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61.
Merer AJ Steeves AH Baraban JH Bechtel HA Field RW 《The Journal of chemical physics》2011,134(24):244310
A systematic analysis of the S(1)-trans (A?(1)A(u)) state of acetylene, using IR-UV double resonance along with one-photon fluorescence excitation spectra, has allowed assignment of at least part of every single vibrational state or polyad up to a vibrational energy of 4200 cm(-1). Four observed vibrational levels remain unassigned, for which no place can be found in the level structure of the trans-well. The most prominent of these lies at 46?175 cm(-1). Its (13)C isotope shift, exceptionally long radiative lifetime, unexpected rotational selection rules, and lack of significant Zeeman effect, combined with the fact that no other singlet electronic states are expected at this energy, indicate that it is a vibrational level of the S(1)-cis isomer (A?(1)A(2)). Guided by ab initio calculations [J. H. Baraban, A. R. Beck, A. H. Steeves, J. F. Stanton, and R. W. Field, J. Chem. Phys. 134, 244311 (2011)] of the cis-well vibrational frequencies, the vibrational assignments of these four levels can be established from their vibrational symmetries together with the (13)C isotope shift of the 46?175 cm(-1) level (assigned here as cis-3(1)6(1)). The S(1)-cis zero-point level is deduced to lie near 44?900 cm(-1), and the ν(6) vibrational frequency of the S(1)-cis well is found to be roughly 565 cm(-1); these values are in remarkably good agreement with the results of recent ab initio calculations. The 46?175 cm(-1) vibrational level is found to have a 3.9 cm(-1) staggering of its K-rotational structure as a result of quantum mechanical tunneling through the isomerization barrier. Such tunneling does not give rise to ammonia-type inversion doubling, because the cis and trans isomers are not equivalent; instead the odd-K rotational levels of a given vibrational level are systematically shifted relative to the even-K rotational levels, leading to a staggering of the K-structure. These various observations represent the first definite assignment of an isomer of acetylene that was previously thought to be unobservable, as well as the first high resolution spectroscopic results describing cis-trans isomerization. 相似文献
62.
Cross-linking mechanisms of arginine and lysine with α,β-dicarbonyl compounds in aqueous solution 总被引:1,自引:0,他引:1
Nasiri R Field MJ Zahedi M Moosavi-Movahedi AA 《The journal of physical chemistry. A》2011,115(46):13542-13555
Cross-linking in proteins by α,β-dicarbonyl compounds is one of the most damaging consequences of reactive carbonyl species in vivo and in foodstuffs. In this article we investigate computationally the cross-linking of glyoxal and methylglyoxal with lysine and arginine residues using density functional theory and the wB97XD dispersion-corrected functional. Five pathways, A-E, have been characterized. In pathways A and B, the reaction proceeds via formation of the Schiff base, aldimine, followed by addition of arginine. In contrast, in pathways C-E, direct addition of arginine to the dicarbonyl compounds occurs first, leading to a dihydroxyimidazolidine intermediate, which then reacts with lysine after dehydration and proton transfer reactions. The results reveal that pathways A, C, and E are competitive whereas reactions via pathways B and D are much less favorable. Inclusion of up to five explicit water molecules in the proton transfer and dehydration steps is found to lower the energy barriers in the feasible pathways by about 5-20 kcal/mol. Comparison of the mechanisms of methylglyoxal-derived imidazolium cross-linking (MODIC) and glyoxal-derived imidazolium cross-linking (GODIC) shows that the activation barriers are lower for GODIC than MODIC, in agreement with experimental observations. 相似文献
63.
Health psychology has studied the cross-sectional, stationary relationships linking stress, social support, and health. Levels of stress-related illness are generally modeled by including a nonlinear multiplicative or 'buffering' effect, corresponding to the interaction of stressor levels with social support from family and friends. The motivation of the present research is to extend an iterative, dynamic model of this well-investigated psychological process using a dynamical systems model expressed as a set of continuous, nonlinear differential equations similar to those of the 'Oregonator,' a model of a nonlinear dynamic chemical system. This model of the behavior of an individual is amenable to numerical investigation of its stationary-state stability properties, temporal evolution, and cause-effect relationships. The continuous variables in this new approach refer to varying states of an individual; they are Perceived stress (X), Symptoms (Y), and Social support (Z). It is expected that poor health in this model, represented by Symptoms (Y), is directly related to Perceived stress, as well as being tied in more complicated ways to Social support. A number of such models may be envisioned, some including a multiplicative, 'buffering' (- X x Z) effect of social support dependent on stress levels. We explore the behavior of this model over ranges of parameter values and initial conditions and relate these results to how an individual reacts to environmental challenges at various levels of stressors and social-support recruitment. Data generated by the model are in turn analyzed with a traditional cross-sectional statistical technique. Similarities and differences between chemical and psychological systems are discussed. 相似文献
64.
Allan J. Field 《Fresenius' Journal of Analytical Chemistry》1918,57(2):112
Ohne Zusammenfassung 相似文献
65.
J. A. Muller C. Reinhardt C. Fischbach A. Siebenschub V. Stanek N. M. Randall K. Bogoluboff H. Wdowiszewski F. Garrat D. J. Demorest J. R. Cain H. E. Walters F. C. T. Daniels A. J. Field A. Terni P. Malaguti B. S. Evans L. W. Winkler O. L. Barnebey G. L. Kelley J. A. Wiley E. Little J. Costa M. Gröger H. O. Ward P. Slawik W. Hild und F. Simion 《Fresenius' Journal of Analytical Chemistry》1923,63(9):348-359
Ohne Zusammenfassung 相似文献
66.
67.
68.
Bruce D Jacobs Soon-Jae Kwon Leslie D Field Robert K Norris David Randles Karen Wilson Timothy A Wright 《Tetrahedron letters》1985,26(29):3495-3498
The SRN1 reaction between sterically hindered p-nitrobenzylic substrates and tertiary carbanions gives C-alkylated products whose yields depend on the steric bulk of both the benzylic substrate and the carbanion, and on the nature of the groups in the carbanion. 相似文献
69.
1,2-Diaminoethane and 2-aminoethanol-1 were added to the isobutane plasma of a chemical ionization mass spectrometer. The resulting reactant gas mixture did not react with additives containing a single oxygen functional group. Addition reactions were observed with some additives containing multiple oxygen functions. Additives containing nitrogen functions were protonated by the reactant mixture. The relative proportion of protonation to addition depended on the ability of the additive to chelate the reactant ion and on the basicity of the additive. This use of 1,2-diaminoethane and 2-aminoethanol-1 provides a convenient method of varying the reactivity of the plasma in a chemical ionization source. 相似文献
70.
We determine the invariant cross section for pp→ψ(3100)+X near x6=0 at NAL and ISR energies using the assumption that all large p⊥ single leptons originate from the ψ. We adequately reproduce the single lepton data, and by suitable extrapolarion in x6 ensure agreement with the NAL ψ production data (x6?0.3). The magnitude of the resulting ψ production cross section is, however, roughly a factor of 3 larger than that observed by the recent CCRS-ISR experiment. 相似文献