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61.
Jeffs L Arquier D Kariuki B Bethell D Page PC Hutchings GJ 《Organic & biomolecular chemistry》2011,9(4):1079-1084
By synthesising S-2-phenyl-N-(4-nitrophenyl)aziridine from S-phenylglycinol, it has been demonstrated that the aziridination of styrene by [N-(4-nitrobenzenesulfonyl)imino]phenyliodinane (nosyliminophenyliodinane, PhINNs) in the presence of S,S-2,2'-isopropylidene-bis(4-phenyl-2-oxazoline), catalysed by copper(II) triflate in CH(3)CN solution or heterogeneously by CuHY, has predominantly an R-configuration. The enantioselectivity of the aziridination of styrene by [N-arenesulfonylimino]-phenyliodinanes catalysed by copper-exchanged zeolite Y (CuHY), in conjunction with a chiral bis-oxazoline ligand, has been re-examined. In the case of PhINNs, it is shown that the product mixture of enantiomeric aziridines, on treatment with hexane, gives rise to a solid phase of low enantiomeric excess (ee) and a solution phase of high ee. Separation of the solid phase and recrystallisation afforded a true racemate (racemic compound), which has been confirmed by X-ray crystallography. The aziridine obtained from the solution phase could be recrystallised to produce the pure enantiomer originally in excess. A consequence of the new findings is that previous reports on the enantioselectivity of copper-catalysed aziridination, both in heterogeneous and homogeneous conditions, should be regarded with caution if the analytical procedure involved HPLC with injection of the enantiomeric mixture in a hexane-rich solvent. Such a method has been used in previous work from this laboratory, but has also been used elsewhere, following the procedure developed by Evans and co-workers when the (homogeneous) copper-catalysed aziridination by PhINTs was first discovered. Evidently, the change of substituent in the benzenesulfonyl group reduces the solubility in hexane, affording a solution phase of enhanced ee. 相似文献
62.
Page MJ Mahon MF Whittlesey MK 《Dalton transactions (Cambridge, England : 2003)》2011,40(31):7858-7865
Thermolysis of [Ru(PPh(3))(dppe)(CO)HCl] (dppe = 1,2-bis(diphenylphosphino)ethane) with the N-heterocyclic carbenes I(i)Pr(2)Me(2) (1,3-diisopropyl-4,5-dimethyl-imidazol-2-ylidene), IEt(2)Me(2) (1,3-diethyl-4,5-dimethyl-imidazol-2-ylidene) or ICy (1,3-dicyclohexylimidazol-2-ylidene) gave the cyclometallated carbene complexes [Ru(NHC)'(dppe)(CO)H] (NHC = I(i)Pr(2)Me(2), 4; IEt(2)Me(2), 5; ICy, 6). Dissolution of 4 in CH(2)Cl(2) or CHCl(3) gave the trans-Cl-Ru-P complex [Ru(I(i)Pr(2)Me(2))'(dppe)(CO)Cl] (7), which converted over hours at room temperature to the trans-Cl-Ru-CO isomer 7'. Chloride abstraction from 7 by NaBPh(4) under an atmosphere of H(2) produced the cationic mono-hydride complex [Ru(I(i)Pr(2)Me(2))(dppe)(CO)H][BPh(4)] (9), which could also be formed by protonating 4 with 1 eq HBF(4)·OEt(2). Treatment of 4 with excess HBF(4)·OEt(2) followed by extraction into MeCN produced the dicationic acetonitrile complex [Ru(I(i)Pr(2)Me(2))(dppe)(CO)(NCMe)(2)][BF(4)](2) (10). The structures of 6, 7, 7' and 10 have been determined by X-ray crystallography. 相似文献
63.
Edwards HG Herschy B Page K Munshi T Scowen IJ 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,78(1):191-195
The aim of this work is to investigate the viability and potential of three groups of organic compounds as biomarkers in a future robotic analytical exploration of Mars. The three compounds have been identified as suitable candidates for potential biomarkers for extant or extinct life from the terrestrial fossil record. The three groups of compound were all similar in structure, being either tetra- or penta-cyclic compounds. The limits of detection for a sample were also tested to estimate what concentrations it would still be amenable to Raman spectroscopic investigation. This was investigated using both solid mixtures and liquid solutions. The spectra of these compounds are characterised so that they can be added to the Raman database for future Mars missions. This involved identifying functional group characteristics, assigning peaks for each individual sample and characteristic features which would categorise the samples. 相似文献
64.
Extensive studies have been carried out on the optical conversion of F and F-aggregate colour centres produced in lithium
fluoride single crystal on gamma irradiation. Using 308 nm XeCl laser it has been shown that significantly large population
build-up of F
3
+
centre and reduction in the population of undesirable F2 centres can be achieved in gamma irradiated crystal at room temperature due to multistep photoionization processes. These
and other investigations have provided a scheme for possible laser action based on F
3
+
colour centres in LiF crystal at room temperature. 相似文献
65.
66.
Philip C. Bulman Page Genna A. Parkes Harry Heaney J. Steven Wailes 《Tetrahedron letters》2008,49(49):6951-6954
A number of oxazolidines derived from ketones and aminoalcohols have been prepared in excellent yields using microwave irradiation. In most cases, conventional reflux failed to provide any of the desired products. 相似文献
67.
It is shown how the invariance of the Born—Oppenheimer potential energy to overall translations and rotations of a molecule can be used to reduce the computational labor required for derivative evaluations at various orders. 相似文献
68.
69.
Numerical solutions have been obtained for the exact equations describing the propagation of periodic axisymmetric waves in a rigid cylindrical tube. Results were obtained for air over a range of conditions corresponding to shear wave numbers (s = R √?ω/μ) from 0·2 to 5000 and reduced frequencies (k = ωR/a) from 0·01 to 6. For conciseness and convenient application, the results for the attenuation and phase shift coefficients are given in the form of simple polynomials for the ranges 5 ? s ? 5000 and 0·01 ? k ? 6. This range covers virtually all values of tube diameter and sound frequency likely to be met in practical situations that are consistent with a continuum gas model. 相似文献
70.