全文获取类型
收费全文 | 5768篇 |
免费 | 121篇 |
国内免费 | 15篇 |
专业分类
化学 | 3835篇 |
晶体学 | 46篇 |
力学 | 89篇 |
数学 | 960篇 |
物理学 | 974篇 |
出版年
2019年 | 49篇 |
2018年 | 42篇 |
2016年 | 87篇 |
2015年 | 71篇 |
2014年 | 88篇 |
2013年 | 171篇 |
2012年 | 170篇 |
2011年 | 200篇 |
2010年 | 123篇 |
2009年 | 111篇 |
2008年 | 191篇 |
2007年 | 179篇 |
2006年 | 181篇 |
2005年 | 176篇 |
2004年 | 174篇 |
2003年 | 163篇 |
2002年 | 147篇 |
2001年 | 99篇 |
2000年 | 123篇 |
1999年 | 84篇 |
1998年 | 85篇 |
1997年 | 76篇 |
1996年 | 100篇 |
1995年 | 128篇 |
1994年 | 105篇 |
1993年 | 80篇 |
1992年 | 89篇 |
1991年 | 84篇 |
1990年 | 81篇 |
1989年 | 90篇 |
1988年 | 95篇 |
1987年 | 75篇 |
1986年 | 76篇 |
1985年 | 113篇 |
1984年 | 84篇 |
1983年 | 100篇 |
1982年 | 117篇 |
1981年 | 101篇 |
1980年 | 91篇 |
1979年 | 105篇 |
1978年 | 82篇 |
1977年 | 84篇 |
1976年 | 77篇 |
1975年 | 67篇 |
1974年 | 74篇 |
1973年 | 79篇 |
1972年 | 50篇 |
1971年 | 64篇 |
1970年 | 45篇 |
1966年 | 40篇 |
排序方式: 共有5904条查询结果,搜索用时 15 毫秒
991.
Shukoor MI Natalio F Tahir MN Ksenofontov V Therese HA Theato P Schröder HC Müller WE Tremel W 《Chemical communications (Cambridge, England)》2007,(44):4677-4679
Polymer coated superparamagnetic gamma-Fe(2)O(3) nanoparticles were derivatized with a synthetic double-stranded RNA [poly(IC)], a known allosteric activator of the latent (2-5)A synthetase, to separate a single 35 kDa protein from a crude extract which cross reacted with antibodies raised against the sponge enzyme. 相似文献
992.
Notaras EG Fazekas M Doyle JJ Blau WJ Senge MO 《Chemical communications (Cambridge, England)》2007,(21):2166-2168
A(2)B(2)-type push-pull porphyrins with a strong intramolecular dipole moment have been prepared via Heck and Suzuki coupling reactions as novel materials for use in nonlinear optics (NLO); they display saturable (SA) and reverse saturable absorption (RSA) properties at 532 nm and their nonlinear optical response is characterized by RSA occurring at lower intensity levels whereas the onset of SA prevails at higher levels. 相似文献
993.
Ruthenium bis(beta-diketonato) complexes have been prepared at both the RuII and RuIII oxidation levels and with protonated and deprotonated pyridine-imidazole ligands. RuII(acac)2(py-imH) (1), [RuIII(acac)2(py-imH)]OTf (2), RuIII(acac)2(py-im) (3), RuII(hfac)2(py-imH) (4), and [DBU-H][RuII(hfac)2(py-im)] (5) have been fully characterized, including X-ray crystal structures (acac = 2,4-pentanedionato, hfac = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionato, py-imH = 2-(2'-pyridyl)imidazole, DBU = 1,8-diazabicyclo[5.4.0]undec-7-ene). For the acac-imidazole complexes 1 and 2, cyclic voltammetry in MeCN shows the RuIII/II reduction potential (E1/2) to be -0.64 V versus Cp2Fe+/0. E1/2 for the deprotonated imidazolate complex 3 (-1.00 V) is 0.36 V more negative. The RuII bis-hfac analogues 4 and 5 show the same DeltaE1/2 = 0.36 V but are 0.93 V harder to oxidize than the acac derivatives (0.29 and -0.07 V). The difference in acidity between the acac and hfac derivatives is much smaller, with pKa values of 22.1 and 19.3 in MeCN for 1 and 4, respectively. From the E1/2 and pKa values, the bond dissociation free energies (BDFEs) of the N-H bonds in 1 and 4 are calculated to be 62.0 and 79.6 kcal mol(-1) in MeCN - a remarkable difference of 17.6 kcal mol(-1) for such structurally similar compounds. Consistent with these values, there is a facile net hydrogen atom transfer from 1 to TEMPO* (2,2,6,6-tetramethylpiperidine-1-oxyl radical) to give 3 and TEMPO-H. The DeltaG degrees for this reaction is -4.5 kcal mol(-1). 4 is not oxidized by TEMPO* (DeltaG degrees = +13.1 kcal mol(-1)), but in the reverse direction TEMPO-H readily reduces in situ generated RuIII(hfac)2(py-im) (6). A RuII-imidazoline analogue of 1, RuII(acac)2(py-imnH) (7), reacts with 3 equiv of TEMPO* to give the imidazolate 3 and TEMPO-H, with dehydrogenation of the imidazoline ring. 相似文献
994.
Glass-Maujean M Klumpp S Werner L Ehresmann A Schmoranzer H 《The Journal of chemical physics》2007,126(14):144303
The transition probabilities, the dissociation widths, and the associated Fano parameters for rovibronic lines with J"=0,...,3 of the absorption bands of the B"B 1Sigmau+ state out of the X 1Sigmag+ v"=0 ground state were measured over the complete vibrational progression, showing clearly that only the inner-well state with B" 4psigma character can absorb vuv light and predissociate efficiently. The absolute values of these transition probablities, predissociation widths, and Fano parameters were found to agree well with ab initio calculations if one takes into account that the calculations neglect nonadiabatic couplings. 相似文献
995.
A new explicitly correlated CCSD(T)-F12 approximation is presented and tested for 23 molecules and 15 chemical reactions. The F12 correction strongly improves the basis set convergence of correlation and reaction energies. Errors of the Hartree-Fock contributions are effectively removed by including MP2 single excitations into the auxiliary basis set. Using aug-cc-pVTZ basis sets the CCSD(T)-F12 calculations are more accurate and two orders of magnitude faster than standard CCSD(T)/aug-cc-pV5Z calculations. 相似文献
996.
The existence of electrophoretic mobility at high electrolyte concentrations defines a remarkable peculiarity in the electrosurface characteristics of soft particles. According to Ohshima [H. Ohshima, Colloids Surf. 103 (1995) 249], this effect is caused by the electroosmotic flow within the soft particle shell. An explanation supporting Ohshima's conclusion can be derived from classic electrokinetic theories. Based on the Henry theory [D.C. Henry, Proc. R. Soc. London Ser. A 133 (1931) 106], we demonstrate that the electrophoretic mobility of soft particles does not disappear at decinormal concentration. 相似文献
997.
Bettucci L Bianchini C Claver C Suarez EJ Ruiz A Meli A Oberhauser W 《Dalton transactions (Cambridge, England : 2003)》2007,(47):5590-5602
In this paper we report on a comparative study of the non-alternating CO-C(2)H(4) copolymerization catalyzed by neutral Pd(II) complexes with the phosphine-sulfonate ligands bis(o-methoxyphenyl)phosphinophenylenesulfonate and bis(o-methoxyphenyl)phosphino-ethylenesulfonate. The former ligand, featuring a lower skeletal flexibility, has been found to form more active catalysts as well as produce polyketones with higher molecular weight and higher extra-ethylene incorporation. Operando high-pressure NMR studies have allowed us to intercept, for the first time, Pd(II)(phosphine-sulfonate) beta-chelates in the non-alternating copolymerization cycle, while model organometallic reactions have contributed to demonstrate that Pd(II) (phosphine-sulfonate) fragments do not form stable carbonyl complexes. The opening of the beta-chelates has been found to be a viable process by either comonomer, which contrasts with the behaviour of Pd(II) (chelating diphosphine) catalysts for the perfectly alternating copolymerization. 相似文献
998.
Amarie S Standfuss J Barros T Kühlbrandt W Dreuw A Wachtveitl J 《The journal of physical chemistry. B》2007,111(13):3481-3487
Nonphotochemical quenching (NPQ) is a fundamental mechanism in photosynthesis which protects plants against excess excitation energy and is of crucial importance for their survival and fitness. Recently, carotenoid radical cation (Car*+) formation has been discovered to be a key step for the feedback deexcitation quenching mechanism (qE), a component of NPQ, of which the molecular mechanism and location is still unknown. We have generated and characterized carotenoid radical cations by means of resonant two color, two photon ionization (R2C2PI) spectroscopy. The Car*+ bands have maxima located at 830 nm (violaxanthin), 880 nm (lutein), 900 nm (zeaxanthin), and 920 nm (beta-carotene). The positions of these maxima depend strongly on solution conditions, the number of conjugated C=C bonds, and molecular structure. Furthermore, R2C2PI measurements on the light-harvesting complex of photosystem II (LHC II) samples with or without zeaxanthin (Zea) reveal the violaxanthin (Vio) radical cation (Vio*+) band at 909 nm and the Zea*+ band at 983 nm. The replacement of Vio by Zea in the light-harvesting complex II (LHC II) has no influence on the Chl excitation lifetime, and by exciting the Chls lowest excited state, no additional rise and decay corresponding to the Car*+ signal observed previously during qE was detected in the spectral range investigated (800-1050 nm). On the basis of our findings, the mechanism of qE involving the simple replacement of Vio with Zea in LHC II needs to be reconsidered. 相似文献
999.
Andreas Eichhorn Nicole Grwe‐Kuska Andrea Liebscher Werner Rmisch Gorden Spangardt Isabel Wegner 《PAMM》2004,4(1):3-6
We present a mathematical model with stochastic input data for mean‐risk optimization of electricity portfolios containing several physical components and energy derivative products. The model is designed for the optimization horizon of one year in hourly discretization. The aim consists in maximizing the mean book value of the portfolio at the end of the optimization horizon and, at the same time, in minimizing the risk of the portfolio decisions. The risk is measured by the conditional value‐at‐risk and by some multiperiod extension of CVaR, respectively.We present numerical results for a large‐scale realistic problem adapted to a municipal power utility and study the effects of varying weighting of risk. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
1000.
Rameshwar Adhikari Matthias Buschnakowski Sven Henning Sylvia Goerlitz Trinh An Huy Werner Lebek Reinhold Godehardt Georg Hannes Michler Ralf Lach Kalman Geiger Konrad Knoll 《Macromolecular rapid communications》2004,25(5):653-658
Summary: The morphology and tensile deformation behaviour of a highly asymmetric styrene/butadiene star block copolymer (polystyrene (PS) content = 74%) containing random PS‐co‐PB (polybutadiene) copolymer as a rubbery phase were investigated. The existence of double yielding, similar to that observed in some semicrystalline polymers, was detected in this nanostructured amorphous polymer. The observed phenomenon may be correlated with two different micromechanical processes taking place at the initial stage of deformation.