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991.
The infrared and Raman spectra of gaseous and solid (CH3)3 GeNCO and solid (CH3)3GeNCS have been recorded over the frequency range 20–4000 cm?1 . The Raman spectra of the liquids have also been recorded. Assignments of the normal modes have been made on the bases of band types, Raman depolarization values, and characteristic frequencies. Spectral data indicate that (CH3)3 GeNCO is non-linear in all phases and that (CH3)3GeNCS has a linear or quasi-linear heavy atom skeleton in the fluid phases. 相似文献
992.
Cyclisation of the title compounds leads to mixtures of the expected 4H-cyclopental[b]pyrrol-4-ones (1), the corresponding 6-ones (3) by a single rearrangement, and the cyclopenta[c]pyrrol-4-ones (4) by a double rearrangement, the proportions depending upon the substituents.The 1H NMR spectra of 2-methyl-4H-cyctopenta[b]thiophen-6-one (3f) shows 6J long range coupling, but this is absent in the corresponding pyrroles (3c,d). The 13C spectra of 1 and 3 cannot be interpreted on the basis of substituent chemical shifts in pyrroles and thiophens, and are clearly -CH = CH-X (X = NMe, NPh, S) bridged derivatives of cyclopent-2-enone. 相似文献
993.
In order to test the effects of the replacement of phenylalanine by carboranylalanine (Car) in biological ligand-acceptor interactions, Z · Ala-Ala-Car · OH (1) and Ac · Car · OEt (2) were synthesized and their reactions with chymotrypsin studied. The two compounds proved to be good inhibitors with K(i) values of 3 · 10?4M (1) and 8.6 · 104M (2) ; the K(i) of Z · Ala-Ala-Phe · OH (1a) is 1 · 10?3M . The inhibition constants were determined by a new photolytic technique, inhibition of photoaffinity labelling by Z · Ala-Ala-Phe(pN3) · OH. Ac · Car · OEt is not hydrolysed by chymotrypsin. The findings indicate that the carboranyl group can interact with the ‘phenyl recognition site’ of the enzyme to produce the binding that is characteristic of aromatic amino acid residues. However, some kind of distortion in the region of the ‘mechanistic site’ must be postulated in order to account for the failure of hydrolysis. Some possible effects of the replacement of aromatic amino acids by Car in peptide hormones on hormone-receptor interactions are discussed. 相似文献
994.
The silicate compounds Sc2Si2O7 and In2Si2O7 have been converted from thortveitite type to pyrochlore type at 1000°C, 120 kbar, with resulting cell constants of 9.287(3) and 9.413(3) Å, respectively. Invariant reflection intensities in the X-ray powder diffraction patterns allowed precise absorption corrections to be made, and refinement of thermal parameters and of the single structural parameter x gave values of 0.4313(21) and 0.4272(15), respectively. The corresponding six-coordinate SiO distances were 1.761(7) and 1.800(5) Å, and the average eight-coordinate distances for ScO8 and InO8 were 2.267 and 2.275 Å. Values of structure-refined bond lengths for compounds containing six-coordinate silicon are surveyed, and overall weighted average octahedral distances of 1.782(14) Å for SiO and 2.520(18) Å for OO are derived. Pyrochlore phases were not produced from rare-earth disilicate or monosilicate phases subjected to the same reaction conditions as the Sc and In compounds. 相似文献
995.
Dihydroprotoberberine salts 5, 10, and 14, rearrange in base to the spirobenzylisoquinolines 8, 12, and 16, respectively. But the dihydroprotoberberine salt 18, which does not possess a phenolic function in ring D, rearranges to the dibenzocyclopent[b]azepine 21 through the intermediacy of the aziridinium ion 20. 相似文献
996.
Zusammenfassung Bei der Einwirkung von elementarem Schwefel auf Phenacyl-sulfenylmorpholid entsteht unter H2S-Abspaltung Phenylglyoxyl-säurethionmorpholid. Durch Einsatz von radioaktivem Schwefel wurde festgestellt, daß diese Umlagerungsreaktion über die Stufe einergem. Dimercaptoverbindung verläuft.
47. Mitt.:F. Asinger, W. Schäfer undA. Saus, Mh. Chem.96, 1265 (1965).
Teil der DissertationA. Saus, Techn. Hochsch. Aachen, 1964. 相似文献
Reaction of elementary sulfur with phenacylsulfenylmorpholide gives phenylglyoxylic acid thionmorpholide while hydrogen sulfide is eliminated. The rearrangement proceeds, as was shown by use of radioactive sulfur, via agem. dimercaptocompound as intermediate.
47. Mitt.:F. Asinger, W. Schäfer undA. Saus, Mh. Chem.96, 1265 (1965).
Teil der DissertationA. Saus, Techn. Hochsch. Aachen, 1964. 相似文献
997.
New procedures have been developed for determining the alumina contents of silicate material (rocks and refractories). The material is first taken into solution by a peroxide sinter technique, followed by dissolving the sinter in warm water and the addition of sufficient hydrochloric acid to render the solution acid to litmus. A different technique is used for silicates containing less than 5% alumina. The majority of the silica is first removed by treating with hydrofluoric-sulphuric acids and the residue is fused with potassium bisulphate. Extractions with cupferron are next employed to remove iron, titanium, zirconium etc., and the aluminium is subsequently separated from other sample constituents by precipitating as its insoluble benzoate. After filtration the aluminium benzoate is dissolved in hydrochloric acid and the aluminium concentration determined volumetrically with ethylenediaminetetraacetic acid. 相似文献
998.
Zusammenfassung Für das binäre System n-Hexan(1)/Methylamin(2) werden die molare Exzeßenthalpie, die molare Exzeßentropie und die freie molare Zusatzenthalpie aus Dampfdruckdaten berechnet. Für die Berechnung der beiden ersten Größen wird sowohl die Ableitung der Parameter der verwendeten Ansätze als auch die Ableitung der freien molaren Zusatzenthalpie verwendet, die beiden Methoden werden verglichen. Zur Glättung der Ergebnisse werden die Parameter bzw. die freie Zusatzenthalpie durch Parabeln verschiedener Ordnung angenähert. Die Berechnung der vorliegenden Arbeit wurde auf der UNIVAC-490-Anlage des Rechen-Zentrums Graz durchgeführt*.
Mit 5 Abbildungen
1. bis 6. Mitt.:F. Gölles, Mh. Chem.92, 981 (1961);93, 191, 201 (1962);94, 1108 (1963);95, 1656 (1964);96, 1366 (1965); 7. bis 9. Mitt.:F. Gölles undA. Höpfner, Mh. Chem.97, 368, 911 (1966);99, 230 (1968); 10. Mitt.:F. Gölles undO. Wolfbauer, Mh. Chem.99, 1814 (1968). 相似文献
Determination and verification by calculation of thermodynamic data from experimentally obtained values, XI.: Contribution to the calculation of molar excess enthalpies from vapour pressure data using the treatments of Redlich-Kister and Musil-Breitenhuber
The molar heat of mixing and the molar excess entropy and the excessGibbs energy of the binary system n-hexane(1)/methylamine(2) are calculated using vapor-pressure data. As method the authors use differentiation of parameters of the statements as well as differentiation of the free molar excess enthalpy; both methods are compared. For smoothening the results the parameters resp. the free molar excess enthalpyG E are approximated by polynomals of different degree. The programm is written in FORTRAN IV and the UNIVAC-490-computer of the Graz Computer Centre has been used*.
Mit 5 Abbildungen
1. bis 6. Mitt.:F. Gölles, Mh. Chem.92, 981 (1961);93, 191, 201 (1962);94, 1108 (1963);95, 1656 (1964);96, 1366 (1965); 7. bis 9. Mitt.:F. Gölles undA. Höpfner, Mh. Chem.97, 368, 911 (1966);99, 230 (1968); 10. Mitt.:F. Gölles undO. Wolfbauer, Mh. Chem.99, 1814 (1968). 相似文献
999.
1000.
Traces of antimony, tin and arsenic in cadmium products were determined by pulse polarography. Arsenic was distilled, while antimony and tin were precipitated as hydroxides with manganese dioxide as carrier; some lead was coprecipitated with tin, hence these elements were further separated by distillation. In all cases quantitative recoveries were obtained. Antimony(III) was determined in a hydrochloric acid-sodium hypophosphite mixture, tin(IV) in a hydrochloric-hydrobromic acid mixture and arsenic(III) in sulphuric acid as supporting electrolytes; for arsenic(III), methylene blue had to be added. A sample weight of 10 g and an end volume of 10 ml allowed the determination down to about 0.004 p.p.m. antimony, 0.006 p.p.m. tin and 0.003 p.p.m. arsenic in cadmium. Several synthetic samples and commercially available cadmium products were analysed. 相似文献