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91.
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. 相似文献
92.
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. 相似文献
93.
A capillary electrophoresis (CE) method was developed for the separation of heparin oligosaccharides compatible to study the interactions between the oligosaccharides and granulocyte-colony stimulating factor (G-CSF). Unfractionated heparin was eliminitively degraded to heparin oligosaccharides by an endolytic heparinase. The degraded smaller oligosaccharides (M(r) < 1000) were baseline-separated by CE under a 50 mM phosphate buffer (pH 9.0) in 10 min. Standard heparin disaccharides and larger oligosaccharides (1000 < M(r) < 8000) were all separated under optimized separation conditions. Compared with standard heparin disaccharides, smaller oligosaccharides contained one nonsulfated, two monosulfated, and two disulfated disaccharides, but trisulfated disaccharides were not found. The smaller oligosaccharides were also identified and molecular mass was deduced by electrospray ionization-mass spectrometry (ESI-MS). Furthermore, interactions between G-CSF and the oligosaccharides were studied by using capillary zone electrophoresis (CZE) under the above separation conditions. It was found that larger oligosaccharides could interact with G-CSF while smaller oligosaccharides were not observed to bind to G-CSF under the experimental conditions. In conclusion, the purified heparinase could selectively degrade heparin into oligosaccharides and the interaction between G-CSF and heparin was correlated with the chain length of heparin. 相似文献
94.
Determination of phenols in soil by supercritical fluid extraction-capillary electrochromatography 总被引:2,自引:0,他引:2
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. 相似文献
95.
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. 相似文献
96.
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. 相似文献
97.
98.
Electrochemical insertion of magnesium ions into V2O5 from aprotic electrolytes with varied water content 总被引:2,自引:0,他引:2
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. 相似文献
99.
Xiao Long WANG Jian Peng FENG Xin Gang XIE Xiao Ping CAO* Xin Fu PAN* Department of Chemistry & State Key Laboratory of Applied Organic Chemistry Lanzhou University Lanzhou 《中国化学快报》2004,(9)
Aiphanol was isolated from the seeds of Aiphanes aculeate Willd. (Arecaceae) collected in Peru and was reported to exhibit significant inhibitory activities against cyclooxyge- nases-1 and -2. The structure of aiphanol was elucidated by spectroscopic methods as an unprecedented stilbenolignan skeleton in which a stilbene moiety is linked to a phenylpropane unit through a dioxane bridge1. In our previous works the synthetic approach to 1,4-benzodioxane lignans were achieved2. Since aiphanol… 相似文献
100.
Yanli Zeng Lingpeng Meng Shijun Zheng Maofa Ge Dianxun Wang 《Chemical physics letters》2004,400(4-6):394-400
A cluster DFT (B3LYP) calculation study of ClN3 and BrN3 dissociation pathways catalyzed by molecular sieve is reported. A three-tetrahedral molecular sieve cluster (Al(OHSiH3)(OSiH3)(OH)2, called T3) has been chosen in this study. Triplet-state products ClN and BrN are more easily produced with T3 molecular sieve cluster. Although the potential energy surfaces with T3 molecular sieve cluster are similar with those without T3 molecular sieve cluster, the dissociation process of ClN3 and BrN3 with T3 molecular sieve cluster becomes easier, which can be attributed to smaller energy gaps from the ground state reactant to the intersystem crossing point. 相似文献