D,L-1,2,2-三甲基环戊烷-1,3-二胺硝酸镍配合物的合成、结构及其和手性D-(+)-1,2,2-三甲基环戊烷-1,3-二胺氯化镍配合物的对比分析

0IntroductionAsweknow,camphoricderivativespossessingtwochiralcarbonatomsintheirmoleculesoccupyalargebranchoforganiccompoundsandhavebeenusedwidelyinorganicsynthesis.D鄄,L鄄andD,L鄄1,2,2鄄trimethylcyclopentane鄄1,3鄄diaminesareveryusefulintermediatesinorgan     

一种新颖有机-无机杂化配位聚合物[(C_(10)H_(16)N)_2(Pb_2I_6)·2DMF·H_2O]_n的自组装合成和晶体结构

0IntroductionConstructionoflow鄄dimensionalorganic鄄inorgan鄄icsupramoleculararrayswithnovelpropertiesrepre鄄sentsnewdirectionsinsolid鄄statechemistry[1,2].Gener鄄allythephysicalpropertiesofsuchlowdimensionalcompoundsdifferfromthoseoftheparentcompound.Our     

(R)-1,1''''-联萘手性单元通过溶胶凝胶法合成杂化硅干凝胶

0IntroductionSol鄄gel鄄derivedhybridorganic鄄inorganicmateri鄄alsarereceivingmuchattentionsincetheycanexhib鄄itpropertiesassociatedwithboththeorganicmoieties(optical,electrical,molecularimprinting)andinorgan鄄icamorphousframework(porosity,hydrophilicity)[     

PVP存在下液液界面生长法制备硒纳米线(英)

0IntroductionSelenium(Se)iswellknownforitsphotoelectri鄄calandsemiconductorpropertiesandhasbeensuc鄄cessfullyusedinsolarcells,rectifiers,photographicexposuremetersandxerography[1].Itcouldbeexpect鄄edthattheuniquestructureandthequalityofone鄄di鄄mensional(     

CHINESE JOURNAL OF INORGANIC CHEMISTRY Vol.20 No.1～12 2004 CONTENTS

CONTENTSReviewTheStructureDirectingandTemplat鄄ingEffectsintheFormationofMicro鄄porousCompounds………………LIJi鄄Yang熏YUJi鄄Hong熏XURu鄄Ren(1)Preparation,StructuresandPropertiesofCopper髤Phosphonates………………………………YAOHong鄄Chang,ZHENGLi鄄Min,XIN     

3，5-二羟基-2，4，6-三硝基苯酚铷的晶体结构和热行为

0IntroductionSom e nitrogen鄄rich alkaline and alkali鄄earth m et鄄als com pounds of polynitro hydroxybenzenes can beused environm entally friendly prim ary explosives[1￣5].2,4,6鄄Trinitro鄄1,3,5鄄trihydroxybenzene(trinitrophloroglu鄄cinol,TNPG)belongs to a polynitro hydroxybenzeneand has been used in chem icalindustry as an ingredi鄄entfor prim ing com position,percussion caps and deto鄄nator form ulations[6].Therefore,in recent years,ithasbeen exploited to prepare a num ber of salts of ba…     

DFT法研究离子液中EMIM~ 催化丁烯双键异构反应机理(II)

用密度泛函理论(DFT)在B3LYP/6鄄31G(d,p)的计算水平上研究了离子液中1鄄乙基鄄3鄄甲基咪唑阳离子(EMIM )的4鄄H和5鄄H原子催化丁烯双键异构反应的可能途径,优化了反应体系的平衡态和过渡态的几何构型,分析了反应过程中键参数的变化,通过振动分析对平衡态和过渡态进行了验证.计算结果表明,离子液中的EMIM 首先通过4鄄H和5鄄H原子吸附丁烯,进而催化丁烯的双键异构反应,EMIM 的4鄄H和5鄄H催化1鄄丁烯异构为2鄄丁烯的正反应活化能分别为204.2和207.3kJ·mol-1,逆反应活化能约为220.9和223.8kJ·mol-1,反应为基元反应.     

多金属氧酸盐四硫富瓦烯衍生物荷移盐超薄导电膜(英)

0IntroductionThecharge鄄transfer(CT)saltsbasedplanarπ鄄electrondonorETasaclassofmolecule鄄basedmate鄄rialshavebeenstudiedextensivelyinthepasttwentyyears,becauseoftheirmetallicconductivityandevensuperconductivity[1~6].Inrecentyears,polyoxometalateshaveatt     

一种新颖一维铅碘聚合物[(Pb_2I_5)(L-H~ )·2DMF]_n(L=Piperazine)的自组装合成和晶体结构(英文)

0IntroductionIncreasinginterestisfocusedonthestudyofmagnetic,electronicandoptoelectronicpropertiesoflow鄄dimensionalorganic鄄inorganichybridcompoun鄄ds[1~3].Studiesshowthatcomplexconsistingoforganicandinorganiccomponentshavegreatpotentialforthecreationoff…     

{[Gd(DMF)_3(DMSO)(H_2O)_3](μ-CN)[Fe(CN)_5]}·2H_2O的合成,结构表征和磁性(英文)

0IntroductionThefirstmolecule鄄basedmagnetswerereportedin1986[1].Duringthelasttwodecades,moreandmoreattentionhasbeenpaidtothesynthesisofmolecule鄄basedmagnets,especiallytoPrussianBlueanalogu鄄es[2].TheoldPrussianBlueanalogueshavebeenbroughtuptodateduetoth…     

Non-respiring rat liver mitochondria do not have a Ca2+/2H+ antiporter

Liver mitochondria take up Ca2+ by the Ca2+ uniporter, whereas at steady state efflux is believed to occur mainly by means of a ruthenium red-insensitive Ca2+/2H+ antiporter. The latter activity was studied in respiration-inhibited mitochondria in the presence of ruthenium red and was measured as Ca2+ uptake following acidification of the matrix by addition of nigericin, which catalyzes K+/H+ exchange. Ca2+ uptake was stimulated by protonophorous uncoupling agents and inhibited by increasing the concentration of ruthenium red. However, the rates were always smaller than those obtained by addition of valinomycin instead of nigericin. This indicates that under these conditions, Ca2+ fluxes are not mediated by a Ca2+/2H+ antiporter but by residual uniporter activity.     

八核茂铁-钌金属大环对钙离子的电化学和荧光识别(英)

The ruthenium unit was introduced into the redox-active molecular polygon to assembly new Ru-Fc metallocycles (Compound 1), in which the redox active (ferrocene) and fluoresecent (ruthenium) signaling subunits are directly attached by the putative cation-binding sites. The compound 1 displayed high selectivity for Ca^2 by electrochemical tests. The measurements of the fluorescence spectra on titration of 1 with Ca^2 , Li^ , Na^ , K^ , Mg^2 or Ba^2 ion indicate the unique ability of 1 to detect Ca^2 ions selectively.     

3-Nitroso-4-hydroxy-5,6-benzocoumarin as a selective reagent for the spectrophotometric determination of ruthenium(III)

The pinkish-violet complex developed on interaction of ruthenium(III) with 3-nitroso-4-hydroxy-5,6-benzocoumarin (NHBC) in the pH range 5.5-8.0 can be extracted into n-butanol. The complex has an absorption maximum at 520 nm. Maximum colour development takes place after heating for 20 min on a steam-bath and the extracted complex is stable for at least 92 hr. Beer's law is followed up to 7.4 ppm of ruthenium. The molar absorptivity is 1.04 x 10(4) 1.mole(-1).cm(-1). The composition of the complex is 1 : 2 (ruthenium: NHBC). None of the other platinum metals was found to interfere in the determination of ruthenium, even though present in large excess.     

Calcium-binding protein regucalcin stimulates the uptake of Ca2+ by rat liver mitochondria

The effect of the calcium-binding protein regucalcin on the Ca2+ transport system in rat liver mitochondria was investigated. Ca2+ transport was assayed by the method of Millipore filtration to estimate mitochondrial 45Ca2+ accumulation. 45Ca2+ uptake was stimulated by the presence of regucalcin (1.0 and 2.0 microM). This stimulation was remarkable during 1.0 min after 45Ca2+ addition, while appreciable stimulation was no longer seen at 3 min. Regucalcin (2.0 microM)-induced stimulation of 45Ca2+ uptake was prevented by the presence of ruthenium red (1.0 microM) and lanthanum chloride (0.1 mM). Regucalcin (2.0 microM) did not increase the mitochondrial adenosine triphosphatase (ATPase) activity during 3.0 min after Ca2+ addition. Meanwhile, 45Ca2+, which accumulated in the mitochondria during 5.0 min after 45Ca2+ addition, was not released by the addition of regucalcin. Regucalcin may stimulate Ca2+ uptake in rat liver mitochondria independently of the energy.     

Ruthenium(II) 2-hydroxybenzophenone N(4)-substituted thiosemicarbazone complexes

New ruthenium(II) complexes with 2-hydroxybenzophenone N(4)-substituted (Me, Ph and/or piperidyl) thiosemicarbazones have been prepared and characterised by elemental analysis, molar conductivity, thermal analysis, spectroscopy (i.r., ¹H-n.m.r. and u.v.–vis.) and by cyclic voltammetry. The thiosemicarbazones coordinate to ruthenium(II) as mononegative tridentate ligands via the deprotonated hydroxyl group, N¹ nitrogen and thione sulphur centres. The redox properties, nature of the electrode processes and the stability of the complexes towards oxidation in CH₂Cl₂ are discussed. The change in the E _1/2 values of the complexes can be related to the basicity of the N(4)-substituents. All the complexes display an irreversible one-electron charge-transfer couple in the potential range studied. This revised version was published online in June 2006 with corrections to the Cover Date.     

Diverse polyanions based on MnBi4 and MnSb4 tetrahedra: polymorphism, structure, and bonding in Ca21Mn4Bi18 and Ca21Mn4Sb18

New transition-metal-containing Zintl phases, Ca21Mn4Bi18 and Ca21Mn4Sb18, have been synthesized by high-temperature reactions, and their structures have been determined by single-crystal X-ray diffraction. Ca21Mn4Bi18 crystallizes in the monoclinic space group C2/c (No. 15, Z = 4) with a = 17.470(2) A, b = 17.392(2) A, c = 17.208(2) A, beta = 93.253(2) degrees (R1 = 0.0405, wR2 = 0.0840) and is isostructural with the recently reported Ca21Mn4Sb18. The compound with the same formula, which is also reported herein, is in turn a new polymorph of Ca21Mn4Sb18 and crystallizes in the monoclinic space group C2/m (No. 12, Z = 4) with a = 17.415(6) A, b = 16.567(6) A, c = 17.047(6) A, beta = 92.068(4) degrees (R1 = 0.0432, wR2 = 0.0788). This new polymorph of Ca21Mn4Sb18 is isostructural with another related compound, Sr21Mn4Sb18. Despite the similarity in their chemical formulas, the structures of Ca21Mn4Bi18 and Ca21Mn4Sb18 are very different: Ca21Mn4Bi18 contains unique [Mn4Bi10] cluster anions made up of four MnBi4 tetrahedra connected through edge-sharing. The structure of Ca21Mn4Sb18 features edge- and corner-shared MnSb4 tetrahedra, which make [Mn4Sb11] tetramers. The latter are linked to each other through external Sb-Sb bonds to form larger isolated [Mn8Sb22] polyanions. Electronic band structure calculations performed using the TB-LMTO-ASA method show a small band gap at the Fermi level, suggesting narrow-gap semiconducting behavior for both compounds.     

Synthesis, characterization and electrochemical studies of mixed ligand complexes of ruthenium(ii) with DNA

Two mixed ligand complexes of ruthenium(ii) [Ru(bzimpy)(bpy)(OH(2))](2+) (1) and [Ru(bzimpy)(phen)(OH(2))](2+) (2) have been synthesized and characterized by FAB mass, (1)H NMR, cyclic voltammetry and spectroelectrochemical measurements. Controlled potential electrolysis of these complexes results in the conversion of ruthenium(ii) to ruthenium(iii) at 0.6 V and ruthenium(iii) to ruthenium(iv) at 0.8 V vs. SCE. The binding constant of these complexes with DNA has been determined electrochemically and found to be (3.58 +/- 0.25) x 10(4) and (2.87+/- 0.2) x 10(4) M(-1). Viscosity measurements suggest that these complexes bind with DNA through intercalation. Such intercalative binding to DNA has been found to induce chirality to the two complexes. Electrochemically generated ruthenium(iv) species of these complexes have been found to bring about oxidative cleavage in DNA.     

Site and oxidation-state specificity yielding dimensional control in perovskite ruthenates

Sr(3)CaRu(2)O(9), a new 2:1 B-site ordered perovskite ruthenate, was synthesized and its structure determined based on powder X-ray, neutron and electron diffraction data. It is composed of one layer of CaO(6) alternating with two layers of RuO(6) perpendicular to the [111] axis of the cubic perovskite structure. The ordering leads to a [-Ru-Ru-Ca-] repeat unit along each of the pseudocubic directions. Sr(3)CaRu(2)O(9) is the first example of this structure-type to include a majority metal with d electrons (Ru(V), d(3)). Three-dimensional Sr(3)CaRu(2)O(9) can be transformed to the layered Ruddlesden-Popper phase Sr(1.5)Ca(0.5)RuO(4) (i.e., Sr(3)CaRu(2)O(8)) by reduction at 1200 degrees C in flowing argon. The original structure can be restored by oxidation of Sr(1.5)Ca(0.5)RuO(4) at 1000 degrees C in flowing oxygen. This remarkable transformation highlights the structural versatility afforded by the combination of ruthenium and calcium.     

An enyne metathesis/(4 + 2)-dimerization route to (+/-)-differolide

[formula: see text] A concise total synthesis of (+/-)-differolide (1) has been achieved. 2-Vinylbutenolide (2) was prepared by enyne metathesis of allyl propynoate (3) using the Grubbs initiator 4. This reaction was examined by 1H NMR spectroscopy, which led to the hypothesis that low concentration of ruthenium species and high concentration of enyne substrate would be advantageous. Accordingly, slow addition of 4 to solutions of enyne 3 was found to be beneficial. Spontaneous dimerization of 2 gave (+/-)-differolide (1) and an isomer.     

Determination of ruthenium and osmium in each other's presence in chloride solutions by direct and third-order derivative spectrophotometry

Ruthenium and osmium (up to 20 mug Ru(Os) ml(-1)) can be determined in chloride solutions directly after absorption of RuO(4) and OsO(4) in hydrochloric acid. In 9 M HCl, RuO(4) and OsO(4) are quantitatively converted into RuCl(6)(2-) (lambda(max) = 480.0 nm, epsilon = 4.8 x 10(3) l mol(-1) cm(-1)) and OsCl(6)(2-) (lambda(max) = 334.8 nm, epsilon = 8.4 x 10(3) l mol(-1) cm(-1)) respectively. Osmium does not interfere with the determination of ruthenium in the form of the RuCl(6)(2-) complex by direct spectrophotometry. The absorbance of the obtained solution at lambda(max) = 480.0 nm corresponds only to the concentration of ruthenium. A derivative spectrophotometric method using numerical calculation of absorption spectra of the RuCl(6)(2-) and OsCl(6)(2-) complexes has been developed for the determination of osmium in a mixture with ruthenium. The interfering effect of ruthenium on the determination of osmium can be eliminated by measuring the value of a third-order derivative spectrum of the OsCl(6)(2-) complex at 350.0 nm ("zero-crossing point" of ruthenium). Simple and rapid determination of ruthenium and osmium in a calibration standard solution of the noble metals (Ru, Rh, Pd, Os, Ir, Pt and Au) for plasma spectroscopy using the proposed methods has been achieved.