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71.
Reto Stahl Renato Galli Rolf Güller Hans-Jürg Borschberg 《Helvetica chimica acta》1994,77(8):2125-2132
The oxidative transformation of synthetic (+)-aristoteline ((+)- 6 ) into other metabolites which had been isolated from Aristotelia species was investigated. Thus, treatment of (+)- 6 with I2 as the single oxidant furnished the naturally occurring indole alkaloids (+)-makonine ((+)- 9 ),(+)-aristotelinone ((+)- 11 ), or (+)-11, 12-didehydroaristoteline ((+)- 7 ) in good yields, the selectivity of the oxidation process depending on the chosen reaction conditions. 相似文献
72.
On the Preparation of Di(i-propyl)thiosulfonium Salts [1] The preparation of the mercaptosulfonium salts (i-C3H7)2SSX+SbCl6? (X = H, D) and of the chlorothiosulfonium salts (i-C3H7)2SSCl+MF6? (M = As, Sb) and (i-C3H7)2SSSCl+SbCl6? is reported. They are formed by reaction of chlorinated or protonated (i-C3H7)2S with excess H2S or SCl2 and S2Cl2. The thiosulfonium compounds are characterized by vibrational and NMR spectroscopic methods. 相似文献
73.
The primary all-trans to 13-cis chromophore isomerization of the light driven chloride pump halorhodopsin has been studied by means of transient absorption spectroscopy in the visible and mid-infrared regime at a time resolution of better than 100 and 220 fs, respectively. The picosecond vibrational dynamics are dominated by two time constants, i.e., 2 and 7.7 ps in accordance with the biphasic decay of the retinal excited electronic state and electronic ground state formation with 1.5 and 6.6 ps. The transient vibrational spectra of the participating electronic states strongly suggest the existence of two distinct S1 populations as a result of an early branching reaction. It is shown that the 13-cis product is formed with the fast time constant, whereas the all-trans educt state is repopulated via both time constants. Concomitant protein dynamics are indicated by spectral changes on a similar time scale in the amide region. 相似文献
74.
Rolf Gleiter Jens Spanget-Larsen Erik W. Thulstrup Ichiro Murata Kazuhiro Nakasuji Christian Jutz 《Helvetica chimica acta》1976,59(5):1459-1468
The photoelectron (PE.) spectra of azuleno[l, 2, 3-cd]phenalene ( 1 ) and azuleno- [5,6,7-cd]phenalene( 2 ) have been recorded. The first five bands of both compounds could be assigned to transitions corresponding to removal of electrons from 4a2, 6b1, 5b1, 3a2 and 4bl orbitals. This assignment is based mainly on a comparison between the observed ionization potentials and orbital energies calculated in a HMO and a PPP model. The UV./VIS. polarized absorption spectrum of 1 in the region 10000–45000 cm?1 has been measured by means of the stretched film technique. The measurements were performed in polyethylene sheets at 77°K. Several bands could be assigned to π* ← π transitions calculated by a PPP-CI method. A comparison between the electronic structures of 1 and 2 is made by means of a simple HMO diagram. 相似文献
75.
Lothar Metzger Günter G. Willems und Rolf Neeb 《Fresenius' Journal of Analytical Chemistry》1978,292(1):20-22
Zusammenfassung Die starke Temperaturabhängigkeit des polarographischen Zinn(II/0)-Signals in Lösungen des vierwertigen Zinns ermöglicht bei –32° C in methanolischer salzsaurer Grundlösung die Bestimmung des Bleis neben hohem Zinnüberschuß. Eine Anwendung des Verfahrens zur wechselstrompolarographischen Bestimmung des Bleis in Rohzinn wird beschrieben.
Investigations on the simultaneous electrochemical determination of lead and tinII. Polarographic determination of lead in the presence of tin at lower temperatures
Summary The strong temperature dependence of the polarographic tin(II/0) signal in solutions containing tin(IV) renders possible the determination of lead in the presence of a high excess of tin at working temperatures of –32° C in hydrochloric methanol as supporting electrolyte solution. An application of the procedure to the ac-polarographic determination of lead in crude tin is described.
Die vorliegende Arbeit wurde in dankenswerter Weise durch Mittel der Deutschen Forschungsgemeinschaft und des Verbandes der Chemischen Industrie ermöglicht. 相似文献
76.
Investigation of the complexing of Na+, K+, Ca2+ and Ba2+ with some uncharged ligands by 13C-chemical shift and spin-lattice relaxation time measurements The influence of Na+, K+, Ca2+ and Ba2+ ions on 13C chemical shifts and on spin-lattice relaxation times of some electrically neutral ion carriers was investigated. In the solvents CD3CN and CD3OD and in presence of an excess of metal ions ligand 4 (see the Scheme) forms complexes of 1:1 stoichiometry. All four oxygen atoms of the ligand as well as solvent molecules take part in the coordination. In CDCl3 as solvent, for all ions investigated except sodium, only 1:2 complexes (metal/ligand) were observed with 4 . Sodium ions form both 1:1 and 1:2 complexes in this solvent. In the 1:2 complexes of the investigated monovalent ions only one, in those of the divalent ions both amide carbonyl groups of ligand 4 take part in the coordination. 相似文献
77.
On the Reactions of CH3OCl, CF3OCl, CF3OF, and CF3OH with the Superacid System HF/MF5 (M = As, Sb). Preparation and Characterization of CH3OCl(H)+MF6? and CF3OCl(H)+MF6? The preparation of the chlorine oxoniumsalts CH3OCl(H)+MF6? and CF3OCl(H)+MF6? by protonation of CH3OCl and CF3OCl in the superacid solution of HF/MF5 (M = As, Sb) is described. However CF3OF and CF3OH have not been protonated under the same conditions. In the case of CF3OH the formation of F2CO · MF5 is observed. The novel compounds are characterized by nmr- and vibrational spectroscopy. 相似文献
78.
The linear dichroic absorption spectrum of 1,3,6,8-trans-15, 16-hexamethyl-dihydropyrene has been measured in stretched polyethylene at 77K, and CNDO-CI calculations with inclusion of singly and doubly excited configurations have been carried out on a series of alkyl bridged [14] annulenes with pyrene- and anthracene-shaped perimeters. Transitions to e3g → e4u type 1B states are well described, and the results indicate that additional low-energy excited states originate from e3g→ e5g and e2u → e4u type configurations interacting strongly with doubly excited configurations of the e3g, e3g → e4u, e4u type. The second excited singlet state responsible for the weak transition observed between the 1L bands may be assigned to one of these additional states, but it is probably of complex nature, similar to the ‘phantom’ state in linear polyenes. 相似文献
79.
The anomalous reactivity of the bicyclo [2.2.1] heptene double bond is interpreted in terms of hyperconjugative effects, leading to an exceptionally low endo out-of-plane deformation potential. 相似文献
80.
Cooperative effects in binuclear zirconocenes: Their synthesis and use as catalyst in propene polymerization 总被引:3,自引:0,他引:3
Stephan Jüngling Rolf MüllhauptHerbert Plenio 《Journal of organometallic chemistry》1993,460(2):191-195
The mono- and bis-cyclopentadienyl compounds 1-(Cp″)-4-(CH3)C6H4 (1) and 1, 4-(Cp″)2C6H4 (2) (Cp″ = 3,4-dimethylcyclopenta-1,3-diene-1-yl) have been synthesized. The reactions of the lithium salts of 1 and 2 with CpZrCl3 · dme (dme = dimethoxyethane) and Cp*ZrCl3(CP* = C5(CH3)5) yielded the mono- and bi-nuclear bridged zirconocenes 1-(Cp″ZrCpCl2)-4-(CH3)C6H4 (3), 1,4-(Cp″ZrCpCl2)2C6H4 (4) and 1,4-(Cp″ZrCp*Cl2)2C6H4 (5). When activated with methylaluminoxane (MAO), the mono- and bi-nuclear zirconocenes 3 and 4 catalyse the polymerization of propene. The influence of the catalyst composition on the polymerization kinetics and molecular weight is discussed. 相似文献