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91.
A smog chamber and modeling study of the gas phase NOx–air photooxidation of toluene and the cresols
Roger Atkinson William P. L. Carter Karen R. Darnall Arthur M. Winer James N. Pitts 《国际化学动力学杂志》1980,12(11):779-836
An experimental and modeling study of irradiated toluene–NOx–air, toluene–benzaldehyde–NOx–air, and cresol–NOx–air mixtures at part-per-million concentrations has been carried out. These mixtures were irradiated at 303 ± 1 K in a 5800-liter Teflon-lined, evacuable environmental chamber, with temperature, humidity, light intensity, spectral distribution, and the concentrations of O3, NO, NO2, toluene, PAN, formaldehyde, benzaldehyde, o-cresol, m-nitrotoluene, and methyl nitrate beingmonitored as a function of time. For the toluene and toluene–benzaldehyde–NOx–air runs a variety of initial reactant concentrations were investigated. Cresol–NOx–air runs were observed to be much less reactive in terms of O3 formation and NO to NO2 conversion rates than toluene–NOx–air runs, with the relative reactivity of the cresol isomers being in the order meta » ortho > para. The addition of benzaldehyde to toluene–NOx–air mixtures decreased the reactivity, in agreement with previous studies. Alternative mechanistic pathways for the NOx photooxidations of aromaticsystems in general are discussed, and the effects of varying these mechanistic alternatives on the model predictions for the toluene and o-cresol–NOx–air systems are examined. Fits of the calculations to most of the experimental concentration–time profiles could be obtained to within the experimental uncertainty for two of the mechanistic options considered. In both cases it is assumed that (1) O2 adds to the OH–toluene adduct ~75% of the time forming, after a further addition of O2, a C7 bicyclic peroxy radical, and (2) this C7 bicyclic peroxy radical reacts with NO ~75% of the time to ultimately form α-dicarbonyls and conjugated γ-dicarbonyls (e.g., methylglyoxal + 2-butene-1,4-dial) and ~25% of the time to form organic nitrates. The major uncertainties in the mechanisms concern (1) the structure of the bicyclicperoxy intermediate, and (2) the γ-dicarbonyl photooxidation mechanism. Good fits to the o-cresol concentration–time profiles in the toluene–NOx runs are obtained if it is assumed that o7-cresol reacts rapidly with NO3 radicals. However, it is observed that the model underpredicts nitrotoluene yields by a factor of ~10, but this is in any case a minor product. It is concluded that further experimental work will be required toadequately validate the assumptions incorporated in the aromatic photooxidation mechanisms presented here. 相似文献
92.
S.F. Biagi M. Bourquin A.J. Britten R.M. Brown H. Burchhart A.A. Carter J.R. Carter Ch. Doré P. Extermann M. Gailloud C.N.P. Gee W.M. Gibson J.C. Gordon R.J. Gray P. Igo-Kemenes W.C. Louis T. Modis P. Mühlemann R. Weill 《Physics letters. [Part B]》1982,112(3):265-270
The α parameter for Ξ? → Λπ? decay has been determined to be αΞ?=?0.462 ± 0.015, from a sample of 1.5 × 105 events recorded in the CERN SPS hyperon beam. This value is 2.5 standard deviations higher than the current world average. 相似文献
93.
Shevchenko A Carter J Fearick RW Förtsch SV Fujita H Fujita Y Kalmykov Y Lacroix D Lawrie JJ von Neumann-Cosel P Neveling R Ponomarev VY Richter A Sideras-Haddad E Smit FD Wambach J 《Physical review letters》2004,93(12):122501
Fine structure in the energy region of the isoscalar giant quadrupole resonance in nuclei is observed in high-resolution proton scattering experiments at iThemba LABS over a wide mass range. A novel method based on wavelet transforms is introduced for the extraction of scales characterizing the fine structure. A comparison with microscopic model calculations including two-particle two-hole (2p2h) degrees of freedom identifies the coupling to surface vibrations as the main source of the observed scales. A generic pattern is also found for the stochastic coupling to the background of the more complex states. 相似文献
94.
Deposition of S onto a monolayer of Ag/Ru(0001) transforms the herringbone pattern of the clean Ag film into a strikingly regular array of 2D-vacancy islands [Nature (London) 397, 238 (1999)]]. Time-resolved scanning tunneling microscopy reveals that this nanometer-scale restructuring occurs by a cooperative mechanism involving the sequential formation of triangular regions with fcc and hcp stacking. Using a 2D Frenkel-Kontorova model, we can simulate the creation of these triangular building blocks via basic dislocation motions and reactions. 相似文献
95.
We demonstrate experimentally and numerically that, by spectrally filtering the delayed optical feedback into a semiconductor laser, one can elicit novel dynamics in the frequency of the laser output light on a time scale that is set by the delay time of the feedback. In particular, we show that through a judicious choice of the filter bandwidth, and its frequency relative to that of the laser, one can produce controlled oscillations in the frequency of light from the laser. 相似文献
96.
Carter EB Culver SL Fox PA Goode RD Ntai I Tickell MD Traylor RK Hoffman NW Davis JH 《Chemical communications (Cambridge, England)》2004,(6):630-631
The anions of the sweeteners saccharin and acesulfame form ionic liquids when paired with a variety of organic cations. 相似文献
97.
The efficient syntheses of the ABCD ring system of the originally proposed structure of azaspiracid-1 and the ABCDE ring system of the revised structure of azaspiracid-1 containing the correct stereochemistry at C(6), C(10), C(13), C(14), C(16), C(17), C(19), C(21), C(22), C(24) and C(25) have been achieved. 相似文献
98.
Stereoselectivity of nitrile oxide cycloadditions to chiral allylic fluorides: experiment and theory
Prakesch M Grée D Grée R Carter J Washington I Houk KN 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(22):5664-5672
The cycloadditions of nitrile oxides with new and previously studied allylic fluorides were examined. The 1,3-dipolar cycloaddition reactions were also investigated theoretically with density functional theory (B3LYP) based transition-state modelling. The predictions provided reasonable agreement with experiment, indicating that both steric and electronic effects have important influences on the stereoselectivities of these reactions. 相似文献
99.
Nucleobase radicals (e.g., 1) are the major family of reactive intermediates formed when DNA is exposed to gamma-radiolysis. Independent generation of 1 in chemically synthesized oligonucleotides reveals that formation of this nucleobase radical under aerobic conditions results in the formation of tandem lesions approximately 65% of the time. The distribution of lesions formed with the 5'- and 3'-adjacent nucleotides is dependent upon the secondary structure of duplex DNA. Tandem lesions, which are defined as two contiguously, damaged nucleotides in a single DNA strand, are of significant biological interest. The yield of tandem lesions from 1 is much greater than was previously believed. The observations presented could have significant ramifications on how scientists interpret the effects of gamma-radiolysis on DNA. 相似文献
100.
White JD Carter RG Sundermann KF Wartmann M 《Journal of the American Chemical Society》2001,123(23):5407-5413
The phosphonium salt 35, representing one of the two principal subunits of the epothilones, was prepared from propargyl alcohol via heptenone 22. A Wittig reaction of the phosphorane from 35 with aldehyde 33, obtained from aldol condensation of ketone 27 with aldehyde 28, afforded 37. Seco acid 42 derived from 37 underwent lactonization to give cis-9,10-dehydroepothilone D (43) which was selectively reduced with diimide to yield epothilone D (4) and, after epoxidation, epothilone B (2). An alternative route to epothilone D employed alkyne 39, obtained from 33, in a Castro-Stephens reaction with allylic bromide 34 to furnish enyne 40. The latter was semi-hydrogenated to provide 37. Alkyne 46, prepared from alcohol 45, was converted to trans-vinylstannane 47 which, in a Stille coupling with allylic chloride 50, gave 51. Seco acid 52 derived from 51 underwent lactonization to give trans-9,10-dehydroepothilone D (54). Bioassay data comparing the antiproliferative activity and tubulin polymerization of 43 and 54 with epothilone B (2), epothilone D (4), and paclitaxel (7) showed that the synthetic analogues were less potent than their natural counterparts, although both retain full antiproliferative activity against a paclitaxel-resistant cell line. No significant difference in potency was noted between cis analogue 43 and its trans isomer 54. 相似文献