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41.
Mitotane is a cytotoxic drug used in the treatment of inoperable adrenocortical carcinoma, it inhibits steroidogenesis as well, and therefore monitoring the level of steroid hormones in patients treated with mitotane is a crucial point of therapy. Hence, we have developed a simple, fast, and efficient electrophoretic method combined with reverse polarity sweeping as online preconcentration technique and dispersive liquid–liquid microextraction for the simultaneous determination of mitotane, its main metabolite DDA, and five steroid hormones (progesterone, testosterone, epitestosterone, cortisol, and corticosterone) in urine samples. In addition, a new sample matrix consisting of β-CD2SDS1 complexes for a high hydrophobic compounds solubilization was developed. Approach based on the application of β-cyclodextrin and SDS complex of a ratio 2:1 allowed for hydrodynamic injection into the capillary of a solution containing both mitotane and other analytes. The detection limits of the analytes for the reverse polarity sweeping-dispersive liquid–liquid microextraction method were found to be in the range of 1.5–3 ng/mL, which were approximately 1000 times lower than in the conventional hydrodynamic injection (5 s, 0.5 psi) without any preconcentration procedure. All analytes were completely resolved in less than 13 min by uncoated silica capillary with an inner diameter of 75 μm (ID) × 60 cm. Electrophoretic separation was performed in reverse polarity with a voltage of –25 kV with a background electrolyte (BGE) consisting of 100 mM SDS, 25% ACN, 25 mM phosphate buffer (pH 2.5), and 7 mM β-cyclodextrin.  相似文献   
42.
The purpose of the study was to select an environmentally friendly plant biopesticide to protect seed potatoes against phytopathogens. The scope included the evaluation of the antimicrobial activities of 22 plant water extracts, 22 water-glycol extracts, and 3 subcritical carbon dioxide extracts using the agar diffusion method against 10 potato phytopathogens. For the most effective extracts, minimal inhibitory concentration (MIC), chemical composition analysis by gas chromatography–mass spectrometry and in situ assays on seed potatoes were performed. Garlic water extract was finally selected as the most effective in phytopathogen growth inhibition, both in vitro and in situ, with MIC values ranging between 6.3–25 mg/mL. 5-Hydroxymethylfurfural was determined to be the main component of this extract (33.24%). Garlic water extract was proposed as a potential biopesticide against potato phytopathogens.  相似文献   
43.
A new method of analysis has allowed the exonucleolytic cleavage by human 3'-exonuclease to be determined. Hydrolysis by human plasma 3'-exonuclease proceeds with retention of configuration at phosphorus. The new method determines the sense of chirality at phosphorus in isotopomeric adenosine 5'-O-[(18)O]phosphorothioates. This is based on stereospecific two-step conversion of the mono-thionucleotide into the corresponding deoxyadenosine 5'-O-alpha-[(18)O]thiotriphosphate, followed by the use of terminal deoxyribonucleotidyl transferase and MALDI TOF mass spectrometry of the resulting elongated primer. Retention of configuration in the reaction of plasma 3'-exonuclease implies a two-step mechanism with two displacements on phosphorus. Inversion at each step leads to overall retention.  相似文献   
44.
A charge-transfer-induced spin transition (CTIST) is observed in the discrete cyanide-bridged complex, {[Co(tmphen)2]3[Fe(CN)6]2}. Single-crystal X-ray diffraction, 57Fe M?ssbauer spectroscopy, and magnetic susceptibility were used collectively to describe the oxidation states of the Co and Fe ions in this cluster as a function of temperature. This pentanuclear complex represents the first example of a CTIST at the discrete molecular level.  相似文献   
45.
The half-life, 3.8755(12) s, and superallowed branching ratio, 0.5315(12), for 22Mg beta decay have been measured with high precision. The latter depended on gamma-ray intensities being measured with an HPGe detector calibrated for relative efficiencies to an unprecedented 0.15%. Previous precise measurements of 0+ --> 0+ transitions have been restricted to the nine that populate stable daughter nuclei. No more such cases exist, and any improvement in a critical Cabibbo-Kobayashi-Maskawa unitarity test must depend on precise measurements of more exotic nuclei. With this branching-ratio measurement, we show those to be possible for T(z)=-1 parents. We obtain a corrected Ft value of 3071(9) s, in good agreement with expectations.  相似文献   
46.
47.
    
The leakage of aqueous contents of neutral (dipalmitoylphosphatidylcholine/cholesterol) liposomes as induced by Rz1, a proline-rich lipoprotein, the bacteriophage Rz1 gene product, was studied. Fluorescence enhancement assay with Tb3+/dipicolinic acid and self-quenching assays with carboxyfluorescein and fluorescein isothiocyanaten-dextran were used to monitor the Rz1-induced leakage from neutral liposomes. The results demonstrated that Rz1 caused local membrane destabilization leading to the leakage of the liposome contents. The extent of the leakage was independent of the molecular mass of the liposome-entrapped solutes in the range of 376–4000 Da. The kinetics of Rz1-liposome leakage was very similar to that obtained with detergent Triton X-100 for all the solutes used. The results suggested that Rz1 can act as a detergent; i.e., by interacting with lipids on both sides of the liposome membranes (inducing perturbation in the lipid packing within the bilayer), it facilitates the transfer of encapsulated molecules into the external liposome environment. The importance of this result for Rz1 physiological function is discussed.  相似文献   
48.
49.
The modern catalytic or enzymatic advances allow the production of novel biofuel. Among them, 1,3-dioxolane can be produced from formaldehyde and ethylene glycol, both can be obtained from biomass. In this study, the oxidation of 1,3-dioxolane is studied at stoichiometric conditions. The ignition delay times of 1,3-dioxolane/O2/inert mixtures were measured in a shock tube and in a rapid compression machine at pressures of 20 to 40 bar and temperatures ranging from 630 to 1300 K. The pressure profiles recorded in the rapid compression machine show a first stage of ignition enlightening the influence of the low temperature chemistry of combustion. Furthermore, mole fraction profiles of the stable intermediates produced during the oxidation of 1,3-dioxolane were measured in a jet-stirred reactor at 10 bar. Following these observations, a detailed kinetic model was developed with reaction rate coefficients and thermochemical data calculated by theoretical calculations or estimated by analogies to suitable molecules. In order to get an insight into the most important reaction pathways brute force sensitivity analysis and reaction pathway analysis were performed with the proposed model and discussed. It became clear that in the fuel-in-air case for the alkylhydroperoxide of 1,3-dioxolane the ring opening beta-scission pathway is favored against the further alkane-like second addition to molecular oxygen, which leads to a limited negative temperature coefficient.  相似文献   
50.
Assembly of orotic acid (H3Or, 1,2,3,6-tetrahydro-2,6-dioxo-4-pyrimidinecarboxylic) and Cd(NO3)·6H2O yielded a coordination polymer, [(Cd(Hor)·2.5H2O)2]n (1), which has been characterized by X-ray single-crystal diffraction, TGA, and ?uorescence spectra. Single-crystal X-ray structural analyses reveal that 1 is a hydrogen-bonded binuclear Cd-orotate coordination polymer in which both Cd2+ ions have different coordination environments with identical distorted octahedral geometry. Crystal data for 1: monoclinic, space group P21/n, a = 7.0209(10) Å, b = 13.974(2) Å, c = 17.541(3) Å, β = 98.842(2)°, V = 1700.5(4) Å, Z = 4, R1 = 0.0269, wR2 = 0.0612, θmax = 25.960. The emission spectrum of the Cd-complex recorded with 265 nm excitation wavelength reveals the complex has strong blue luminescence with the peak maximum 420 nm (2.95 eV) as a result of the nπ* and ππ* transitions on the H3Or ligand.  相似文献   
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