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991.
The mechanism of the generation of dioxygen at the oxygen-evolving complex (OEC) of photosystem II (PSII), a crucial step in photosynthesis, is still under debate. The simplest unit present in the OEC that can produce O2 is a dinuclear oxo-bridge manganese complex within the tetranuclear Mn4 cluster. In this paper we report a theoretical study of the model complexes [Mn2(mu-O)2(NH3)6(H2O)2]n+ (n = 2-5), for which density functional calculations have been carried out for several electronic configurations. The molecular orbital picture deduced from the calculations indicates that one-electron oxidation of the Mn2IV,IV/(O2-)2 complex (n = 4) mostly affects the oxygen atoms, thus ruling out the existence of a MnV oxidation state in this context, while the incipient formation of an O-O bond in the O2(3-) transient species evolves exothermally toward the dissociation of dioxygen and a Mn2II,III couple. These results identify the electronic features that could be needed to enable an intramolecular mechanism of oxygen-oxygen bond formation to exist at the OEC during photosynthesis. 相似文献
992.
Bernhardt PV Bozoglian F Macpherson BP Martínez M Merbach AE González G Sienra B 《Inorganic chemistry》2004,43(22):7187-7195
The outer-sphere oxidation of Fe(II) in the mixed-valence complex trans-[L(14S)Co(III)NCFe(II)(CN)(6)](-), being L(14S) an N(3)S(2) macrocylic donor set on the cobalt(III) center, has been studied. The comparison with the known processes of N(5) macrocycle complexes has been carried out in view of the important differences occurring on the redox potential of the cobalt center. The results indicate that the outer-sphere oxidation reactions with S(2)O(8)(2-) and [Co(ox)(3)](3-) involve a great amount of solvent-assisted hydrogen bonding that, as a consequence from the change from two amines to sulfur donors, are more restricted. This is shown by the more positive values found for DeltaS(#) and DeltaV(#). The X-ray structure of the oxidized complex has been determined, and it is clearly indicative of the above-mentioned solvent-assisted hydrogen bonding between nitrogen and cyanide donors on the cobalt and iron centers, respectively. trans-[L(14S)Co(III)NCFe(III)(CN)(6)], as well as the analogous N(5) systems trans-[L(14)Co(III)NCFe(III)(CN)(6)], trans-[L(15)Co(III)NCFe(III)(CN)(6)], and cis-[L(13)Co(III)NCFe(III)(CN)(6)], oxidize water to hydrogen peroxide at pH > 10 with a rather simple stoichiometry, i.e., [L(n)()Co(III)NCFe(III)(CN)(5)] + OH(-) --> [L(n)()Co(III)NCFe(II)(CN)(5)](-) + (1)/(2)H(2)O(2). In this way, the reversibility of the iron oxidation process is achieved. The determination of kinetic and thermal and pressure activation parameters for this water to hydrogen peroxide oxidation leads to the kinetic determination of a cyanide based OH(-) adduct of the complex. A second-order dependence on the base concentration is associated with deprotonation of this adduct to produce the final inner-sphere reduction process. The activation enthalpies are found to be extremely low (15 to 35 kJ mol(-1)) and responsible for the very fast reaction observed. The values of DeltaS(#) and DeltaV(#) (-76 to -113 J K(-1) mol(-1) and -5.5 to -8.9 cm(3) mol(-1), respectively) indicate a highly organized but not very compressed transition state in agreement with the inner-sphere one-electron transfer from O(2-) to Fe(III). 相似文献
993.
The response of a molecule to an applied external magnetic field can be evaluated by a graphical representation of the induced magnetic field. We have applied this technique to four representative, cyclic organic molecules, that is, to aromatic (C(6)H(6), D(6h)), anti-aromatic (C(4)H(4), D(2h)) and non-aromatic (C(4)H(8), D(4h), and C(6)H(12), D(3d)) molecules. The results show that molecules that contain a pi system possess a long-range magnetic response, while the induced magnetic field is short-range for molecules without pi systems. The induced magnetic field of aromatic molecules shields the external field. In contrast, the anti-aromatic molecules increase the applied field inside the ring. Aromatic, anti-aromatic, and non-aromatic molecules can be characterized by the appearance of the magnetic response. We also show that the magnetic response is directly connected to nucleus-independent chemical shifts (NICS). 相似文献
994.
Gabriel FergusonAbdelaziz Nait Ajjou 《Tetrahedron letters》2003,44(51):9139-9142
The catalytic system composed of CuCl2 and 2,2′-biquinoline-4,4′-dicarboxylic acid dipotassium salt (BQC), was found to be highly efficient for the selective oxidation of secondary benzylic, allylic and propargylic alcohols to the corresponding ketones, with aqueous t-butyl hydroperoxide under phase-transfer catalysis conditions. The catalytic system is stable and can be recycled and reused several times without loss of activity. 相似文献
995.
Gabriel P. de Carvalho e Silveira 《Tetrahedron letters》2005,46(38):6477-6481
We describe herein a new and straightforward enantioselective approach to R-(+)-2-ethyl-2,3-dihydrofuran carboxylic acid, the direct precursor of (+)-efaroxan, an α2 adrenoreceptor antagonist, which is indicated to be used for the treatment of neurodegenerative diseases (Alzheimer and Parkinson), migraine and type II diabetes. Our goal was accomplished using a Baylis-Hillman adduct as starting material. The dihydrobenzofuran acid was obtained in eight steps with an overall yield of 14%. 相似文献
996.
Cyclohexane (1), oxygen-, sulfur-, and/or nitrogen-containing six-membered heterocycles 2-5, cyclohexanone (6), and cyclohexanone derivatives 7-16 were studied theoretically [B3LYP/6-31G(d,p) and PP/IGLO-III//B3LYP/6-31G(d,p) methods] to determine the structural (in particular C-H bond distances) and spectroscopic (specifically, one bond (1)J(C-H) NMR coupling constants) consequences of stereoelectronic hyperconjugative effects. The results confirm the importance of n(X) --> sigma*(C-H)(app) (where X = O, N), sigma(C-H)(ax) --> pi*(C=O), sigma(S-C) --> sigma*(C-H)(app), sigma(C-S)-->sigma*(C-H)(app), beta-n(O) --> sigma*(C-H), and sigma(C-H) --> sigma*(C-H)(app) hyperconjugation, as advanced in previous theoretical models. Calculated r(C-H) bond lengths and (1)J(C-H) coupling constants for C-H bonds participating in more than one hyperconjugative interaction show additivity of the effects. 相似文献
997.
Water-soluble gadofullerenes: toward high-relaxivity, pH-responsive MRI contrast agents 总被引:6,自引:0,他引:6
Tóth E Bolskar RD Borel A González G Helm L Merbach AE Sitharaman B Wilson LJ 《Journal of the American Chemical Society》2005,127(2):799-805
The water-soluble endohedral gadofullerene derivatives, Gd@C(60)(OH)(x) and Gd@C(60)[C(COOH)(2)](10), have been characterized with regard to their MRI contrast agent properties. Water-proton relaxivities have been measured in aqueous solution at variable temperature (278-335 K), and for the first time for gadofullerenes, relaxivities as a function of magnetic field (5 x 10(-4) to 9.4 T; NMRD profiles) are also reported. Both compounds show relaxivity maxima at high magnetic fields (30-60 MHz) with a maximum relaxivity of 10.4 mM(-1) s(-1) for Gd@C(60)[C(COOH)(2)](10) and 38.5 mM(-1) s(-1) for Gd@C(60)(OH)(x) at 299 K. Variable-temperature, transverse and longitudinal (17)O relaxation rates, and chemical shifts have been measured at three magnetic fields (B = 1.41, 4.7, and 9.4 T), and the results point exclusively to an outer sphere relaxation mechanism. The NMRD profiles have been analyzed in terms of slow rotational motion with a long rotational correlation time calculated to be tau(R)(298) = 2.6 ns. The proton exchange rate obtained for Gd@C(60)[C(COOH)(2)](10) is k(ex)(298) = 1.4 x 10(7) s(-1) which is consistent with the exchange rate previously determined for malonic acid. The proton relaxivities for both gadofullerene derivatives increase strongly with decreasing pH (pH: 3-12). This behavior results from a pH-dependent aggregation of Gd@C(60)(OH)(x) and Gd@C(60)[C(COOH)(2)](10), which has been characterized by dynamic light scattering measurements. The pH dependency of the proton relaxivities makes these gadofullerene derivatives prime candidates for pH-responsive MRI contrast agent applications. 相似文献
998.
Zhang F Baralia G Boborodea A Bailly C Nysten B Jonas AM 《Langmuir : the ACS journal of surfaces and colloids》2005,21(16):7427-7432
The effect of roughness on the dewetting behavior of polyethylene thin films on silicon dioxide substrates is presented. Smooth and rough silicon dioxide substrates of 0.3 and 3.2-3.9 nm root-mean-square roughness were prepared by thermal oxidation of silicon wafers and plasma-enhanced chemical vapor deposition on silicon wafers, respectively. Polymer thin films of approximately 80 nm thickness were deposited by spin-coating on these substrates. Subsequent dewetting and crystallization of the polyethylene were observed by hot-stage optical microscopy in reflection mode. During heating, the polymer films melt and dewet on both substrates. Further observations after cooling indicate that, whereas complete dewetting occurs on the smooth substrate surface, partial dewetting occurs for the polymer film on the rough surface. The average thickness of the residual film on the rough surface was determined by ellipsometry to be a few nanometers, and the spatial distribution of the polymer in the cavities of the rough surface could be obtained by X-ray reflectometry. The residual film originates from the impregnation of the porous surface by the polymer fluid, leading to the observed partial dewetting behavior. This new type of partial dewetting should have important practical consequences, as most real surfaces exhibit significant roughness. 相似文献
999.
Bowen GJ Chesson L Nielson K Cerling TE Ehleringer JR 《Rapid communications in mass spectrometry : RCM》2005,19(17):2371-2378
The structural proteins that comprise approximately 90% of animal hair have the potential to record environmentally and physiologically determined variation in delta2H and delta18O values of body water. Broad, systematic, geospatial variation in stable hydrogen and oxygen isotopes of environmental water and the capacity for rapid, precise measurement via methods such as high-temperature conversion elemental analyzer/isotope ratio mass spectrometry (TC/EA-IRMS) make these isotope systems particularly well suited for applications requiring the geolocation of hair samples. In order for such applications to be successful, however, methods must exist for the accurate determination of hair delta2H and delta18O values reflecting the primary products of biosynthesis. Here, we present the results of experiments designed to examine two potential inaccuracies affecting delta2H and delta18O measurements of hair: the contribution of non-biologic hydrogen and oxygen to samples in the form of sorbed molecular water, and the exchange of hydroxyl-bound hydrogen between hair keratin and ambient water vapor. We show that rapid sorption of molecular water from the atmosphere can have a substantial effect on measured delta2H and delta18O values of hair (comprising approximately 7.7% of the measured isotopic signal for H and up to approximately 10.6% for O), but that this contribution can be effectively removed through vacuum-drying of samples for 6 days. Hydrogen exchange between hair keratin and ambient vapor is also rapid (reaching equilibrium within 3-4 days), with 9-16% of the total hydrogen available for exchange at room temperature. Based on the results of these experiments, we outline a recommended sample treatment procedure for routine measurement of delta2H and delta18O in mammal hair. 相似文献
1000.
Rodriguez-Rivera GJ Kim WB Evans ST Voitl T Dumesic JA 《Journal of the American Chemical Society》2005,127(31):10790-10791
Aqueous polyoxometalate (H3PMo12O40) solution reduced by CO with liquid water using gold nanoparticle catalysts at room temperature, which contains protons in liquid water and electrons associated with the reduced polyoxometalate, can produce gaseous H2 or can hydrogenate benzene over an electrochemical cell consisting of a simple carbon anode, a proton-exchange membrane, and a Pt- or Rh-based cathode. In the present cell, H2 can be produced from the reduced H3PMo12O40 solution at voltages that are lower by about 1.15 V compared to water electrolysis. 相似文献