2-(N'-乙基咔唑-3'-烯基)-8-羟基喹啉的合成及理论研究

设计合成了2-(N'-乙基咔唑-3'-烯基)-8-羟基喹啉. 以UV-Vis, ¹H NMR, FT-IR, 元素分析和MS进行了结构表征, 并测定了产物的光致发光(PL)性质. 运用Gaussian98量子化学程序包, 采用B3LYP密度泛函(DFT)的方法, 在6-31G(d,p)水平上对分子的几何构型进行结构优化; 预测目标产物的振动光谱, 结果表明与实验值相符.     

Rare earth metal-rich indides RE 4IrIn ( RE = Gd–Er), RE 4IrInO0.25 ( RE = Gd, Er), and RE 4 T In1– x Mg x ( RE = Y, Gd; T = Rh, Ir)

The rare earth-transition metal-indides RE ₄IrIn (RE = Gd–Er) and the solid solutions RE ₄ TIn_1–x Mg _x (RE = Y, Gd; T = Rh, Ir) were prepared by arc-melting of the elements and subsequent annealing. The rare earth sesquioxides were used as oxygen source for the suboxides RE ₄IrInO_0.25 (RE = Gd, Er). Single crystals of the indides were grown via slowly cooling of the samples and they were investigated via X-ray powder diffraction and single crystal diffractometer data: Gd₄RhIn type, F 3m, a = 1372.3(6) pm for Gd₄IrIn, a = 1365.3(6) pm for Tb₄IrIn, a = 1356.7(4) pm for Dy₄IrIn, a = 1353.9(4) pm for Ho₄IrIn, a = 1344.1(4) pm for Er₄IrIn, a = 1370.3(5) pm for Y₄RhIn_0.54Mg_0.46, a = 1375.6(5) pm for Gd₄IrIn_0.55Mg_0.45, a = 1373.0(3) pm for Gd₄IrInO_0.25, and a = 1345.1(4) pm for Er₄IrInO_0.25. The rhodium and iridium atoms have a trigonal prismatic rare earth coordination. Condensation of the RhRE ₆ and IrRE ₆ prisms leads to three-dimensional networks which leave voids that are filled by regular In₄ or mixed In_4–x Mg _x tetrahedra. The indium (magnesium) atoms have twelve nearest neighbors (3In(Mg) + 9RE) in icosahedral coordination. The rare earth atoms build up a three-dimensional, adamantane-like network of condensed, edge and face-sharing octahedra. For Gd₄IrInO_0.25 and Er₄IrInO_0.25 the RE1₆ octahedra are filled with oxygen. The crystal chemical peculiarities of these rare earth rich compounds are discussed. Correspondence: Rainer P?ttgen, Institut für Anorganische und Analytische Chemie, Westf?lische Wilhelms-Universit?t Münster, Germany.     

Rare earth metal-rich indides RE 4IrIn ( RE = Gd–Er), RE 4IrInO0.25 ( RE = Gd, Er), and RE 4 T In1– x Mg x ( RE = Y, Gd; T = Rh, Ir)

The rare earth-transition metal-indides RE ₄IrIn (RE = Gd–Er) and the solid solutions RE ₄ TIn_1–x Mg _x (RE = Y, Gd; T = Rh, Ir) were prepared by arc-melting of the elements and subsequent annealing. The rare earth sesquioxides were used as oxygen source for the suboxides RE ₄IrInO_0.25 (RE = Gd, Er). Single crystals of the indides were grown via slowly cooling of the samples and they were investigated via X-ray powder diffraction and single crystal diffractometer data: Gd₄RhIn type, F [`4]\bar 4 3m, a = 1372.3(6) pm for Gd₄IrIn, a = 1365.3(6) pm for Tb₄IrIn, a = 1356.7(4) pm for Dy₄IrIn, a = 1353.9(4) pm for Ho₄IrIn, a = 1344.1(4) pm for Er₄IrIn, a = 1370.3(5) pm for Y₄RhIn_0.54Mg_0.46, a = 1375.6(5) pm for Gd₄IrIn_0.55Mg_0.45, a = 1373.0(3) pm for Gd₄IrInO_0.25, and a = 1345.1(4) pm for Er₄IrInO_0.25. The rhodium and iridium atoms have a trigonal prismatic rare earth coordination. Condensation of the RhRE ₆ and IrRE ₆ prisms leads to three-dimensional networks which leave voids that are filled by regular In₄ or mixed In_4–x Mg _x tetrahedra. The indium (magnesium) atoms have twelve nearest neighbors (3In(Mg) + 9RE) in icosahedral coordination. The rare earth atoms build up a three-dimensional, adamantane-like network of condensed, edge and face-sharing octahedra. For Gd₄IrInO_0.25 and Er₄IrInO_0.25 the RE1₆ octahedra are filled with oxygen. The crystal chemical peculiarities of these rare earth rich compounds are discussed.     

Automatic simulation of electrochemical transients by the adaptive Huber method for Volterra integral equations involving Kernel terms exp[?α(t ? τ)]erex{[β(t ? τ)]1/2} and exp[?α(t ? τ)]daw {[β(t ? τ)]1/2}

Development of fully automatic methods for the simulation of transient experiments in electroanalytical chemistry is a desirable element of the contemporary trends of laboratory automation in electrochemistry. In accord with this idea, the adaptive Huber method, elaborated by the present author, is intended to solve automatically integral equations of Volterra type, encountered in the theory of controlled-potential transients. The coefficients of the method have been recently obtained for integral transformation kernels involving terms K(t, τ) = exp[−α(t − τ)]erex{[β(t − τ)]^1/2} and K(t, τ) = exp[−α(t − τ)]daw{[β(t − τ)]^1/2} with α ≥ 0 and β ≥ 0, which are known to occur in the above integral equations. In this work the validity of the resulting method, for electrochemical simulations, is examined using representative examples of electroanalytical models involving integral equations with various special cases of such kernel terms. The performance of the method is found similar to that previously reported for integral equations involving exclusively kernels K(t, τ) = 1, K(t, τ) = (t − τ)^−1/2, and K(t, τ) = exp[−λ (t − τ)](t − τ)^−1/2 with λ > 0.     

Kinetic effects in n -CdAs2, p -ZnAs2, and Cd x Zn1 ? x As2 solid solutions

The electrical resistivity and Hall factor in n-CdAs₂, p-ZnAs₂, and n-Cd _x Zn_{1 − x} As₂ were measured at hydrostatic pressures up to 9 GPa and quasi-hydrostatic pressures up to 50 GPa at room temperature. For n-CdAs₂, a phase transition was discovered at p = 5.5 GPa; for p-ZnAs₂, two phase transitions were discovered: one at P = 10–15 GPa and the other at p = 35–40 GPa. No anomalies were found on ρ(p) and R(p) curves for Cd _x Zn_{1 − x} As₂ when p ≤ 9 GPa. Original Russian Text ? A.Yu. Mollaev, I.K. Kamilov, R.K. Arslanov, L.A. Saipulaeva, R.G. Dzhamamedov, S.F. Marenkin, A.N. Babushkin, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 1, pp. 122–125.     

Platinum(II) extraction by N,N′-dipentylethylenediamine-N′-thiocarbaldehyde from hydrochloric acid solutions

Platinum(II) extraction by N,N′-dipentylethylenediamine-N′-thiocarbaldehyde from 0.1 M HCl into chloroform and toluene diluents was studied at 25°C and a phase contact time of 5 min. The extraction had a coordination mechanism with a Pt ← S bond formed in the extracted complex PtCl₂S₂. Concentration constants and thermodynamic parameters of the extraction reaction were calculated. Original Russian Text ? R.A. Khisamutdinov, Yu.I. Murinov, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 1, pp. 156–162.     

Studies on the radiolytic stability of N,N,N′,N′-tetra-2-ethylhexyl diglycolamide in n-dodecane solution containing different phase modifiers

The radiolytic stability of a branched diglycolamide extractant, namely N,N,N′,N′-tetra-2-ethylhexyl diglycolamide (T2EHDGA) dissolved in n-dodecane containing several phase modifiers, viz. N,N-dihexyloctanamide (DHOA), tri-n-butyl phosphate (TBP), 1-decanol and iso-decanol has been investigated. The distribution ratio of Am(III) decreased with increased radiation dose studied up to 1000 kGy. Nevertheless, all the composition of extractants showed satisfactory results up to 500 kGy, beyond which the extractants degraded drastically. The stripping behaviour of Am(III) with 0.2 M HNO₃ was found to be unaffected even with the ligand solution irradiated up to 1000 kGy. Extraction of fission product and structural elements was also investigated using the irradiated solvents and was found to be not significantly affected with increasing absorbed dose with the exception of Mo which showed sharp rise in the distribution coefficient values. Loading of Nd in the organic phase decreased with the irradiated solvent due to degradation of the carrier. The effect of the absorbed dose on physical parameters such as density, viscosity and interfacial tension of the solvents has also been investigated.     

D-谷氨酰胺的制备

报道了以化学合成和生物转化的方法制备光学纯D-谷氨酰胺. 首先在中试规模上用化学方法合成DL-谷氨酰胺. 即以廉价的DL-谷氨酸为原料, 采用邻苯二甲酰基作为保护基保护L-谷氨酸的α-氨基, 醋酐回流15 min, 使其分子内脱水生成N-邻苯二甲酰-DL-谷氨酸酐, 在常温、常压条件下, 分别与2 mol/L氨水反应生成中间产物N-邻苯二甲酰-DL-谷氨酰胺, 中间产物在室温条件下与0.5 mol/L水合肼反应48 h脱除保护基, 以57%总收率得到DL-谷氨酰胺. 在37 ℃, pH 4.8的条件下, 利用大肠杆菌(E. coli. AS 1.505)脱羧酶将底物浓度30 g/L的DL-谷氨酰胺中L型对映体在8 h内完全转化为4-氨基丁酰胺, 分离得到D-谷氨酰胺.     

CH3SOx (x＝0, 1)与三线态Oy (y＝1, 2, 3)反应机理的理论研究

采用B3LYP方法和6-311G(d, p)基组对CH₃S及其氧化后继物CH₃SO与O_y (y＝1, 2, 3)反应形成酸雨的微观机理进行了理论研究. 对反应势能面上的各驻点进行几何构型全优化. 振动分析和IRC计算证实了中间体和过渡态的真实性和相互连接关系. 找到了7条生成SO₂的反应途径, 其中CH₃S与O直接反应得到产物CH₃和SO最容易进行; CH₃S先与O₃反应, 其产物再与O₃反应得到CH₃SO₂, CH₃SO₂最后分解得到CH₃S和SO₂较容易进行, 其它的反应较难进行.     

(p, ρ, T, x) properties for CO2/isobutane binary mixtures at T = (280 to 440) K and (3 to 200) MPa

The (p, ρ, T, x) properties for binary mixtures of CO₂ (volume fraction purity 0.99999) and isobutane (mole fraction purity 0.99988) {x₁ CO₂ + x₂ isobutane (x₁ = 0.2482, 0.4718, and 0.7506)} were measured in the compressed liquid phase using a metal-bellows variable volumometer. Measurements were conducted from T = (280 to 440) K and (3 to 200) MPa. The expanded uncertainties (k = 2) were estimated to be: temperature, <3 mK; pressure, 1.5 kPa (p ? 7 MPa), 0.06% (7 MPa < p ? 50 MPa), 0.1% (50 MPa < p ? 150 MPa), 0.2% (p > 150 MPa); density, 0.10%; and composition, 4.4 · 10⁻⁴. At >100 MPa and T = (280 or 440) K, the uncertainties in the density measurements increased to 0.14% and 0.22%, respectively. The data are compared with the available equation of state. The excess molar volumes, , of the mixtures were calculated and plotted as a function of temperature and pressure.     

Stabilities and coordination modes of glycinephosphonic acid in copper(II) heteroligand complexes with ethylenediamine, diethylenetriamine or N,N,N′,N′,N″-pentamethyldiethylene triamine in aqueous solution

Solution equilibrium studies on the Cu(II)-polyamine-(aminomethyl)phosphonic acid (glycinephosphonic acid) ternary systems (polyamine: ethylenediamine (en), diethylenetriamine (dien), N,N,N′,N′,N″-pentamethyldiethylenetriamine (Me₅dien)) have been performed by pH-potentiometry, UV–vis spectrophotometry and EPR methods. The obtained results suggest the formation of the heteroligand complexes with [Cu(A)(Gly(P))] stoichiometry in all studied systems. Additionally, in the systems with dien the protonated [Cu(dien)(H–Gly(P))]⁺ species also exists in acid solution and in the system with en the [Cu(en)(Gly(P))H_-1]⁻ species is formed in the basic solution. Our spectroscopic results indicate the tetragonal geometry for the [Cu(en)(Gly(P))] species, the geometry slightly deviated from square pyramidal for the [Cu(dien)(Gly(P))] complex and strongly deviated from square pyramidal towards trigonal bipyramidal for the [Cu(Me₅dien)(Gly(P))] species. The coordination modes in these heteroligand complexes are discussed.     

Extraction of europium and americium into phenyltrifluoromethyl sulfone by using hydrogen dicarbollylcobaltate in the presence of N,N′-diethyl-N,N′-diphenyl-2,6-dipicolinamide

Extraction of microamounts of europium and americium by a phenyltrifluoromethyl sulfone (FS 13) solution of hydrogen dicarbollylcobaltate (H⁺B⁻) in the presence of N,N,N′,N′-tetraethyl-2,6-dipicolinamide (TEtDPA, L) has been investigated. The equilibrium data have been explained assuming that the species HL⁺, \textHL ₂ ⁺ , {\text{HL}}_{ 2}^{ + } , \textML₂^{3 +} {\text{ML}_{2}^{3 +}} and \textML ₃ ³⁺ {\text{ML}_{ 3}^{ 3+}} (M³⁺ = Eu³⁺, Am³⁺) are extracted into the organic phase. The values of extraction and stability constants of the cationic complex species in FS 13 saturated with water have been determined. It was found that the stability constants of the corresponding complexes \textEuL_n ³⁺ {\text{EuL}}_{n}^{ 3+ } and \textAmL_n ³⁺ {\text{AmL}}_{n}^{ 3+ }, where n = 2, 3 and L is TEtDPA, in the mentioned FS 13 medium are comparable.     

Stabilities and Coordination Modes of α-Alaninephosphonic Acid in Copper(II) Heteroligand Complexes with Ethylenediamine, Diethylenetriamine or N,N,N′,N′,N″-Pentamethyldiethylene Triamine in Aqueous Solution

Solution equilibrium studies on Cu²⁺–L₁–L₂ ternary systems have been performed by pH-potentiometry, UV–Vis spectrophotometry and EPR methods (L₁ corresponds to polyamines such as ethylenediamine (en), diethylenetriamine (dien), or N,N,N′,N′,N″-pentamethyldiethylenetriamine (Me₅dien) and L₂ represents 1-aminoethylphosphonic acid (α-alaninephosphonic acid)). The obtained results suggest the formation of heteroligand complexes with [Cu(L₁)(α-Ala(P))] stoichiometry in all studied systems. Additionally, in the system with en the [Cu(en)(α-Ala(P))H₋₁]⁻ species is formed in basic solution. Our spectroscopic results indicate tetragonal geometry for the [Cu(en)(α-Ala(P))] species, geometry slightly deviated from square pyramidal for the [Cu(dien)(α-Ala(P))] complex and strongly deviated from square pyramidal towards trigonal bipyramidal for the [Cu(Me₅dien)(α-Ala(P))] species. The coordination modes in these heteroligand complexes are discussed.     

Solvent extraction of calcium and strontium into nitrobenzene by using a synergistic mixture of hydrogen dicarbollylcobaltate and N,N,N′,N′-tetraisobutyl-2,6-dipicolinamide

Extraction of microamounts of calcium and strontium by a nitrobenzene solution of hydrogen dicarbollylcobaltate (H⁺B⁻) in the presence of N,N,N′,N′-tetraisobutyl-2,6-dipicolinamide [T(iBu)DPA, L] has been investigated. The equilibrium data have been explained assuming that the species HL⁺, HL₂ ⁺, CaL₂ ²⁺, SrL₂ ²⁺ and SrL₃ ²⁺ are extracted into the organic phase. The values of extraction and stability constants of the cationic complexes in nitrobenzene saturated with water have been determined.     

Synthesis and crystal structure of a new tetradecker complex: Tetra(μ4-N,N′-Ethylen-bis(3-Methoxysalicylideneamine)-bis(μ2-perchlorato-O,O′)-tetranickel(II)-tripotassium perchlorate

The title tetradecker complex C₇₂H₇₂Cl₃K₃N₈Ni₄O₂₈ has been synthesized and structurally characterized. The four NiL (L = N, N-ethylene-bis(3-methoxysalicylideneiminate) segments were linked into a discrete tetradecker structure by three K⁺ cation coordinated to the phenolic oxygen atoms of the neighboring NiL units and the oxygen atom of the ClO₄⁻ anions acting as bridges. The two bicephalous K⁺ cations are nine-coordinated, while the middle one is involved in a distorted bipentagonal pyramid. For the Ni²⁺ ion, it is involved in a square planar coordination sphere formed by a N₂O₂ unit from the Schiff base ligand.     

Converting dipyrrinones to lactim ethers to fluorescent N,N′-difluoroboryl derivatives

A high-yield straightforward conversion of lactams to lactim ethers is shown by the conversion of (10H)-dipyrrin-1-ones to (11H)-dipyrrin-1-ol methyl and ethyl ethers in 90% yield from heating in neat trimethyl or triethyl phosphite at 160°C. Unlike the parent dipyrrinones, which form intermolecularly hydrogen-bonded dimers in CHCl₃, their lactim ethers are shown to be monomeric by vapor pressure osmometry. The latter react with boron trifluoride etherate to N,N′-bridged BF₂ derivatives that exhibit strong fluorescence (φ_F 0.6–0.8) near 535 nm. X-Ray crystal structures were obtained of the lactim ethyl ether of kryptopyrromethenone and the BF₂ derivative of the lactim ethyl ether 2,3-diethyl-7,8-dimethyl-(10H)-dipyrrin-1-one.     

10 α -Hydroxy- β -isomorphine, a by-product of the synthesis of 10 α -hydroxymorphine

Abstract  

A new compound was isolated from the reaction mixture after O-demethylation of 6-O-acetyl-10α-acetoxycodeine with boron tribromide. The structure of this compound, 10α-hydroxy-β-isomorphine, was elucidated by spectral data, and its spatial arrangement was deduced from an NOE experiment. Capillary zone electrophoresis was used for separation of morphine and its 10-hydroxy analogues.     

鞘磷脂和神经节苷脂对磷脂酰乙醇胺混合脂超分子体系液晶态立方相Im3m和Pn3m结构影响的研究

用磷脂酰乙醇胺(DEPE)、鞘磷脂(Sphingomyeline, Sph)、神经节苷脂(Gm1)和胆固醇(Chol)模拟了生物膜超分子体系液晶态结构, 通过用小角X射线衍射(SAXD)对混合脂体系液晶态结构进行了研究, 鉴定出了两种立方相: 即Im3m(Q²²⁹)和Pn3m(Q²²⁴)结构. 实验发现, 鞘磷脂的含量对DEPE膜的结构有一定的影响, 随着鞘磷脂浓度的增加, 混合脂体系的液晶态结构发生了由Im3m(Q²²⁹)到Pn3m(Q²²⁴)的变化. 神经节苷脂(Gm1)的含量对混合脂体系的液晶态结构也有一定的影响, 当神经节苷脂(Gm1)含量达到某一临界值时, 混合脂体系的液晶态结构发生了从Im3m(Q²²⁹)到Pn3m(Q²²⁴) 的变化. 当DEPE-Shp-Gm1超分子聚集体中含有胆固醇时, 胆固醇的极性头部(—OH)与磷脂酰乙醇胺(DEPE)、鞘磷脂(Shp)、神经节苷脂(Gm1)的极性头部通过氢键相互作用形成液晶态立方相Im3m(Q²²⁹)结构, 再通过疏水/亲水相互作用形成稳定的Pn3m (Q²²⁴)结构.     

聚二甲基硅氧烷-溴代环己烷体系沉降系数的压力改正与s-M,[η]-M单分散关系

对聚二甲基硅氧烷-溴代环己烷θ溶液(28℃)体系进行了沉降速度法测定分子量分布及沉降系数压力改正的研究。提出了一种新的直接测定沉降系数的压力改正的方法,即在沉降池中加入不同量的溶液以得到不同的液柱高来改变静压,测定溶液界面在不同静压下的浮升速度计算压力系数。所得适用 于静压为200大气压以下的沉降系数的压力改正系数α=1.44×10~(-3)_(大气压)~(-1)。从沉降系数分布、(?)_ω、[η]_θ及[η]_(甲苯)的测定,订定了聚二甲基硅氧烷在28℃θ条件下的s-M,[η]_θ-M及在甲苯(25℃,良溶剂)中的[η]-M单分散关系为。 s_1=6.30×10~(16)M~(0.50)(溴代环己烷,28℃) [η]=7.41×10~(-2)M~(0.50)(溴代环己烷,28℃) [η]=9.53×10~(-3)M~(0.71)(甲苯,25℃)