The reaction of a mixture of 2-(1-naphthyl)benzothiazoline (HL1) and 2,6-diphenylbenzo[1,2-d:4,5-d']bisthiazoline (H3L2) with nickel(II) acetate tetrahydrate yielded three kinds of square-planar nickel(II) complexes: one nickel(II) complex with innocent ligands ([Ni(L1)2] (1c)) and two nickel(II) complexes with non-innocent ligands ([Ni(L1-L1)] (1a) and [Ni(L1-L2)] (1b)). The complex 1c has two bidentate-N,S ligands, which are formed via ring opening of HL1. On the other hand, the two complexes 1a and 1b contain a tetradentate-N2S2 ligand, which is created via ring opening of HL1 and H3L2, followed by bond formation between imino carbon atoms. Complexes 1a and 1b show very intense absorptions in the near-infrared (NIR) region, characteristic of square-planar complexes with non-innocent ligands. The third nickel(II) complex having a non-innocent tetradentate-N2S2 ligand ([Ni(L2-L2)] (2)) was prepared from H3L2 and nickel(II) acetate tetrahydrate. The electronic spectrum of 2 exhibits a very intense absorption at 981 nm (epsilon = 3.6 x 10(4) M-1 cm-1), which is significantly red-shifted compared with those of 1a (837 nm and 4.4 x 10(4) M-1 cm-1) and 1b (885 nm and 4.5 x 10(4) M-1 cm-1), indicating the presence of an extended pi delocalization. The reaction of 2,6-bis(3,5-dichlorophenyl)benzo[1,2-d:4,5-d']bisthiazoline (H3L3) with nickel(II) acetate tetrahydrate also led to the formation of a nickel(II) complex with a non-innocent ligand ([Ni(L3-L3)] (3)). While complex 3 is analogous to 2, its electrical conductivity is much higher than that of 2. The molecular structures of 1b, 1c, 2, and 3 were determined by X-ray crystallography. 相似文献
A new chemiluminescence biochemical oxygen demand (BODCL) determining method was studied by employing redox reaction between quinone and Baker's yeast. The measurement was carried out by utilizing luminol chemiluminescence (CL) reaction catalyzed by ferricyanide with oxidized quinone of menadione, and Saccharomyces cerevisiae using a batch-type luminometer. In this study, dimethyl sulfoxide was used as a solvent for menadione. After optimization of the measuring conditions, the CL response to hydrogen peroxide in the incubation mixture had a linear response between 0.1 and 100 μM H2O2 (r2 = 0.9999, 8 points, n = 3, average of relative standard deviation; R.S.D.av = 4.22%). Next, a practical relationship between the BODCL response and the glucose glutamic acid concentration was obtained over a range of 11-220 mg O2 L−1 (6 points, n = 3, R.S.D.av 3.71%) with a detection limit of 5.5 mg O2 L−1 when using a reaction mixture and incubating for only 5 min. Subsequently, the characterization of this method was studied. First, the BODCL responses to 16 pure organic substances were examined. Second, the influences of chloride ions, artificial seawater, and heavy metal ions on the BODCL response were investigated. Real sample measurements using river water were performed. Finally, BODCL responses were obtained for at least 8 days when the S. cerevisiae suspension was stored at 4 °C (response reduction, 69.9%; R.S.D. for 5 testing days, 18.7%). BODCL responses after 8 days and 24 days were decreased to 69.9% and 35.8%, respectively, from their original values (R.S.D. for 8 days involving 5 testing days, 18.7%). 相似文献
The high pressure behavior of gallium phosphide, GaP, has been examined using the synchrotron X-ray diffraction technique in a diamond anvil cell up to 27?GPa and 900?K. The transition from a semiconducting to a metallic phase was observed. This transition occurred at 22.2?GPa and room temperature, and a negative dependence of temperature of this transition was found. The transition boundary was determined to be P (GPa)?=?22.6???0.0014?×?T (K). 相似文献
Fast ring opening of mesoionic 1,3-dioxolium-4-olates, generated by Rh(2)(OAc)(4)-catalyzed decomposition of phenyldiazoacetic anhydride derivatives, to acyloxyphenylketenes was demonstrated by trapping the ketenes with several ketenophiles. Reactions of phenyldiazoacetic anhydride derivatives with several ketenophiles such as dihydrofuran, carbodiimides, and imines were carried out. No 1,3-dipolar cycloadducts of the latter with 1,3-dioxolium-4-olates were observed. Instead, only their [2 + 2]-cycloadducts with the acyloxyketenes generated by ring-opening of the initially formed 1,3-dioxolium-4-olates were isolated. In the reaction with cyclopentadiene, 1,3-dipolar cycloadducts with 1,3-dioxolium-4-olates were formed as main products along with the [2 + 2]-ketene adduct. PM3 calculation of heats of formation of 2,5-diphenyl-1,3-dioxolium-4-olate and the corresponding benzoyloxyphenylketene indicates that the ring-opened acyloxyketenes are ca. 9 kcal/mol more stable than the corresponding 1,3-dioxolium-4-olates. 相似文献
2-(N-Cyanoimino)-5-[(E)-4-styrylbenzylidene]-4-oxothiazolidine (FPFS-410) is a newly synthesized thiazolidine derivative having not only antidiabetic but also lipid-lowering activities. However, this compound has an extremely low aqueous solubility (2.8 (+/-0.33) x 10(-8) M (0.0094+/-0.0011 microg/ml) in 1.0 M phosphate buffer (pH 7.0) at 25 degrees C). In this study, we investigated the effect of various hydrophilic cyclodextrins (CyDs) on the solubility of FPFS-410 to select a CyD suitable for formulations of the compound. Among various CyDs, 2-hydroxypropyl-beta-CyD (HP-beta-CyD) had the highest solubilizing ability to FPFS-410, e.g., the solubility of the compound was increased 200000-fold by the addition of 40 mM HP-beta-CyD, which was attributable to the formation of the 1 : 2 (guest : host) inclusion complexes. The interaction of HP-beta-CyD with FPFS-410 was studied using 1H-nuclear magnetic resonance (NMR) spectroscopies including ROESY spectroscopy and a molecular modeling calculation. These results suggested that HP-beta-CyD forms a 1:2 (guest : host) inclusion complex with FPFS-410 by including both the stilbene and thiazolidine moieties. FPFS-410/HP-beta-CyD solid complexes with various stoichiometries were prepared by the spray drying and cogrinding methods, and confirmed by powder X-ray diffractometry that these complexes are in an amorphous state. The dissolution of FPFS-410 in water was significantly accelerated by the complexation with HP-beta-CyD. In vivo studies revealed that HP-beta-CyD markedly increases the bioavailability of FPFS-410 after oral administration in dogs. The present results suggest that HP-beta-CyD is useful for improvement of the extremely low bioavailability of FPFS-410. 相似文献
The synthesis of a series of hydrosilylboronates via the selective iridium- or nickel-catalyzed monoborylation of dihydrosilane Si–H bonds is described. The synthesized silylboronates, which bear a single Si–H bond, can be used as novel silicon nucleophiles in the presence of transition-metal catalysts or bases. The first 29Si{1H} NMR spectroscopic evidence for the formation of (t-Bu)2HSiLi, generated by the reaction of (t-Bu)2HSi–B(pin) with MeLi, is reported as the first example of a dialkylhydorosilyl lithium species.Monoborylation of a dihydrosilane Si–H bond can be achieved in the presence of iridium- or nickel-based catalysts, yielding novel hydrosilylboronates that bear a hydrogen atom at the silicon center.相似文献
Using a modified method developed from Vonk's method, detailed values of crystallinity and crystal disorder were obtained by wide angle X-ray diffraction (WAXD). In Vonk's method, the crystallinity (w) is determined by extrapolation of the WAXD experimental curve back to zero scattering angle, while the distortion factor (k) is determined by the inclination of the experimental curve at zero scattering angle. In our new method, both w and k are determined at the same time by using the least squares method. In order to show the efficiency of our method, the new fitting procedure was applied to the experimental values of polyethylene and polyethylene terephthalate as measured by Vonk, and the values of w and k determined by our new method were compared with those found by Vonk's method. The new fitting method has the advantage that it uses the whole experimental curve. Moreover, our modified Vonk's method enables us to discuss crystal distortions as arising from first-kind (thermal) disorder and second-kind (paracrystalline) disorder. 相似文献
Poly‐(N‐isopropylacrylamide) (PNIPA) hydrogel films doped with uniaxially aligned liquid crystalline (LC) nanosheets adsorbed with a dye are synthesized and its anomalous photothermal deformation is demonstrated. The alignment of the nanosheet LC at the cm‐scale is easily achieved by the application of an in‐plane or out‐of‐plane AC electric field during photo‐polymerization. A photoresponsive pattern is printable onto the gel with μm‐scale resolution by adsorption of the dye through a pattern‐holed silicone rubber. When the gel is irradiated with light, only the colored part is photothermally deformed. Interestingly, the photo‐irradiated gel shows temporal expansion along one direction followed by anisotropic shrinkage, which is an anomalous behavior for a conventional PNIPA gel.
The reaction of η(2)-iminozirconocene chloride complexes with trimethylsilylethynyl lithium leads to rapid C-C coupling at room temperature to yield the corresponding five-membered aza-zirconacycloallenoids. Such compounds were also obtained by trapping of in situ generated zirconocene with alkynyl imines. 相似文献