IR,Raman, and Surface‐enhanced Raman Spectroscopic Study on Triruthenium Dipyridylamide Diruthenium Nickel Dipyridylamide Family: Metal‐metal Bonding and Structures

We report the infrared, Raman, and surface‐enhanced Raman scattering (SERS) spectra of triruthenium dipyridylamido complexes and of diruthenium mixed nickel metal‐string complexes. From the results of analysis on the vibrational modes, we assigned their vibrational frequencies and structures. The infrared band at 323–326 cm^?1 is assigned to the Ru₃ asymmetric stretching mode for [Ru₃(dpa)₄Cl₂]^0–2+. In these complexes we observed no Raman band corresponding to the Ru₃ symmetric stretching mode although this mode is expected to have substantial Raman intensity. There is no frequency shift in the Ru₃ asymmetric stretching modes for the complexes with varied oxidational states. No splitting in Raman spectra for the pyridyl breathing line indicates similar bonding environment for both pyridyls in dpa^– , thus a delocalized structure in the [Ru₃]^6–8+ unit is proposed. For Ru₃(dpa)₄(CN)₂ complex series, we assign the infrared band at 302 cm^?1 to the Ru₃ asymmetric stretching mode and the weak Raman line at 285 cm^?1 to the Ru₃ symmetric stretching. Coordination to the strong axial ligand CN^– weakens the Ru‐Ru bonding. For the diruthenium nickel complex [Ru₂Ni(dpa)₄Cl₂]^0–1+, the diruthenium stretching mode ν_Ru‐Ru is assigned to the intense band at 327 and 333 cm^?1 in the Raman spectra for the neutral and oxidized forms, respectively. This implies a strong Ru‐Ru metal‐metal bonding.     

Noninvasive imaging of cell death using an Hsp90 ligand

Cell death plays a central role in normal physiology and in disease. Common to apoptotic and necrotic cell death is the eventual loss of plasma membrane integrity. We have produced a small organoarsenical compound, 4-(N-(S-glutathionylacetyl)amino)phenylarsonous acid, that rapidly accumulates in the cytosol of dying cells coincident with loss of plasma membrane integrity. The compound is retained in the cytosol predominantly by covalent reaction with the 90 kDa heat shock protein (Hsp90), the most abundant molecular chaperone of the eukaryotic cytoplasm. The organoarsenical was tagged with either optical or radioisotope reporting groups to image cell death in cultured cells and in murine tumors ex vivo and in situ. Tumor cell death in mice was noninvasively imaged by SPECT/CT using an (111)In-tagged compound. This versatile compound should enable the imaging of cell death in most experimental settings.     

Effect of organic vapors and potential-dependent Raman scattering of 2,6-dimethylphenylisocyanide on platinum nanoaggregates

The surface-enhanced Raman scattering characteristics of 2,6-dimethylphenylisocyanide (2,6-DMPI) on Pt nanoaggregates, in ambient and electrochemical environments and in the presence of organic vapors, were examined and compared with those on Au nanoaggregates. Due to the exclusive adsorption via the isocyanide group, the NC stretching band was very susceptible to the measurement conditions although the ring associated bands showed negligible peak shifts. In ambient conditions, the peak shift of the NC stretching vibration on Pt (29 cm(-1)) was one half of that on Au (61 cm(-1)), suggesting that the electron donation capability of the isocyanide group to Au was greater than that to Pt. In the electrochemical environment, the NC stretching peak varied linearly with slopes of ～42 and ～36 cm(-1) V(-1) on Pt and Au, respectively. On the other hand, the NC stretching bands of 2,6-DMPI on Pt red-shifted by as much as 15 and 41 cm(-1), in the presence of acetone and ammonia, respectively, corresponding to the lowering of the surface potential of Pt nanoaggregates from +0.2 to -0.2 and -0.8 V, respectively. On Au nanoaggregates, however, acetone appeared to increase the surface potential of Au from +0.2 to +0.3 V, although ammonia decreased the surface potential from +0.2 to -0.4 V. Acetone must then act as an electron donor when interacting with Pt while it serves as an electron acceptor when interacting with Au, in agreement with an ab initio quantum mechanical calculation.     

非对称铺层复合材料层合板质量优化设计

复合材料广泛应用于航空航天等领域,追求轻量化设计已经成为研究重点。对复合材料层合板质量优化设计,可以减少层合板的纤维用量,减小层合板的质量,降低成本。首先研究复合材料层合板在承受轴向载荷时,产生的形变量、应力示意图,分析容易发生失效部位;以层合板铺层厚度为设计变量,最大应变、铺层比例等为约束条件,最小化层合板质量为优化目标,对碳纤维复合材料层合板铺层厚度等设计变量进行优化,利用强度理论对优化结果进行校核,结合力学试验对比分析优化前后层合板力学性能。结果表明:碳纤维复合材料层合板经过优化后,总质量减轻约16.7%,优化后的层合板满足复合材料强度理论,实验结果与软件仿真具有一致性,说明优化方法是合理可靠的。     

An ion-selective electrode for methylamine

A simple electrode is described for the assay of methylamine in the concentration range 10^-5–10^-2 M. The electrode is based on the air-gap sensor principle. In the range of linear response, the relative standard deviation is about 1.4 % when the measurement time is 24 min, and about 5 % when the equilibration time is 12 min. Some interference is noted from dimethylamine and ammonium chloride.     

Structural properties of inner amenable groups

For infinite discrete groups, Effros introduced the notion of inner amenability which gives a new classification of discrete groups. The inner amenability is a considerably weaker condition than amenability, but closely related to the quite deep property Γ of groups. In this paper the author investigates the structures of inner amenable groups by theoretical set theory. A sequence of characterizations of inner amenable groups is given here by developing the well-known Folner's conditions for amenable locally compact groups. This work is partly supported by the National Science Foundation of China.     

An artificial intelligence system for computer-aided mass spectra interpretation of saturated aliphatic monohydric alcohols

The mass spectra of saturated monohydric alcohols are used in structure elucidation by means of computer programs of the artificial intelligence type. The structure generator is constrained by a structure predictor to show the sub-group structure in a fairly definite area, and spectral characteristics are also predicted. According to the commands of the structure predictor, sub-groups conforming to the mass spectra studied are then combined into molecular structures which are ranked for output. The system was tested for 218 mass spectra of 115 alcohols from different laboratories: all the correct answers were included in the 6 highest scores, with 78% for the highest score and 91% for the highest 2 scores.     

A specific enzyme electrode for L-phenylalanine

A specific enzyme electrode procedure is described for the rapid assay of L-phenyl- alanine. The enzyme L-phenylalanine ammonia lyase is used, which cleaves L-phenyl-alanine to ammonia. The ammonia liberated is measured with an air-gap electrode. The procedure is specific; L-tyrosine and other amino acids do not interfere, nor do Na⁺ or K⁺ ions. As little as 5 · 10^-5 M L-phenylalanine can be determined.     

Eta1 and eta2 complexes of lambda3-1,2,4,6-thiatriazinyls with CpCr(CO)x

The title heterocyclic radicals coordinate to either 17e CpCr(CO)3 or 15e CpCr(CO)2 moieties as one-electron or as three-electron donors, respectively; in the former the bonding is via the perpendicular p orbital of the sulfur atom, while in the latter bonding is via p(pi) orbitals on both sulfur and nitrogen.