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991.
Wenhua Chen Xue Yao Zhenghui Huang Fei Mao Longfei Guan Yun Tang Hualiang Jiang Jian Li Jin Huang Lubin Jiang Jin Zhu 《中国化学快报》2019,30(1):250-254
A series of novel 2,4-diaminopyrimidine-modified compounds was designed and synthesized. Compound 14 showed micromolar dual inhibitory effect on both FP-2 and PfDHFR, and potential inhibition to the proliferation of P. falciparum 3D7 strain and chloroquine-resistant P. falciparum Dd2 strain. 相似文献
992.
A new approach to isoprostanes and neuroprostanes featuring cis-dialkyl stereochemistry at the cyclopentane ring has been developed by employing an intramolecular cross-coupling reaction of an alkyl iodide and a tethered alkenylsiloxane for stereoselective installation of a functionalized omega-side chain. 相似文献
993.
Nian Yun YANG Shi Hui QIAN Jin Ao DUAN Ping LI Li Juan TIAN Jiangsu Academy of Traditional Chinese Medicine Nanjing China Pharmaceutical University Nanjing Jinling Pharmaceutical Company Limited Nanjing 《中国化学快报》2005,16(9)
Various germacrane sesquiterpenes have been isolated from many species of the Eupatorium.In recent years these compounds have been increasing interest due to their insecticidal,cytotoxic,antitumor-promoting and insect-antifeedant activities1.In our present study,we have investigated the chemical constituents of Eupatorium lindleyanum DC.,which is a geo-authentic medicine of Jiangsu province.It is used as a antipyretic drug.Two novel germacrane sesquiterpenes(Figure1)were found by us from th… 相似文献
994.
Analysis of scopolamine and its eighteen metabolites in rat urine by liquid chromatography-tandem mass spectrometry 总被引:1,自引:0,他引:1
A rapid and sensitive method is described for the determination of scopolamine and its metabolites in rat urine by combining liquid chromatography and tandem mass spectrometry (LC–MS/MS). Various extraction techniques (free fraction, acid hydrolyses and enzyme hydrolyses) and their comparison were carried out for investigation of the metabolism of scopolamine. After extraction procedure, the pretreated samples were injected into a reversed-phase C18 column with mobile phase of methanol/ ammonium acetate (2 mM, adjusted to pH 3.5 with formic acid) (70:30, v/v) and detected by an on-line MS/MS system. Identification and structural elucidation of the metabolites were performed by comparing their changes in molecular masses (ΔM), retention-times and full scan MSn spectra with those of the parent drug. The results revealed that at least 18 metabolites (norscopine, scopine, tropic acid, aponorscopolamine, aposcopolamine, norscopolamine, hydroxyscopolamine, hydroxyscopolamine N-oxide, p-hydroxy-m-methoxyscopolamine, trihydroxyscopolamine, dihydroxy-methoxyscopolamine, hydroxyl-dimethoxyscopolamine, glucuronide conjugates and sulfate conjugates of norscopolamine, hydroxyscopolamine and the parent drug) and the parent drug existed in urine after ingesting 55 mg/kg scopolamine to healthy rats. Hydroxyscopolamine, p-hydroxy-m-methoxyscopolamine and the parent drug were detected in rat urine for up 106 h after ingestion of scopolamine. 相似文献
995.
Boñaga LV Zhang HC Moretto AF Ye H Gauthier DA Li J Leo GC Maryanoff BE 《Journal of the American Chemical Society》2005,127(10):3473-3485
We investigated the formation of macrocycles from alpha,omega-diynes in cobalt-mediated co-cyclotrimerization reactions. Long-chain alpha,omega-diynes underwent metal-mediated [2 + 2 + 2] cycloadditions with nitriles, cyanamides, or isocyanates in the presence of CpCo(CO)2 (Cp = cyclopentadienide) to yield pyridine-containing macrocycles, i.e., meta- and para-pyridinophanes, such as 5m/5p, 35m/35p, and 41m/41p. The regioselectivity of these reactions was affected by the length and type of linker unit between the alkyne groups, as well as by certain stereoelectronic factors. An analogous alpha,omega-cyano-alkyne, 28, combined with an alkyne to yield two isomeric meta-pyridinophanes, such as 5m and 29m, and an ortho cycloadduct (benzannulation product), such as 29o. We developed a reaction protocol for these cobalt-based [2 + 2 + 2] cycloadditions that involves markedly improved conditions such that this process offers a convenient, flexible synthetic approach to macrocyclic pyridine-containing compounds. For example, diyne 6 reacted with p-tolunitrile in 1,4-dioxane to give 7p and 7m (7:1 ratio) in 87% yield at a moderate temperature of ca. 100 degrees C in 24 h without photoirradiation or syringe-pump addition. Isocyanates were also effective reactants, as exemplified by the formation of 44p almost exclusively (44p:44m > 50:1) in 64% yield from diyne 8 and 2-phenylethylisocyanate. By using this improved protocol we were able to co-cyclotrimerize long-chain alpha,omega-diynes with alkynes in certain cases to demonstrate a successful macrocyclic variant of the Vollhardt reaction. For instance, diyne 6 reacted with dipropylacetylene to give paracyclophane 57p and benzannulene 57o (2:1 ratio) in 29% yield. 相似文献
996.
Alternating adsorption of poly(acrylic acid) and a polyethylenimine-Pd(II) complex on alumina and subsequent reduction of Pd(II) by NaBH4 yield catalytic Pd nanoparticles embedded in multilayer polyelectrolyte films. The polyelectrolytes limit aggregation of the particles and impart catalytic selectivity in the hydrogenation of alpha-substituted unsaturated alcohols by restricting access to catalytic sites. Hydrogenation of allyl alcohol by encapsulated Pd(0) nanoparticles can occur as much as 24-fold faster than hydrogenation of 3-methyl-1-penten-3-ol. Additionally, the nanoparticle/polyelectrolyte system suppresses unwanted substrate isomerization, when compared to a commercial palladium catalyst. Selective diffusion through poly(acrylic acid)/polyethlyenimine membranes suggests that hydrogenation selectivities are due to different rates of diffusion to nanoparticle catalysts. First-order kinetics are also consistent with a diffusion-limited mechanism. Further exploitation of the versatility of polyelectrolyte films should increase selectivity in hydrogenation as well as other reactions. 相似文献
997.
Jin J Sioutis I Tarczay G Gopalakrishnan S Bezant A Miller TA 《The Journal of chemical physics》2004,121(23):11780-11797
Dispersed fluorescence (DF) spectra of 1-propoxy, 1-butoxy, 2-propoxy, and 2-butoxy radicals have been observed under supersonic jet cooling conditions by pumping different vibronic bands of the B-X laser induced fluorescence excitation spectrum. The DF spectra were recorded for both conformers of 1-propoxy, three conformers of the possible five of 1-butoxy, the one possible conformer of 2-propoxy, and two conformers of the possible three of 2-butoxy. Analysis of the spectra yields the energy separations of the vibrationless levels of the ground X and low-lying A electronic state as well as their vibrational frequencies. In all cases, the vibrational structure of the DF spectra is dominated by a CO stretch progression yielding the nuCO stretching frequency for the X state and in most cases for the A state. In addition to the experimental work, quantum chemical calculations were carried out to aid the assignment of the vibrational levels of the X state and for some conformers the A state as well. Geometry optimizations of the different conformers of the isomers were performed and their energy differences in the ground states were determined. The results of the calculation of the energy separations of the close-lying X and A states of the different conformations are provided for comparison with the experimental observations. 相似文献
998.
We report a series of experiments and a theoretical model designed to systematically define and evaluate the relative importance of nanoparticle, oligonucleotide, and environmental variables that contribute to the observed sharp melting transitions associated with DNA-linked nanoparticle structures. These variables include the size of the nanoparticles, the surface density of the oligonucleotides on the nanoparticles, the dielectric constant of the surrounding medium, target concentration, and the position of the nanoparticles with respect to one another within the aggregate. The experimental data may be understood in terms of a thermodynamic model that attributes the sharp melting to a cooperative mechanism that results from two key factors: the presence of multiple DNA linkers between each pair of nanoparticles and a decrease in the melting temperature as DNA strands melt due to a concomitant reduction in local salt concentration. The cooperative melting effect, originating from short-range duplex-to-duplex interactions, is independent of DNA base sequences studied and should be universal for any type of nanostructured probe that is heavily functionalized with oligonucleotides. Understanding the fundamental origins of the melting properties of DNA-linked nanoparticle aggregates (or monolayers) is of paramount importance because these properties directly impact one's ability to formulate high sensitivity and selectivity DNA detection systems and construct materials from these novel nanoparticle materials. 相似文献
999.
p-tert-Butylcalix[8]arene bonded capillaries for open-tubular capillary electrochromatography were prepared with γ-glycidoxypropyltrimethoxysilane as a bridge. The bonded capillary displayed low and steady electroosmotic flow (EOF) values over the pH range from 4 to 9. Detection limits for direct spectrophotometric detection at 277 nm for benzenediols (at a signal to noise ratio of 2) were 0.96 mg l−1 for the unbonded capillary and 1.48 mg l−1 for the bonded capillary, showing that the bonded layer did not show significant absorbance and hence decreased sensitivity. The bonded capillaries showed good separation selectivity for o-, m- and p-benzenediols, α- and β-naphthols, and α- and β-naphthylamines. This selectivity was attributed to significant interactions between the analytes and the bonded p-tert-butylcalix[8]arene, which contributed to the electrochromatographic separation mechanism. The bonded capillaries gave high stability and reproducibility. 相似文献
1000.
Jin Hong 《Journal of Molecular Structure》2003,655(3):435-441
X-ray crystallographic analysis and density functional B3LYP/6-31G(d) calculation confirm that dimeric water is embedded within a hydrophobic cavity of tetra-(p-tert-butyl)thiacalix[4]arene and stabilized by hydrogen bondings of aromatic π?H2O(1) and methyl?H2O(2) in the dimeric water inclusion complex with binding energies of 1.4 and 0.9 kcal mol−1 respectively, and by hydrogen bonding formed between H2O(2) and four phenolic OH groups from an adjacent tetra-(p-tert-butyl)thiacalix[4]arene, with binding energy of 3.8-4.2 kcal mol−1. 相似文献