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951.
Granados AM Fracaroli AM de Rossi RH Fuertes P Torroba T 《Chemical communications (Cambridge, England)》2008,(4):483-485
A phenylethynyl Fischer carbene complex was used as a traceless directing group for the regioselective cycloaddition of dithiolethiones to arylacetylene, which constitutes the first synthesis of E-dithiafulvene thione or dithioesters. 相似文献
952.
953.
Monti S Manet I Manoli F Marconi G 《Physical chemistry chemical physics : PCCP》2008,10(44):6597-6606
In the present contribution we address the study of the interaction of a flavonoid-derivative licochalcone A (LA) with human serum albumin (HSA). The application of circular dichroism, UV-Vis absorption, fluorescence and laser flash photolysis combined with molecular mechanics, molecular dynamics and quantum mechanical calculations of rotational strength afforded a clear picture of the modes of association of the LA neutral molecule to HSA, evidencing specific interactions with protein amino acids and their photophysical consequences. The drug is primarily associated in subdomain IIA where a strong interaction with Trp214 is established. At least two different positions of LA with respect to tryptophan are possible, one with the phenolic ring of the drug facing the aromatic ring of Trp214 and the other with the methoxyphenolic ring of LA in proximity to Trp214. In both cases LA is at ca. 4 angstroms from Trp214. This vicinity does not affect much the S1 singlet state deactivation of the bound drug, which exhibits a slightly higher fluorescence quantum yield and fluorescence lifetime on the order of that of the free molecule. The LA triplet lifetime appears to be somewhat shortened in this site. The secondary binding site is in subdomain IIIA. Here, the carbonyl group of LA experiences a strong H-bond with the OH-phenolic substituent of Tyr411. This interaction reduces substantially the LA molecular degrees of freedom, thereby determining a decrease of both radiative and nonradiative rate constants for decay of the singlet. The overall rigidity of the structure causes a lengthening of the triplet lifetime. 相似文献
954.
Gaining an insight into the photoreactivity of a drug in a protein environment: a case study on nalidixic acid and serum albumin 总被引:1,自引:0,他引:1
Monti S Manet I Manoli F Capobianco ML Marconi G 《The journal of physical chemistry. B》2008,112(18):5742-5754
The binding of nalidixic acid (NA) with human and bovine serum albumin (HSA and BSA) in buffer solution at pH 7.4 was investigated using circular dichroism (CD), UV absorption and fluorescence spectroscopy. Global analysis of multiwavelength spectroscopic data afforded the equilibrium constants of the most stable noncovalent drug/protein adducts of 1:1 and 2:1 stoichiometry and their individual CD, UV absorption, and fluorescence spectra. The primary binding site of the drug was located in subdomain IIIA (Sudlow Site II), whereas the secondary one was assigned to subdomain IIA. Conformational and CD calculations afforded the binding geometries. In the complexes, the fluorescence of the protein was strongly quenched by energy transfer and that of the drug was suppressed by electron transfer. Laser flash photolysis at 355 nm evidenced the formation of a radical pair consisting of a tyroxyl radical (lambdamax = 410 nm) and a reduced nalidixate anion radical NA(2-)* (lambdamax = 640 nm) with quantum yield of 0.4-0.5. Strong evidence was obtained that the process that involves Tyr411 in HSA (Tyr409 in BSA). A further transient with lambdamax approximately 780 nm observed in HSA was attributed to oxidation of the -(S200-S246)- bridge upon electron transfer to NA(-)*. Decay of the confined radical pairs occurred with rates approximately 10(7) s(-1). Formation of covalent drug-protein adducts in mixtures irradiated at lambdairr> 324 nm was proved using HPLC with fluorescence detection. 相似文献
955.
Corsaro C Spooren J Branca C Leone N Broccio M Kim C Chen SH Stanley HE Mallamace F 《The journal of physical chemistry. B》2008,112(34):10449-10454
Proton nuclear magnetic resonance (1H NMR) experiments have been performed to measure the spin-lattice, T1, and spin-spin, T2, relaxation times of the three functional groups in water/methanol mixtures at different methanol molar fractions (XMeOH=0, 0.04, 0.1, 0.24, 0.5, 1) as a function of temperature in the range 205 K相似文献
956.
We describe a simple, rapid combined method for extracting the antimalarial compound artemisinin from the leaves of Artemisia annua L. cultivated for the first time in Burundi, and quantitating the active principle by high-performance liquid chromatography-electrospray mass spectrometry. 相似文献
957.
Markovitch O Chen H Izvekov S Paesani F Voth GA Agmon N 《The journal of physical chemistry. B》2008,112(31):9456-9466
Conditional and time-dependent radial distribution functions reveal the details of the water structure surrounding the hydronium during the proton mobility process. Using this methodology for classical multistate empirical valence bond (MS-EVB) and ab initio molecular dynamics trajectories, as well as quantal MS-EVB trajectories, we supply statistical proof that proton hops in liquid water occur by a transition from the H3O+[3H2O] Eigen-complex, via the H5O2+ Zundel-complex, to a H3O+[3H2O] centered on a neighboring water molecule. In the "resting period" before a transition, there is a distorted hydronium with one of its water ligands at a shorter distance and another at a longer distance than average. The identity of this "special partner" interchanges rapidly within the three first-shell water ligands. This is coupled to cleavage of an acceptor-type hydrogen bond. Just before the transition, a partner is selected by an additional translation of the H3O+ moiety in its direction, possibly enabled by loosening of donor-type hydrogen bonds on the opposite side. We monitor the transition in real time, showing how the average structure is converted to a distorted H5O2+ cation constituting the transitional complex for proton hopping between water molecules. 相似文献
958.
959.
Francesco P. Ballistreri Gaetano A. Tomaselli Rosa M. Toscano 《Tetrahedron letters》2008,49(20):3291-3293
Aromatic and aliphatic thiols are oxidized in acetonitrile at 20 °C by hydrogen peroxide in the presence of methyltrioxorhenium as the catalyst to yield the corresponding sulfonic acids in high isolated yields (85-94%). 相似文献
960.
Enea Pagliano Claudio Broglia Miguel Molero Casado Francesco Malatesta 《Journal of solution chemistry》2008,37(10):1393-1409
Activity coefficients of the highly charged electrolytes Mgds, La2ds3, and [Co(en)3]2ds3 (en = ethylenediamine, ds2−=1,5-naphthalenedisulfonate anion), were determined at 298.15 K using liquid-membrane cells. These salts are found not to
display large negative deviations from the Debye-Hückel limiting slope in the dilute regions, which characterize the corresponding
sulfate salts. Theoretical calculations based on the primitive model (charged hard spheres in an unstructured dielectric medium)
reproduce the behavior of these salts correctly up to concentrations of 0.01 mol⋅kg−1 or more (0.1 mol⋅kg−1 for Mgds), although ds2−, far from resembling a charged sphere, is a planar ion with charges distant from one another. The Pitzer model parameter
values are reported for the activity and osmotic coefficients. 相似文献