新颍Mo-Cu-Se簇合物{MoCu3Se3I}(PPh3)3O·0.5CH2Cl2的合成及晶体结构

新颍Mo-Cu-Se簇合物{MoCu₃Se₃I}(PPh₃)₃O·0.5CH₂Cl₂是由［Et₄N］₂MoSe₄、Cu(PPh₃)₂NO₃和KI在乙腈和二氯甲烷1∶1的混合溶剂中反应所得。晶体属单斜晶系，空间群P2_{1相似文献}   

Synthesis and biological activity of novel epothilone aziridines

[reaction: see text]. A series of 12alpha,13alpha-aziridinyl epothilone derivatives were synthesized in an efficient manner from epothilone A. The final semisynthetic route involves a formal double-inversion of stereochemistry at both the C12 and C13 positions. All aziridine analogues were tested for effects on tubulin binding polymerization and cytotoxicity. The results indicate that the aziridine moiety is a viable isosteric replacement for the epoxide in the case of epothilones.     

Temporal Response of SERS to the Potential for 4-Cyanopyridine Adsorbed on Ag Electrode

Time-resolved surface-enhanced Raman scattering (SERS) was applied to study the response of Raman bands from 4-cyanopyridine (PyCN) adsorbed on a Ag electrode to variation of the potential; the temporal resolution was 0.1 s. The response of the SERS signals of PyCN was instantaneous to the oxidation potential of Ag electrode. However, delay of the SERS signals was observed while AgCl was reducing. The decay and growth of the SERS bands look place within 1 s in the cases of desorption and adsorption of PyCN on the electrode. It took much longer for PyCN to alter from one adsorption geometry to another on the electrode.     

Concise total syntheses of the bioactive mesotricyclic diterpenoids jatrophatrione and citlalitrione

The highly functionalized [5.9.5] tricyclic framework resident in jatrophatrione (1) and citlalitrione (2) has been synthesized. The route begins with the tandem anionic oxy-Cope rearrangement/methylation/transannular ene cyclization of 21 and subsequent introduction of a conjugated enone double bond. Hydroxyl-directed 1,4-reduction of this functionality in 25 with LiAlH(4)/CuI/hexamethylphosphoramide/tetrahydrofuran sets the stage for the implementation of a Grob fragmentation and expedited generation of 27. Stereocontrolled intramolecular hydrosilylation allows for the subsequent introduction of a cyclic carbonate as in 53. This intermediate undergoes remarkably efficient, fully regiocontrolled Treibs reaction to generate 54, with this maneuver serving as a pivotal step for making 1 available five steps later. Treatment of 1 with m-chloroperbenzoic acid leads to 2, with attack occurring preferentially on a alpha-face of the double bond more remote to the carbonyl.     

Systematic investigation of the hydrothermal syntheses of Pr(III)-PDA (PDA = pyridine-2,6-dicarboxylate anion) metal-organic frameworks

A series of novel two-dimensional (2D) and three-dimensional (3D) praseodymium coordination polymers, namely, {[Pr3(PDA)4(HPDA)(H2O)8] x 8H2O}n (2), {[Pr2(PDA)3(H2O)3] x H2O}n (3), {[Pr(PDA)(H2O)4] x ClO4}n (4), and { [Pr2(PDA)2(H2O)5SO4] x 2H2O}n (5) (PDA = pyridine-2,6-dicarboxylic anion), was designed and synthesized under hydrothermal conditions. Complexes 1-3 (chainlike polymer, {[Pr(PDA)(HPDA)(H2O)2] x 4H2O}n (1) was also obtained independently by us, although it has been reported recently by Ghosh et al.) were fabricated successfully by simply tuning the Pr/PDA ratio and exhibited various and intriguing topological structures from a 1D chain to a 3D network. While the synthetic strategy of 5 was triggered and further performed only after 1 was structurally characterized. The complexes were characterized by X-ray single-crystal determination, spectroscopic, and variable-temperature magnetic susceptibility analyses. In complex 2 an unusual nanosized square motif as a building block constructed by eight Pr ions was further assembled into a highly ordered 2D grid compound. In complex 3 the decanuclear Pr metal-based structure as a repeat unit interpenetrated to form a novel 3D polymer. Complex 4 was a 3D network polymer fabricated through a hexanuclear Pr ring as a building block, and ClO4- anions as guests were trapped in the cavity. In complex 5 six Pr atoms, two SO4(2-) anions, and carboxylic oxygen bridges constructed an intriguing rectangle structure as a repeat unit in the grid to form a 2D coordination polymer in which the unique bi-bidentate coordination mode of SO4(2-) anion was observed.     

Determination of phenols in soil by supercritical fluid extraction-capillary electrochromatography

A new analytical procedure is developed to couple supercritical fluid extraction with capillary electrochromatography (SFE-CEC) to extract and determine phenols in soil. Ten phenols consisting of phenol, methylphenols (p-cresol and o-cresol), dimethylphenols (3,5-xylenol, 3,4-xylenol and 2,6-xylenol), trimethylphenol, ethylphenols (p-ethylphenol and o-ethylphenol), and o-isopropylphenol are investigated. The use of supercritical CO2 with 10% methanol as the organic modifier was found to give satisfactory extraction of alkylphenols from soil at 1200 p.s.i. and 50 degrees C for 45 min under a total extractant flow-rate of 0.2 ml/min (1 p.s.i.=6894.76 Pa). Baseline resolution was achieved for the 10 selected phenols under optimised CEC conditions at 20 kV in a mobile phase of acetonitrile-4 mM Tris, pH 7.0 (35:65) in a 45 cm (25 cm packed with 3 microm ODS) x 75 microm I.D. fused-silica capillary column. Using SFE with a 10-fold preconcentration factor, all alkyl-substituted phenols in soil can be determined with detection limits ranging from 0.0032 to 0.014 mg/kg and working range from 0.019 to 2.72 mg/kg. The SFE-CEC procedure developed has been applied successfully to determine phenols extracted from real soil sample contaminated with medical disinfectant. It will provide a rapid method for the direct determination of phenol and alkyl-substituted phenol in soils, with capability for confirmation of unknown peaks.     

Molecular design of free volume as a route to low-kappa dielectric materials

Polymers incorporating the triptycene subunit were prepared for the molecular-level design of low dielectric constant (low-kappa) materials that can be used to manufacture faster integrated circuits. Triptycenes having restricted rotation by multiple point attachment to the polymer backbone are shown to introduce free volume into the films, thereby lowering their dielectric constants. The triptycene containing polymers exhibit a number of desirable properties including low-water absorption and high thermal stability. Systematic studies wherein comparisons are made between two separate classes of triptycene polymers and their non-triptycene containing analogues demonstrate that proper insertion of triptycenes into a polymer backbone can give rise to a reduction in the material's dielectric constant while also improving its mechanical properties. These characteristics are desired by the semiconductor industry for the next generation of microprocessors and memory to provide insulation of the increasingly shrinking features.     

Preparation of a Star Network PEG-based Gel Polymer Electrolyte and Its Application to Electrochromic Devices

A star network polymer with a pentaerythritol core linking four PEG-block polymeric arms was synthesized, and its corresponding gel polymer electrolyte based on lithium perchlorate and plasticizers EC/PC with the character being colorless and highly transparent has been also prepared. The polymer host was characterized and confirmed to be of a star network and an amorphous structure by FTIR, ^1H NMR and XRD studies. The polymer host hold good mechanical properties for pentaerythritol cross-linking. Maximum ionic conductivity of the prepared polymer electrolyte has reached 8.83 × 10 ^-4 S·cm^-1 at room temperature. Thermogravimetry （TG） of the polymer electrolyte showed that the thermal stability was up to at least 150 ℃. The gel polymer electrolyte was further evaluated in electrochromic devices fabricated by transparent PET-ITO and electrochromically active viologen derivative films, and its excellent performance promised the usage of the gel polymer electrolyte as ionic conductor material in electrochrornic devices.     

Electrochemical insertion of magnesium ions into V2O5 from aprotic electrolytes with varied water content

The electrochemical performance of V2O5 has been studied in propylene carbonate (PC)-containing magnesium perchlorate [Mg(ClO4)2] electrolytes in view of their application as positive electrode in the rechargeable magnesium batteries. V2O5 exhibited good properties in hosting magnesium ions and its electrochemical performance depended on the amount of H2O in the electrolytes. The highest first discharge specific capacities of V2O5 electrode was up to 158.6 mAh/g in 1 mol dm(-3) Mg(ClO4)2 + 1.79 mol dm(-3) H2O/PC electrolytes. Electrochemical impedance spectroscopy (EIS) and charging-discharging tests showed that a reasonable amount of H2O in the electrolyte solution facilitated the electrochemical performance of V2O5 electrodes.     

Elucidating dominant factors of PO43-, Cd2+ and nitrobenzene removal by biochar: A comparative investigation based on distinguishable biochars

Four distinct biochars were employed to remove three typical pollutants, meanwhile, path analysis, a multi-statistical regression method, was performed to elucidate the dominant factors of biochar adsorption. This work can provide a new insight to prepare a targeted biochar as adsorbents.