Synthesis and Crystal Structure of a Novel Compound of （C2N2H8O2） H6V10O28

A novel vanadate decamer, involving all vanadium atoms present in +5 oxidation and one formhydroxamic acid dimer cation readical, has been synthesized. The single-crystal X-ray diffraction shows that the orange crystal is formed in the triclinic system, space group Pi, a = 8. 4960 (17), b = 10.447 (2), c = 11.299 (2) A, α= 68. 82 (3)°,β= 87.35 (3)°, γ = 66.97(3)°. V = 855. 3(3) A3, Z = 8, R1 = 0. 0857, wR2=0. 2551. X-ray crystallographic and packing in superlattice studies showed that the crystal structure was constructed by electrostatic attraction of O-H…O hydrogen bonds between formhydroxamic acid dimer cation and decavanadate polyanion. Formhydroxamic acid dimer is got through controlling the condition of the reaction using formhydroxamic acid.     

Biradicals/zwitterions from thermolysis of enyne-isocyanates. Application to the synthesis of 2(1H)-pyridones, benzofuro[3,2-c]pyridin-1(2H)-ones, 2,5-dihydro-1H-pyrido[4,3-b]indol-1-ones, and related compounds

Thermolysis of benzannulated enyne-isocyanates 13 and enyne-isocyanates 36 and 37 promoted the cycloaromatization reactions to generate in situ O,4-didehydro-2-hydroxyquinolines and O,4-didehydro-2-hydroxypyridines, respectively, as reactive intermediates. These cycloaromatized intermediates could be captured either as biradicals and/or as zwitterions depending on the nature of the substituent at the alkynyl terminus. The intermediate derived from cycloaromatization of 13a bearing a phenyl substituent could be regarded as biradical 14, which then abstracts hydrogen atoms from gamma-terpinene leading to 2(1H)-quinolinone 15. Alternatively, the same intermediate could also be regarded as zwitterion 14', which then undergoes an initial hydride abstraction from gamma-terpinene followed by protonation to produce 15. The presence of a 2-phenylethyl substituent in 13b and 37a or a 2-methylphenyl substituent in 37b also allowed the resulting intermediates to be captured intramolecularly either as biradicals or as zwitterions, producing 2(1H)-quinolinone 19, 2(1H)-pyridone 39, and benzopyranopyridine 43, respectively. On the other hand, with a 2-methoxyphenyl, a 2-(dimethylamino)phenyl, or a 3-methoxypropyl substituent, the chemical behavior of the cycloaromatized adduct could be best accounted for in terms of a zwitterionic intermediate leading to benzofuro[3,2-c]quinolin-6(5H)-one (20), 5,11-dihydro-11-methyl-6H-indolo[3,2-c]quinolin-6-one (25), benzofuro[3,2-c]pyridin-1(2H)-one 44, 2,5-dihydro-2,5-dimethyl-1H-pyrido[4,3-b]indol-1-one 46, and related compounds. Interestingly, thermolysis of 37f bearing a 2-(methoxymethyl)phenyl substituent at the alkynyl terminus produced the unexpected benzopyranopyridine 56 as the major product in a process involving the cleavage of the bond between the methoxyl oxygen and the adjacent methylene carbon. The efficiency and selectivity of the cycloaromatization reaction could also be enhanced by the introduction of 1.1 to 10 equiv of dimethylphenylsilyl chloride to the reaction mixture to capture the resulting zwitterion.     

Detection-dependent kinetics as a probe of folding landscape microstructure

The folding landscapes of polypeptides and proteins exhibit a hierarchy of local minima. The causes range from proline isomerization all the way down to microstructure in the free energy caused by residual frustration inherent in even the best 20 amino acid design. The corresponding time scales range from hours to submicroseconds. The smallest microstructures are difficult to detect. We have measured the folding/unfolding kinetics of the engineered trpzip2 peptide at different tryptophan fluorescence wavelengths, each yielding a different rate. Wavelength-dependent folding kinetics on 0.1-2 mus time scales show that different microstructures with a range of solvent exposure and local dynamics are populated. We estimate a lower limit for the roughness of the free energy surface based on the range of rates observed.     

Water-soluble silica-overcoated CdS:Mn/ZnS semiconductor quantum dots

Highly luminescent and photostable CdS:Mn/ZnS core/shell quantum dots are not water soluble because of their hydrophobicity. To create water-soluble quantum dots by an appropriate surface functionalization, CdS:Mn/ZnS quantum dots synthesized in a water-in-oil (W/O) microemulsion system (reverse micelles) were consecutively overcoated with a very thin silica layer ( approximately 2.5 nm thick) within the same reverse micellar system. The water droplet serves as a nanosized reactor for the controlled hydrolysis and condensation of a silica precursor, tetraethyl orthosilicate (TEOS), using an ammonium hydroxide (NH4OH) catalyst. Structural characterizations with transmission electron microscopy (TEM) and x-ray photoelectron spectroscopy (XPS) indicate that the silica-quantum dot nanocomposites consist of a layered structure. Owing to the amorphous, porous nature of a silica layer, the optical and photophysical properties of silica-overcoated CdS:Mn/ZnS quantum dots are found to remain close to those of uncoated counterparts.     

四磺酸基酞菁锌在水和非水溶剂中的电化学性质研究

在非水溶剂（二甲基亚砜（ＤＭＳＯ）及Ｎ,Ｎ＿二甲基甲酰胺（ＤＭＦ））中的伏安曲线．呈现三对电流峰,表明存在三个可逆或准可逆酞菁配体的单电子转移过程,而在水溶液中则不呈现准可逆行为,且波形改变很大．此外,还比较了四磺酸基酞菁锌的水溶液在自然光和红光（６００～７００ｎｍ）照射下的循环伏安曲线,其氧化还原峰的数目和峰电位基本不变,但在红光照射下比自然光照射下的峰电流明显增大．     

Hydrothermal Synthesis and Structural Characterization of a Tubular Arsenic-Vanadate: [CoII(2,2′-bpy)2]2[AsIII8VIV14O42(H2O)]·H2O

The hydrothermal reaction of VOSO₄, As₂O₃, CoC₂O₄·2H₂O and 2,2-bipy yields a novel arsenic-vanadate [Co^II(2,2-bpy)₂]₂[As^III₈V^IV ₁₄O₄₂(H₂O)]·H₂O (1), which is characterized by IR, elemental analysis, TGA, magnetic susceptibility and single crystal X-ray diffraction analysis. X-ray diffraction shows that compound 1 is the first example of tubular arsenic–vanadium cluster containing infinite {[Co(2,2-bpy)₂]₂[As₈V₁₄O₄₂(H₂O)]} chain constructed from [As₈V₁₄O₄₂(H₂O)] clusters interconnected through [Co(2,2-bpy)]²⁺ units. Crystal data: 1, orthorhombic, P 2₁2₁2₁, a=12.1401(2) Å, b=15.8722(1) Å, c=39.9533(5) Å, Z=4.Graphical Abstract: A novel polyoxoarsenicvanadate, [Co^II(2,2-bipy)₂]₂ [As^III₈V^IV ₁₄O₄₂(H₂O)]·H₂O, is depicted along with a tubular hybrid solid with a rhombic tube formed within the chain.     

Raman mapping and in situ SERS spectroelectrochemical studies of 6-mercaptopurine SAMs on the gold electrode

The self-assembled monolayers (SAMs) of 6-mercaptopurine (6MP) were formed at the roughened polycrystalline gold surfaces in acid and alkaline media. The time-dependent Raman mapping spectral analysis in conjunction with the quantum calculations for the vibrational modes using ab initio BLYP/6-31G method suggested that both of the resulted 6MP SAMs adopted the same adsorption mode through the S atom of pyrimidine moiety and the N7 atom of the imidazole moiety anchoring the gold surface in a vertical way. The in situ surface-enhanced Raman scattering spectroelectrochemical experiment was conducted to examine the stability of the SAMs at various bias potentials. It was found that the detaching process of the 6MP SAMs from the surface involved one electron reduction as the voltage was applied at ca. 0.7 V vs a standard calomel electrode.     

Determination of lutetium by fluorimetry, using BPMPHD and CTMAB

Lutetium(III) forms an association compound with a new synthetic reagent, 1,6-bi(1-phenyl-3-methyl-5-pyrazolone-4)hexandione (BPMPHD), and cetyltrimethylammonium bromide (CTMAB). The compound enhances the natural fluorescence of BPMPHD remarkably, upon which a new fluorescence method was developed for determining lutetium in rare earth (RE) samples. The determination range was 1.80 × 10^–7–8.8 × 10^–6 g/ml. The determination limit was 29 ng/ml. The composition of the ion associate was [Lu(BPMPHD)₂]–CTMAB⁺.     

Synthesis and Insulin—sensitizing Activity of a Series of 2—Benzyl—1,3—dicarbonyl Derivatives

A series of 2-benzyl-1,3-dicabonyl derivatives was synthesized.Their insulin-sensitizing activity was evaluated in 3T3-L1 preadipocyte cells.Compounds3,26 and 27 were found to possess strong insulin-sensitizing activity in vitro and were selected for further hypoglycemic evaluation in vivo.     

Photoinduced self-substitution of haloquinones

A series of novel oligo(halobenzoquinoid) compounds have been obtained from the photoinduced self-substitution of 2,5-dibromo-1,4-benzoquinone (1a), 2,6-dibromo-1,4-benzoquinone (1b), 2-chloro-1,4-benzoquinone (1c), 2-bromo-5-chloro-1,4-benzoquinone (1d), 2,3,5,6-tetrachloro-1,4-benzoquinone (1e) and 1,4-benzoquinone (1f) in the presence of N,N-dimethyl-t-butylamine (2) in acetonitrile. Dimers, trimers and/or pentamers of these haloquinones were found to be the major products.