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871.
The concentration dependence of the apparent molar volumes of lithium halides (and electrolytes in general) in alcohols (and
solvents permitting association in general) is, in the first instance, due to changes in the degree of association and to
the inherent difference between the apparent molar volumes of the ions and of the ion pairs. Previous publications on the
molar volumes of electrolytes in organic solvents, disregarding altogether ion pairing, appear to be incorrect. Data from
the literature for lithium chloride and lithium bromide in normal primary alcohols and several branched alcohols from C1 to C8 and data from our laboratory for lithium halides in 1-hexanol and 2-ethyl-1-hexanol served for the determination of φ
V
and φ
E
. Electrical and structural contributions to the values of these functions for the ions and for the ion pairs are discussed. 相似文献
872.
The free NH3 molecule and the [Zn(NH3)4]2+ ion were studied by the kinematic coupling approach. The pure effects of this coupling were found to be small, and some modifications had to be introduced in order to get a reasonable force field. The force constants deduced for the skeletal vibrations are comparable with those of a quasi-exact force field. Calculated frequencies for [68Zn(NH3)4]2+ and [64Zn(ND3)4]2+ are reported in addition to those of [64Zn(NH3)4]2+. Mean amplitudes of vibration for [64Zn(NH3)4]2+ are given. 相似文献
873.
Chloride1), borohydrides2) and hydrides3) of dicyclopentadienyl thallium (III) and diindenyl thallium (III) have already been reported. The present communication deals with a study on the preparation and characterization of difluorenyl thallium (III) chloride, -hydride and -borohydride. 相似文献
874.
Miss Itawati Pratanata L. R. Williams R. N. Williams 《Journal of mass spectrometry : JMS》1974,9(4):418-421
When subjected to electron-impact, chloromethyl aryl sulphones (II, X = Cl) fragment predominantly by the loss of CH2Cl from the molecular ion followed by the loss of SO2 and in most cases the appropriate metastable peaks are present to confirm the transitions. In addition, alkyl–oxygen bond formation in the molecular ion was revealed by the presence of prominent peaks corresponding to the [R? ?-SO]+ ions. In most spectra no evidence for aryl–oxygen bond formation could be found and thus the presence of the chlorine atom was able to effectively reverse the direction of skeletal rearrangement reported for aryl methyl sulphones. 相似文献
875.
876.
M. F. Shostakovskii A. S. Atavin E. P. Vyalykh B. A. Trofimov N. A. Vodhol'skaya V. V. Keiko 《Russian Chemical Bulletin》1966,15(7):1239-1240
Conclusions Cyclic alkoxysilanes — 1,3-dioxa-2-silacyclanes — and their oligomers are decomposed by organomagnesium compounds with the formation of the corresponding silanols (disiloxanes) and tetraalkylsilanols.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1283–1285, July, 1966. 相似文献
877.
A. A. Pud G. S. Shapoval V. K. Skubin N. V. Kondrashova Yu. V. Kontsur G. M. Tel'biz 《Theoretical and Experimental Chemistry》1989,25(6):653-658
A study has been made of the electrochemical reductive breakdown (ECRB) of solid-phase chlorinated butyl rubber (CBR). It has been established that CBR does not accept electrons under conditions of fast sweep of electrode potential; however, with prolonged cathodic polarization of the substrate at the polymer/cathode/solution three-phase boundary, it undergoes reduction and subsequent chemical conversion, including intermolecular cross-linking and breakdown of the macromolecules. The rate of ECRB of the CBR depends on the potential and materials of the cathode, and also on the nature of the solvent. In a aprotic medium, the process of CBR breakdown leads to the formation of long polyconjugated structures that color its surface black in the vicinity of the three-phase boundary. In an aqueous medium, no such color is observed, but the products of ECRB are found to contain conjugated double bonds with a shorter conjugation chain than in the case of the aprotic medium. It has been established that he starting reaction in ECRB of CBR is reduction of the C-Cl bond and subsequent elimination of Cl–.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 6, pp. 710–715, November–December, 1989. 相似文献
878.
Electroreduction of benzo-1,2,3-dithiazolium salts and their selenium analogs in nonaqueous solution
V. Sh. Tsveniashvili M. V. Malashkhiya V. N. Gaprindashvili B. Kh. Strelets M. M. Gel'mont Yu. I. Akulin 《Chemistry of Heterocyclic Compounds》1985,21(2):181-184
The electroreduction of benzo-1,2,3-dithiazolium cations and their selenium analogs in aprotic solvents takes place in two steps. The first step is a reversible, one-electron transfer leading to the formation of stable radicals detected by EPR. As a result of further electroreduction, the radicals obtained combine with six electrons to form the corresponding o-aminothio(seleno)phenols. Analysis of the reduction potentials of the compounds studied shows that the substitution of a selenium atom for a sulfur in these cations, especially in the 2 position of the heterocycle, facilitates their electrochemical reduction. The electrochemical activity and the kinetics of nulceophilic substitution in the cations studied are compared.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 219–222, February, 1985. 相似文献
879.
A.N. Nesmeyanov V.V. Krivykh P.V. Petrovskii V.S. Kaganovich M.I. Rybinskaya 《Journal of organometallic chemistry》1978,162(3):323-342
Irradiation of alkenylarene tricarbonyl-chromium, -molybdenum, and -tungsten compounds in which the double bond is separated from the arene moiety by a two- or three-atom bridge results in intramolecular cyclization to give stable chelate alkenylarenedicarbonylmetal complexes. Chelate complexes containing four-atom bridges have low stabilities, and those with monoatomic bridges were not formed at all. Irradiation of styrenetricarbonyl-chromium and -molybdenum leads to dinuclear tricarbonylmetal—dicarbonylmetal complexes. The chelate complexes obtained have been studied by IR, proton NMR, and 13C NMR spectroscopy. The electron density distributions and the stereochemistry of the complexes are discussed. With nonsymmetric arenes, diastereoisomers are formed; the predominant isomers have been isolated in the pure form. According to the proton NMR data the double bond in alkenylarenechromium chelates is parallel of nearly parallel to the arene ring plane. 相似文献
880.
Kadysh V. P. Stradyn' Ya. P. Goncharova I. N. 《Chemistry of Heterocyclic Compounds》1977,13(12):1340-1343
The polarographic reduction of adenine and its 9-(,)-dihydroxy-2-alkyl) derivatives on a short-period mercury electrode in strongly acidic media is determined by the rate of diffusion of the corresponding cations and, at pH values that exceed the pKa values, by the kinetics of surface protonation of the uncharged molecules; this was proved by the dependence of the limiting current on the height of the mercury column, the temperature, and the depolarizer concentration. The polarographic reduction of adenine, adenosine, 9-(,-di-hydroxy-2-alkyl)adenines, and the corresponding phosphates in acidic media proceeds with the loss of sic electrons per molecule. The similar trends of the change in the half-wave potentials and the numerical pKa values is associated with the fact that the site of protonation is simultaneously the site of nucleophilic attack by the electron during electrical reduction.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1675–1678, December, 1977. 相似文献