辅酶NAD(P)H模型分子的研究进展

辅酶NAD(P)H在生物体内起着重要的调节作用, 已引起了有机化学工作者极大的兴趣, 尤其是在还原反应的立体选择性上, 人们已经开展了大量的研究工作. 讨论了NAD(P)H模型分子进行立体专一性还原反应的影响因素, 并对NAD(P)H模型分子的研究工作做了总结.     

Immunosuppressive ent‐Kaurene Diterpenoids from Isodon serra

Three new enmein‐type ent‐kaurenoids, i.e., the two pairs 1 and 2 of 20‐epimers and the (20R)‐isomer 3 , besides the seven known diterpenoids 4 – 10 , were isolated from the aerial parts of Isodon serra. Their structures were elucidated by spectroscopic techniques and X‐ray diffraction. The immunosuppressive effect for T‐lymphocytes proliferation induced by Con A in BALB/c mouse was evaluated for the isolates 1 – 10 . They all displayed a remarkable inhibitory effect, with multi‐glycosides of Tripterygium wilfordii as positive reference substance (Table 3).     

A vanadium(IV) phosphite with a pillared layered structure: hydrothermal synthesis and characterization of (VO)4(4,4'-bpy)2(HPO3)4

A novel vanadium(IV) phosphite, (VO)(4)(4,4'-bpy)(2)(HPO(3))(4), was hydrothermally synthesized and characterized by single-crystal X-ray diffraction. This compound crystallizes in the monoclinic system with the space group C2/c and cell parameters a = 35.970(3) A, b = 15.9400(13) A, c = 10.7681(7) A, beta = 101.073(4) degrees, and Z = 8 with R(1) = 0.0482. The structure of the compound consists of trigonal bipyramidal [VO(4)N] and pseudopyramidal [HPO(3)] blocks, which are connected by corner-sharing, to form vanadium phosphite layers in the bc plane. These layers are further linked through 4,4'-bpy pillars, generating a 3D framework. Thermogravimetric analysis and magnetic susceptibility data for this compound are given.     

Adsorption of NH3 onto activated carbon prepared from palm shells impregnated with H2SO4

Adsorption of ammonia (NH3) onto activated carbons prepared from palm shells impregnated with sulfuric acid (H2SO4) was investigated. The effects of activation temperature and acid concentration on pore surface area development were studied. The relatively large micropore surface areas of the palm-shell activated carbons prepared by H2SO4 activation suggest their potential applications in gas adsorption. Adsorption experiments at a fixed temperature showed that the amounts of NH3 adsorbed onto the chemically activated carbons, unlike those prepared by CO2 thermal activation, were not solely dependent on the specific pore surface areas of the adsorbents. Further adsorption tests for a wide range of temperatures suggested combined physisorption and chemisorption of NH3. Desorption tests at the same temperature as adsorption and at an elevated temperature were carried out to confirm the occurrence of chemisorption due to the interaction between NH3 and some oxygen functional groups via hydrogen bonding. The surface functional groups on the adsorbent surface were detected by Fourier transform infrared spectroscopy. The amounts of NH3 adsorbed by chemisorption were correlated with the contents of elemental oxygen present in the adsorbents. Mechanisms for chemical activation and adsorption processes are proposed based on the observed phenomena.     

Temperature-sensitive polypeptide brushes-coated mesoporous silica nanoparticles for dual-responsive drug release

A multifunctional nanohybrid based on mesoporous silica nanoparticle and biocompatible polypeptide was fabricated for targeted and dual-responsive therapy of tumor cells.     

Special Mixing Behavior of Chelate-based Ionic Liquid with Methanol

Compared to the general ionic liquids (ILs), a significant deviation of the binary mixtures of 1-decyl-3-methylimidazolium tri(hexafluoroacetylaceto)-copper(II) ([C₁₀mim][Cu(hfacac)₃]) with methanol was found, indicating the way methanol interacts with ILs might be governed by the special structure of the chelating anion. IR results showed that the (C2-H) of 1-decyl-3-methylimidazolium hexafluoroacetylacetonate ([C₁₀mim][hfacac]) blue-shifted more significantly than that of [C₁₀mim][Cu(hfacac)₃], meanwhile the (C=O) red-shifted in [C₁₀mim][Cu(hfacac)₃], which is contrast with that in [C₁₀mim][hfacac]. Two-dimensional correlation analysis of the FTIR spectra indicated that the chelating cavity has little effect on the sequence of the ILs sites that interact with methanol. Combined with small angle X-ray scattering (SAXS) results, the picture of mixing processes in these two systems were proposed. Methanol interacts directly with the anion followed by the cation in [C₁₀mim][hfacac], while methanol preferentially enters the chelating cavity and enhances the packing effect in the [C₁₀mim][Cu(hfacac)₃] system.     

Synthesis, Characterization and Two-Photon Absorption Properties of a Novel Pyridinium Salt

A novel pyridinium salt, 2,4-bis[p-(N,N-dimethylamino)styryll-N-metlayl pyridinium iodide (BMSPI) was synthesized and characterized by TG, ^1H NMR spectroscopy and elemental analysis, and the reaction process was studied by using ES-MS. When BMSPI was pumped by a pulsed 1064 nm, 50 ps laser beam, it manifests highly efficient TPA (Two-Photon Absorption) and up-conversion superradiance. The up-conversion efficiency was 6.0% at the pump energy of 4-6 mJ and the lifetime of two-photon fluorescence was measured as 59 ps.     

Speciation of inorganic arsenic by electrochemical hydride generation atomic absorption spectrometry

A simple procedure was developed for the speciation of inorganic arsenic by electrochemical hydride generation atomic absorption spectrometry (EcHG–AAS), without pre-reduction of As(V). Glassy carbon was selected as cathode material in the flow cell. An optimum catholyte concentration for simultaneous generation of arsine from As(III) and As(V) was 0.06 mol l⁻¹ H₂SO₄. Under the optimized conditions, adequate sensitivity and difference in ratio of slopes of the calibration curves for As(III) and As(V) can be achieved at the electrolytic currents of 0.6 and 1 A. The speciation of inorganic arsenic can be performed by controlling the electrolytic currents, and the concentration of As(III) and As(V) in the sample can be calculated according to the equations of absorbance additivity obtained at two selected electrolytic currents. The calibration curves were linear up to 50 ng ml⁻¹ for both As(III) and As(V) at 0.6 and 1 A. The detection limits of the method were 0.2 and 0.5 ng ml⁻¹ for As(III) and As(V) at 0.6 A, respectively. The relative standard deviations were of 2.1% for 20 ng ml⁻¹ As(III) and 2.5% for 20 ng ml⁻¹ As(V). The method was validated by the analysis of human hair certified reference material and successfully applied to speciation of soluble inorganic arsenic in Chinese medicine.     

Electrochemical studies of the oxidation mechanism of polyamide on glassy carbon electrode

Polyamides containing N-methyl pyrroles and N-methyl imidazoles are a type of small molecule that can bind and recognize the bases of DNA with high affinity and specificity. Five polyamides were studied at glassy carbon electrode in acetate buffer by cyclic and differential pulse voltammetry to clarify their redox pathways. The polyamide electrochemical responses are compared by peak currents and peak potentials. The slopes of the three anodic E_p vs. pH plots of a typical polyamide are linear and show 0.059, 0.057, 0.056 V per pH in acid media, respectively, which correspond to a mechanism involving the equal number of electrons and protons. A possible mechanism for the redox pathway of various polyamides is proposed: the oxidation product of imidazole ring is acylamide and the results of in situ UV–Vis spectroscopy at Pt web electrode support the proposed mechanism. electrospray ionization mass spectroscopy (ESI-MS) indicates that one or two oxygen atoms are added into polyamide molecule after electrochemical oxidation.     

Nafion/Poly(sodium 4‐styrenesulfonate) Mixed Coating Modified Bismuth Film Electrode for the Determination of Trace Metals by Anodic Stripping Voltammetry

To improve the reproducibility, stability, and sensitivity of bismuth film electrode (BiFE), we studied the performances of a mixed coating of two cation‐exchange polymers, Nafion (NA) and poly(sodium 4‐styrenesulfonate) (PSS), modified glassy carbon BiFE (GC/NA‐PSS/BiFE). The characteristics of GC/NA‐PSS/BiFE were investigated by scanning electron microscopy and cyclic voltammetry. Various parameters were studied in terms of their effect on the anodic stripping voltammetry (ASV) signals. Under optimized conditions, the limits of detection were 71 ng L^?1 for Cd(II) and 93 ng L^?1 for Pb(II) with a 10 min preconcentration. The results exhibited that GC/NA‐PSS/BiFE can be a reproducible and robust tool for monitor of trace metals by ASV rapidly and environmentally friendly, even in the presence of surface‐active compounds.