Zinc, cadmium, and mercury 1,2-benzenedithiolates with intramolecular NH...S hydrogen bonds

Mononuclear Zn, Cd, and Hg 1,2-benzenedithiolates with intramolecular NH...S hydrogen bonds, [M(II){1,2-S2-3,6-(RCONH)2C6H2}2](2-) (R = CH 3, t-Bu; M = Zn, Cd, Hg), were synthesized and characterized by X-ray analysis and spectral measurements. The presence of intramolecular NH...S hydrogen bonds was established by the IR spectra. (199)Hg and (113)Cd nuclear magnetic resonance showed a stabilized four-thiolate coordinated structure and suggested the influence of the NH...S hydrogen bonds to ppi(Hg)-ppi(S) interactions. The NH stretching bands show that the NH...S hydrogen bonds in Cd and Hg complexes are stronger than those in the corresponding Zn complex. These results are supported by theoretical calculations. The experimental and theoretical results suggested that the NH...S hydrogen bond influences the efficient capture of toxic Cd and Hg ions by metallothioneins.     

Preparation of carbocycles via base-catalyzed endo-mode cyclization of allenes

A new and reliable procedure for constructing five- to seven-membered carbocycles via an endo-mode ring-closing reaction of 1-phenylsulfonylallenes with a substituent that has a terminal active methine moiety at the C1-position has been developed. Trisubstituted 1-phenylsulfonylallenes underwent a similar endo-mode ring-closing reaction to produce the corresponding five- to seven-membered carbocycles, while the formation of six- and seven-membered carbocycles from the corresponding tetrasubstituted allene was not realized. In addition, the introduction of an aromatic ring to the alkyl side chain of the starting allenes made possible the construction not only of normal-sized carbocycles but also an eight-membered framework.     

Inhibition of Thermus thermophilus HB8 thioredoxin activity by platinum(II)

A 1:1 thioredoxin-Pt(bpy) complex was prepared by adding [Pt(bpy)(en)]Cl(2)(bpy = 2,2'-bipyridine, en = ethylenediamine) to Thermus thermophilus HB8 thioredoxin in pH 8 phosphate buffer. Matrix-assisted laser desorption-ionization time of flight mass spectrometry (MALDI-TOF MS) and UV spectra of indicate the formation of Pt(bpy)(cys-Ala-Pro-cys-containing peptide fragment). These findings suggest that the Pt(bpy)(2+) unit binds to the active site of thioredoxin. The thioredoxin-platinum complex has no catalytic activity for the reduction of glutathione disulfide in the presence of NADPH and thioredoxin reductase, so that the platinum complex functions as an inhibitor.     

Synthesis and Crystal Structure of Two Lanthanide Complexes with Benzenecarboxylic Derivatives

Two novel lanthanide coordination polymers, [La(tpaa)₃(H₂O)₂] ( 1 ) and [Eu₂(BDC)₃(DMF)₂(H₂O)₂] ( 2 ) (Htpaa = terephthalamic acid, H₂BDC = 1,4‐benzenedicarboxylic acid, DMF = N,N‐dimethylformamide), were hydro(solvo)thermally synthesized by reactions of the corresponding lanthanide nitrate salts with 1,3,5‐triazine‐2,4,6‐tri(4‐benzenecarboxylate) ( L ), in which a simultaneous hydrolysis of the ligand L occurred. Single‐crystal X‐ray analysis revealed that complex 1 comprises one‐dimensional chains that are further interlinked via hydrogen bonds, resulting in a two‐dimensional network; while complex 2 is a three‐dimensional interpenetrated coordination architecture.     

The Navier–Stokes Equations Under a Unilateral Boundary Condition of Signorini’s Type

We propose a new outflow boundary condition, a unilateral condition of Signorini’s type, for the incompressible Navier–Stokes equations. The condition is a generalization of the standard free-traction condition. Its variational formulation is given by a variational inequality. We also consider a penalty approximation, a kind of the Robin condition, to deduce a suitable formulation for numerical computations. Under those conditions, we can obtain energy inequalities that are key features for numerical computations. The main contribution of this paper is to establish the well-posedness of the Navier–Stokes equations under those boundary conditions. Particularly, we prove the unique existence of strong solutions of Ladyzhenskaya’s class using the standard Galerkin’s method. For the proof of the existence of pressures, however, we offer a new method of analysis.     

Syntheses, structures and properties of silver(I) complexes with flexible 1,3,5-tris(pyridylmethoxyl)benzene ligands

Five new silver(I) complexes [Ag₂(L₂)₂](BF₄)₂·CH₃CN·CH₃OH (1), [Ag(L₂)(CF₃SO₃)] (2), [Ag(L₃)]ClO₄·CH₃OH (3), [Ag₂(L₃)₂](CF₃SO₃)₂·CH₃CN·CH₃OH·H₂O (4) and [Ag(L₃)]PF₆·2CH₃CN (5) [L₂=1,3,5-tris(2-pyridylmethoxyl)benzene, L₃=1,3,5-tris(3-pyridylmethoxyl)benzene] were synthesized and characterized by single crystal X-ray diffraction analyses. In complexes 1-5, ligands L₂ and L₃ show different conformations and act as three-connectors, while the Ag(I) atom serves as three-connecting node to result in the formation of 2D and 3D frameworks. Complexes 1 and 2 with different counteranions have similar 2D network structure with the same (4,8²) topology. Complex 3 has a 3D structure with (10,3)-a topology while complexes 4 and 5 have the same 2D (6,3) topological structure. The results showed that the structure of organic ligands and counteranions play subtle but important role in determining the structure of the complexes. In addition, the photoluminescence and anion-exchange properties of the complexes were investigated in the solid state at room temperature.     

Cadmium(II) and copper(II) complexes with imidazole-containing tripodal polyamine ligands: pH and anion effects on carbon dioxide fixation and assembling

A new Cd(II) complex [Cd3(L)3(mu3-CO3)](ClO4)4.2CH3CN (1) with two-dimensional (2D) network structure was obtained by reaction of an imidazole-containing tripodal polyamine ligand N1-(2-aminoethyl)-N1-(2-imidazolethyl)-ethane-1,2-diamine (L) with Cd(ClO4)2.6H2O at pH 9.0 in air. The carbonate anions (CO3(2-)) are from the hydration of the atmospheric carbon dioxide, which is the same as in the previously reported Cu(II) complex [Cu3(L)3(mu3-CO3)](ClO4)4.3CH3CN (2). However, the coordination mode of CO3(2-) in 1 is mu3-eta2:eta2:eta2 while the one in 2 is mu3-eta1:eta1:eta1. One-dimensional (1D) chain Cd(II) and Cu(II) complexes [Cd(L)Cl]ClO4.H2O (3) and [Cu(L)(H2O)](ClO4)2 (4) without CO3(2-) were prepared by a similar method as that for 1 and 2 except for the different reaction pH, namely, 3 and 4 were obtained at pH 7 while 1 and 2 were obtained at pH 9. In addition, when Cu(NO3)2 was used to react with L at pH 9, a unique 1D double-stranded helical chain complex [Cu(L)Cl]NO3.1.25H2O (5) was obtained. The results revealed that the reaction pH and the counteranion have great impact on the carbon dioxide absorption and hydration as well as on the assembling and structure of the complexes. The magnetic property of complex 2 was investigated in the temperature range of 1.8-300 K, and weak ferromagnetic coupling among the mu3-eta1:eta1:eta1-CO3(2-) bridged Cu(II) atoms was observed.     

Photoinduced switching of intramolecular hydrogen bond between amide NH and carboxyl oxygen

In this study, we synthesized two novel carboxylic acid and carboxylate compounds, both of which had an amide group linked with an azomethine moiety to introduce photoinduced switching of the intramolecular NH...O hydrogen bond. We suggest that the cis-carboxylate compound forms a stronger intramolecular NH...O hydrogen bond than the cis-carboxylic acid compound.