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51.
Probing the water coordination of protein-targeted MRI contrast agents by pulsed ENDOR spectroscopy.
Stephan G Zech Wei-Chuan Sun Vincent Jacques Peter Caravan Andrei V Astashkin Arnold M Raitsimring 《Chemphyschem》2005,6(12):2570-2577
A novel methodology based on electron-nuclear double resonance (ENDOR) spectroscopy is used for the direct determination of the water coordination number (q) of gadolinium-based magnetic resonance imaging (MRI) contrast agents. Proton ENDOR spectra can be obtained at approximately physiological concentrations for metal complexes in frozen aqueous solutions either in the presence or absence of protein targets. It is shown that, depending on the structure of the co-ligand, the water hydration number of a complex in aqueous solution can be significantly different to when the complex is noncovalently bound to a protein. From the ENDOR spectra of the exchangeable protons, precise information on the metal-proton distance can be derived as well. These essential parameters directly correlate with the efficacy of MRI contrast agents and should therefore aid the development of novel, highly efficient compounds targeted to various proteins. 相似文献
52.
Addition-elimination reactions from germanium heterocycles . III. 2,2-Diethyl-2-germa-1,-3-oxazolidines (R = Et; X = O; Y = NH, NMe) . The reactions of 2,2-diethyl-2-germa-1,3-oxazolidines with heterocumulenes (PhNCO, PhNCS, CS2, CO2, CH2?C?O) and carbonyl compounds (aldehydes and ketones) are studied. Generally, monoinsertion derivatives are formed by addition of one molecule of the unsaturated compound accross the Ge? N bond. This bond is always the most reactive center of the molecule. In the case of the carbonyl compounds used, diinsertion may occur in a second step by a further addition across a Ge? O bond. Generally, this latter reaction is reversible. By thermal eliminat on of (Et2GeO)n or (Et2GeS)3 the monoaddition derivatives yield the corresponding oxazolidines and thiooxazolidines. The mechanisms of these reactions are discussed. 相似文献
53.
Muriel Lepère Ghislain Blanquet Jacques Walrand Jean-Pierre Bouanich 《Journal of Molecular Spectroscopy》1996,180(2):218-226
Infrared absolute line intensities of the ν6band of CH3F have been measured around 8.5 μm using a diode-laser spectrometer. These line strengths were obtained by the equivalent width method and, for 13 lines, by fitting a Rautian profile to the measured shape of the lines. From these results, we have deduced the vibrational band strength to beS0v= 9.66 ± 0.13 cm−2atm−1at 296 K and the first Herman–Wallis factors. 相似文献
54.
55.
56.
Jacques E. Desnoyers Gérald Perron Sylvain Léger Byron Y. Okamoto Terrence H. Lilley Robert H. Wood 《Journal of solution chemistry》1978,7(3):165-178
The freezing-point depression of the ternary systems tetraalkylammonium bromides-t-butanol-water for the first five homologs of R4NBr was measured. In the case of Bu4NBr, the effect of size of the alcohol (methahol ton-butanol) was also investigated. From the corresponding freezing-point data for the binary systems the apparent salting constants
were calculated. The true salting constantsk
s were obtained by extrapolation to infinite dilution. These are all very close to zero at the freezing temperature. From the
corresponding thermochemical data the temperature dependence ofk
s was calculated, and above 5°C all the R4NBr salts int-butanol; the salting-in increases with temperature and with the size of the hydrophobic cations. The scaled-particle theory
is at present the only one which can account semiquantitatively for the temperature dependence of the salting-in effect.
On leave of absence from Chemistry Department, The University, Sheffield S3 7HF, England
To whom correspondence should be addressed. 相似文献
57.
Jacques Lievin Jacques Breulet Philippe Clercq Jean -Yves Metz 《Theoretical chemistry accounts》1982,61(6):513-537
A simplified method of determining the molecular correlation energy by two separate calculations, one for the internal and
one for the non-internal correlation energies, is extended to multiconfigurational zeroth-order wavefunctions. This extension
offers the possibility of deriving correlated potential energy curves or surfaces for processes involving configurational
changes. The internal correlation energy is shown to be correctly determined by an MC/CI procedure combining the use of minimal
and extended basis sets. An original semi-empirical “atoms-in-molecules” method based on the L.C.A.O. expansion of the molecular
wavefunction is proposed for the non-internal correlation energy calculations. This method is shown to be able to overcome
some of the shortcomings of a previous populations analysis approach. Test calculations concern potential curve parameters
(D
e
,T
e
,R
e
,W
e
) of the ground and some excited states of the NH, C2, HCN and CN molecules. The results are found to be in good agreement with corresponding experimental and large CI results.
Aspirant du Fonds National Belge de la Recherche Scientifique
Boursier I.R.S.I.A. 相似文献
58.
Nicole Desrosiers Gérald Perron John G. Mathieson Brian E. Conway Jacques E. Desnoyers 《Journal of solution chemistry》1974,3(10):789-806
The apparent molal volume φv, expansibility φE, compressibility φK, and heat capacity φc of NaCl were measured in urea-water mixtures, as a function of salt (<1.5m) and urea (<13m) concentrations at 25°C. At a fixed urea concentration, the transfer functions from H2O to 3m urea are linear functions of the NaCl aquamolality. At a fixed salt aquamolality, (0.1m), the sign of the transfer functions is in the direction of a decrease in the structure-breaking effect, and the absolute values of the transfer functions tend to level off at high urea concentrations (13m). The functions φv, φE, φK, φc, and (?φv/?T)p were measured for the sodium halides and alkali, bromides (chlorides in the case of φK) at a fixed salt aquamolality of 0.1m and fixed urea molality of 3m. The corresponding transfer functions from H2O to 3m urea are opposite those from H2O to D2O and similarly are relatively independent of ionic size. This suggests that urea, shows no specific interaction affinity for ions and that the overall number of water molecules influenced by the ions is relatively constant for all alkali halides. The lithium halides are an exception in that Li+ seems to have hardly any structure-breaking effect. 相似文献
59.
We present in this paper two new effects observed in the state of molecular iodine: a very high diamagnetic correction in the vibrational level υ′ = 62 and an important orientation of the optically excited molecules due to predissociation. Both effects can be interpreted by taking into consideration the perturbation of the B state by other electronic states. 相似文献
60.
D. VarechJ. Jacques 《Tetrahedron》1972,28(22):5671-5679
A series of bicyclo[2.2.2]octane derivatives whose absolute configurations are known through chemical correlations with confirmed reference products (bicyclo[2.2.2]octanol, bicyclo[2.2.2]octene carboxylic acid) have been prepared. 相似文献