零维到三维结构中三核铜自旋阻挫簇单元的磁构关系和反对称交换

量子自旋液体是最近几年刚被人们证实除铁磁体、反铁磁体之外的第三种磁性类型,因其有望解释高温超导的运行机制、改变计算机硬盘信息存储方式而在物理、材料等领域备受关注。自旋阻挫作为量子自旋液体的最小单元可能是解开量子自旋液体诸多问题的钥匙,所以在磁学、电学研究领域再一次成为人们研究的热点。基于文献报道的三核铜配合物[Cu3(μ3-OH)(μ-OPz)3(NO3)2(H2O)2]·CH3OH(1),我们合成了三维金属有机框架配合物{[Ag(HOPz)Cu3(μ3-OH)(NO3)3(OPz)2Ag(NO3)]·6H2O}n(2)(HOPz=甲基(2-吡嗪基)酮肟),并从自旋阻挫的角度对二者磁性质进行对比和详细分析。磁化率数据表明自旋间有很强的反铁磁相互作用和反对称交换。通过包含各向同性和反对称交换的哈密顿算符对两者磁学数据进行拟合并研究其磁构关系,所获最佳拟合参数为:配合物1:Jav=-426 cm^-1,g⊥=1.83,g∥=2.00;配合物2:Jav=-401 cm^-1,g⊥=1.85,g∥=2.00。     

Recent advances on the use of active anodes in environmental electrochemistry

Active anodes, especially those consisting of metal mixed oxides (MMOs) containing Ru and/or Ir oxides, have been applied in the treatment of wastewater, especially when chloride ions are present. Their characteristics continuously drive the study of applications of these materials, be they in the degradation of different organic molecules, the preparation of new electrode materials and in the association of various processes to increase pollutant removal. Thus, this brief review aims to present some of the recent advances in the application of active anode materials in environmental electrochemistry. Focussing on the 2018–2020 period, it is possible to note many applied studies, using commercially available materials, covering a wide range of target pollutants. Still other studies aim to modify the catalyst surfaces to increase the mineralization capacity, and the use of these anodes in the production of free chlorine species to mediate indirect organic reduction is observed.     

Microextraction of metal ions based on solidification of a floating drop: Basics and recent updates

This review provides a comprehensive evaluation of solidified floating organic drop microextraction (SFODME) procedures for metal ions preconcentration and their contributions to green chemistry. In this article we focused on the modifications that have been performed in the recent years to improve this environmentally friendly procedure. Among the most important of these modifications are the inclusion of ultrasonic energy, vortex and air agitation to enhance the dispersion process. The article also discussed new challenges in the procedure by using more ecofriendly solvents as extractants such as ionic liquids, deep eutectic. and supramolecular solvents. The coupling of SFODME with solid phase extraction increases selectivity and efficiency of the preconcentration procedure.     

Extended Open-Chain Polyenides as Versatile Delocalized Anion Ligands for Metal Chain Clusters

Although small cyclic- and open-chain unsaturated hydrocarbon anions such as cyclopentadienide and open-chain pentadienide are used as the strongly electron-donating auxiliary ligands for metal complexes, more extended π-conjugated unsaturated hydrocarbon anions have rarely been used in coordination chemistry, despite their potential ability to serve as the multiply bridging π-ligands for metal clusters. This work reports isolation of metal chain clusters bearing the multi-dentate, open-chain extended unsaturated hydrocarbon anion ligands. The extended open-chain π-conjugated polyenyl ligands could effectively stabilize oxidized palladium chains, including an unprecedented [Pd₄]⁴⁺ chain.     

Fused vs. spiro: Kinetic,not thermodynamic preference may direct the reaction of α-carbonyl oxonium ylides

Rh(II)-catalyzed decomposition of certain cyclic α-diazocarbonyl compounds in the presence of cyclic ethers has been shown to give bicyclic ring expansion products. These are thought to arise from a [1,4]-alkyl shift toward the carbonyl oxygen atom and are in contrast with the recently observed spirocyclic products of a Stevens-type [1,2]-alkyl shift within the postulated oxonium ylide intermediate. Quantum chemical calculations performed at the B3LYP/6-31G* level of theory showed that the former reaction pathway (toward fused bicycles) is kinetically preferred.     

Spectroscopic characterization of core and shell regions in monolayer protected gold nanoparticles

We report studies on the structure of the metallic core and the alkyl cap layer in monolayer protected gold nanoparticles having sizes down to 1.6 nm. These particles are obtained by laser ablating gold targets in alkane-thiol solutions at different concentrations. The electronic structure of gold core and the vibrational properties of the capping hydrocarbon chains reveal effects connected with the nanosized nature of the particles.     

Structures and stability of Al<Subscript><Emphasis Type="Bold">7</Emphasis></Subscript>C and Al<Subscript><Emphasis Type="Bold">7</Emphasis></Subscript>N clusters

We report results of the atomic and electronic structures of Al₇C cluster using ab initio molecular dynamics with ultrasoft pseudopotentials and generalized gradient approximation. The lowest energy structure is found to be the one in which carbon atom occupies an interstitial position in Al₇ cluster. The electronic structure shows that the recent observation [Chem. Phys. Lett. 316, 31 (2000)] of magic behavior of Al₇C^- cluster is due to a large highest occupied and lowest unoccupied molecular orbital (HOMO-LUMO) gap which makes Al₇C^- chemically inert. These results have further led us to the finding of a new neutral magic cluster Al₇N which has the same number of valence electrons as in Al₇C^- and a large HOMO-LUMO gap of 1.99 eV. Further, calculations have been carried out on (Al₇N)₂ to study interaction between magic clusters. Received 28 July 2001     

Reciprocating sliding wear behavior of laser-clad small amplitude Mo2Ni3Si/NiSi metal silicide composite coatings

Mo₂Ni₃Si/NiSi metal silicide composite coatings with a fine microstructure consisting of Mo₂Ni₃Si primary dendrites and the interdendritic Mo₂Ni₃Si/NiSi eutectics were fabricated on austenitic stainless steel AISI 321 by laser cladding process. Small amplitude reciprocating sliding wear resistance of the coatings is evaluated as functions of normal load and slip amplitude and the wear mechanisms were discussed based on worn surface morphology observations. Results showed that the Mo₂Ni₃Si/NiSi coatings have excellent small amplitude reciprocating sliding wear resistance.     

Towards molecular-scale electronics and biomolecular self-assembly

This paper provides an overview of recent research developments in the field of nanoelectronics with organic materials such as carbon nanotubes and DNA-templated nanowires. Carbon nanotubes and gold electrodes are chemically functionalized in order to contact carbon nanotubes by self-assembly. The transport properties of these nanotubes are dominated by charging effects and display clear Coulomb blockade behaviour. A different approach towards nanoscale electronics is based on the molecular recognition properties of biomolecules such as DNA. As an example, DNA is stretched between electrodes using a molecular combing technique. A two-step metallization procedure leads to the formation of highly conductive gold nanowires.     

Multiple Window and Cluster Size Scan Procedures

Researchers apply scan statistics to test for unusually large clusters of events within a time window of specified length w, or alternatively an unusually small window w that contains a specified number of events. In some cases, the researcher is interested in testing for a range of specified window lengths, or a set of several specified number of events k (cluster sizes). In this paper, we derive accurate approximations for the joint distributions of scan statistics for a range of values of w, or of k, that can be used to set an experiment-wide level of significance that takes into account the multiple comparisons involved. We use these methods to compare different ways of choosing the window sizes for the different cluster sizes. One special case is a multiple comparison procedure based on a generalized likelihood ratio test (GLRT) for a range of window sizes. We compare the power of the GLRT with another method for allocating the window sizes. We find that the GLRT is sensitive for very small window sizes at the expense of moderate and larger window sizes. We illustrate these results on two examples, one involving clustering of translocation breakpoints in DNA, and the other involving disease clusters.