全文获取类型
收费全文 | 736篇 |
免费 | 43篇 |
国内免费 | 1篇 |
专业分类
化学 | 560篇 |
晶体学 | 2篇 |
力学 | 7篇 |
数学 | 89篇 |
物理学 | 122篇 |
出版年
2023年 | 6篇 |
2022年 | 15篇 |
2021年 | 13篇 |
2020年 | 15篇 |
2019年 | 26篇 |
2018年 | 15篇 |
2017年 | 7篇 |
2016年 | 28篇 |
2015年 | 39篇 |
2014年 | 28篇 |
2013年 | 49篇 |
2012年 | 48篇 |
2011年 | 35篇 |
2010年 | 29篇 |
2009年 | 25篇 |
2008年 | 31篇 |
2007年 | 33篇 |
2006年 | 48篇 |
2005年 | 45篇 |
2004年 | 46篇 |
2003年 | 30篇 |
2002年 | 24篇 |
2001年 | 10篇 |
2000年 | 13篇 |
1999年 | 9篇 |
1998年 | 9篇 |
1997年 | 11篇 |
1996年 | 10篇 |
1995年 | 4篇 |
1994年 | 5篇 |
1993年 | 3篇 |
1992年 | 4篇 |
1990年 | 2篇 |
1989年 | 4篇 |
1988年 | 4篇 |
1987年 | 6篇 |
1986年 | 4篇 |
1985年 | 5篇 |
1984年 | 5篇 |
1983年 | 3篇 |
1981年 | 3篇 |
1980年 | 3篇 |
1979年 | 2篇 |
1976年 | 4篇 |
1975年 | 2篇 |
1974年 | 2篇 |
1973年 | 3篇 |
1972年 | 2篇 |
1962年 | 2篇 |
1936年 | 1篇 |
排序方式: 共有780条查询结果,搜索用时 15 毫秒
1.
Employing a cleavable carbohydrate–peptide linker, a new strategy for single-bead analysis of multivalent cyclic neoglycopeptides based on Edman degradation is described. Edman degradation of glycopeptides is hampered by the acid lability of the glycosidic bond and potential incompatibilities of phenylthiohydantoin (PTH) derivatives of glycosylated amino acids with PTH derivatives of the proteinogenic amino acids. To overcome this problem, carbohydrates are detached from the cyclopeptide templates before single-bead analysis, allowing for micro sequencing under routine conditions. With this strategy, application of multivalent cyclic neoglycopeptides in split-mix libraries with a subsequent screening process becomes possible for the first time. 相似文献
2.
3.
Zusammenfassung Zunächst wird im Zusammenhang mit Messungen der Fällungsgeschwindigkeit von Thorium X in sulfathaltigen Lösungen eine Methode beschrieben, die es gestattet, während der Fällung, und zwar ohne Störung des Fällungsvorganges, diejenigen Mengen von Thorium X zu bestimmen, die sich jeweils zu bestimmten Zeitpunkten noch in Lösung befinden; dabei konnte der Gehalt an Th X mit Hilfe einer Emanationsmethode genau ermittelt werden.Die Versuchsergebnisse, die in Kurven wiedergegeben sind, lassen deutlich erkennen, daß die Fällung von Th X nicht momentan erfolgt, sondern eine gewisse Zeit beansprucht, die von der Konzentration der zugesetzten Sulfat- und Bariumchloridlösung sowie vom Zusatz anderer Fremdionen abhängig ist; es wird jedoch schließlich immer der gleiche Endzustand vollständiger Ausfällung erreicht, wenn mit äquivalenten Mengen gearbeitet wird.Die Annahme, daß die Fällung momentan erfolgt, daß aber das Fällungsprodukt sich im Laufe der Zeit von einem feinkristallinischen Zustand mit großer Emanierfähigkeit in einen grobkristallinen mit geringer Emanationsabgabe umwandelt, konnte durch besondere Experimente widerlegt werden.Schließlich wird noch eine Apparatur zur Messung des Thorongehalts angegeben, die auch für Untersuchungen des Thoriumgehalts von Quellwässern Anwendung finden kann.
Summary A method has been worked out which makes it possible to determine the rate of precipitation of thorium X in solutions containing sulphate ion. The amount of thorium X is determined rapidly and accurately by the thorium emanation—thoron—evolved under fixed conditions. Determinations have been made every 5 minute during the time following precipitation, and the results are given graphically.They bring forward, very clearly, that the precipitation of thorium X requires a certain length of time, depending on the concentration of the sulphate and barium-chloride solutions used and on the presence of other ions. However, if equivalent quantities of barium- and sulphate ions are used, the same final result is always reached.It might have been supposed that the precipitation takes place instantaneously but that in course of time, the precipitate undergoes changes through recrystallisations and that the emanating power changes accordingly. That hypothesis, however, could be disproved by special experiments.At last an apparatus for measuring the thoron content is given which can also be applied for investigations of the thorium content of source waters.
Résumé Les auteurs décrivent une méthode qui leur a permis de déterminer la vitesse de précipitation du thorium X en solutions contenant de l'ion sulfurique. Le thorium X est dosé par son émanation — le thoron — sous des conditions fixées, et les dosages peuvent se faire à intervalles régulières pendant le temps que demande la précipitation.Les résultats montrent que la précipitation du thorium X ne se fait point à l'instant, mais demande un certain temps, dépendant de la concentration des solutions de sulfate et de chlorure de baryum ajoutées et aussi de la présence d'ions étrangers.Les auteurs réfutent par leurs expériences la théorie que la précipitation se fait momentanément et que le précipité change peu à peu son état cristallin et par cela même, sa faculté de dégager l'émanation.Enfin les auteurs décrivent un appareil pour les dosages de thoron, qui pourra servir de même pour déterminer la teneur en thorium dans les eaux vives.相似文献
4.
5.
Polyethers, which are produced by alcoholysis of oxiranes, are often used as solvents in chemical plants. The spectra of the products can be influenced by the choice of the catalyst (acid or base). The results of the base-catalyzed ethanolysis of 1,2-epoxybutane are displayed. The reaction was investigated calorimetrically by varying the molar ratio between ethanol and 1,2-epoxybutane, the starting temperature and the concentration of the catalyst sodium hydroxide. Additionally, the influence of the used alcohol will be shown in one example. To determine the activation parameters, the experiments were evaluated by the nonlinear software package TA-kin v3.3. 相似文献
6.
Dunahay Terri G. Jarvis Eric E. Dais Sonja S. Roessler Paul G. 《Applied biochemistry and biotechnology》1996,57(1):223-231
Applied Biochemistry and Biotechnology - Genetic transformation of two species of diatoms has been accomplished by introducing chimeric plasmid vectors containing a bacterial antibiotic resistance... 相似文献
7.
M. Schneider A. Hinz A. Groh K. M. Evenson W. Urban 《Applied physics. B, Lasers and optics》1987,44(4):241-245
Frequency stabilization of the CO laser using a CO lamb-dip is achieved in the range from 5.0–6.3 m. The CO saturation signal is obtained from a low-pressure discharge in absorption and is detected using optogalvanic, detection. The frequency stability and reproducibility has been verified to be better than 100 kHz; this is an improvement of more than one order of magnitude compared with locking techniques using CO laser gain profiles.Alexander von Humboldt Awardee from National Bureau of Standards, Boulder, Colorado, USA 相似文献
8.
Bühl M Grigoleit S Kabrede H Mauschick FT 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,12(2):477-488
59Co chemical shifts were computed at the GIAO-B3LYP level for [Co(CN)6]3-, [Co(H2O)6]3+, [Co(NH3)6]3+, and [Co(CO)4]- in water. The aqueous solutions were modeled by Car-Parrinello molecular dynamics (CPMD) simulations, or by propagation on a hybrid quantum-mechanical/molecular-mechanical Born-Oppenheimer surface (QM/MM-BOMD). Mean absolute deviations from experiment obtained with these methods are on the order of 400 and 600 ppm, respectively, over a total delta(59Co) range of about 18,000 ppm. The effect of the solvent on delta(59Co) is mostly indirect, resulting primarily from substantial metal-ligand bond contractions on going from the gas phase to the bulk. The simulated solvent effects on geometries and delta(59Co) values are well reproduced by using a polarizable continuum model (PCM), based on optimization and perturbational evaluation of quantum-mechanical zero-point corrections. 相似文献
9.
[RhH(CO)(PPh3)2] (1) reacts with Et3N·3HF to give the fluoro compound [RhF(CO)(PPh3)2] (2). In a comparable reaction [RhF(PEt3)3] (5) has been obtained from [RhH(PEt3)3] (3) or [RhH(PEt3)4] (4) with substoichiometric amounts of Et3N·3HF in THF. If the latter reaction is carried out in benzene, the complexes 5, cis-mer-[Rh(H)2F(PEt3)3] (6) and cis-fac-[Rh(H)2F(PEt3)3] (7) are obtained. Treatment of 5 with HCl in ether effects the generation of [RhCl(PEt3)3] (8) and the bifluoride compound [Rh(FHF)(PEt3)3] (9), which can be converted into 5 in the presence of Et3N and Cs2CO3. Treatment of 5 with HSiR2Ph (R=Ph, Me) leads to the formation of 3 and the rhodium(III) silyl complexes fac-[Rh(H)2(SiR2Ph)(PEt3)3] (10: R=Ph, 11: R=Me). 相似文献
10.
Novel representatives of the important group of biologically active dibenzosuberone derivatives were prepared: 3,7-dibromo-5-(dimethylaminoethyl- oxyimino)-10,11-dihydro-5H-dibenzo[a,d]cyclohepta-1,4-diene (1), 3,7-dibromo-5-(3- dimethylaminopropylidene)-10,11-dihydro-5H-dibenzo[a,d]cycloheptene (2) and 1,7- dibromo-5-(3-dimethylaminopropylidene)-10,11-dihydro-5H-dibenzo-[a,d]-cycloheptene (3). These compounds are potential tricyclic antidepressants (TCAs), which are still the most frequently prescribed antidepressants in many countries. 相似文献