全文获取类型
收费全文 | 2770篇 |
免费 | 58篇 |
国内免费 | 8篇 |
专业分类
化学 | 1838篇 |
晶体学 | 29篇 |
力学 | 38篇 |
数学 | 587篇 |
物理学 | 344篇 |
出版年
2022年 | 19篇 |
2020年 | 49篇 |
2019年 | 29篇 |
2018年 | 19篇 |
2017年 | 25篇 |
2016年 | 44篇 |
2015年 | 69篇 |
2014年 | 58篇 |
2013年 | 102篇 |
2012年 | 99篇 |
2011年 | 115篇 |
2010年 | 86篇 |
2009年 | 64篇 |
2008年 | 130篇 |
2007年 | 115篇 |
2006年 | 100篇 |
2005年 | 105篇 |
2004年 | 83篇 |
2003年 | 68篇 |
2002年 | 52篇 |
2001年 | 24篇 |
2000年 | 34篇 |
1999年 | 27篇 |
1998年 | 34篇 |
1997年 | 24篇 |
1996年 | 24篇 |
1995年 | 29篇 |
1994年 | 31篇 |
1993年 | 41篇 |
1992年 | 33篇 |
1991年 | 24篇 |
1989年 | 30篇 |
1988年 | 33篇 |
1987年 | 30篇 |
1985年 | 36篇 |
1984年 | 50篇 |
1983年 | 27篇 |
1982年 | 24篇 |
1981年 | 34篇 |
1980年 | 39篇 |
1979年 | 29篇 |
1978年 | 25篇 |
1977年 | 29篇 |
1976年 | 25篇 |
1975年 | 29篇 |
1974年 | 27篇 |
1972年 | 18篇 |
1966年 | 20篇 |
1965年 | 18篇 |
1956年 | 26篇 |
排序方式: 共有2836条查询结果,搜索用时 0 毫秒
31.
Josef Edinger Heinz Falk Walter Jungwirth Norbert Müller Ulrich Zrunek 《Monatshefte für Chemie / Chemical Monthly》1984,115(8-9):1081-1099
From an investigation of the ICD of bilatrienes-abc and 2,3-dihydrobilatrienes-abc induced by mixtures of CCl4 with (+)-cis-Pinane, (–)-lactic and (+)-tartaric acid esters it is concluded that specific interactions between chromophore and the chiral reagents afford a partial resolution of the labile racemate of helices. Attaching chiral residues covalently to the chromophore induces very low resolution of the same kind in case of apolar ligands like a cholesteryl-residue. However, with polar ligands as in the case ofBoc-lysyl derivatives enantiomeric excesses up to 90% are achieved depending on the solvent used.
Herrn Prof. Dr.Karl Schlögl zu seinem 60. Geburtstag gewidmet. 相似文献
32.
33.
Katsufumi Hashimoto Jií íek Josef Paldus 《International journal of quantum chemistry》1988,34(5):407-415
The ground state energies of finite Hubbard molecules are calculated by numerically solving the Lieb–Wu equations for a complex Hubbard repulsion parameter U. From the positions of the singular points located in the complex plane, the radii of convergence of the perturbation expansions for the ground state energies are determined. 相似文献
34.
The model of two interacting ethylene molecules having D
2h symmetry was studied using generalized Hückel method. The validity of - separation was tested on this model. The general character of the ground state and lower lying excited states of the model was discussed and the implications drawn concerning transannular interaction and excimer formation. The values obtained for the dissociation energy of the first excited state of our model and corresponding equilibrium intermolecular distance are of right order of magnitude.
Zusammenfassung Mittels der verallgemeinerten Hückel-Methode wurde das Modell von zwei Äthylenmolekülen mit der Symmetrie D 2h studiert. An diesem Modell wurde die Gültigkeit der - -Separation geprüft. Der allgemeine Charakter des Grundzustandes und der niedriger liegenden angeregten Zustände des Modells wird erörtert und die Folgerungen in Bezug auf transannulare Wechselwirkung und Excimer-Entstehung diskutiert. Die erhaltenen Werte für die Dissoziationsenergie des ersten angeregten Zustandes von unserem Modell und den entsprechenden intermolekularen Gleichgewichtsabstand haben die richtige Größenordnung.
Résumé Le modèle à symétrie D 2h de deux molécules d'éthylène en interaction a été étudié en utilisant la méthode généralisée de Hückel. On a examiné la validité de la séparation - sur ce modèle. Le caractère général de l'état fondamental et celui des états excités inférieurs du modèle furent discutés et on a fait des déductions sur l'interaction transannulaire et sur la formation d'«excimères». Les valeurs obtenues pour l'énergie de dissociation du premier état excité de notre modèle et la distance intermoléculaire d'équilibre corréspondante ont l'ordre de magnitude correct.相似文献
35.
Shelby E. Thames Josef F. McClesky Phillip L. Kelly 《Journal of heterocyclic chemistry》1968,5(6):749-752
The preparation of several 2-furyl-, 2-thienyl-, benzyl-, and allylsubstituted silanes is reported. Such derivatives, when treated with aziridine in the presence of a metal catalyst, afford good yields of silylaziridines and silyldiaziridines. A qualitative study of electronic and steric requirements of the displacement reaction is reported. 相似文献
36.
Summary An isotope dilution method for the determination of rare earth impurities in uranium has been developed and Ce, Nd, Sm, Eu and Gd have been determined in uranium oxide samples. The method involves isotopic dilution with enriched isotopes of the rare earths being measured, followed by the separation of rare earths from uranium. A mass spectrometer with thermionic source was used to determine the relative isotopic abundances in each of these rare earths. All these five elements were analysed selectively by preferential evaporation technique. Trace concentrations down to parts per billion range can be measured with good sensitivity and accuracy.
Bestimmung von Verunreinigungen an Seltenen Erden in hochreinem Uran durch Isotopenverdünnungsanalyse
Zusammenfassung Eine Isotopenverdünnungsmethode wurde ausgearbeitet zur Bestimmung von Ce, Nd, Sm, Eu und Gd in Uranoxidproben. Das Verfahren umfaßt isotopische Verdünnung mit angereicherten Isotopen der zu bestimmenden Elemente und nachfolgende Abtrennung der Seltenen Erden von Uran. Die relativen Isotopenhäufigkeiten wurden mit Hilfe eines Massenspektrometers mit thermischer Ionenquelle bestimmt. Alle fünf Elemente wurden durch selektive Verdampfung analysiert. Spurenkonzentrationen bis herab zum ppb-Bereich konnten mit guter Empfindlichkeit und Genauigkeit erfaßt werden.相似文献
37.
38.
39.
The prediction of migration time of electroosmotic flow (EOF) marker was achieved by applying artificial neural networks (ANN) model based on principal component analysis (PCA) and standard normal distribution simulation to the input variables. The voltage of performance, the temperature in the capillary, the pH and the ionic strength of background electrolytes (BGE) were applied as the input variables to ANN. The range of the performance voltage studied was from 15 to 27 kV, and that of the temperature in the capillary was from 20 to 30 °C. For the pH values studied, the range was from 5.15 to 8.04. The range of the ionic strength investigated in this paper was from 0.040 to 0.097. The prediction abilities of ANN with different pre-processing procedure to the input variables were compared. Under the same performance conditions, the average prediction error of the migration time of the EOF marker was 5.46% with RSD = 1.76% according to 10 parallel runs of the optimized ANN structure by the proposed approach, and that of the 10 parallel predictions of the optimal ANN structure for the different performance conditions was 12.95% with RSD = 2.29% according to the proposed approach. The study showed that the proposed method could give better predicted results than other approaches discussed. 相似文献
40.
Treatment of a solution of excess PCl(3) and PS (PS = "proton sponge" = 1,8-dimethylamino naphthalene) with arachno-4-CB(8)H(14) (1) in CH(2)Cl(2), followed by hydrolysis of the reaction mixture, resulted in the isolation of the eleven-vertex diphosphacarbaborane nido-7,8,9-P(2)CB(8)H(10) (2) (yield 34%) as the main product. Other products isolated from this reaction were the phosphacarboranes nido-7,8,9,10-P(3)CB(7)H(8) (3) (yield 5%) and closo-2,1-PCB(8)H(9) (4) (yield 15%). Compound 2 can be deprotonated by PS in CH(2)Cl(2) or NaH in diethyl ether to give the [nido-7,8,9-P(2)CB(8)H(9)](-) (2(-)()) anion, which gives back the original compound, 2, upon re-protonation. Thermal rearrangement of anion 2(-) (Na(+) salt) at 350 degrees C for 2 h produced the isomeric [nido-7,8,10-P(2)CB(8)H(9)](-) (5(-)()) anion, which was isolated as a PPh(4)(+) salt (yield 86%). Multinuclear ((1)H, (11)B, (31)P, and (13)C), two-dimensional [(11)B-(11)B] COSY, (1)H{(11)B(selective)}, (1)H{(31)P(selective)}, and gradient-enhanced ([(1)H-(13)C] HSQC) magnetic resonance measurements led to complete assignments of all resonances which are in excellent agreement with the structures proposed. Coupling constants, (1)J((31)P,(13)C), (2)J((31)P,C,(1)H), and (1)J((31)P,(31)P), were calculated using the DFT method B3LYP/6-311+G(d,p). The molecular geometries of all compounds were optimized ab initio at a correlated level of theory (RMP2(fc)) using the 6-31G basis set, and their correctness was assessed by comparison of the experimental (11)B and (13)C chemical shifts with those calculated by the GIAO-SCF/II//RMP2(fc)/6-31G method. The computations also include the structures and chemical shieldings of the still unknown isomers [nido-7,10,8-P(2)CB(8)H(9)](-) (6(-)) and [nido-7,9,8-P(2)CB(8)H(9)](-) (7(-)). 相似文献