR analysis of the tolylene-2,4-diisocyanate – methanol reaction

<正>Tolylene-2,4-diisocyanate(2,4-TDI) 1 reacts with methanol through two simultaneous paths in the polyurethane reaction,which involve two different intermediates-tolylene-4-carbamatic-2-isocyanate 2 and tolylene-2-carbamatic-4-isocyanate 3,and the final product is tolylene-2,4-dicarbamate 4.The-CH_3 chemical shifts in benzene ring in compounds 1,2,3 and 4 can be easily tested and well distinguished,through which those four compounds are quantified and their kinetics are investigated.It shows that four rate constants for the tolylene-2,4-diisocyanate-methanol reaction in CCl_4 at 50℃are k_1=9.6×10~(-2)h~(-2)mol~(-2)min~(-1), k_2=1.4×10~(-2)h~(-2)mol~(-2)min~(-1),k_3=4.0×10~(-3)h~(-2)mol~(-2)min~(-1),k_4=1.4×10~(-3)h~(-2)mol~(-2)min~(-1).(k_1 is the reaction rate constant from compounds 1 to 2;k_2 is the reaction rate constant from compounds 1 to 3;k_3 is the reaction rate constant from compounds 3 to 4;k_4 is the reaction rate constant from compounds 2 to 4).     

CRYSTAL AND MOLECULAR STRUCTURE OF 1-ETHOXYCAR-BONYLMETHYL-2 N-(DIMETHYLAMINO)THIOCARBONYL 3-PR-OPYL 2,4-DIOXO 1,3,2-BENZODIAZAPHOSPHORIN (1)

<正> The title compound,C17H24N3O4PS(Mr = 405. 42) ,is a new compound of six-membered benzoheterocycle in which the five atoms N(1),C(1),C(11),C(16) andN(2) are coplanar with the and groups in trans-cross conformations. The crystal belongs to triclinic system,space group P1,with cell parameters a = 8. 580(2),b = 10.015 (4),c= 11. 896 (4) A ,α= 90. 65(3) ,β= 105. 70(3). γ= 89. 52(3)% V = 983. 9 A3,Z=2,Dx = 1. 37g/cm3. The final refinement converged with R=0. 074,Rw = 0. 090.     

THE HYDROSILYLATION REACTION OF LADDERLIKE POLYVINYLSILSESQUIOXANE WITH 1, 1, 3, 3-TETRAMETHYLDISILOXANE

The hydrosilylation reaction of ladderlike polyvinylsilsesquioxane (Vi-T)with 1, 1, 3, 3-tetramethyldisiloxane (H- MM ) catalyzed by dicyclopentadienyl-dichloroplat-inium (Cp_2PtCl_2) was carried out well in tetrahydrofuran (THF) to produce a soluble whitesolid. This product was characterized by IR, ~1H-NMR, ~(13)C-NMR, ~(29)Si-NMR, DSC, X-raydiffraction method, gel permeation chromatography (GPC), vapour pressure osmometry(VPO), atomic force microscopy (AFM) and molecular simulation. These results provethat the product contains nanoscale tubular structure.     

SYNTHESIS AND CHARACTERIZATION OF ZEROVALENT PALLADIUM COMPLEXES

A series of nine Pd(0)complexes(L)Pd(L')[L=bis(diphenylphosphino)methane(dppm),1,2-bis(diphenylphosphino)ethane(dppe),and 1,1'-bis(diphenyl-phosphino)ferrocene(dppf),respectively;L=dibenzylideneacetone(dba),2,3,5,6-tetrachloro-1.4-benzoquinone(q)and 2,3-dichloro-1,4-naphthoquinone(nq)]were synthesized and characterized by means of elemental analyses,IR,UV,1~H-NMR and~(31)P-NMR spectra.The redox wave peak potentials of the ferrocenylgroup of complexes with dppf were measured by using CV method.Results showedthat all the diphosphorus ligands behaved as chelating bidentate ligand anddba,q,nq were coordinated to the Pd(0)atom through their C=C moieties,nottheir carbonyl ones.Analytical data also showed that there were interactionsbetween the two different ligands in each complex.     

天然产物Combretastatin A-1和Combretastatin B-1的合成

基于Perkin反应策略合成了具有强效抗肿瘤、抗血管活性的天然产物Combretastatin A-1(CA1)和Combretastatin B-1(CB1).以2,3,4-三羟基苯甲醛(1)为起始物, 经单甲基化反应得到2,3-二羟基-4-甲氧基苯甲醛(2), 再经酚羟基保护得到2,3-二异丙基-4-甲氧基苯甲醛(3), 该化合物与3,4,5-三甲氧基苯乙酸(4)发生Perkin反应分离得到E-2-(3,4,5-三甲氧基苯基)-3-(2',3'-二异丙氧基-4'-甲氧基)丙烯酸(E-5), 经脱羧反应得到Z-3,4,4',5-四甲氧基-2',3'-二异丙氧基二苯乙烯(6), 最后经脱保护反应得到CA1.另外, 将E-2-(3,4,5-三甲氧基苯基)-3-(2',3'-二异丙氧基-4'-甲氧基)丙烯酸(E-5)脱去保护基得到E-2-(3,4,5-三甲氧基苯基)-3-(2',3'-二羟基-4'-甲氧基)丙烯酸(7), 该化合物经脱羧-异构化反应得到E-3,4,4',5-四甲氧基-2',3'-二羟基二苯乙烯(E-CA1), 最后经催化氢化得到CB1.     

Synthesis and Evaluation of Two Novel Naphthol Derivatives as Novel Cholinesterase Inhibitors

Two novel naphthol derivatives(1 and 2) were synthesized and characterized via IR,~1H NMR,and HRMS.The structure of compound 2 was verified by single-crystal X-ray crystallography.It crystallizes in monoclinic,space group C2/c with a = 21.6725(9),b = 6.0127(3),c = 25.5405(14) ?,β = 94.716(5)o,V = 3316.9(3) ?~3,Z = 8,F(000) = 1384,D_c = 1.511 Mg/m~3,M_r = 377.22 and μ = 2.487 mm~(-1).In addition,their cholinesterase inhibitory activities in vitro toward Electrophorus electricus acetylcholinesterase(eel ACh E) and horse serum butyrylcholinesterase(eq BCh E) were further determined.The results showed that compound 1 as a new acetylcholinesterase(ACh E) inhibitor displayed higher ACh E inhibitory activity(IC_(50) = 1.4 μM),which could be considered for Alzheimer's disease therapeutics.     

Synthesis and Crystal Structure of 3-（1-Ethyl-1H-indole-3-carbonyl）aminopropionic Acid

3-(1-Ethyl-1H-indole-3-carbonyl)aminopropionic acid has been synthesized by alkylation of 3-(1H-indole-3-carbonyl)aminopropionic acid methyl ester with bromoethane,follo-wed by saponifying and acidating,in 89.0% yield.Its crystal structure was gotten and determined by X-ray diffraction method.The crystal is of orthorhombic,space group P212121 with a = 8.9490(12),b = 11.1010(15),c = 13.0475(18) ,V = 1296.2(3) 3,Z = 4,Dc = 1.334 g/cm3,λ = 0.71073 ,μ(MoKα) = 0.095 mm-1,Mr = 260.29 and F(000) = 552.The structure was refined to R = 0.0306 and wR = 0.1445 for 2612 observed reflections with I 2σ(I).In the crystal structure,molecules are linked to each other through hydrogen bonds of N(2)-H(2)···O(1) and O(3)-H(3)···O(1),generating a three-dimensional network.     

Studies on electrical properties of system La_(2-x)(Sr_(1-y)Ca_y)_xNiO_4

A new series of solid solutions of composition La_(2-x)(Sr_(2-y)Ca_y)_xNiO_4(0相似文献   

Discovery of naphthalimide conjugates as fluorescent probes for α_1-adrenoceptors

α_1-Adrenoceptors(α_1-ARs), including at least three subtypes, α_(1A), α_(1B) and α_(1D), which play essential roles in G protein-coupled receptors(GPCRs), can convey multiple pivotal extracellular signals in varied tissues and organs. In this research, a series of napthalimide-based small-molecule fluorescent probes(1a–1f) for α_1-ARs, including two parts, a pharmacophore(quinazoline and phenylpiperazine) for α_1-AR recognition and a fluorophore(naphthalimide) for visualization, were designed and synthesized successfully. These compounds display excellent fluorescence property and high affinity to receptors,which were used successfully for in vitro visualization of α_1-adrenoceptors.     

A Pair of 3D Homochiral Coordination Polymers with Open Channels Constructed by Lactic Acid Derivative Ligands and In-situ Formed Anions

With the help of in-situ formed CH_3COO~- anion, a pair of 3D homochiral coordination polymers with open channels were constructed by the assembly of lactic acid derivative ligands, 1.4-DIB ligands and Cd(II) ions, namely [Cd_3((R)-CIA)_2(CH_3CO_2)_2(1.4-DIB)_2(H_2O)_2]·x(Guest)(1-D) and [Cd_3((S)-CIA)2(CH_3CO_2)_2(1.4-DIB)_2(H_2O)_2]·x(Guest)(1-L). They contain 1D interesting ladder-like Cd-(R)-CIA~(3-) chains and exhibit SHG-active behavior and photoluminescent property.     

Syntheses,Crystal Structures and Optoelectronic Properties of Two New Inorganic Thioantimonates

Two new thioantimonates,(NH_4)_2Sb_(10)S_(16) (1) and K_(1.4)(NH_4)_(0.6)Sb_(10)S_(16) (2),have been synthesized by solvothermal method with the yields of 80%and 85%,respectively.Single-crystal X-ray diffraction (SCXRD)study reveals that 1 crystallizes in the monoclinic space group of Pn with a=8.1284(4),b=19.4587(9),c=9.1030(4)?,β=91.736(5)°,V=1439.14(12)?~3,Z=2,D_c=4.077 g·cm~(-3),F(000)=1576,μ=10.389 mm~(-1),R=0.0343 and w R=0.0624 (I2σ(I));2 also crystallizes in the monoclinic space group of Pn with a=8.0989(6),b=19.3730(17),c=9.0411(6)?,β=91.879(6)°,V=1417.79(19)?~3,Z=2,D_c=4.207 g·cm~(-3),F(000)=1598,μ=10.748 mm~(-1),R=0.0323 and w R=0.0664 (I2σ(I)).The anionic frameworks of two compounds both feature two-dimensional (2D)[Sb_(10)S_(16)]_n~(2n-)layers.The stabilities and optoelectronic properties of 1 and 2 have been characterized.In particular,they are stable under acidic or alkaline conditions (pH=0 or 12.5),showing excellent acid-based resistance.     

铁氰化钾-Fe(Ⅲ)体系测定盐酸异丙肾上腺素

本文建立了以铁氰化钾-Fe(Ⅲ)体系测定盐酸异丙肾上腺素的方法。研究表明,在pH 3.0,盐酸异丙肾上腺素可使Fe(Ⅲ)还原为Fe(Ⅱ),生成的Fe(Ⅱ)可以与K_3[Fe(CN)_6]反应生成可溶性普鲁士蓝(KFe~(Ⅲ)[Fe~(Ⅱ)(CN)_6)。盐酸异丙肾上腺素的浓度在0.03~5.00μg·m L~(-1)范围内与吸光度呈现良好线性关系,线性回归方程A=0.017+0.57779C(μg·m L~(-1)),相关系数R=0.9997,检出限为0.025μg·m L~(-1),相对标准偏差R.S.D.=1.05%(n=11),间接测定盐酸异丙肾上腺素的摩尔吸光系数ε=1.4×105L·mol~(-1)·cm~(-1)。本方法成功用于药物制剂和生物样品中盐酸异丙肾上腺素含量的测定,结果满意。     

BIS(TETRAMETHYLCYCLOPENTADIENYL)RUTHENIUM(Ⅱ)——A FULLY ECLIPSED SANDWICH COMPOUND

<正> A new compound, bis(tetraunethylcyclopentadienyl)ruthenium has been synthesized by reduction reaction of tetramethylcyclopentadiene, RuCl3 and Zn in situ. The results of X-ray diffraction studies demonstrate the compound to be of a fully eclipsed conformation. The crystal belongs to monoclinic system, space group C2/c with cell parameters a = 22.075(3), b =10.674(3),c=14.135(2) A,β= 101.74(1)°,V = 3261.1A3,Dc=1.4 gcm-3, Z = 8.Several cycles of block matrix least-squares refinement gave the final R = 0.034.     

SELECTIVE REDUCTION OF 3,17—DIOXO—STEROIDS TO 17β-HYDROXY-3-OXO-STEROIDS

11β-Hydroxy-androst-4-en-3,17-dione(1a),androst-4,9(11)-dien-3,17-dione-(2a),androst-4-en-3,11,17-trione(3a),11α-methoxy-androst-4-en-3,17-dione(4a)and 11β-metboxy-androst-4-en-3,17-dione(Sa)were selectively reduced tothe corresponding 17β-OH derivatives in one step without the protection of 3-oxo(and 11-oxo,in the case of 3a)group with the yields ranging from 65% to79%.In these reactions,the ditute NaBH_4(or KBH_4)solution in methanol wasadded dropwise to the 3,17-dioxo-steroids solution in methanol-benzene-pyridine,while the reaction mixtures were well stirred at -5～5℃.Acid(such as gtacialacetic acid)was added to quench the reactions.The resulted testosteronederivatives(1b～5b)were purified by flash chromatography.This method appties to the reduction of other 3,17-dioxo-steroids such as△~1-3-one,△~(1.4)-3-one,△~(4.6)-3-one,△~(1.4.6)-3-one containing compounds.