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151.
The sequential reaction of the amino(trimethylsilyl)carbene complex [(CO)5W=C(NH2)C≡CSiMe3] ( 1 ) with nBuLi and [I‐Fe(CO)2Cp] affords the C(carbene)‐N bridged heterobinuclear complex [(CO)5W=C{NHFe(CO)2Cp}C≡CSiMe3] ( 2 ). Desilylation of 1 is achieved by treatment with KF in THF/MeOH. From the reaction of the resulting complex [(CO)5W=C(NH2)C≡CH] ( 3 ) with nBuLi and [I‐Fe(CO)2Cp] two binuclear WFe compounds in a ratio of approximately 1:1 are obtained: the C(carbene)‐C≡C bridged complex 4 and the C(carbene)‐N bridged complex 5 . Repetition of the deprotonation/metallation sequence yields the trinuclear WFe2 complex 6 . One Fe(CO)2Cp fragment in 6 is bonded to the amino group and the other one to the terminal carbon atom of the ethynyl substituent. The analogous reaction of 3 with nBuLi and [Br‐Ni(PMe2Ph)2Mes] gives a ca. 1:1 mixture of two heterobinuclear complexes ( 7 and 8 ). Complex 7 is bridged by the C(carbene)‐C≡C and complex 8 by the C(carbene)‐N fragment. Subsequent reaction of 7 with BuLi and [Br‐Ni(PMe2Ph)2Mes] finally affords the trinuclear WNi2 complex 9 related to 6 . The solid‐state structure of 2 is established by an X‐ray diffraction analysis. The spectroscopic data of the bi‐ and trinuclear complexes indicate electronic communication between the metal centers through the bridging group. 相似文献
152.
Didier Legroux Jean-Paul Schoeni Christiane Pont Jean-Pierre Fleury 《Helvetica chimica acta》1987,70(1):187-195
2-Aza-1,3-dienes. Access to N-Aminoimidazoles, 3H-Pyrroles, [1,2,4]Triazolo[1,5-a]pyrazines, or Imidazo[1,2-a]pyrazines Nucleophilic attack of 5-(dialkylamino)-2-aza-1,3-diene-1,1-dicarbonitriles (or their 1-methoxycarbonyl analogous) by hydrazines or hydrazdes gives substituted N-aminoimidazoles, [1,2,4]triazolo-[1,5-a]pyrazines, or α-dihydrazino derivatives. With α-amino esters (or analogous), imidazo[1,2-a]pyrazines are produced. Addtion of cyanide anions occurs also with formation of substituted 3H-pyrroles. Structures and rationalisation of this nucleophilic attack are discussed. 相似文献
153.
Fritz Gerd Weber Christiane Kaatz Reiner Radeglia Hubert Köppel 《Monatshefte für Chemie / Chemical Monthly》1992,123(1-2):81-92
Summary The first synthesis ofthreo chalcone bromohydrins was realized by reaction oftrans chalcone epoxides with SnBr4 in molar ratios from 1:1 to 2:1. The compounds were obtained in high yields and isomeric purity. Their configuration was determined asthreo by different methods based on13C-NMR shifts of C- and C- atoms. 相似文献
154.
Martine Croisy-Delcey Emile Bisagni Christiane Huel Danielle Zilberfarb Alain Croisy 《Journal of heterocyclic chemistry》1991,28(1):65-71
Using 2-methoxy- and 2,5-dimethoxyacetophenones 8a and 8b as starting materials, 1-chloro-4-methylisoquinoline-5,8-quinone ( 6 ) and its 6-bromo derivative 7 were obtained via multistep sequences. Whereas Diels-Alder condensation of the former compound with homophthalic anhydride ( 22 ) led to a mixture of the two possible isomers: 1-chloro-11-hydroxy-4-methylnaphtho[2,3-g]isoquinoline-5,12-quinone ( 23 ) and 1-chloro-6-hydroxy-4-methylnaphtho[2,3-g]isoquinoline-5,12-quinone ( 24 ), this last tetracyclic chloroquinone was specifically obtained from 6-bromo-1-chloro-4-methylisoquinoline-5,8-quinone ( 7 ) and homophthalic anhydride. The 6,11-dihydroxy derivative was then prepared by ammonium nitrate oxidation or photochemically by cycloaddition of benzocyclobutenedione ( 28 ) and 1-chloro-4-methylisoquinoline-5,8-quinone ( 6 ). Chloro compounds were easily substituted by diamines to provide corresponding 1-amino substituted hydroxy tetracyclic quinones. 相似文献
155.
Indole alkaloids lacking the three carbon unit at C-15 such as deplancheine and flavopereirine can be biogenetically related to 4,21-dehydrogeissoschizine . A biomimetic transformation of into 5,6-dihydroflavopereirine supports this proposal. 相似文献
156.
Christiane Bonnelle 《Mikrochimica acta》2002,138(3-4):275-282
The possibilities presented by low-energy electron-induced X-ray emission spectroscopy to study chemical interactions in
solids are discussed. Examples of change observed for the emissions between core levels as a function of the chemical environment
of the emitting atoms are given. By comparing the partial densities of the valence states associated to each type of atoms
in the compound, it is shown that the strength of the metal-ligand interactions can be obtained. Information on the charge
densities around each type of atoms can be deduced. Application to the study of the interactions at the atomic scale to solid–solid
interfaces is presented. 相似文献
157.
Yvan Guindon Christiane Yoakim Michael A. Bernstein Howard E. Morton 《Tetrahedron letters》1985,26(9):1185-1188
The synthesis of Ethyl 5(S),6-Epoxy-3(R)-(methoxymethoxy)hexanoate, a key chiral synthon for the β-hydroxy-δ-lactone portion of Mevinolin and Compactin, a regiospecific ring opening of a tetrahydrofuran derivative by dimethylboron bromide, is described. 相似文献
158.
Benoit Coasne Christiane Alba-Simionesco Fabrice Audonnet Gilberte Dosseh Keith E. Gubbins 《Adsorption》2007,13(5-6):485-490
Grand Canonical Monte Carlo simulations are used to study the adsorption of benzene at 298 K in an atomistic cylindrical silica
nanopore of a diameter 3.6 nm. The adsorption involves a transition from a partially filled pore (a two layers thick film
at the pore surface) to a completely filled pore configuration. Strong layering of the benzene molecules at the pore surface
is observed. It is found that the layering decays as the distance to the pore surface increases. The position of the peaks
for the density of the C, H atoms and the center of mass of the molecules shows that benzene molecules prefer an orientation
in which their ring is perpendicular to the pore surface. This result is corroborated by calculating orientational order parameters
and examining the distribution of the distances between the H and C atoms of the benzene molecules and the H and O atoms of
the silica substrate. 相似文献
159.
Thomasser Christiane Danner Herbert Neureiter Markus Saidi Bamusi Braun Rudolf 《Applied biochemistry and biotechnology》2002,98(1-9):765-773
Lignocellulosic biomass has great potential as a cheap feedstock in biological processes to produce biofuels or chemicals;
however, dilute acid pretreatment at high temperatures produces undesirable compounds. Toxicity tests were done with inhibitors
in standard media, to predict the growth-limiting effects on thermophilic strains. The 22 inhibitors included furfural, levulinic
acid, acetic acid, and cinnamaldehyde. Neutralizing reagents and additional treatment steps have been tested. 相似文献
160.
Arnold J. Hoff Peter Gast Sergei A. Dzuba Christiane R. Timmel Catherine E. Fursman P.J. Hore 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》1998,54(14):2283-2293
We describe in some detail the new method of distance determination for a photoinduced radical pair. Emphasis is on giving the nuts and bolts of the calculations that result in analytical expressions for in- and out-of-phase electron spin echo (ESE) envelope modulations, pulse flip-angle dependencies, zero- and double-quantum coherences, and the distance between the two radicals. The theoretical results are illustrated by a set of recent experiments on photosynthetic reaction centers. 相似文献