A Cu(Ⅱ) Complex with IM-MeImz-к2 N,O Mode in [Cu(IM-MeImz)2]·(SCN)2: Synthesis, Crystal Structure and Magnetic Properties

A new copper(Ⅱ) compound with imino nitroxide radicals [Cu(IM-MeImz)2]·(SCN)2 (IM-meImz =2-(5-methylimidazol-4-yl)-4,4,5,5-tetramethyl-2-imidazoline-1-oxyl) has been synthesized and characterized structurally and magnetically. It crystallizes in monoclinic, space group P21/c with a = 9.3604(7), b = 10.3012(7), c = 16.6684(12) (A), β = 105.0290(10)°, V = 1552.25(19)(A)3, C24H34CuN10O2S2, Mr = 622.27, Z = 2, Dc = 1.331 g/cm3, μ(MoKα) = 0.876 mm-1, F(000) =650, the final R = 0.0374 and wR = 0.1079. X-ray analysis demonstrates that the IM-MeImz ligand is coordinated to the copper(Ⅱ) ion as an unusual didentate chelate with a κ2 N(MeImz),O(IM) mode in the complex. The square-planar coordination sites at Cu(Ⅱ) are occupied by two O and two N atoms from the imino nitroxide radicals. The complex molecules are connected as a onedimensional polymer structure by intermolecular interactions. Magnetic measurements show that there are intramolecular antiferromagnetic interactions between the Cu(Ⅱ) ion and radicals.     

Anomalies of the partition coefficient and properties of crystals in the region of low concentrations of an isomorphous admixture. 1. Unusual decomposition of solid solutions of the NaCl—CdCl2 system

Solid solutions NaCl—CdCl₂ were studied in an interval of CdCl₂ concentrations of 0.05—3 mol.% by Raman spectroscopy. The molecular form Na₂CdCl₄ decomposes: Na₂CdCl₄ 2Na⁺ + Cd²⁺ + 2Cl₂ ^– + 2e^–; 2Na + 2e^– 2Na⁰. Free sodium atoms form color centers of crystal (F centers) in the region of jumpwise changing the partition coefficient of CdCl₂ in NaCl (K jump).     

On kaonic hydrogen. Phenomenological quantum field theoretic model revisited

We argue that due to isospin and U-spin invariance of strong low-energy interactions the S-wave scattering lengths a ⁰ ₀ and a ¹ ₀ of ˉN scattering with isospin I = 0 and I = 1 satisfy the low-energy theorem a ⁰ ₀ +3a ¹ ₀ = 0 valid to leading order in chiral expansion. In the model of strong low-energy ˉN interactions at threshold (Eur. Phys. J. A 21, 11 (2004)) we revisit the contribution of the Σ(1750) resonance, which does not saturate the low-energy theorem a ⁰ ₀ +3a ¹ ₀ = 0, and replace it by the baryon background with properties of an SU(3) octet. We calculate the S-wave scattering amplitudes of K^-N and K^-d scattering at threshold. We calculate the energy level displacements of the ground states of kaonic hydrogen and deuterium. The result obtained for kaonic hydrogen agrees well with recent experimental data by the DEAR Collaboration. We analyse the cross-sections for elastic and inelastic K^-p scattering for laboratory momenta 70MeV/c < p _K < 150MeV/c of the incident K^--meson. The theoretical results agree with the available experimental data within two standard deviations.     

Reductive opening of aziridines with polymethylhydrosiloxane

Regio and chemoselective reductive opening of aziridines is achieved using catalytic palladium on charcoal and polymethylhydrosiloxane (PMHS) as a soluble hydrogen source.     

X-ray transitions from antiprotonic noble gases

The onset of antiprotonic X-ray transitions at high principal quantum numbers and the occurrence of electronic X-rays in antiprotonic argon, krypton, and xenon has been analyzed with the help of Multiconfiguration Dirac-Fock calculations. The shell-by-shell ionisation by Auger electron emission, characterised by appearance and disappearance of X-ray lines, is followed through the antiprotonic cascade by considering transition and binding energies of both the antiproton and the remaining electrons. Electronic lines could be attributed partly to specific states of the antiprotonic atom de-excitation.     

Zur Kristallchemie der Oxometallate des Hafniums

On the Crystal Chemistry of Oxometallates of Hafnium The contribution shows Hf⁴⁺ in oxides and oxometallates with typical and untypical coordination by oxygen. First of all the HfO6‐octahedra exist besides the Oxides of Hafnium in different Hf‐molybdates and ‐vanadates. A special feature is the formation of complex surroundings of to each other isolated HfO₆‐octahedra, forming [HfO₃(Mo₆O₂₁)]⁸⁻‐, [HfO₃(Mo₁₂O₃₉)]⁸⁻‐ and [HfO₃(Rb₂O₁₅)]³⁰⁻‐groups. HfO₆‐octahedra are incorporated in polyhedra chains too. Interesting points of view of the crystal chemistry of Hf‐oxometallates are Hf/O‐polyhedra showing coordination numbers C.N. > 6. For example two times capped trigonal prisms (hp/ht‐HfMo₂O₈) and three times capped trigonal prisms ht/hp‐HfO₂ (Cottunnit‐Type) are representative polyhedra with C.N. = 8 and C.N. = 9. In the fluorite related compounds (Ca₂Hf₇O₁₆) Hf⁴⁺ is situated inside a damaged cube (one corner is missing). At least hexagonal HfO₁₂‐antiprisms (C.N. = 12) had been found in one of the trigonal form of HfMo₂O₈. In the same crystal structure it shows (C.N. = 6) trigonal HfO₆‐Prismens. Hf⁴⁺ has in addition no problems to accept statistical distributions with other elements. It adapts crystal structures of pyrochlores and perowskites of different distortion. Finally one compound, nearly free of oxygen (Hf₉Mo₄NiO_0,84) is reported, it shows interesting metal clusters.     

Investigation into Sonogashira reaction on 5-iodo-1-(phenyl/p-halophenyl)imidazole-4-carbonitrile compounds

Investigation into Sonogashira reaction on 5-iodo-1-(phenyl/p-halophenyl)imidazole-4-carbonitrile compounds had been developed by introducing an iodo atom at the C-5 position of the imidazole ring of 5-amino-1-(phenyl/p-halophenyl)imidazole-4-carbonitrile compounds. Specifically, 5-iodo-1-(4-iodophenyl)imidazole-4-carbonitrile compound had shown double Sonogashira coupling reactions with two differently substituted iodine along with the formation of two other compounds where an unusual coupling product with self-aggregation property was obtained. In other cases, monocoupling had been observed together with another compound where iodine atom present at C5 position of imidazole was replaced by hydrogen atom.     

The Quest for Mononuclear Gold(II) and Its Potential Role in Photocatalysis and Drug Action

The chemistry of gold strongly focuses on the ubiquitous oxidation states +I and +III. The intermediate oxidation state +II is generally avoided in mononuclear gold species. In recent years, gold(II) has been increasingly suggested as a key intermediate in artificial photosynthesis systems, with gold(III) moieties acting as electron acceptors, as well as in gold‐catalyzed photoredox catalysis and radical chemistry. This Minireview provides a concise summary of confirmed and characterized mononuclear open‐shell gold(II) complexes. Recent findings on structural motifs and reactivity patterns will be discussed. Exciting developments in the fields of photosynthesis, photocatalysis, and potential roles in medicinal chemistry will be outlined.     

Visualisation of inter loop tertiary base pairing and stacking interactions in an unusual slipped loop DNA structure

The conformation of an unusual slipped loop DNA structure exhibited by the sequence d(GAATTCCCGAATTC)₂ is determined using a combination of geometrical and molecular mechanics methods. This sequence is known to form a B-DNA-like duplex with the central non-complementary cytosines extruded into single stranded loop regions. The unusual feature is that the interior guanine does not pair with the cytosine across, instead, it pairs with the cytosine upstream by skipping two cytosines, leading to a slipped loop DNA structure with the loops staggered by two base pairs. The two loops, despite being very small, can fold across minor or major groove symmetrically or asymmetrically disposed, with one of the loop bases partially blocking the major or minor groove. Most interestingly, for certain conformations, the loop bases approach one another at close proximity so as to engage even in base pairing as well as base stacking interactions across the major groove. While such pairing and stacking are common in the tertiary folds of RNA, this is the first time that such an interaction is visualized in a DNA. This observation demonstrates that a W-C pair can readily be accomplished in a typical slipped loop structure postulated for DNA. Such tertiary loop interaction may prevent access to regulatory proteins across the major groove of the duplex DNA, thus providing a structure-function relation for the occurrence of slipped loop structure in DNA. Contribution no. 839 from this department     

基于时间序列建模和控制图的异常交易检测方法

可疑交易识别是打击洗钱犯罪所要面对的一项重要任务.为辅助反洗钱分析人员从海量金融交易信息中甄别客户异常交易,本文提出一种新的基于非线性马尔科夫随机过程、相空间重构和隐马尔科夫链的非线性随机方法,用于对金融交易时序进行建模拟合,然后应用鲁棒控制图对估计误差进行检验以发现异常.应用该算法对实际交易数据和仿真数据的分析验证了所提方法的有效性和可行性,可以被用于异常交易的监测.