全文获取类型
收费全文 | 1102篇 |
免费 | 44篇 |
国内免费 | 4篇 |
专业分类
化学 | 664篇 |
晶体学 | 26篇 |
力学 | 33篇 |
数学 | 84篇 |
物理学 | 343篇 |
出版年
2023年 | 13篇 |
2022年 | 16篇 |
2021年 | 26篇 |
2020年 | 16篇 |
2019年 | 27篇 |
2018年 | 30篇 |
2017年 | 18篇 |
2016年 | 38篇 |
2015年 | 35篇 |
2014年 | 38篇 |
2013年 | 100篇 |
2012年 | 77篇 |
2011年 | 80篇 |
2010年 | 58篇 |
2009年 | 47篇 |
2008年 | 65篇 |
2007年 | 57篇 |
2006年 | 56篇 |
2005年 | 50篇 |
2004年 | 39篇 |
2003年 | 38篇 |
2002年 | 28篇 |
2001年 | 8篇 |
2000年 | 11篇 |
1999年 | 10篇 |
1998年 | 8篇 |
1997年 | 7篇 |
1996年 | 13篇 |
1995年 | 17篇 |
1994年 | 13篇 |
1993年 | 7篇 |
1992年 | 6篇 |
1991年 | 3篇 |
1990年 | 3篇 |
1989年 | 4篇 |
1985年 | 3篇 |
1983年 | 4篇 |
1982年 | 7篇 |
1981年 | 5篇 |
1980年 | 7篇 |
1978年 | 4篇 |
1976年 | 7篇 |
1975年 | 4篇 |
1970年 | 3篇 |
1968年 | 3篇 |
1967年 | 2篇 |
1937年 | 2篇 |
1930年 | 10篇 |
1929年 | 4篇 |
1906年 | 2篇 |
排序方式: 共有1150条查询结果,搜索用时 296 毫秒
21.
Synthesis of recently isolated bioactive natural products chaetomellic acid A anhydride (1) and a novel 1,7(Z)-nonadecadiene-2,3-dicarboxylic acid (2) have been described. Chemoselective carbon[bond]carbon S(N)2' coupling reactions of appropriate Grignard reagents with dimethyl bromomethylfumarate (7) in diethyl ether in the presence of HMPA at room temperature furnished the corresponding diesters 8 and 15 in 60-62% yields. The formed diesters 8 and 15 on hydrolysis gave respectively the corresponding desired diacids 9 and 2 in quantitative yields. Acetic anhydride induced ring closure of diacids 9 and 2 respectively gave the chaetomellic acid A anhydride (1) and isochaetomellic acid B anhydride (16) with 38-39% overall yields in five steps. 相似文献
22.
Summary The amount of adsorption and exchange of lead on the electrode membrane as a function of time was correlated to the potential measurement stability. The adsorption and exchange of lead in various organic solvents tend to be increased relating to the increase in the dielectric constant of solvents. Removal of O2 and CO2 and addition of methanol and formaldehyde are very effective means to improve the potential stability. The behavior of lead ISE exposed to solutions containing lead and other interfering ions was also studied.
Radiochemische Untersuchung der Adsorptions- und Austauschreaktionen bleiionenspezifischer Elektroden
Zusammenfassung Adsorption und Austausch von Blei an der Elektrodenmembran als Funktion der Zeit wurden zur Stabilität der Potentialmessung in Beziehung gesetzt. In verschiedenen organischen Lösungsmitteln steigen Adsorption und Austausch mit der Dielektrizitätskonstante an. Die Entfernung von O2 und CO2 sowie der Zusatz von Methanol und Formaldehyd verbessern die Stabilität des Potentials. Das Verhalten von bleiionenspezifischen Elektroden gegenüber Lösungen, die Blei und andere störende Ionen enthalten, wurde untersucht.相似文献
23.
Reaction of Cu(ClO(4))(2) x 6H(2)O with a racemic mixture of the novel chiral ligand N-(1,2-bis(2-pyridyl)ethyl)pyridine-2-carboxamide (PEAH) affords only the homochiral dimeric copper(II) complexes [Cu(2)((R)()PEA)(2)](ClO(4))(2) and [Cu(2)((S)()PEA)(2)](ClO(4))(2) in a 1:1 ratio. The phenomenon of molecular self-recognition is also observed when a racemic mixture of the monomeric copper(II) complex [Cu((R(S))()PEA)(Cl)(H(2)O)] is converted into the homochiral dimeric species [Cu(2)((R(S))()PEA)(2)](ClO(4))(2) via reaction with Ag(+) ion. This is the first report of direct conversion of a racemic mixture of a chiral monomeric copper(II) complex to a mixture of the homochiral dimers. 相似文献
24.
Anirban Kar 《Tetrahedron》2005,61(22):5297-5302
Starting from citraconic anhydride (13), a simple multistep (9-10 steps) synthesis of naturally occurring butyrolactones maculalactone A (3), maculalactone B (1), maculalactone C (2) and nostoclide I (4) have been described with good overall yields via dibenzylmaleic anhydride (20) and benzylisopropylmaleic anhydride (27). The two anhydrides 20 and 27 were prepared by SN2′ coupling reactions of appropriate Grignard reagents with dimethyl bromomethylfumarate (14), LiOH-induced hydrolysis of esters to acids, bromination of carbon-carbon double bond, in situ dehydration followed by dehydrobromination and chemoselective allylic substitution of bromoatom in disubstituted anhydrides 19 and 26 with appropriate Grignard reagents. The NaBH4 reduction of these anhydrides 20 and 27 furnished the desired lactones 21 and 29, respectively. The lactone 21 on Knoevenagel condensation with benzaldehyde, furnished maculalactone B (1), which on isomerization gave maculalactone C (2). Selective catalytic hydrogenation of 1 gave maculalactone A (3). The conversion of lactone 29 to nostoclide I (4) is known. 相似文献
25.
Pradip K. Bhowmik Haesook Han James J. Cebe Ronald A. Burchett Ananda M. Sarker 《Journal of polymer science. Part A, Polymer chemistry》2002,40(5):659-674
A series of viologen polymers with bromide, tosylate, and triflimide as counterions were prepared by either the Menshutkin reaction or metathesis reaction in a common organic solvent. Their polyelectrolyte behavior in methanol was determined by solution viscosity measurements, and their chemical structures were determined by Fourier transform infrared and Fourier transform NMR spectroscopy. They were characterized for their thermotropic liquid‐crystalline properties with a number of experimental techniques. Each of the viologen polymers with organic counterions had a low melting transition or fusion temperature above which it formed either a high‐order smectic phase or a low‐order smectic phase. Each of them also exhibited a smectic‐to‐isotropic transition. The ranges of the liquid‐crystalline phase were 80–88 °C for viologen polymers with tosylate as a counterion and 120–146 °C for viologen polymers with triflimide as a counterion. They had excellent thermal stability. The ranges of thermal stability were 288–329 °C for viologen polymers with tosylate as a counterion and 343–350 °C for viologen polymers with triflimide as a counterion. The fluorescence property for all of the viologen polymers in either aqueous or methanol solution was also included in this study. For example, the viologen polymer containing the 4,4′‐bipyridinium and p‐xylyl units along the backbone of the polymer chain with triflimide as a counterion had an absorption spectrum (λmax = 265 nm), an excitation spectrum (λex values = 357, 443, and 454 with monitoring at 533 nm), and an emission spectrum (λem = 536 nm with excitation at 430 and 450 nm) in methanol. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 659–674, 2002; DOI 10.1002/pola.10134 相似文献
26.
Pradip K. Bhowmik Robert W. Lenz 《Journal of polymer science. Part A, Polymer chemistry》1994,32(4):651-659
A series of fully aromatic, thermotropic polyesters based on 1,1′-binaphthyl-4,4′-diol, BND, was prepared by the melt polycondensation method and characterized for their thermotropic behavior by a variety of experimental techniques. The homopolymer of BND with terephthalic acid formed a nematic melt at 353°C. In contrast, the polyester from BND and 2,6-naphthalenedicarboxylic acid had a melting transition, Tm, above 400°C, so it was not possible with the equipment available to determine whether it formed a nematic melt. All of the copolymers of BND formed nematic melts at much lower Tm values than those of its respective homopolymers, as expected, because of the copolymerization effect of the added monomer. Moreover, all of the copolymers had higher glass transition temperatures, Tg, than those of other liquid crystalline polyesters and higher thermal stabilities. © 1994 John Wiley & Sons, Inc. 相似文献
27.
Summary Investigations were carried out on the isomerization and base hydrolysis ofcis andtrans forms of dithiosulphatobis-(ethylenediamine)cobalt(III) ions. Thecis form isomerizes to thetrans form in neutral aqueous medium, rates being 1.15, 2.30 and 4.0×10–5s–1, respectively at 42, 50 and 58 °C. Thetrans complex isomerizes to thecis form in basic solution only, the rate varying with pH in a sigmoid pattern. In presence of OH–, an acid-base equilibrium of the complex ion sets in, but only the basic form takes part in the isomerization reaction. Hydrolysis of thecis isomer proceeds through a base-dependent path only, but that of thetrans isomer proceeds both through base-dependent and base-independent paths. The mechanisms are associative in nature. Thetrans form reacts faster thancis in all cases. 相似文献
28.
N-Bromosuccinimide-dibenzoyl peroxide/azobisisobutyronitrile is used to carry out several types of Z- to E-alkene isomerizations. The NBS-bromination conditions are sufficient for both allylic bromination and alkene isomerization. When the allylic hydrogens are not available in substrates, only the isomerization of the alkene takes place. The present conditions for isomerization of carbon-carbon double bonds are mild and efficient. 相似文献
29.
Two new iron nitrosyls derived from two designed pentadentate ligands N,N-bis(2-pyridylmethyl)-amine-N'-(2-pyridylmethyl)acetamide and N,N-bis(2-pyridylmethyl)-amine-N'-[1-(2-pyridinyl)ethyl]acetamide (PcPy(3)H and MePcPy(3)H, respectively, where H is the dissociable amide proton) have been structurally characterized. These complexes are similar to a previously reported (Fe-NO)6 complex, [(PaPy(3))Fe(NO)](ClO(4))(2) (1) that releases NO under mild conditions. The present nitrosyls, namely [(PcPy(3))Fe(NO)](ClO(4))(2) (2) and [(MePcPy(3))Fe(NO)](ClO(4))(2) (3), belong to the same (Fe-NO)6 family and exhibit (a) clean (1)H NMR spectra in CD(3)CN indicating S = 0 ground state, (b) almost linear Fe-N-O angles (177.3(5) degrees and 177.6(4) degrees for 2 and 3, respectively), and (c) N-O stretching frequencies (nu(NO)) in the range 1900-1925 cm(-)(1). The binding of NO at the non-heme iron centers of 1-3 is completely reversible and all three nitrosyls rapidly release NO when exposed to light (50 W tungsten bulb). In addition to acting as photoactive NO-donors, these complexes also nitrosylate thiols such as N-acetylpenicillamine, 3-mercaptopropionic acid, and N-acetyl-cysteine-methyl-ester in yields that range from 30 to 90% in the absence of light. The addition of alkyl or aryl thiolate (RS(-)) to the (Fe-NO)6 complexes in the absence of dioxygen results in the reduction of the iron metal center to afford the corresponding (Fe-NO)7 species. 相似文献
30.
[reactions: see text] [(Ph3P)CuH]6 effectively catalyzes the hydrostannation of activated alkynes with exclusive regioselectivity for alpha-stannation. Syn hydrostannation is observed exclusively for alkynoates. Anti or syn hydrostannation adducts are obtained as products for alkynone substrates. 相似文献