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991.
Song -Cheng Sun David E. Reed John K. Cullison Lyman H. Rickard Fred M. Hawkridge 《Mikrochimica acta》1988,96(1-6):97-104
The heterogeneous electron transfer reactions of cytochromec occurring at platinum, gold and mercury electrodes are shown to be quasi-reversible. In each case the electrodes have not been modified and the cytochromec samples are native. This work extends previous work and demonstrates that biological molecule electron transfer reactions can be studied at clean metal surfaces to gain fundamental knowledge of the mechanisms of these reactions. 相似文献
992.
Two published procedures for glass capillary column production are applied to produce capillaries for chromatography of polar natural compounds. Soda lime glass capillaries, after leaching with aqueous HCL, are either treated with colloidal silicic acid or with barium carbonate and coated with either Silar 7CP or SE 52. A test mixture as well as polar carbohydrate and peptide mixtures are chromatographed on the different columns and their chromatographic properties are evaluated. Combined capillary gas chromatography-electron impact and chemical ionization mass spectrometry are used for identification of the peptide sequence. 相似文献
993.
D. V. Aleksanyan V. A. Kozlov I. L. Odinets P. V. Petrovskii T. A. Mastryukova 《Russian Chemical Bulletin》2007,56(5):1049-1052
Diethoxyphosphorylthioacetamide in the reaction with 2,3-dichloroquinoxaline acted as a thionating reagent, giving diethoxyphosphorylacetonitrile
and 2-chloro-3-[(3-chloro-2-quinoxalinyl)thio]quinoxaline. Reactions of phosphorylthioacetamides with N-methylquinoxalinium iodide in alcohol media in the presence of a base proceeded stereoselectively to afford cis-3-phosphoryl-1,3,3a,4,9,9a-hexahydro-2H-pyrrolo[2,3-b]quinoxaline-2-thiones.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1010–1013, May, 2007. 相似文献
994.
There are particular benefits in spectrum simulation for the interpretation of characteristic X-ray peaks below about 2 keV
in energy, where peak overlaps, a sloping background and changing detector efficiency make it difficult to measure true peak
intensities. Despite these difficulties, we have shown that a useful accuracy of simulation is possible without major revision
of the existing theory, allowing the electron microprobe user to compare on-line a measured spectrum with one synthesised
from an assumed sample composition.
As part of a wider study, we have used a database of X-ray spectra from 150 samples of known composition to confirm the accuracy
of simulation over the energy range from 0.28–1.9 keV, finding an RMS error of better than 8%. The database included 181 Kα,
Lα and Mα peaks from elements of atomic number 6–77, excited by beam voltages from 5–30 kV. Central to the method is the use
of the ratio of (Peak Intensity)/(Total Background Intensity), which allows spectra to be compared from instruments of differing
collection efficiency, thereby easing the collection of data over a wide range of conditions.
Examples are given to illustrate the use of the simulator in helping to choose the best conditions for analysis, and as an
aid in interpreting the spectra so obtained. Both modes of operation are iterative in nature and require a fast and accurate
simulator that is easy to use. Further development will be guided by experience in its use. 相似文献
995.
Enkhtsetseg Dashjav Guido Kreiner Walter Schnelle Frank R. Wagner Rüdiger Kniep 《无机化学与普通化学杂志》2004,630(5):689-696
Carbometalates: Complex Anions equation/tex2gif-stack-4.gif [MoC4/26—] in the Crystal Structure of Pr equation/tex2gif-stack-5.gif [MoIIC2] Criteria for the existence of carbometalates are established and discussed in a broader context. The concept is then applied to the novel compound Pr2[MoC2], which is characterized by chemical analyses, X‐ray diffraction and metallography. The crystal structure (tetragonal, P42/mnm, Z = 4, a = 581.29(8) pm, c = 1032.53(14) pm) consists of layered polyanions equation/tex2gif-stack-6.gif[MoC4/26—] of distorted vertex and edge sharing MoC4 tetrahedra. Praseodymium is also in a distorted tetrahedral coordination by carbon. The physical properties show “bad metal” behaviour and localized magnetic 4f‐moments in agreement with the existence of Pr3+‐species. A detailed bonding analysis using both the electron localization function ELF and the COHP method justifies the interpretation of the title compound as a carbomolybdate(II). 相似文献
996.
Luis A.?León Rafael?Notario Jairo?QuijanoEmail author Ederley?Vélez Claudia?Sánchez J. Camilo?Quijano Nouria?Al-Awadi 《Theoretical chemistry accounts》2003,110(6):387-394
Theoretical studies on the thermolysis in the gas phase of 4-arylideneimino-1,2,4-triazol-3(2H)-ones and 4-arylideneimino-1,2,4-triazol-3(2H)-thiones were carried out using density functional theory methods, at the B3LYP/6-31G(d) and B3LYP/6-311+G(2d,p) levels of theory. The proposed reaction mechanism occurs in one step, leading to the formation of 3-hydroxy-(2H)-1,2,4-triazole or 3-mercapto-(2H)-1,2,4-triazole and a 4-substituted benzonitrile, via a six-membered cyclic transition state. The progress of the reactions was followed by means of the Wiberg bond indices. The results indicate that the transition states have character intermediate between reactants and products, and the calculated synchronicities show that the reactions are slightly asynchronous, in the case of triazolones, and show a higher asynchronicity in the case of triazolthiones. The bond-breaking processes are slightly more advanced than the bond-forming ones, indicating a small bond deficiency in the transition states. Kinetic and activation parameters for the reactions studied have been calculated and compared with available experimental data.From the Proceedings of the 28th Congreso deQuímicos Teóricos de Expresión Latina (QUITEL 2002) 相似文献
997.
L. A. Leites A. V. Zabula S. S. Bukalov P. S. Koroteev O. S. Maslennikova M. P. Egorov O. M. Nefedov 《Russian Chemical Bulletin》2005,54(5):1117-1120
The vibrational spectra of tetravalent metal halides (M = Si, Ge, Sn) and the corresponding dihalocarbene analogs MIIHal2, obtained by the authors, and the relevant published data are compared. The spectra of the MIIHal2 species exhibit inversion of the M-Hal stretching frequencies (νs(MIIHal) > ν as(MIIHal)). This can be used for analytical purposes and allows one to distinguish between the spectra of the MIV and MII halides. The IR and Raman spectra of the complexes of dihalogermylenes and -stannylenes with triphenylphosphine and 1,4-dioxane
also exhibit inversion of the ν(MHal) stretching frequencies. This confirms the conclusion drawn earlier based on the analysis
of the geometric parameters and reactivities of the complexes in question that the divalent state of the M atom in these species
is retained.
Dedicated to Academician N. K. Kochetkov on the occasion of his 90th birthday.
__________
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1089–1092, May, 2005. 相似文献
998.
F. Sigeneger Yu. B. Golubovskii I. A. Porokhova R. Winkler 《Plasma Chemistry and Plasma Processing》1998,18(2):153-180
The nonlocal behavior of the electrons in strongly modulated and period-averaged electric fields typical of s- and p-striations in neon glow discharge plasmas is investigated by numerically solving the axially inhomogeneous electron Boltzmann equation. A good agreement between the period lengths measured in the striations and those obtained from the spatially periodic electron relaxation in the period-averaged field of the striations is found confirming the close relation of both phenomena. The s- and p-striations represent the fundamental and first harmonics of the inherent periodic electron relaxation. Furthermore, starting from different boundary conditions the establishment of the velocity distribution function and of selected macroscopic quantities of the electrons into unique periodic states under the action of strongly modulated striation-like fields is investigated. It is shown that the same damping processes that cause in homogeneous fields a relaxation into homogeneous states lead to unique periodic states in strongly modulated fields. 相似文献
999.
A. Müller E. Krickemeyer F. El-Katri D. Rehder A. Stammler H. Bgge F. Hellweg 《无机化学与普通化学杂志》1995,621(7):1160-1170
Simple Trithio- and Perthiocarbonato Complexes with Interesting Bond Properties: [E(CS3)2]2? (E = Sn, Zn, Cd), [E(CS3)3]3? (E = As, Sb, Bi, Co), {Cu(CS3)?}∞ and [Zn(CS4)2]2? By reactions of potassium trithiocarbonate ( 1 ) with solutions of zinc(II)- acetylacetonate, cadmium(II)-chloride, tin(II)-chloride, arsenic(III)-sulfide (suspension), antimony(III)-chloride, bismuth(III)-chloride and copper(II)-chloride in dimethyl sulfoxide, as well as of trisodium hexanitrito cobaltate(III) in water, and the precipitation of the complexes with an aqueous solution of tetraphenylphosphonium chloride the compounds (PPh4)2[Zn(CS3)2] ( 2 ), (PPh4)2[Cd(CS3)2] ( 3 ), (PPh4)2[Sn(CS3)2] ( 4 ), (PPh4)3[As(CS3)3] ( 5 ), (PPh4)3[Sb(CS3)3] ( 6 ), (PPh4)3[Bi(CS3)3] ( 7 ), (PPh4)3[Co(CS3)3] ( 8 ) and (PPh4)Cu(CS3) ( 9 ) have been isolated. (PPh4)2[Zn(CS4)2] · CH3NO2 ( 10 ) has been prepared by heating a solution of 2 in nitromethane to 60--70°C in presence of air. The reaction of 1 in dimethyl sulfoxide with an aqueous tetraphenylphosphonium chloride solution in presence of oxygen leads to (PPh4)2[C2S6] ( 11 ). The compounds have been characterized by spectroscopical studies (IR, Raman, UV/Vis, 113Cd/59Co-NMR), magnetic susceptibility measurements, powder diffractometry, elemental analyses and single crystal X-ray structure analysis ( 4 – 7 , 10 and 11 ). The difficult growing of single crystals has been reported in detail. For crystal data see Inhaltsübersicht. 相似文献
1000.
Marjan Kočevar Bojan Verček Branko Stanovnik Miha Tišler 《Monatshefte für Chemie / Chemical Monthly》1982,113(6-7):731-744
Pyrazine- and pyridinecarboxamidoximes with an amino, potentially tautomeric hydroxy or mercapto group inortho position could be transformed in the appropriate condensed azines. In this manner, representatives of pyrazolo(3,4-b)pyrazine, isoxazolo(4,5-b)pyrazine and isothiazolo(5,4-b)pyridine ring system were synthesized and some transformations investigated.Presented in part at the 8th International Congress of Heterocyclic Chemistry, Graz, 1981. 相似文献