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111.
Rosu F Gabelica V Houssier C Colson P Pauw ED 《Rapid communications in mass spectrometry : RCM》2002,16(18):1729-1736
DNA triplex and quadruplex structures have been successfully detected by electrospray ionization mass spectrometry (ESI-MS). Circular dichroism and UV-melting experiments show that these structures are stable in 150 mM ammonium acetate at pH 7 for the quadruplexes and pH 5.5 for the triplexes. The studied quadruplexes were the tetramer [d(TGGGGT)](4), the dimer [d(GGGGTTTTGGGG)](2), and the intramolecular folded strand dGGG(TTAGGG)(3), which is an analog of the human telomeric sequence. The absence of sodium contamination allowed demonstration of the specific inclusion of n - 1 ammonium cations in the quadruplex structures, where n is the number of consecutive G-tetrads. We also detected the complexes between the quadruplexes and the quadruplex-specific drug mesoporphyrin IX. MS/MS spectra of [d(TGGGGT)](4) and the complex with the drug are also reported. As the drug does not displace the ammonium cations, one can conclude that the drug binds at the exterior of the tetrads, and not between them. For the triplex structure the ESI-MS spectra show the detection of the specific triplex, at m/z values typically higher than those typically observed for duplex species. Upon MS/MS the antigene strand, which is bound into the major groove of the duplex, separates from the triplex. This is the same dissociation pathway as in solution. To our knowledge this is the first report of a triplex DNA structure by electrospray mass spectrometry. 相似文献
112.
A. A. Vilisov V. P. Germogenov N. K. Maksimova L. E. Épiktetova 《Russian Physics Journal》1980,23(4):284-289
A calculation is made of the dependences of the coefficient of the tellurium distribution KTe and the electron concentration n in AlxGa1–xSb on the composition of the solid solution and the growth temperature. It is shown that KTe must decrease with increasing x. The dependence of KTe on the temperature is also determined by x. Experimental results were obtained on AlxGa1–x Sb (0 x 0.74) films grown by liquid epitaxy. The electron concentration in the films was measured through the thermoelectric power and the capacitance-voltage characteristics of Schottky barriers. Satisfactory agreement with the results of the calculation was obtained.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 4, pp. 19–25, April, 1980.We thank G. K. Arbuzov for assistance in preparing the surface-barrier structures. 相似文献
113.
The new mercury vanadium phosphate hydrate Hg(4)(-)(x)()O(1)(-)(y)()(VO)(PO(4))(2).H(2)O has been synthesized under hydrothermal conditions. X-ray investigations led to orthorhombic symmetry, space group P2(1)2(1)2(1) (No. 19), a = 6.3632(2) A, b = 12.4155(5) A, c = 14.2292(6) A, Z = 4. The crystal structure was solved and refined from single-crystal diffractometer data to residuals R[F(2) > 2sigmaF(2)] = 0.039, R(w)(F(2)) = 0.055. The VPO framework consists of infinite one-dimensional [VO(PO(4))(2)]( infinity ) chains with corner-connected VO(6) octahedra and PO(4) tetrahedra. The chains run along the [100] direction and are held together by the unprecedented tetrahedral cationic units [Hg(4)(-)(x)()O(1)(-)(y)()](4+). Presence of Hg-Hg bonding contacts is proved from theoretical calculations. 相似文献
114.
Érika Pinto Marinho A. G. Souza Danniely S. de Melo Iêda M. G. Santos Dulce M. A. Melo Walquíria J. da Silva 《Journal of Thermal Analysis and Calorimetry》2007,87(3):801-804
Because
of their electrical, magnetic and catalytic properties rare earth and transition
metal mixed oxides are important compounds. Lanthanum chromites have been
extensively used as solid oxide fuel cell (SOFC) interconnect materials. In
this work, lanthanum chromites partially substituted by alkaline earth metals
were synthesized by the urea combustion process. TG and DSC techniques were
used to evaluate the presence of the organic material in the powder after
reaction on the hot plate. The powders were calcinated at 900°C and characterized
by XRD and SEM. The results show that the particles have nanometric dimensions
and the perovskite structure was formed. 相似文献
115.
Chlorine trioxide, Cl(2)O(6), reacts with Au metal, AuCl(3), or HAuCl(4).nH(2)O to yield the well-defined chloryl salt, ClO(2)Au(ClO(4))(4). The crystal and molecular structure of ClO(2)Au(ClO(4))(4) was solved by a Rietveld analysis of powder X-ray diffraction data. The salt crystallizes in a monoclinic cell, space group C2/c, with cell parameters a = 15.074(5), b = 5.2944(2), and c = 22.2020(2) A and beta = 128.325(2) degrees. The structure displays discrete ClO(2)(+) ions lying in channels formed by Au(ClO(4))(4)(-) stacks. Au is located in a distorted square planar environment: Au-O = 1.87 and 2.06 A. [ClO(4)] groups are monodentate with ClO(b) = 1.53 and ClO(t) = 1.39 A (mean distances; O(b), oxygen bonded to Au; O(t), free terminal oxygen). A full vibrational study of the Au(ClO(4))(4)(-) anion is supported by DFT calculations. 相似文献
116.
Jerkiewicz G DeBlois M Radovic-Hrapovic Z Tessier JP Perreault F Lessard J 《Langmuir : the ACS journal of surfaces and colloids》2005,21(8):3511-3520
The Pt(111) electrode is modified by an overlayer of C6H6 (ads) upon its cycling in the 0.05-0.80 V range in aq H2SO4 + 1 mM C6H6. The C6H6 (ads) overlayer significantly changes the underpotential-deposited H (H(UPD)) and anion adsorption, and cyclic-voltammetry (CV) profiles show a sharp cathodic peak and an asymmetric anodic one in the 0.05-0.80 V potential range. The C6H6 (ads) layer blocks the (bi)sulfate adsorption but facilitates the adsorption of one monolayer of H(UPD). Cycling of the benzene-modified Pt(111) in benzene-free aq 0.05 H2SO4 from 0.05 to 0.80 V results in a partial desorption of C6H6 (ads) and in a partial recovery of the CV profile characteristic of an unmodified Pt(111). The peak potential of the cathodic and anodic feature is independent of the scan rate, s (10 < or = s < or = 100 mV s(-1)), and the peak current density increases linearly with an increase of the scan rate. Temperature variation modifies the peak potential and current density but does not affect the charge density of the cathodic or anodic feature. Temperature-dependent studies allow us to determine the thermodynamic state function for the H(UPD) adsorption and desorption. Delta G degrees(ads)(H(UPD))assumes values from -4 to -12 kJ mol(-1), while has values from 9 to 14 kJ mol(-1). The values of delta Delta G degrees (delta Delta G degrees = delat Delta G degrees(ads) + delta Delta D degrees(des)) decrease almost linearly from 6 kJ mol(-1) at theta(H(UPD) --> 0 to 0 kJ mol(-1) at theta(H(UPD) --> 1. The nonzero values of delta Delta G degrees testify that the adsorbing and desorbing H(UPD) adatoms interact with an energetically different substrate. The lateral interactions changed from repulsive (omega = 29 kJ mol(-1) at theta(H(UPD) --> 0) to attractive (omega = -28 kJ mol(-1) at theta(H(UPD) --> 1) as the H(UPD) coverage increases. The values of delta S degrees(ads)(H(UPD)) increase from 19 to 56 J K(-1) mol(-1), while those of delta S degrees(des)(H(UPD)) decrease from 45 to -30 J K(-1) mol(-1) with an increase of H(UPD) coverage. The values of delta H degrees(des)(H(UPD)) and delta H degrees(des)(H(UPD)) vary from 0 to 27 kJ mol(-1). The Pt(111)-H(UPD) surface bond energy at the benzene-modified Pt(111) electrode falls in the 191-218 kJ mol(-1) range and is weaker than in the case of the unmodified Pt(111) electrode in the same electrolyte. 相似文献
117.
Laurent Soulre Pascal Hoffmanna Frdric Bringaud 《Journal of heterocyclic chemistry》2003,40(5):943-947
N‐(p‐Nitrophenoxy)carbonyl‐3‐morpholino‐sydnonimine (NCMS) has been prepared from 3‐morpholinosydnonimine hydrochloride. Using the Griess assay and the superoxide‐mediated reduction of ferricytochrome c, the nitric oxide (NO?) and superoxide anion (O2?‐) ‐ releasing properties in phosphate buffer pH 7.4 of this novel peroxynitrite donor was studied and compared with the known 3‐morpholino‐sydnonimine (SIN‐1). From compound NCMS, a series of N‐substituted sydnonimine derivatives were easily prepared that contain purine or melaminophenyl groups which specify a recognition by a trypanosomal purine transporter. The ability of these new sydnonimines to inhibit the uptake of [23H]adenosine on Trypanosoma equiperdum was studied. 相似文献
118.
Within the Born-Oppenheimer adiabatic perturbation theory, an equation was obtained for the intensity of fast electron scattering
by polyatomic molecules. All of its parameters are explicitly defined by vibronic interaction in a molecule; due to this,
quantum chemical calculations are fully applicable to electron diffraction studies of molecular geometries.
Engels Anti-Aircraft Missile Higher Military School. Translated fromZhurmal Strukturnoi Khimii, Vol. 35, No. 2, pp. 40–45, March–April, 1994.
Translated by L. Smolina 相似文献
119.
Eddy Thiriot Sébastien Canneaux Eric Hénon Frédéric Bohr 《Reaction Kinetics and Catalysis Letters》2005,85(1):123-129
Summary We show the presence of an ether group in alkoxy radicals significantly lowers the activation energy of the b-C-H dissociation and only slightly increases the isomerization barrier. Moreover, an 1-6 isomerization mechanism involving a 7-membered transition state may compete with the usual 1-5 isomerization. 相似文献
120.
Yu. B. Vysotskii V. V. Volodarets É. G. Éilazyan L. S. Gutyrya 《Theoretical and Experimental Chemistry》1995,31(4):184-188
A MINDO/3 calculation based on the Hartree—Fock perturbation theory gave the atom—atom self- and mutual polarizabilities of a series of hydrocarbons. A study was carried out on the effect of the perturbation-induced distortion of the electron—electron interaction and molecular relaxation on the calculated values.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 31, No. 4, pp. 227–231, July–August, 1995. 相似文献