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151.
The microbiological transformation of 7-oxo-ent-kaur-16-ene by the fungus Gibberella fujikuroi gave fujenoic acid as the main compound, whilst the incubation of 18-hydroxy-7-oxo-ent-kaur-16-ene and 3α,18-dihydroxy-7-oxo-ent-kaur-16-ene afforded the corresponding 6β-hydroxy-derivatives. These facts indicate that the formation of fujenoic acid in this biotransformation should occur via a 7-oxo-6β-hydroxy derivative. In the three biotransformations, an 11β-hydroxylation was also produced, in low yield, indicating that a 7-oxo-group also directs hydroxylation at C-11. 相似文献
152.
Dominik Huber P. G. Anil Kumar Paul S. Pregosin Igor S. Mikhel Antonio Mezzetti 《Helvetica chimica acta》2006,89(8):1696-1715
Chloride abstraction from the half‐sandwich complexes [RuCl2(η6‐p‐cymene)(P*‐κP)] ( 2a : P* = (Sa,R,R)‐ 1a = (1Sa)‐[1,1′‐binaphthalene]‐2,2′‐diyl bis[(1R)‐1‐phenylethyl)]phosphoramidite; 2b : P* = (Sa,R,R)‐ 1b = (1Sa)‐[1,1′‐binaphthalene]‐2,2′‐diyl bis[(1R)‐(1‐(1‐naphthalen‐1‐yl)ethyl]phosphoramidite) with (Et3O)[PF6] or Tl[PF6] gives the cationic, 18‐electron complexes dichloro(η6‐p‐cymene){(1Sa)‐[1,1′‐binaphthalene]‐2,2′‐diyl {(1R)‐1‐[(1,2‐η)‐phenyl]ethyl}[(1R)‐1‐phenylethyl]phosphoramidite‐κP}ruthenium(II) hexafluorophosphate ( 3a ) and [Ru(S)]‐dichloro(η6‐p‐cymene){(1Sa)‐[1,1′‐binaphthalene]‐2,2′‐diyl {(1R)‐1‐[(1,2‐η)‐naphthalen‐1‐yl]ethyl}[(1R)‐1‐(naphthalen‐1‐yl)ethyl]phosphoramidite‐κP)ruthenium(II) hexafluorophosphate ( 3b ), which feature the η2‐coordination of one aryl substituent of the phosphoramidite ligand, as indicated by 1H‐, 13C‐, and 31P‐NMR spectroscopy and confirmed by an X‐ray study of 3b . Additionally, the dissociation of p‐cymene from 2a and 3a gives dichloro{(1Sa)‐[1,1′‐binaphthalene]‐2,2′‐diyl [(1R)‐(1‐(η6‐phenyl)ethyl][(1R)‐1‐phenylethyl]phosphoramidite‐κP)ruthenium(II) ( 4a ) and di‐μ‐chlorobis{(1Sa)‐[1,1′‐binaphthalene]‐2,2′‐diyl [(1R)‐1‐(η6‐phenyl)ethyl][(1R)‐1‐phenylethyl]phosphoramidite‐κP}diruthenium(II) bis(hexafluorophosphate) ( 5a ), respectively, in which one phenyl group of the N‐substituents is η6‐coordinated to the Ru‐center. Complexes 3a and 3b catalyze the asymmetric cyclopropanation of α‐methylstyrene with ethyl diazoacetate with up to 86 and 87% ee for the cis‐ and the trans‐isomers, respectively. 相似文献
153.
Raimund Winkler 《Fresenius' Journal of Analytical Chemistry》1973,267(4):261-266
Zusammenfassung Eisen-55 wurde in Neuherberg bei München seit März 1970 in monatlich gesammelten Luftstaubproben und seit Januar 1971 in Monatsniederschlagsproben bestimmt. Nach dem Veraschen der Proben wurde Eisen durch Extraktion' mit Di-iso-propyläther abgetrennt. Zur weiteren Entfernung störender Radionuklide des Fallouts wurde eine Ionenaustauschertrennung angeschlossen. Nach der elektrolytischen Abscheidung des Eisens auf Kupferplättchen wurden die Röntgenspektren mit einem Proportionalzähler sowie einem Si(Li)-Detektor aufgenommen.Die mittlere spezifische Luftaktivität betrug in Neuherberg 1,0 fCi/m3 im Jahr 1970 (ab März), 1,2 fCi/m3 im Jahr 1971 und 0,36 fCi/m3 im Jahr 1972. Die dem Boden durch den Niederschlag zugeführte Aktivität wurde zu 697 pCi/m2 · Jahr für 1971 und 178 pCi/m2 · Jahr für 1972 bestimmt.Vortrag anläßlich der Tagung Spurenanalyse, 2. bis 5. April 1973 in Erlangen. 相似文献
154.
Ab initio molecular orbital theory and density functional theory have been used to study nine isomers of N7 ionic clusters with low spin at the HF/6-31G*, MP2/6-31G*, B3LYP/6-31G*, and B3LYP/6-311(+)G* levels of theory. All stationary
points are examined with harmonic vibrational frequency analyses. Four N7
+ isomers and five N7
− isomers are determined to be local minima or very close to the minima on their potential-energy hypersurfaces, respectively.
For N7
+ and N7
−, the energetically low lying isomers are open-chain structures (C
2
v
and C
2
v
or C2). The results are very similar to those of other known odd-number nitrogen ions, such as N5
+, N9
+, and N9
−, for which the open-chain structures are also the global minima. This research suggests that the N7 ionic clusters are likely to be stable and to be potential high-energy-density materials if they could be synthesized.
Received: 16 July 2001 / Accepted: 8 October 2001 / Published online: 21 January 2002 相似文献
155.
Low-temperature heat capacities of the compound Na(C4H7O5)·H2O(s) have been measured with an automated adiabatic calorimeter. A solid-solid phase transition and dehydration occur at 290-318 K and 367-373 K, respectively. The enthalpy and entropy of the solid-solid transition are ΔtransHm = (5.75 ± 0.01) kJ mol−1 and ΔtransSm = (18.47 ± 0.02) J K−1 mol−1. The enthalpy and entropy of the dehydration are ΔdHm = (15.35 ± 0.03) kJ mol−1 and ΔdSm = (41.35 ± 0.08) J K−1 mol−1. Experimental values of heat capacities for the solids (I and II) and the solid-liquid mixture (III) have been fitted to polynomial equations. 相似文献
156.
J. Ch. Pomerol 《Mathematical Programming》1980,19(1):352-355
We give a new minisup theorem for noncompact strategy sets. Our result is of the type of the Matthies-Strang-Christiansen minimax theorem where the hyperplane should be replaced by any closed convex set. As an application, we derive a slight generalization of the Matthies-Strang-Christiansen minimax theorem. 相似文献
157.
158.
W.Franklin Smyth Clare Joyce Venkataraman N. Ramachandran Edmund O’Kane Danny Coulter 《Analytica chimica acta》2004,506(2):203-214
The electrospray ionisation-ion trap mass spectrometry (ESI-MSn) of selected hypnotic drugs, i.e. zopiclone, zolpidem, flunitrazepam and their metabolites have been investigated. Sequential product ion fragmentation experiments (MSn) have been performed in order to elucidate the degradation pathways for the [M+H]+ ions and their predominant fragment ions. These MSn experiments show certain characteristic fragmentations in that functional groups are generally cleaved from the ring systems as neutral molecules such as H2O, CO, CO2, NO2, amines and HF. When an aromatic entity is present in a drug molecule together with a nitrogen-containing saturated ring structure as with zopiclone and its N-desmethyl metabolite fragmentation initially occurs at the latter ring with the former being resistant to fragmentation. The structures of fragment ions proposed for ESI-MSn can be supported by electrospray ionisation-quadrupole time-of-flight mass spectrometry (ESI-QTOF-MS).These molecules can be identified and determined in mixtures at low ng/ml concentrations by the application of liquid chromatography (LC)-ESI-MSn which can be used for their analysis in saliva samples.This paper includes a tabulation of mass losses/signals at low m/z values for these hypnotic drugs and many others in recent publications which will be of value in the characterisation of drug metabolites of unknown structure and also natural product pharmaceuticals isolated from plants, etc. 相似文献
159.
Ya. V. Voznyi M. O. Dekaprilevich D. S. Yufit Yu. T. Struchkov 《Russian Chemical Bulletin》1992,41(6):1072-1075
A method was developed for the production of derivatives of 4-trifluoromethyl-7-hydroxycoumarin with electron-withdrawing groups (CN, CF3CO) at position 3. The structure of 3-cyano-4-trifluoromethyl-7-acetoxycoumarin was proved by x-ray crystallographic investigation. The effect of the substituents on the geometry of the molecule is discussed.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. A. N. Nesmeyanov Institute of Heteroorganic Compounds, Russian Academy of Sciences, 117813 Moscow. Institute of Biochemistry, Academy of Sciences of Armenia, 375044 Erevan. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 6, pp. 1371–1375, June, 1992. 相似文献
160.
Herman Gershon Donald D. Clarke Muriel Gershon 《Monatshefte für Chemie / Chemical Monthly》1994,125(1):51-59
Summary A study was made of the fungitoxicity of 2-, 3-, 4-, 5-, 6- and 7-chloro and bromo-8-quinolinols againstAspergillus niger,A. oryzae,Myrothecium verrucaria,Trichoderma viride andTrichophyton mentagrophytes in Sabouraud dextrose broth and in Yeast Nitrogen Base supplemented with 1%D-glucose and 0.088%L-asparagine. Based on the presence or absence of synergism between pairs of substituted 8-quinolinols and reversal or nonreversal of toxicity byL-cysteine or N-acetyl-L-cysteine, the following conclusions were reached: (1) substituents on the quinoline ring change the site(s) of action of the toxicant; (2) the sites of action of the 5-, 6-, and 7-chloro-8-quinolinols are different from each other and from 8-quinolinol and its 2-, 3-, and 4-chloro analogues, and the same is true for the corresponding bromo compounds; (3) 8-quinolinol and its 3- and 4-chloro and bromo analogues appear to share common sites of action; (4) for good antifungal activity the 2 position of the ring must not be substituted by sterically bulky groups; (5) the geometry of the binding sites of action are not so constrained that they cannot accommodate the analogously substituted chloro- and bromo-8-quinolinols.
Nachweis sterischer Faktoren bei der Fungitoxizität von 8-Chinolinol und seinen 2-, 3-, 4-, 5-, 6- und 7-Chlor- und -Brom-Analogen
Zusammenfassung Es wurde eine Studie der Fungitoxizität von 2-, 3-, 4-, 5-, 6- und 7-Chlor- und-Brom-8-chinolinol gegenüberAspergillus niger,A. oryzae,Myrothecium verrucaria,Trichoderma viride undTrichphyton mentagrophytes in Sabouraud Dextrose Nährmedium und in Hefe-N-Base mit 1%D-Glucose und 0.088%L-Asparagin unternommen. Auf der Basis des Zutreffens oder der Abwesenheit eines Synergismus zwischen Paaren von substituierten 8-Chinolinolen und der Umkehrung oder Nichtumkehrung der Toxizität durchL-Cystein oder N-Acetyl-L-cystein wurden folgende Schlußfolgerungen abgeleitet: (1) Substituenten am Chinolin-Ring ändern die Aktionsstelle(n) des Toxikans; (2) Die Angriffsstellen der 5-, 6- und 7-Chlor-8-chinolinole sind untereinander und von 8-Chinolinol und seinen 2-, 3- und 4-Chlor-Analogen verschieden, wobei das auch für die entsprechenden Brom-Verbindungen gilt; (3) 8-Chinolinol und seine 3- und 4-Chlor- und -Brom-Analogen scheinen gemeinsame Aktionsstellen zu teilen; (4) für eine gute antifungale Aktivität darf die 2-Position des Rings nicht mit sterisch anspruchsvollen Gruppen besetzt sein; (5) Die Geometrie des Bindungsstellen der Wirkung ist nicht so gespannt, daß nicht sowohl analoge Chlor- oder Brom-8-chinolinole Platz finden.相似文献