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701.
702.
K. N. Shukla A. Brusly Solomon B. C. Pillai B. Jacob Ruba Singh S. Saravana Kumar 《Heat and Mass Transfer》2012,48(11):1913-1920
Nanofluids are employed as the working medium for a conventional cylindrical heat pipe. A cylindrical copper heat pipe of 19.5?mm outer diameter and 400?mm length was fabricated and tested with two different working fluids. The working fluids used in this study are DI-water and Nano-particles suspension (mixture of copper nano particle and DI-water). The overall heat transfer coefficient of the heat pipe was calculated based on the lumped thermal resistance network and compared with the heat transfer coefficient of base fluid filled heat pipe. There is a quantitative improvement in the heat transfer coefficient using nano-particles suspension as the working medium. A heat transfer correlation was also developed based on multiple regression least square method and the results were compared with that obtained by the experiment. 相似文献
703.
Sarangi R Aboelella N Fujisawa K Tolman WB Hedman B Hodgson KO Solomon EI 《Journal of the American Chemical Society》2006,128(25):8286-8296
The geometric and electronic structures of two mononuclear CuO2 complexes, [Cu(O2){HB(3-Ad-5-(i)Prpz)3}] (1) and [Cu(O2)(beta-diketiminate)] (2), have been evaluated using Cu K- and L-edge X-ray absorption spectroscopy (XAS) studies in combination with valence bond configuration interaction (VBCI) simulations and spin-unrestricted broken symmetry density functional theory (DFT) calculations. Cu K- and L-edge XAS data indicate the Cu(II) and Cu(III) nature of 1 and 2, respectively. The total integrated intensity under the L-edges shows that the 's in 1 and 2 contain 20% and 28% Cu character, respectively, indicative of very covalent ground states in both complexes, although more so in 1. Two-state VBCI simulations also indicate that the ground state in 2 has more Cu (/3d8) character. DFT calculations show that the in both complexes is dominated by O2(n-) character, although the O2(n-) character is higher in 1. It is shown that the ligand L plays an important role in modulating Cu-O2 bonding in these LCuO2 systems and tunes the ground states of 1 and 2 to have dominant Cu(II)-superoxide-like and Cu(III)-peroxide-like character, respectively. The contributions of ligand field (LF) and the charge on the absorbing atom in the molecule (Q(mol)M) to L- and K-edge energy shifts are evaluated using DFT and time-dependent DFT calculations. It is found that LF makes a dominant contribution to the edge energy shift, while the effect of Q(mol)M is minor. The charge on the Cu in the Cu(III) complex is found to be similar to that in Cu(II) complexes, which indicates a much stronger interaction with the ligand, leading to extensive charge transfer. 相似文献
704.
Lugo-Mas P Dey A Xu L Davin SD Benedict J Kaminsky W Hodgson KO Hedman B Solomon EI Kovacs JA 《Journal of the American Chemical Society》2006,128(34):11211-11221
705.
Hatcher LQ Vance MA Narducci Sarjeant AA Solomon EI Karlin KD 《Inorganic chemistry》2006,45(7):3004-3013
The variation of ligand para substituents on pyridyl donor groups of tridentate amine copper(I) complexes was carried out in order to probe electronic effects on the equilibrium between mu-eta2:eta2-(side-on)-peroxo [Cu(II)2(O2(2-))]2+ and bis(mu-oxo) [Cu(III)2(O(2-))2] species formed upon reaction with O2. [Cu(I)(R-PYAN)(MeCN)n]B(C6F5)4 (R-PYAN = N-[2-(4-R-pyridin-2-yl)-ethyl]-N,N',N'-trimethyl-propane-1,3-diamine, R = NMe2, OMe, H, and Cl) (1R) vary over a narrow range in their Cu(II)/Cu(I) redox potentials (E(1/2) vs Fe(cp)2(+/0) = -0.40 V for 1(NMe2), -0.38 V for 1(OMe), -0.33 V for 1H, and -0.32 V for 1Cl) and in C-O stretching frequencies of their carbonyl adducts, 1R-CO: nu(C-O) = 2080, 2086, 2088, and 2090 cm(-1) for R = NMe2, OMe, H, and Cl, respectively. However, within this range of electronic properties for 1R, dioxygen reactivity is significantly affected. The reaction of 1Cl or 1H with O2 at -78 degrees C in CH2Cl2 gives UV-vis and resonance Raman spectra indicative of a mu-eta2:eta2-(side-on)-peroxo dicopper(II) adduct (2R). Compound 1(OMe) reacts with O2, yielding equilibrium mixtures of side-on peroxo (2(OMe)) and bis(mu-oxo) (3(OMe)) species. Oxygenation of 1(NMe2) leads to the sole generation of the bis(mu-oxo) dicopper(III) complex (3(NMe2)). A solvent effect was also observed; in acetone or THF, increased ratios of bis(mu-oxo) relative to side-on peroxo complex are observed. Thus, the equilibrium between a dicopper side-on peroxo and bis(mu-oxo) species can be tuned by ligand design-specifically, more electron donating ligands favor the formation of the latter isomer, and the peroxo/bis(mu-oxo) equilibrium can be shifted from one extreme to the other within the same ligand system. Observations concerning the reactivity of the dioxygen adducts 2H and 3(NMe2) toward external substrates are also presented. 相似文献
706.
The four-electron reduction of dioxygen to water in multicopper oxidases takes place in a trinuclear copper cluster, which is linked to a mononuclear blue copper site, where the substrates are oxidized. Recently, several intermediates in the catalytic cycle have been spectroscopically characterized, and two possible structural models have been suggested for both the peroxy and native intermediates. In this study, these spectroscopic results are complemented by hybrid quantum and molecular mechanical (QM/MM) calculations, taking advantage of recently available crystal structures with a full complement of copper ions. Thereby, we obtain optimized molecular structures for all of the experimentally studied intermediates involved in the reductive cleavage of the O(2) molecule and energy profiles for individual reaction steps. This allows identification of the experimentally observed intermediates and further insight into the reaction mechanism that is probably relevant for the whole class of multicopper oxidases. We suggest that the peroxy intermediate contains an O(2)(2-) ion, in which one oxygen atom bridges the type 2 copper ion and one of the type 3 copper ions, whereas the other one coordinates to the other type 3 copper ion. One-electron reduction of this intermediate triggers the cleavage of the O-O bond, which involves the uptake of a proton. The product of this cleavage is the observed native intermediate, which we suggest to contain a O(2-) ion coordinated to all three of the copper ions in the center of the cluster. 相似文献
707.
Jean-François Cordeau Federico Pasin Marius M. Solomon 《Annals of Operations Research》2006,144(1):59-82
In this paper we introduce a new formulation of the logistics network design problem encountered in deterministic, single-country,
single-period contexts. Our formulation is flexible and integrates location and capacity choices for plants and warehouses
with supplier and transportation mode selection, product range assignment and product flows. We next describe two approaches
for solving the problem---a simplex-based branch-and-bound and a Benders decomposition approach. We then propose valid inequalities
to strengthen the LP relaxation of the model and improve both algorithms. The computational experiments we conducted on realistic
randomly generated data sets show that Benders decomposition is somewhat more advantageous on the more difficult problems.
They also highlight the considerable performance improvement that the valid inequalities produce in both solution methods.
Furthermore, when these constraints are incorporated in the Benders decomposition algorithm, this offers outstanding reoptimization
capabilities. 相似文献
708.
R. L. de Zafra M. Jaramillo J. Barrett L. K. Emmons A. Parrish P. M. Solomon 《International Journal of Infrared and Millimeter Waves》1990,11(4):463-467
We present a quasi-continuous record of measured atmospheric opacity obtained at 278 GHz (1.1 mm wavelength) from McMurdo Station, Antarctica during austral spring seasons in 1986 and 1987. McMurdo Station, at 78°S, 166°W, is easier to access than the Amundsen-Scott (South Pole) Station, although representing a warmer, sea level site with substantially higher typical opacity: the present record may be of interest to those contemplating mm-wave astronomical or atmospheric observations within the Antarctic region. Observations were made over a 256 MHz bandpass in 1986, during the period August 30 to October 30. In 1987, a 512 MHz bandpass was used, and observations were made during the period September 4 to October 13. All data are reduced to represent opacity in the zenith direction, and measurements were taken approximately every 20 minutes, except during storms or other periods of high opacity. The periods covered represent transitions from the polar winter towards summer conditions, and thus represent neither the best nor the worst that this site has to offer. 相似文献
709.
Measurements have been made which provide information concerning the rate of energy transfer between vibrationally excited HF and atomic fluorine. It was found that HF (v = 1) deactivates about seven times slower than was determined in previous experiments. The deactivation rate constant for HF (v = 2) is about six times larger than for HF (v = 1). 相似文献
710.