全文获取类型
收费全文 | 1561篇 |
免费 | 41篇 |
国内免费 | 4篇 |
专业分类
化学 | 1064篇 |
晶体学 | 10篇 |
力学 | 19篇 |
数学 | 179篇 |
物理学 | 334篇 |
出版年
2023年 | 9篇 |
2022年 | 12篇 |
2021年 | 20篇 |
2020年 | 23篇 |
2019年 | 25篇 |
2018年 | 10篇 |
2017年 | 11篇 |
2016年 | 37篇 |
2015年 | 27篇 |
2014年 | 41篇 |
2013年 | 80篇 |
2012年 | 84篇 |
2011年 | 99篇 |
2010年 | 67篇 |
2009年 | 41篇 |
2008年 | 94篇 |
2007年 | 70篇 |
2006年 | 76篇 |
2005年 | 60篇 |
2004年 | 56篇 |
2003年 | 38篇 |
2002年 | 31篇 |
2001年 | 29篇 |
2000年 | 27篇 |
1999年 | 25篇 |
1997年 | 16篇 |
1996年 | 15篇 |
1995年 | 12篇 |
1994年 | 20篇 |
1993年 | 19篇 |
1992年 | 16篇 |
1991年 | 9篇 |
1990年 | 11篇 |
1989年 | 15篇 |
1988年 | 12篇 |
1987年 | 9篇 |
1986年 | 16篇 |
1985年 | 19篇 |
1984年 | 20篇 |
1983年 | 9篇 |
1982年 | 12篇 |
1981年 | 19篇 |
1980年 | 21篇 |
1979年 | 16篇 |
1978年 | 17篇 |
1977年 | 13篇 |
1975年 | 19篇 |
1974年 | 11篇 |
1973年 | 10篇 |
1928年 | 10篇 |
排序方式: 共有1606条查询结果,搜索用时 15 毫秒
61.
Xu S Held I Kempf B Mayr H Steglich W Zipse H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(16):4751-4757
The acetylation of tert-butanol with acetic anhydride catalyzed by 4-(dimethylamino)pyridine (DMAP) has been studied at the Becke3 LYP/6-311 + G(d,p)//Becke3 LYP/6-31G(d) level of theory. Solvent effects have been estimated through single-point calculations with the PCM/UAHF solvation model. The energetically most favorable pathway proceeds through nucleophilic attack of DMAP at the anhydride carbonyl group and subsequent formation of the corresponding acetylpyridinium/acetate ion pair. Reaction of this ion pair with the alcohol substrate yields the final product, tert-butylacetate. The competing base-catalyzed reaction pathway can either proceed in a concerted or in a stepwise manner. In both cases the reaction barrier far exceeds that of the nucleophilic catalysis mechanism. The reaction mechanism has also been studied experimentally in dichloromethane through analysis of the reaction kinetics for the acetylation of cyclohexanol with acetic anhydride, in the presence of DMAP as catalyst and triethylamine as the auxiliary base. The reaction is found to be first-order with respect to acetic anhydride, cyclohexanol, and DMAP, and zero-order with respect to triethyl amine. Both the theoretical as well as the experimental studies strongly support the nucleophilic catalysis pathway. 相似文献
62.
Nicole Harmgarth Phil Liebing Liane Hilfert Volker Lorenz Felix Engelhardt Sabine Busse Frank T. Edelmann 《无机化学与普通化学杂志》2019,645(17):1101-1109
New homoleptic complexes of selected rare‐earth elements containing the unsymmetrically substituted amidinate ligand [MeC(NEt)(NtBu)]– [= (L)–] were synthesized and fully characterized. Treatment of in situ‐prepared Li(L) ( 1 ) with anhydrous lanthanide(III) chlorides, LnCl3 (Ln = Sc, La, Ce, Ho), afforded three different types of amidinate complexes depending on the ionic radius of the central metal atom. The large La3+ formed the octa‐coordinate DME solvate La(L)3(DME) ( 2 ). Using Ce3+, the octa‐coordinate “ate” complex Li(THF)[Ce(L)4] ( 3 ) was formed. Depending on the crystallization conditions, compound 3 could be crystallized in two modifications differing in the coordination environment around Li. In the case of the smaller Sc3+ and Ho3+ ions, six‐coordinate homoleptic Sc(L)3 ( 4 ) and Ho(L)3 ( 5 ) were isolated. The title compounds were fully characterized by spectroscopic and analytical methods as well as single‐crystal X‐ray diffraction. With Ln = La and Ce, several by‐products incorporating lithium, chlorine and/or oxygen were also isolated and structurally characterized. 相似文献
63.
A. Janke H. Hiller R. Dworzak L. Ebert C. Mayr E. Kroupa G. Koller F. v. Wessely H. Lieb J. Schintlmeister M. Nießner G. Lock G. Ortner 《Mikrochimica acta》1942,30(1-2):181-192
Ohne Zusammenfassung 相似文献
64.
K. -H. Speidel M. Knopp W. Karle M. Mayr F. Hagelberg H. -J. Simonis J. Gerber P. N. Tandon 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1987,6(1):43-48
Effective transient magnetic fields have been measured for single-electron carbon and oxygen ions traversing ferromagnetic Ni and Gd hosts, respectively. The deduced values ofK-shell polarization are well explained considering spin exchange scattering as a dominant mode of polarization. 相似文献
65.
W. Lorenz J. Kusche H. Hahn E. Werle 《Fresenius' Journal of Analytical Chemistry》1968,243(1):259-263
Summary The activities of diamine oxidases (DAO) from submaxillary glands, parotid glands and kidneys, from human serum during the pregnancy and from pig serum and of DAO from pea seedlings and the activities of urease and histidine ammonia-lyase have been determined by measuring NH4
+ released from the corresponding substrates. Ammonia has been determined with the aid of glutamate dehydrogenase reaction in the coupled optic test. The specifity and sensitivity of the method, by which still 3×10–9 Mol of NH4
+ could be measured, is excellent, the performance simple and rapid. The sensitivity could be enhanced by fluorometric determination of NAD+ in strong alkali solution. A method for the preparation of tissues for the spectrophotometric test of DAO is described. The importance of DAO determination in different diseases is briefly discussed.
Supported by a grant from Deutsche Forschungsgemeinschaft. 相似文献
Zusammenfassung Die Aktivität von Diaminoxydasen aus Speicheldrüsen und Nieren, aus menschlichem Serum während der Schwangerschaft und Schweineserum und aus Erbsenkeimlingen sowie die Aktivität der Urease und Histidase wurden anhand der NH3-Abspaltung aus ihren entsprechenden Substraten bestimmt. Das entstehende Ammoniak wurde dabei mit Hilfe der Glutamatdehydrogenasereaktion im gekoppelten optischen Test gemessen. Spezifität und Empfindlichkeit der Methode, mit der noch 3 · 10–9 Mol NH4 + bestimmt werden können, sind ausgezeichnet, die Durchführung einfach und rasch. Die Empfindlichkeit konnte außerdem noch durch die fluorimetrische Bestimmung von NAD+ gesteigert werden. Für die Bestimmung der Diaminoxydasen im Gewebe wird eine Methode der Aufarbeitung des Gewebes angegeben, die praktisch keinen Verlust an Gesamtaktivität gegenüber dem Ausgangshomogenat aufweist. Die Bedeutung der Diaminoxydasebestimmung für die Klinik wird kurz diskutiert.
Supported by a grant from Deutsche Forschungsgemeinschaft. 相似文献
66.
67.
Lorenz V Fischer A Jacob K Brüser W Edelmann FT 《Chemistry (Weinheim an der Bergstrasse, Germany)》2001,7(4):848-857
The preparation and structural characterization of scandium and f-element complexes derived from the disiloxanediolate dianion, [(Ph2SiO)2O]2-, are reported. Reactions of in situ prepared Ln[N(SiMe3)2]3 (Ln = Eu, Sm, Gd) with (Ph2SiOH)2O in different stoichiometries afforded the lanthanide disiloxanediolates [Eu[[(Ph2SiO)2O]Li(Et2O)]3] (1), [[[(Ph2SiO)2O]Li(dme)]2SmCl(dme)] (2), and [[[((Ph2SiO)2O]Li(thf)2]2GdN(SiMe3)2] (3). In situ formed (Ph2SiOLi)2O reacted with anhydrous NdBr3 (molar ratio 3:1) to give polymeric [[Nd[(Ph2SiO)2O]3[mu-Li(thf)]2[mu2LiBrLi(thf)(Et2O)]]n] (4). Treatment of 3 with Ph2Si(OH)2 in the presence of acetonitrile yielded the dilithium trisiloxanediolate derivative [[Ph2Si(OSiPh2O)2][Li(MeCN)]2]2 (5), which according to an X-ray analysis displays an Li4O4 heterocubane structure. The trinuclear scandium complex [[[(Ph2SiO)2O]Sc(acac)2]2Sc(acac)] (6) was obtained by reaction of [(C5Me5)Sc(acac)2] (C5Me5 = eta5-pentamethylcyclopentadienyl) with (Ph2SiOH)2O in a 3:2 molar ratio. Selective formation of the colorless uranium(VI) derivative [U[Ph2Si(OSiPh20)2]2[(Ph2SiO)2O]] (7) was observed when uranocene, U(eta8-C8H8)2, was allowed to react with (Ph2SiOH)2O. An X-ray diffraction study of the solvated derivative [U[Ph2Si(OSiPh2O)2]2[(Ph2SiO)2O]].Et2O.TMEDA (TMEDA= N,N,N',N'-tetramethyl-ethylenediamine) (7a) revealed the presence of both the original [(Ph2SiO)2O]2- dianion as well as the ring-enlarged [Ph2Si(OSiPh2O)2]2- ligand in the same molecule. 相似文献
68.
The Thermal Behaviour of Caesiumchloroferrates(III) and Caesiumehloroferrate(III) Hydrates. II. The Rehydration of Decomposition Products of Cs3[FeCl6] — A Raman Spectroscopic Study under Definite Atmosphere of Water Vapour Cs3[FeCl6] formed by dehydration of Cs3[FeCl6] · H2O at about 160°C does not change at normal atmosphere within 3 till 4 hours. Rehydration under the vapour pressure of the eliminated water yields the monohydrate in nearly the same time. In the same manner rehydration of the solid mixture of Cs[FeCl4] and 2 CsCl formed by thermal decomposition of the metastable Cs3[FeCl6] (280°C) produces the intermediates Cs3[Fe2Cl9] and Cs2[Fe(H2O)Cl5] in mixtures with CsCl and, finally, Cs3[FeCl6] · H2O. The formation of Cs3[Fe2Cl9] from Cs[FeCl4] and CsCl is accelerated by water. The reaction cycle has been studied using Raman and IR spectroscopy. The results will be discussed with respect to thermoanalytical data. 相似文献
69.
70.
The rates of the epoxidation reactions of aldehydes, of the aziridination reactions of aldimines, and of the cyclopropanation reactions of α,β-unsaturated ketones with aryl-stabilized dimethylsulfonium ylides have been determined photometrically in dimethyl sulfoxide (DMSO). All of these sulfur ylide-mediated cyclization reactions as well as the addition reactions of stabilized carbanions to N-tosyl-activated aldimines have been shown to follow a second-order rate law, where the rate constants reflect the (initial) CC bond formation between nucleophile and electrophile. The derived second-order rate constants (log k(2)) have been combined with the known nucleophilicity parameters (N, s(N)) of the aryl-stabilized sulfur ylides 4a,b and of the acceptor-substituted carbanions 4c-h to calculate the electrophilicity parameters E of aromatic and aliphatic aldehydes (1a-i), N-acceptor-substituted aromatic aldimines (2a-e), and α,β-unsaturated ketones (3a-f) according to the linear free-energy relationship log k(2) = s(N)(N + E) as defined in J. Am. Chem. Soc.2001, 123, 9500-9512. The data reported in this work provide the first quantitative comparison of the electrophilic reactivities of aldehydes, imines, and simple Michael acceptors in DMSO with carbocations and cationic metal-π complexes within our comprehensive electrophilicity scale. 相似文献