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991.
An efficient and reliable synthesis of new thiazole-(amino)methylphosphonic, phosphinic acids, and phosphine oxides is reported. The synthetic protocol is based on nucleophilic addition of phosphorous species to thiazole derived imines. Unexpectedly, it was discovered that heating of thiazole-2-yl-(amino)methylphosphonates and phosphinates with aqueous HCl leads to their decomposition resulting in a rupture of the C-P bond, rejecting of the phosphorus containing fragment and formation of the corresponding secondary N-(thiazole-2-yl-methyl)-alkylamines. Two alternative mechanisms for this cleavage are postulated. 相似文献
992.
A model of diffusive transport of benzoic acid through a liquid membrane (LM) separating two aqueous solutions, based on diffusion
layers and the assumption of a steady state, has been developed and tested using experimental results. It has been found that
a model with the apparent partition coefficient dependent on the concentration is able to describe the time dependence of
acid concentration in LM with and without a maximum on that dependence. The quality of the model fit with the single apparent
diffusion coefficient of benzoic acid is the same as the one which takes into account the diffusion of benzoic acid in different
forms (undissociated and dissociated form in aqueous phase, monomer and dimer in organic phase); however, in the second case,
the model becomes overparameterized. Assuming that the partition and diffusion coefficients are constant, the diffusion layer
model corresponds to the model of reversible consecutive reactions. Analytical solution for such case is given. Apart from
the partition equilibrium, also kinetics of partitioning was considered. It was shown that in some basic situations both cases
yield identical results. 相似文献
993.
Piotr Przybylski Marcin Kwit Krystian Pyta Radosław Pankiewicz Grzegorz Schroeder Jacek Gawroński Bogumil Brzezinski 《Tetrahedron: Asymmetry》2010,21(8):973-981
Gossypol Schiff base with (R)-(+)-2-amino-3-benzyloxy-1-propanol 1 was synthesised and resolved by HPLC method into diastereomers to study their atropisomerisation process. The spectroscopic analysis performed by one- and two-dimensional NMR, UV–vis and FT-IR methods indicated that the compound exists in solution as an enamine-oxo tautomer. The ECD measurements and TD-DFT calculations allowed us to unambiguously determine the configuration about the axially chiral biaryl moiety of 1. The conditions of the atropisomerisation processes of diastereopure gossypol Schiff bases (SAX,R)-1 and (RAX,R)-1 were determined on the basis of ECD and NMR measurements. Exposure of the diastereomers of 1 to sunlight and to the light at λ = 254 nm significantly accelerated the atropisomerisation when compared to its rate in the dark. 相似文献
994.
The reaction of [RuHCl(CO)(PPh3)3] with 4-phenylpyrimidine gave a new ruthenium(II) complex, namely [RuHCl(CO)(PPh3)2(pyrim-4-Ph)]. The complex has been studied by IR and UV?Cvis spectroscopy and by X-ray crystallography. The molecular orbitals of the complex have been calculated by density functional theory. The spin-allowed singlet?Csinglet electronic transitions of the complex have been calculated by time-dependent DFT, and the UV?Cvis spectrum of the compound has been discussed on this basis. The emission properties of the complex were also studied. 相似文献
995.
A. Dittmar-Wituski A. Grudziński ?. Lademann A. Miko?ajczyk ?. Andraszyk M. Roszak 《Applied Surface Science》2010,256(15):4789-766
In this paper, we present experimental results of target current (TCS) and LEED investigation of well-oriented InSb(1 1 0) and InSb(1 1 1)-A and InSb(1 1 1)-B crystals. TCS results are interpreted in terms of very low electron diffraction (VLEED) and empty band signatures. To examine to which extent the TCS spectra reflect the bulk or surface electronic properties of InSb(1 1 0), thin layers of indium have been evaporated and the corresponding spectrum changes have been investigated. 相似文献
996.
Agnieszka Górska Halina Hajmowicz Tomasz Kliś Janusz Serwatowski Ludwik Synoradzki 《应用有机金属化学》2011,25(4):294-297
The reaction of arylboronic acids with L ‐O‐benzoyl‐tartaric acid and D ,L ‐malic acid has been studied. The obtained (acyloxy)boranes are moderately stable in solution and decompose to give boroxines. 5‐Carboxymethyl‐2‐(4‐methylthiophenyl)‐1,3,2‐dioxaborolan‐4‐one was obtained in the reaction of 4‐methylthiophenylboronic acid with D ,L ‐malic acid and characterized by X‐ray structural analysis. The use of L ‐(−)‐malic acid afforded the optically pure product which can be used as the powerful chiral reagent in the enantioselective reduction of ketones. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
997.
B. Jańczuk I. Choma A. L. Dawidowicz A. Kliszcz T. Białopiotrowicz 《Chromatographia》1990,30(7-8):382-387
Summary Contact angles for water and diiodomethane drops were measured on the surface of thermally and chemically (by Carbowax 20M
bonding) modified porous glasses and on the surface of naphthalene, diphenyl and anthracene. Using the obtained results to
a modified Young equation, dispersion and nondispersion components of the surface free energy of these glasses and organic
substances were calculated.
The work of adhesion (WA) for benzene, naphthalene, diphenyl, anthracene, nitrobenzene was estimated and correlated with the capacity factors, (k′)
of these substances. On the basis of experimental and calculated data it can be stated that the thermal treatment of porous
glasses increases, their hydrophobicity but the Carbowax layer causes hydrophilicity. There is a linear relationship between
k′ and WA which can be helpful for predicting retention data of chromatographed substances on the base of surface free energy which
can be calculated from contact angle measurements. 相似文献
998.
J. Kwieciński 《Zeitschrift fur Physik C Particles and Fields》1990,45(3):461-469
The shadowing corrections to gluon and quark distributions in nuclei in the region of small values ofx are discussed. They are related to parton distributions in a pomeron which are in principle measurable in hard diffractive processes on the nucleon target. Multiple scattering corrections to shadowing are considered in a model dependent way. The perturbative QCD evolution of shadowing is also taken into account. Various possibilities of the partonic content of a pomeron are considered. It is shown in particular that the conventional parametrizations of parton distributions in a pomeron which are based on the assumption that it consists mostly of gluons imply substantial nuclear shadowing in gluon distributions in heavy nuclei. Possible phenomenological implications of shadowing corrections in nuclear parton distributions for various semi-hard processes with nuclear targets are briefly discussed. 相似文献
999.
1000.
Marta Bugaj Piotr A. Baran Piotr Bernatowicz Patrycja Brożek Krystyna Kamieńska‐Trela Adam Krówczyński Bohdan Kamieński 《Magnetic resonance in chemistry : MRC》2009,47(10):830-842
A series of aryl‐substituted enaminoketones and their thio analogues in CDCl3 solution and in the solid state were studied by the use of high‐resolution 1H and 13C as well as 13C cross polarization magic angle spinning (CP MAS) NMR spectra in combination with gauge including atomic orbitals‐density functional theory (GIAO‐DFT) calculations performed at the B3PW91/6–311 + + G(d,p) level of theory using the B3PW91/6‐311 + + G(d,p)‐optimized geometries. The analysis of the 13C NMR spectra in solution was done by using the Incredible Natural Abundance DoublE QUAntum Transfer Experiment (INADEQUATE) technique, whereas trends observed in the 13C shielding constants, calculated for the compounds studied, were a great help in assigning most of the signals in the 13C CP MAS NMR spectra. It was established on the basis of the experimental and theoretical NMR data that both groups of compounds exist in the form of Z‐s‐Z‐s‐E isomers in CDCl3 solution as well as in the solid state, with the NH hydrogen atom involved in intramolecular hydrogen bonding. This conclusion is in agreement with the fact that some of the compounds studied reveal liquid‐crystalline properties. Three‐bond H, H and C, H coupling constants measured in solution played a crucial role in the structure elucidation. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献