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981.
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
982.
Robert G. Behrens 《Journal of organometallic chemistry》1976,121(3):C63-C65
The results of low temperature heat capacity studies on Mn2(CO)10(s) and Re2(CO)10(s) are compared with literature reports. It is shown that the values of vaporization enthalpies and entropies correspond with those of the low temperature stable phase. 相似文献
983.
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
984.
Jeong Hwan Kim Ji Hoon Ko Byeong-Soo Bae 《Journal of Sol-Gel Science and Technology》2007,41(3):249-255
Multi-scale hybrid nanocomposites containing both ∼15 nm silica colloids and ∼2 nm oligosiloxanes in a methacryl polymer matrix
were newly designed and fabricated. Colloidal silica sols were dispersed in methacryl oligosiloxanes nano-hybrid resins synthesized
by sol-gel reaction of methacryloxypropylmethoxysilane and diphenylsilanediol. On the basis of TEM and SANS analyses, it was
confirmed that the silica colloids were compatibly dispersed and different sizes of colloidal silica and oligosiloxanes co-exist
in the solutions. Multi-scale hybrid nanocomposites fabricated by UV and thermal curing with incorporation of silica colloids
in the nano-hybrid materials show enhanced mechanical and thermal characteristics. 相似文献
985.
YU Ming XU Qiang School of Materials Science Engineering East China University of Science Technology Shanghai China 《Chinese Journal of Reactive Polymers》2006,(1)
1. INTRODUCTIONThese years, HCFC-141b may be the most used blowing agent for its useful properties. But, because of its high global warming effect leading to the destruction of the ozone layer, production of HCFC141b has been forbidden. However, there are… 相似文献
986.
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
987.
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
988.
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
989.
Ivar Ugi Johannes Bauer Klemens Bley Alf Dengler Andreas Dietz Eric Fontain Bernhard Gruber Rainer Herges Michael Knauer Klaus Reitsam Natalie Stein 《Angewandte Chemie (International ed. in English)》1993,32(2):201-227
The topic of this article is the development and the present state of the art of computer chemistry, the computer-assisted solution of chemical problems. Initially the problems in computer chemistry were confined to structure elucidation on the basis of spectroscopic data, then programs for synthesis design based on libraries of reaction data for relatively narrow classes of target compounds were developed, and now computer programs for the solution of a great variety of chemical problems are available or are under development. Previously it was an achievement when any solution of a chemical problem could be generated by computer assistance. Today, the main task is the efficient, transparent, and non-arbitrary selection of meaningful results from the immense set of potential solutions—that also may contain innovative proposals. Chemistry has two aspects, constitutional chemistry and stereochemistry, which are interrelated, but still require different approaches. As a result, about twenty years ago, an algebraic model of the logical structure of chemistry was presented that consisted of two parts: the constitution-oriented algebra of be- and r-matrices, and the theory of the stereochemistry of the chemical identity group. New chemical definitions, concepts, and perspectives are characteristic of this logic-oriented model, as well as the direct mathematical representation of chemical processes. This model enables the implementation of formal reaction generators that can produce conceivable solutions to chemical problems—including unprecedented solutions—without detailed empirical chemical information. New formal selection procedures for computer-generated chemical information are also possible through the above model. It is expedient to combine these with interactive methods of selection. In this review, the Munich project is presented and discussed in detail. It encompasses the further development and implementation of the mathematical model of the logical structure of chemistry as well as the experimental verification of the computer-generated results. The article concludes with a review of new reactions, reagents, and reaction mechanisms that have been found with the PC-programs IGOR and RAIN. 相似文献
990.
Bifurcations of reaction channels are related to valley-ridge inflection points and it is examined what happens when these do not coincide with transition states. Under such conditions there result bifurcating regions. There exist a number of different prototypes for such regions which are discussed explicitly on the basis of the pertinent Taylor expansions. When bifurcations occur close enough to transition states then there result bifurcating transition regions. An example for a bifurcating transition region is exhibited which is obtained from a quantum mechanical ab initio calculation for the ring opening of cyclopropylidene to aliene. In general there exist no orthogonal trajectory patterns which could serve as simplified models for channel bifurcations.Operated for the U.S. Department of Energy by Iowa State University under Contract No. W-7405-ENG-82. This work was supported by the Office of Basic Energy Sciences 相似文献