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61.
Ogawa AK DeMattei JA Scarlato GR Tellew JE Chong LS Armstrong RW 《The Journal of organic chemistry》1996,61(18):6153-6161
We report our synthesis of the C(26)-C(37) fragment of serine/threonine protein phosphatase PP1 and PP2A inhibitor calyculin C (1). Outlined in this paper are synthetic approaches to the two components based on disconnection at the C(33)-N(3) amide bond. We report the successful synthesis of the C(33)-C(37) aza-sugar derived from D-lyxose which was coupled onto a C(26)-C(32) aminooxazole originating from L-pyroglutamic acid. Elaboration of the resulting amide to a fully deprotected C(26)-C(37) fragment of calyculin C completed our synthesis. This provided an appropriate phosphonium salt for use in a Wittig olefination for joining both halves of the natural product. 相似文献
62.
Gerard de Leeuw John S. Field Raymond J. Haines Beth McCulloch Elsie Meintjies Christiaan Monberg Gillian M. Olivier Praveen Ramdial Clifford N. Sampson Beate Sigwarth Nick D. Steen Kandasamy G. Moodley 《Journal of organometallic chemistry》1984,275(1):99-111
Reaction of [Fe2(CO)9] with a half molar amount of R2PYPR2 (Y = CH2, R = Ph, Me, OMe or OPri; Y = N(Et), R = OPh, OMe or OCH2; Y = N(Me), R = OPri or OEt) leads to the ready formation of a product which on irradiation with ultraviolet light rapidly decarbonylates to the heptacarbonyl derivative [Fe2(μ-CO)(CO)6{μ-R2PYPR2}]. Treatment of the latter with a slight excess of the appropriate ligand results, under photochemical conditions, in the formation of the dinuclear pentacarbonyl complex [Fe2(μ-CO)(C))4{μ-R2PYPR2}2] but under thermal conditions in the formation of the mononuclear species [Fe(CO)3{R2PYPR2}]. Reaction of [Ru3(CO)12] with an equimolar amount of (RO)2PN(R′)P(OR)2 (R′ = Me, R = Pri or Et; R′ = Et, R = Ph or Me) under either thermal or photochemical conditions produces [Ru3(CO)10{μ-(RO)2PN(OR)2}] which reacts further with excess (RO)2PN(R′)P(OR)2 on irradiation with ultraviolet light to afford the dinuclear compound [Ru2(μ-CO)(CO4{μ-(RO)2PN(R′)P(OR)2}2]. The molecular structure of [Ru2(μ-CO)(CO)4{μ-(MeO)2PN(Et)P(OMe)2}2], which has been determined by X-ray crystallography, is described. 相似文献
63.
Priscilla E. Greenwood Gerard Hooghiemstra 《Probability Theory and Related Fields》1991,89(2):201-210
Summary Between the operations which produce partial maxima and partial sums of a sequenceY
1,Y
2, ..., lies the inductive operation:X
n
=X
n-1(X
n-1+Y
n
),n1, for 0<<1. If theY
n
are independent random variables with common distributionF, we show that the limiting behavior of normed sequences formed from {X
n
,n1}, is, for 0<<1, parallel to the extreme value case =0. ForFD() we give a full proof of the convergence, whereas forFD()D(), we only succeeded in proving tightness of the involved sequence. The processX
n
is interesting for some applied probability models. 相似文献
64.
B. Balestri P. Y. Bertin B. Coupat G. Fournier A. Gérard E. W. A. Lingemann J. Miller J. Picard B. Saghai K. K. Seth P. Vernin 《Czechoslovak Journal of Physics》1982,32(3):255-257
Elastic scattering differential cross section data of
±
d at 65 MeV and
±
4He at 51 MeV are presented and compared respectively to fully relativistic 3-body and optical potential calculations including true pion absorption.Presented at the symposium Mesons and Light Nuclei, Liblice, Czechoslovakia, June 1981. 相似文献
65.
Henk de Vries Peter J. Hemelaar Alice C. M. Gevers Gerard M. J. Beyersbergen van Henegouwen 《Photochemistry and photobiology》1994,60(3):249-252
Abstract The negative side effects of chlorarnphenicol (CAP) mostly involve blood dyscrasias (e.g. irreversible nondose-dependent aplastic anemia), allergic skin reactions and eye damage. To learn the cause of these side effects, most research focuses on metabolically formed nitroso- and hydroxylamino derivatives in the predisposed patient. In previous investigations it was demonstrated that photochemical decomposition of CAP in vitro by UV-A leads to formation of p-nitrobenzaldehyde (pNB), p-nitrobenzoic acid (pNBA) and p-nitrosobenzoic acid (pNOBA); the latter comprises up to 45 mol% of the starting amount of CAP. Incubation of these photoproducts in rat blood showed that pNB and pNOBA rapidly react and that PNBA is stable under these conditions. Reaction products from pNB (half-life 1.7 min) proved to be pNBA and p-nitrobenzyl alcohol (pNBOH) while pNOBA (half-life 3.7 min) was converted into p-aminobenzoic acid (pABA). Exposure of CAP in rat blood to UV-A yielded the same end products: pNBA, PABA and pNBOH. To estimate the amount of oxidative stress generated in vivo by these compounds, the ability to form methemoglobin (MetHb) in erythrocytes was tested; only pNOBA and p-hydroxylaminobenzoic acid (pHABA), a possible intermediate in the decomposition of pNOBA, proved to be reactive. Ultraviolet-A exposure of rats, after intraperitoneal injection of CAP, led to 3.6 times the basic level of MetHb. In addition, covalent binding of 3H-labeled CAP photoproducts to the skin of the back and to the ears was found, which was 9.1 and 3.2 times higher, respectively, than the dark values. Toxicity toward bone marrow cells of all photoproducts was established in vitro. p-Nitrobenzaldehyde, pNOBA andpHABA were 20, 6 and 6 times more toxic than CAP, respectively. These results show that photodecomposition of CAP in vivo does occur. Its reactive photoproducts are able to cause damage that may lead to (systemic) side effects. The latter is supported by the fact that the nature of the reactive products, nitroso- and hydroxylamino derivatives, is the same as the expected metabolites. 相似文献
66.
Antonius F.M.J. Van Der Ploeg Cornelus E.M. Van Der Kolk Gerard Van Koten 《Journal of organometallic chemistry》1981,212(3):283-290
Arylmercury compounds of the type Ar2Hg and ArHgX (X = Cl, OAc) have been synthesized and characterized by 1H and 13C NMR spectroscopy; the Ar group was either 2-Me2NCH2C6H4 or (S)-2-Me2NCH(Me)C6H4, both of which contain N-donor ligands. The observation of anisochronous NMe resonances in (S)-2-Me2NCH(Me)C6H4HgX (X = Cl, OAc) at low temperature indicates that in solution the mercury centre is three-coordinate as a result of stable intramolecular HgN coordination 相似文献
67.
Kronenburg CM Rijnberg E Jastrzebski JT Kooijman H Lutz M Spek AL Gossage RA van Koten G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,11(1):253-261
(R)-[1-(Dimethylamino)ethyl]benzene reacts with nBuLi in a 1:1 molar ratio in pentane to quantitatively yield a unique hetero-aggregate (2 a) containing the lithiated arene, unreacted nBuLi, and the complexed parent arene in a 1:1:1 ratio. As a model compound, [Li(4)(C(6)H(4)CH(Me)NMe(2)-2)(2)(nBu)(2)] (2 b) was prepared from the quantitative redistribution reaction of the parent lithiated arene Li(C(6)H(4)CH(Me)NMe(2)-2) with nBuLi in a 1:1 molar ratio. The mono-Et(2)O adduct [Li(4)(C(6)H(4)CH(Me)NMe(2)-2)(2)(nBu)(2)(OEt(2))] (2 c) and the bis-Et(2)O adduct [Li(4)(C(6)H(4)CH(Me)NMe(2)-2)(2)(nBu)(2)(OEt(2))(2)] (2 d) were obtained by re-crystallization of 2 b from pentane/Et(2)O and pure Et(2)O, respectively. The single-crystal X-ray structure determinations of 2 b-d show that the overall structural motifs of all three derivatives are closely related. They are all tetranuclear Li aggregates in which the four Li atoms are arranged in an almost regular tetrahedron. These structures can be described as consisting of two linked dimeric units: one Li(2)Ar(2) dimer and a hypothetical Li(2)nBu(2) dimer. The stereochemical aspects of the chiral Li(2)Ar(2) fragment are discussed. The structures as observed in the solid state are apparently retained in solution as revealed by a combination of cryoscopy and (1)H, (13)C, and (6)Li NMR spectroscopy. 相似文献
68.
Gerard A. van Albada Ilpo Mutikainen Urho Turpeinen Jan Reedijk 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(3):m179-m181
The title mononuclear complex, [Cu(CO3)(C8H7N5)(H2O)]·2H2O, was obtained by fixation of CO2 by a mixture of copper(II) tetrafluoroborate and the ligand bis(pyrimidin‐2‐yl)amine in ethanol/water. The CuII ion of the complex has a distorted square‐pyramidal environment, with a basal plane formed by two N atoms of the ligand and two chelating O atoms of the carbonate group, while the apical position is occupied by the O atom of the coordinating water molecule. In the solid state, hydrogen‐bonding interactions are dominant, the most unusual being the Watson–Crick‐type coplanar ligand pairing through two N—H?N bonds. Lattice water molecules also participate in hydrogen bonding. 相似文献
69.
Dong Xiao Brian J. Lavey Anandan Palani Robert G. Aslanian Neng-Yang Shih Gerard P. Randolph Ruth A. Duffy 《Tetrahedron letters》2005,46(44):7653-7656
Unlike the lithiation of N-Boc-2-alkylpiperidines, which occurs at the 6-position, N-Boc-2-phenylpiperidine and N-Boc-2-phenylpyrrolidine can be lithiated exclusively at the 2-position. The tertiary carbanions can be trapped with a variety of electrophiles. This chemistry was used for the synthesis of a potent NK1 ligand (Ki = 0.3 nM). The bioactive configuration at the piperidine quaternary center was determined by X-ray analysis to be (S). 相似文献
70.
E. M. J. Bertin W. Hengartner R. Theodorescu 《Probability Theory and Related Fields》1981,57(3):327-338
Let F be a distribution function and let Q
F(l)=0 for l<0 and Q
F(l)= sup {F(x+l)–F(x): x} for l0 be its Lévy concentration function. This paper has two purposes: to give a characterization of unimodal distribution functions (Theorem 3.5) and a representation theorem for the class of unimodal distribution functions (Theorem 6.2), both in terms of their Lévy concentration functions.Work supported by the Natural Sciences and Engineering Research Council Canada Grants A-7339 and A-7223, by the Québec Action Concertée Grant ER-1023, and by the Deutsche Forschungsgemeinschaft 相似文献