Waugh-型镍钼杂多酸的量子化学计算

采用半经验INDO法，完成了Waugh-型镍钼杂多酸（NH44）6〔NIMO9O32〕·6H2O的量子化学计算，得到146个成键轨道和78个反键轨道，轨道能级，电荷和键序等数据。通过对这些数据的分析，表明杂多酸分子中端氧和Ni都可能为化学活性中心，各原子轨道在分子轨道中都占有一定比例，其HOMO和LUMO能级皆为负值，其体系具有进一步接受电子的能力。这些结论与实验事实一致。     

Mercury(II) complex with terpyridine: structure of the 2∶1 solvate of [Hg(terpy)2](CF3SO3)2 with acetone

[Hg(terpy)₂](CF₃SO₃)₂·0.5(CH₃)₂CO crystallizes in the triclinic space group witha=14.631(6),b=15.258(4),c=18.785(7) Å, =69.66(2), =70.72(1), =88.55(1)°. The crystal structure consists of two independent [Hg(terpy)₂]²⁺ cations, four trifluoromethanesulfonate anions and an acetone molecule in the asymmetric unit. Each mercury atom is coordinated by two tridentate terpyridine ligands forming an irregular six-coordination polyhedron. The Hg–N bond lengths range from 2.27(2) to 2.53(2) Å.     

Metastable decay rates,asymptotic expansions,and analytic continuation of thermodynamic functions

The grand potentialP(z)/kT of the cluster model at fugacityz, neglecting interactions between clusters, is defined by a power series _n Q _n z ⁿ , whereQ _n , which depends on the temperatureT, is the partition function of a cluster of sizen. At low temperatures this series has a finite radius of convergencez _s . Some theorems are proved showing that ifQ _n , considered as a function ofn, is the Laplace transform of a function with suitable properties, thenP(z) can be analytically continued into the complexz plane cut along the real axis fromz _s to + and that (a) the imaginary part ofP(z) on the cut is (apart from a relatively unimportant prefactor) equal to the rate of nucleation of the corresponding metastable state, as given by Becker-Döring theory, and (b) the real part ofP(z) on the cut is approximately equal to the metastable grand potential as calculated by truncating the divergent power series at its smallest term.     

Preparative Separation and Analysis of Complex Mixtures of Leucomycins and Desmycarosyl Leucomycins Using HPLC and Mass Spectrometry

Composition and hydrolysis products of a biotechnical available complex of macrolides were analyzed by HPLC and ESI-CID-MSⁿ. Major components are leucomycin-type antibiotics (leucomycins A₁ (5), A₇ (3), A₉ (2), 9-desoxy-9-oxo-turimycin H₃ (4) and niddamycin B (6). Hydrolysis of the complex mixture yielded 9-, 13-isoforocidins (7, 8, 9, 11) and 9-oxo-forocidin (10). A preparative separation procedure was elaborated furnishing compounds 3 - 11 for semisynthetic experiments.Prof. Dr. Udo Gräfe deceased on 14.2.2003. For obituarity see: Schlegel B (2003) J Peptide Sci 9: 661–661.     

UV-VIS and CD-spectroscopic investigations of intermolecular interactions of bile pigments with small proteins

Summary The intermolecular complex formation of bilirubin and biliverdin with two proteins (basic pancreatic trypsin inhibitor and lysozyme) were studied by optical and chiroptical methods. Evidence for specific intermolecular interactions of biliverdin with both proteins was found. Bilirubin forms a soluble complex only with lysozyme.

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UV-VIS und CD-spektroskopische Untersuchungen intermolekularer Wechselwirkungen von Gallenpigmenten mit kleinen Proteinen

Zusammenfassung Die intermolekulare Komplexbildung von Bilirubin und Biliverdin mit zwei Proteinen (basischer pankreatischer Trypsininhibitor und Lysozym) wurden mittels optischer und chiroptischer Spektroskopie untersucht. Für Biliverdin konnten intermolekulare Wechselwirkungen mit beiden Proteinen nachgewiesen werden. Bilirubin bildet nur mit Lysozym einen löslichen Komplex.

     

An analysis of the complex molecular orbitals method

Numerical results for the ground state of the HN ₂ ⁺ and HCO⁺ molecular ions at their near equilibrium geometry, obtained by the complex molecular orbitals (CMO) method in the extended basis set, are reported. The CMO wavefunction of the HN ₂ ⁺ ion is compared with the CI wavefunction obtained in the same basis set. This reveals the nature of approximations inherent in the CMO method. A peculiar feature of the occupation numbers of the CMO natural orbitals is also explained.Alexander von Humboldt Fellow. On leave from the Institute Rudjer Bokovi, Zagreb, Croatia, Yugoslavia.     

西佛碱大环双核钴（Ⅱ）配合物的合成,光谱及磁性

本文以２．６─二乙酰吡啶和１，３一二氨基一２一丙醇通过模板合成西佛碱大环配体Ｈ＿２Ｌ（图１），并合成了它的Ｃｏ（Ⅱ）、Ｎｉ（Ⅱ）及Ｆｅ（Ⅱ）的双核配合物，重点讨论了Ｃｏ＿２（ＨＬ）（ＣｌＯ＿４）＿２（ＮＯ＿３）·４Ｈ＿２Ｏ配合物的光谱与磁性。变温磁化率数据（４─３００Ｋ）通过用最小二乘法与理论方程拟合，得到磁参数为Ｊ＝－１．２４ｃｍ￣（－１），θ＝－０．２４Ｋ，表明配合物中ｃｏ（Ⅱ）－Ｃｏ（Ⅱ）间存在弱的反铁磁相互作用，分子间也存在反铁磁相互作用。     

Carbonyl allylation of aldehydes catalyzed by a silica-supported poly-γ-diphenylarsinopropylsiloxane palladium(0) complex

A silica-supported poly-γ-diphenylarsinopropylsiloxane palladium(0) complex has been prepared from γ-chloropropyltriethoxysilane via immobilization on fumed silica, followed by reacting with potassium diphenylarsenide and palladium chloride, and then the reduction with hydrazine hydrate. The palladium(0) complex has been found to catalyze the allylation of aldehydes via the formation of π-allylpalladium complexes, using allylic chlorides as allylating agent and SnCl₂ as reducing agent. This polymeric palladium complex can be recovered and reused.     

Synthetic studies on macrolactin A by using a (diene)Fe(CO)3 complex

The stereoselective synthesis of the two segments 3 and 4 of macrolactin A 1 is described. Macrolactin A is a 24-membered polyene macrolide antibiotic, which is of interest due to a strong activity against B16-F10 murine tumor cell and HIV-1 virus. The key step of the synthesis is the 1,2-migration reaction of a (diene)Fe(CO)₃ complex with a introduction of the thiol group to construct the unstable (E,Z)-conjugated dienic moiety (C8-C11).     

Enthalpies of mixing of binary and ternary mixtures containing diisopropylether,benzene and cyclohexane at 303.15 K

Enthalpies of mixing H have been measured for liquid binary mixtures of diisopropylether (DIPE)+benzene or cyclohexane and for liquid ternary mixtures diisopropylether+benzene+cyclohexane at 303.15 K and constant pressure using a C80 calorimeter. A Redlich-Kister type equation was used to correlate experimental results.