全文获取类型
收费全文 | 5680篇 |
免费 | 350篇 |
国内免费 | 33篇 |
专业分类
化学 | 3875篇 |
晶体学 | 90篇 |
力学 | 192篇 |
数学 | 872篇 |
物理学 | 1034篇 |
出版年
2023年 | 37篇 |
2022年 | 50篇 |
2021年 | 186篇 |
2020年 | 120篇 |
2019年 | 218篇 |
2018年 | 177篇 |
2017年 | 130篇 |
2016年 | 280篇 |
2015年 | 188篇 |
2014年 | 298篇 |
2013年 | 566篇 |
2012年 | 334篇 |
2011年 | 350篇 |
2010年 | 246篇 |
2009年 | 237篇 |
2008年 | 257篇 |
2007年 | 239篇 |
2006年 | 229篇 |
2005年 | 186篇 |
2004年 | 173篇 |
2003年 | 142篇 |
2002年 | 189篇 |
2001年 | 91篇 |
2000年 | 126篇 |
1999年 | 76篇 |
1998年 | 53篇 |
1997年 | 51篇 |
1996年 | 46篇 |
1995年 | 55篇 |
1994年 | 46篇 |
1993年 | 43篇 |
1992年 | 43篇 |
1991年 | 34篇 |
1990年 | 23篇 |
1989年 | 36篇 |
1988年 | 32篇 |
1987年 | 24篇 |
1986年 | 21篇 |
1985年 | 45篇 |
1984年 | 42篇 |
1983年 | 32篇 |
1982年 | 31篇 |
1981年 | 35篇 |
1980年 | 28篇 |
1979年 | 23篇 |
1978年 | 24篇 |
1977年 | 17篇 |
1976年 | 22篇 |
1975年 | 20篇 |
1973年 | 12篇 |
排序方式: 共有6063条查询结果,搜索用时 62 毫秒
81.
Brahim Lakhrissi Mohamed Massoui El Mokhtar Essassi Vincent Lequart Nicolas Joly Patrick Martin Grard Goethals 《Journal of heterocyclic chemistry》2004,41(6):1011-1014
Reaction of 1,5‐benzodiazepin‐2,4‐dione with 3‐O‐substituted‐5,6‐anhydro‐1,2‐isopropylidene‐α‐D‐glucofuranose gave the unexpected N,N'‐di‐glucofuranosyl benzimidazol‐2‐one by a novel rearrangement and ring closure reaction. A mechanism is proposed. 相似文献
82.
M. El Bouamri J. P. Gorrichon A. M. Braun E. Oliveros 《Photochemistry and photobiology》1991,54(4):619-623
The quantum yields of Rose Bengal sensitized photooxidation of citronellol and α-thujene have been determined as a function of added acceptor and compared with those of furfuryl alcohol as a standard. The results permitted the calculation of the corresponding rate constants of chemical reaction (kT) and physical quenching (Kq) of singlet oxygen. The sum (kT+ kq) has been verified independently by a Stern-Volmer analysis of the singlet oxygen luminescence quenching. α-Thujene reacts faster with singlet oxygen than citronellol, physical quenching being negligible in both cases. 相似文献
83.
Novel furo, thieno and pyrrolo[2,3‐b]pyrazole cyanine dyes were synthesized. The structure‐photosensitization properties correlation of the dyes were examined in 95% ethanol solution by absorption spectroscopy. The chemical structure of the starting biheterocyclic compounds and their derived cyanine dyes were confirmed by elemental analysis, IR and 1H NMR spectroscopy. 相似文献
84.
Summary The substitution of phosphine in the [RhCl(COD)(phosphine)] complex (1), where phosphine is PPh3 or 1/2 BPS-2 [bis(diphenylphosphinoethyl)tetramethyldisiloxane] and COD is cycloocta-1,5-diene, by 1-hexene is a two-step reversible reaction. All individual rate constants and equilibrium constants were determined spectrophotometrically and associative mechanism occurring via the formation of five-coordinated [RhCl(COD)(phosphine)(1-hexene)] (2) was inferred. The rate-determining step changes from the first- to the second-one as the concentration of 1-hexene increases. An excess of phosphine shifts the equilibrium towards complex (2). 相似文献
85.
D. El Allam E. Hayer M. Gaune-Escard J. P. Bros 《Journal of Thermal Analysis and Calorimetry》1991,37(8):1687-1695
In order to fill the evident gap in the thermodynamic data of nickel-palladium-gallium and nickel-palladium-indium ternary alloys, the enthalpies of formation of these systems in the liquid state have been determined. This was achieved by means of a very high temperature calorimeter (T<1800 K), using the direct drop method, and based on analogous measurements of the respective binary alloys previously published. Complete automation of the calorimeter led to a good precision even at the highest temperatures. The enthalpies of formation of the ternary liquid alloys were measured between 1400 and 1600 K on the whole composition range. As in the limiting binary systems, enthalpies of formation are negative and non temperature dependent at any composition.
Zusammenfassung Um die Lücke hinsichtlich thermodynamischer Daten von Nickel-Palladium-Gallium und Nickel-Palladium-Indium Legierungen zu füllen, wurden die Bildungsenthalpien dieser ternÄren Systeme im flüssigen Zustand bestimmt. Dies erfolgte mittels eines Kalorimeters für sehr hohe Temperaturen (T<1800 K), unter Verwendung der direkten Einwurfmethode auf der Basis früher veröffentlichter Messungen an den entsprechenden binÄren Systemen. Die Bildungsenthalpien der flüssigen ternÄren Legierungen wurden zwischen 1400 und 1600 K über den gesamten Zusammensetzungsbereich bestimmt. VollstÄndige Automation des Kalorimeters bewirkte hohe PrÄzision selbst bei den höchsten Temperaturen. Wie in den begrenzenden binÄren Systemen sind die Bildungsenthalpien negativ und bei allen Zusammensetzungen nicht temperaturabhÄngig.相似文献
86.
N. A. El’tekova Yu. A. El’tekov 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2007,81(4):602-606
The kinetics of the adsorption of a mixture of three polystyrenes (the weight-average molecular weight M w = 8300, 34000, and 195000) on nonporous carbon (carbon black pretreated in the argon flow at 3800 K) from dilute solutions in methyl ethyl ketone at 298 K is studied. The kinetic dependences of the adsorption of polystyrenes on carbon black nanoparticles from solutions in methyl ethyl ketone are described by adsorption kinetics equations previously used for describing the adsorption of aromatic hydrocarbons from aqueous solutions by active carbon. The correlation between the kinetic coefficients and the molecular weights of polystyrenes is discussed. 相似文献
87.
Garrido NM El Hammoumi MM Díez D García M Urones JG 《Molecules (Basel, Switzerland)》2004,9(5):373-382
The asymmetric synthesis of the orthogonally funtionalised compounds tert-butyl 2-N-benzyl-N-alpha-methylbenzylamino-5-methoxycarbonylmethylcyclopentane- 1-carboxylate and methyl 2-N-benzyl-N-alpha-methylbenzylamino-5-carboxymethylcyclo- pentane-1-carboxylate by a domino reaction of tert-butyl methyl (E,E)-octa-2,6- diendioate with lithium N-alpha-methylbenzyl-N-benzylamide initiated by a Michael addition, subsequent 5-exo-trig intramolecular cyclisation and posterior selective hydrolysis with trifluoroacetic acid is reported. 相似文献
88.
Malonate, succinate and glutarate of yttrium were obtained by dissolving Y(OH)3 in a solution of the corresponding acid and crystallization, whereas adipate, pimelate, suberate, azelate and sebacate in the reaction of YCl3 with the ammonium salt of the acid. Yttrium alkanodicarboxylates were prepared as crystalline solids with general formula Y2O3.nH2O, wheren=3, 4, 6, 7. On the basis of IR spectra the way of coordination COO– - Y3+ was established. Yttrium malonate, succinate, glutarate, azelate and sebacate heated lose crystallization water and next anhydrous complexes are transformed to Y2O3, whereas yttrium adipate, pimelate and suberate on heating lose some water molecules and, the mono- or dihydrates formed are decomposed to Y2O3. The properties of the studied complexes change discretely according to odd or even number of carbon atoms in the chain.
Zusammenfassung Durch Auflösen von Y(OH)3 in einer Lösung der entsprechenden Säure und anschliessendem Kristallisieren wurden Yttriummalonat,-succinat und -glutarat dargestellt, das Yttriumadipat, -pimelat-, -suberat und -azelainat und sebacate hingegen in der Reaktion von YCl3 mit dem Ammoniumsalz der Säure. In Form kristalliner Feststoffe wurden Yttriumalkanodicarboxylate der allgemeinen Formel Y2L3,nH2O mitn=3, 4, 6 bzw. 7 hergestellt. Ausgehend von den IR-Spektren konnte die Art der Koordinierung als COO– y3+ festgestellt werden. Beim Erhitzen geben Ytrriummalonat, -succinat, -glutarat, azelainat und -sebazat ihr Kristallwasser ab, aus den anhydratierten Komplexen bildet sich anschliessend Y2O3, während Yttriumadipet, pimelat und -suberat einige Wassermoleküle verlieren und die monooder dihydratierten Formen sich dann zu Y2O3 zersetzen. Die Eigenschaften der untersuchten Komplexe variieren eindeutig in Abhängigkeit davon, ob sich in der Kette eine gerade oder ungerade Anzahl von Kohlenstoffatomen befindet.相似文献
89.
Mangeney C Ferrage F Aujard I Marchi-Artzner V Jullien L Ouari O Rékaï el D Laschewsky A Vikholm I Sadowski JW 《Journal of the American Chemical Society》2002,124(20):5811-5821
Citrate-capped gold nanoparticles as well as planar gold surfaces can be efficiently grafted with a covalently attached polymer monolayer a few nanometers thick, by simple contact of the metal surface with dilute aqueous solutions of hydrophilic polymers that are end-capped with disulfide moieties, as shown by UV/vis absorption, dynamic light scattering, and surface plasmon resonance studies. The hydrophilic polymer-coated gold colloids can be freeze-dried and stored as powders that can be subsequently dissolved to yield stable aqueous dispersions, even at very large concentrations. They allow for applying filtrations, gel permeation chromatography, or centrifugation. They do not suffer from undesirable nonspecific adsorption of proteins while allowing the diffusion of small species within the hydrogel surface coating. In addition, specific properties of the original hydrophilic polymers are retained such as a lower critical solution temperature. The latter feature could be useful to enhance optical responses of functionalized gold surfaces toward interaction with various substrates. 相似文献
90.
Menadione (vitamin K3) undergoes a reversible two-electron transfer involving the quinone structure in acidic medium. As demonstrated by using cyclic voltammetry, the reduced form is more strongly adsorbed than the oxidized one. Stripping voltammetry of an adsorbed layer has been applied to the determination of this molecule after preconcentration of the reduced compound and scanning the potential towards less negative values. Adsorption, which is highly effective when stirring is used, approaches an equilibrium process in quiescent solution, as evidenced by a loss of part of the adsorbed material when stirring is stopped. A square-wave mode has been selected owing to its high sensitivity (the current is 20 times that for the differential pulse mode), but also to its high scan-rate, which minimizes the slow desorption process occurring during the scan. A concentration range from 2 × 10−10 to 5 × 10−7 M is easily investigated, the detection limit being 1.3 × 10−10 M. The influence of several operational parameters has also been considered. 相似文献