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101.
Drug Oxidation by Cytochrome P450BM3: Metabolite Synthesis and Discovering New P450 Reaction Types
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Xinkun Ren Dr. Jake A. Yorke Emily Taylor Ting Zhang Prof. Weihong Zhou Prof. Luet Lok Wong 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(42):15039-15047
There is intense interest in late‐stage catalytic C?H bond functionalization as an integral part of synthesis. Effective catalysts must have a broad substrate range and tolerate diverse functional groups. Drug molecules provide a good test of these attributes of a catalyst. A library of P450BM3 mutants developed from four base mutants with high activity for hydrocarbon oxidation produced human metabolites of a panel of drugs that included neutral (chlorzoxazone, testosterone), cationic (amitriptyline, lidocaine) and anionic (diclofenac, naproxen) compounds. No single mutant was active for all the tested drugs but multiple variants in the library showed high activity with each compound. The high conversions enabled full product characterization that led to the discovery of the new P450 reaction type of oxidative decarboxylation of an α‐hydroxy carboxylic acid and the formation a protected imine from an amine, offering a novel route to α‐functionalization of amines. The substrate range and varied product profiles suggest that this library of enzymes is a good basis for developing late‐stage C?H activation catalysts. 相似文献
102.
Lok Kan Wu 《Phosphorus, sulfur, and silicon and the related elements》2017,192(9):1074-1077
An electrochemistry-based gravimetric method of analysis for the determination of thiosulfate concentrations in aqueous solutions and its application in chemical education are introduced. Nine standard aqueous thiosulfate solutions with triplicate concentrations of 0.02 M, 0.03 M, and 0.04 M were prepared in 1.0 M hydrochloric acid. The elemental sulfur produced in each sample was recovered by filtration, and the mass of the recovered elemental sulfur and the electrochemically determined equilibrium constant of the reaction at 25°C (Keq = 3.5) were used to determine the concentration of thiosulfate in each standard solution. The method % Error is 4.9 ± 3.0, which means that the average method % Error is less than 5.0. 相似文献
103.
Johnson Lui-Lui Tsai Taotao Zou Jia Liu Tianfeng Chen Anna On-Yee Chan Chen Yang Chun-Nam Lok Chi-Ming Che 《Chemical science》2015,6(7):3823-3830
Supramolecular interactions are of paramount importance in biology and chemistry, and can be used to develop new vehicles for drug delivery. Recently, there is a surge of interest on self-assembled functional supramolecular structures driven by intermolecular metal–metal interactions in cellular conditions. Herein we report a series of luminescent Pt(ii) complexes [Pt(C^N^Npyr)(CNR)]+ [HC^N^Npyr = 2-phenyl-6-(1H-pyrazol-3-yl)-pyridine)] containing pincer type ligands having pyrazole moieties. These Pt(ii) complexes exert potent cytotoxicity to a panel of cancer cell lines including primary bladder cancer cells and display strong phosphorescence that is highly sensitive to the local environment. The self-assembly of these complexes is significantly affected by pH of the solution medium. Based on TEM, SEM, ESI-MS, absorption and emission spectroscopy, and fluorescence microscopy together with cell based assays, [Pt(C^N^Npyr)(CNR)]+ complexes were observed to self-assemble into orange phosphorescent polymeric aggregates driven by intermolecular Pt(ii)–Pt(ii) and ligand–ligand interactions in a low-pH physiological medium. Importantly, the intracellular assembly and dis-assembly of [Pt(C^N^Npyr)(CNR)]+ are accompanied by change of emission color from orange to green. These [Pt(C^N^Npyr)(CNR)]+ complexes accumulated in the lysosomes of cancer cells, increased the lysosomal membrane permeability and induced cell death. One of these platinum(ii) complexes formed hydrogels which displayed pH-responsive and sustained release properties, leading to low-pH-stimulated and time-dependent cytotoxicity towards cancer cells. These hydrogels can function as vehicles to deliver anti-cancer agent cargo, such as the bioactive natural products studied in this work. 相似文献
104.
Rodríguez-Abreu C Shrestha LK López Quintela MA 《Journal of colloid and interface science》2007,312(1):108-113
The phase behavior and structure of aggregates in a hydrophobic block copolymer (L121)/double-tailed surfactant (AOT)/water system have been studied by phase study, fluorescence spectrometry, dynamic light scattering, transmission electron microscopy, small angle X-ray scattering (SAXS) and conductivity measurements. An isotropic, one-phase region is found between two biphasic regions containing large vesicles, namely, transparent samples are formed by mixing two turbid solutions. Depending on the AOT/L121 ratio, the isotropic region can be quite stable against temperature. The phase transition between the two regions can be detected by the used techniques, and structural transitions in the aggregates are inferred. The experimental evidence indicates that mixed aggregates are formed at very low concentrations, much lower than the critical micellar concentration of AOT. These micelle-like aggregates contain a mixed hydrophobic core, are small (2-4 nm), and seem to be quasi-spherical, which is an unexpected result since the packing parameters of the single amphiphiles do not favor such small quasi-spherical shapes. This behavior might have interesting implications in the release of substances from vesicles when their structure is disrupted. 相似文献
105.
Shrestha LK Shrestha RG Solans C Aramaki K 《Langmuir : the ACS journal of surfaces and colloids》2007,23(13):6918-6926
We have studied the effect of added water on the nonaqueous foaming properties of diglycerol fatty acid ester nonionic surfactant systems. Diglycerol monomyristate (designated as DGM) could not foam in nonpolar oils squalane and hexadecane at normal room temperature. Nevertheless, addition of a small amount of water induces a dramatic change in foaming properties. Both the foamability and foam stability increases with the amount of added water within the studied concentration range. Phase behavior study showed that in the dilute regions there is dispersion of solid surfactant in the aforementioned oils in the DGM systems. The particle size of the dispersed solid phase was found to be several tens of microns in the water free system, and hence it tends to coagulate and precipitate. In the case of shorter alkyl chain length, diglycerol monolaurate (DGL) surfactant-oil systems, dispersion of lamellar liquid crystal (Lalpha) is observed at room temperature, and the poor foaming properties were attributed to the large particle size of the liquid crystal. In both the DGL and DGM-oil systems, we observed a tendency of the particle size to decrease with the increasing concentration of added water. At higher temperature, the solid surfactant transforms to lamellar liquid crystal phase, and foaming is improved in the DGM/squalane system. Foams are stable for several minutes. Judging from the foaming test and particle size distribution data it can be concluded that the poor foaming in the diglycerol fatty acid esters-oil systems may possibly be due to bigger particle size, which causes precipitation. Addition of water results in the dispersion of smaller particles and improves the foaming behavior. 相似文献
106.
Chi‐Ming Ho Dr. Sammi King‐Woon Yau Dr. Chun‐Nam Lok Dr. Man‐Ho So Chi‐Ming Che Prof. 《化学:亚洲杂志》2010,5(2):285-293
The oxidative dissolution of silver nanoparticles (AgNPs) plays an important role in the synthesis of well‐defined nanostructured materials, and may be responsible for their activities in biological systems. In this study, we use stopped‐flow spectrophotometry to investigate the kinetics and mechanism of the oxidative dissolution of AgNPs by H2O2 in quasi‐physiological conditions. Our results show that the reaction is first order with respect to both [Ag0] and [H2O2], and parallel pathways that involve the oxidation of H2O2 and HO2? are proposed. The order of the reaction is independent of the size of the AgNPs (≈5–20 nm). The rate of dissolution increases with increasing pH from 6.0 to 8.5. At 298 K and I=0.1 M , the value of kb is five orders of magnitude higher than that of ka (where ka and kb are the rate constants for the oxidative dissolution of AgNPs by H2O2 and HO2?, respectively). In addition, the effects of surface coating and the presence of halide ions on the dissolution rates are investigated. A possible mechanism for the oxidative dissolution of AgNPs by H2O2 is proposed. We further demonstrate that the toxicities of AgNPs in both bacteria and mammalian cells are enhanced in the presence of H2O2, thereby highlighting the biological relevance of investigating the oxidative dissolution of AgNPs. 相似文献
107.
Lai SW Liu Y Zhang D Wang B Lok CN Che CM Selke M 《Photochemistry and photobiology》2010,86(6):1414-1420
Luminescent cyclometalated platinum(II) complexes, namely [Pt(Thpy)(PPh3)X]n+ (HThpy = 2-(2′-thienyl)pyridine; X = Cl− ( 1 ), n = 0; X = CH3CN ( 2 ), pyridine ( 3 ), n = 1) and [Pt(Thpy)(HThpy)Y] n + (Y = Cl− ( 4 ), n = 0; Y = pyridine ( 5 ), n = 1), exhibit structured emission with peak maximum at ∼556 and 598 nm in degassed acetonitrile and with emission quantum yield and lifetime of up to 0.38 and 26 μs, respectively. These complexes are efficient photosensitizers of singlet oxygen with yields up to >90%. Complex 5 exhibited photocytotoxicity towards cancer cells and fluorescence microscopic images of cells incubated with 5 reveal substantial uptake at the nucleus and mitochondria. 相似文献
108.
Gambarota G van Laarhoven HW Philippens M Lok J van der Kogel A Punt CJ Heerschap A 《Magnetic resonance imaging》2006,24(3):279-286
OBJECTIVES: The characterization of tumor vasculature is essential in studying tumor physiology. The aim of this study was to develop a new method - based on water proton MR density measurements, in combination with ultrasmall superparamagnetic iron oxide (USPIO) administration - to measure absolute blood volume (BV) in murine colon carcinoma. MATERIALS AND METHODS: MRI experiments were performed at 7 T. CPMG imaging was performed on subcutaneous murine colon carcinoma in six mice before and after administration of an USPIO blood-pool contrast agent. Density maps were obtained from the signal amplitude at TE=0 of the CPMG decay fit. Post-USPIO density maps were subtracted from pre-USPIO density maps to quantitatively yield absolute tumor BV maps. In a separate group of mice (n=6), the relative vascular area (RVA) of tumors was determined by immunohistochemistry. RESULTS: Ultrasmall superparamagnetic iron oxide administration resulted in a small decrease in the water proton MR density. The BV averaged over the six tumors was 4.6+/-1.6%. The value of the RVA measured by immunohistochemical staining was equal to 3.9+/-2.2%. CONCLUSIONS: After administration of an USPIO blood-pool agent (T(2) relaxivity > 100 mM(-1) s(-1)), the blood water protons become MRI invisible, and pixel-by-pixel BV map can be obtained by subtracting the calculated post-USPIO density map from the pre-USPIO density map. The value of absolute BV obtained with this novel MR approach is in good agreement with the value of the relative vascular measured by immunohistochemical staining. 相似文献
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