全文获取类型
收费全文 | 1690篇 |
免费 | 85篇 |
国内免费 | 11篇 |
专业分类
化学 | 1247篇 |
晶体学 | 2篇 |
力学 | 24篇 |
数学 | 270篇 |
物理学 | 243篇 |
出版年
2023年 | 8篇 |
2022年 | 17篇 |
2021年 | 24篇 |
2020年 | 37篇 |
2019年 | 48篇 |
2018年 | 23篇 |
2017年 | 24篇 |
2016年 | 41篇 |
2015年 | 54篇 |
2014年 | 69篇 |
2013年 | 85篇 |
2012年 | 159篇 |
2011年 | 186篇 |
2010年 | 78篇 |
2009年 | 46篇 |
2008年 | 120篇 |
2007年 | 112篇 |
2006年 | 116篇 |
2005年 | 102篇 |
2004年 | 73篇 |
2003年 | 67篇 |
2002年 | 38篇 |
2001年 | 16篇 |
2000年 | 14篇 |
1999年 | 12篇 |
1998年 | 13篇 |
1997年 | 19篇 |
1996年 | 10篇 |
1995年 | 6篇 |
1994年 | 14篇 |
1992年 | 8篇 |
1991年 | 8篇 |
1990年 | 7篇 |
1989年 | 11篇 |
1988年 | 5篇 |
1986年 | 4篇 |
1985年 | 9篇 |
1984年 | 8篇 |
1983年 | 6篇 |
1982年 | 5篇 |
1981年 | 11篇 |
1980年 | 5篇 |
1979年 | 6篇 |
1978年 | 9篇 |
1977年 | 6篇 |
1975年 | 3篇 |
1974年 | 8篇 |
1973年 | 10篇 |
1972年 | 4篇 |
1968年 | 3篇 |
排序方式: 共有1786条查询结果,搜索用时 31 毫秒
91.
Lau KH Ren C Park SH Szleifer I Messersmith PB 《Langmuir : the ACS journal of surfaces and colloids》2012,28(4):2288-2298
Surface-grafted water-soluble polymer brushes are being intensely investigated for preventing protein adsorption to improve biomedical device function, prevent marine fouling, and enable applications in biosensing and tissue engineering. In this contribution, we present an experimental-theoretical analysis of a peptidomimetic polymer brush system with regard to the critical brush density required for preventing protein adsorption at varying chain lengths. A mussel adhesive-inspired DOPA-Lys (DOPA = 3,4-dihydroxy-phenylalanine; Lys = lysine) pentapeptide surface grafting motif enabled aqueous deposition of our peptidomimetic polypeptoid brushes over a wide range of chain densities. Critical densities of 0.88 nm(-2) for a relatively short polypeptoid 10-mer to 0.42 nm(-2) for a 50-mer were identified from measurements of protein adsorption. The experiments were also compared with the protein adsorption isotherms predicted by a molecular theory. Excellent agreements in terms of both the polymer brush structure and the critical chain density were obtained. Furthermore, atomic force microscopy (AFM) imaging is shown to be useful in verifying the critical brush density for preventing protein adsorption. The present coanalysis of experimental and theoretical results demonstrates the significance of characterizing the critical brush density in evaluating the performance of an antifouling polymer brush system. The high fidelity of the agreement between the experiments and molecular theory also indicate that the theoretical approach presented can aid in the practical design of antifouling polymer brush systems. 相似文献
92.
93.
Abernethy Colin D. Baker Robert J. Cole Marcus L. Davies Aaron J. Jones Cameron 《Transition Metal Chemistry》2003,28(3):296-299
The reactivity of the carbene stabilised indium trihydride complex, [InH3(IMes)] IMes = 1,3-dimesitylimidazol-2-ylidene, toward a variety of transition metal complexes has been investigated. The study has shown that the InH3 complex can act as a carbene and/or hydride transfer reagent to transition metal centres but does not yield heterobimetallic materials. Two new complexes, [Cp2Ti(-Cl)2Zn(IMes)Cl] and [CpNi(H)(IMes)], have resulted from this work, both of which have been spectroscopically and structurally characterised. 相似文献
94.
Jessada Mahatthananchai Dr. Aaron M. Dumas Prof. Dr. Jeffrey W. Bode 《Angewandte Chemie (International ed. in English)》2012,51(44):10954-10990
Complete control of the product of a catalytic reaction can be achieved on the basis of catalyst structure, even when the reaction conditions are nearly identical. Catalyst‐controlled selectivity is well established for enantioselective catalysis but less formulated for catalytic regio‐, chemo‐, or product‐selective reactions. This Review describes selective transformations of the same starting materials into two or more different products simply by the choice of catalyst. By collecting and highlighting examples of selective catalysis, we hope that the field will be encouraged by the progress that has been made while bringing attention to unmet needs in the design and mechanistic understanding of selective catalysts. 相似文献
95.
Dr. Delphine Crozet Dr. Aitor Gual Dr. David McKay Dr. Chiara Dinoi Dr. Cyril Godard Prof. Martine Urrutigoïty Dr. Jean‐Claude Daran Prof. Laurent Maron Prof. Carmen Claver Prof. Philippe Kalck 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(23):7128-7140
The reactivity of [Rh(CO)2{(R,R)‐Ph? BPE}]BF4 ( 2 ) toward amine, CO and/or H2 was examined by high‐pressure NMR and IR spectroscopy. The two cationic pentacoordinated species [Rh(CO)3{(R,R)‐Ph? BPE}]BF4 ( 4 ) and [Rh(CO)2(NHC5H10){(R,R)‐Ph‐BPE}]BF4 ( 8 ) were identified. The transformation of 2 into the neutral complex [RhH(CO)2{(R,R)‐Ph? BPE}] ( 3 ) under hydroaminomethylation conditions (CO/H2, amine) was investigated. The full mechanisms related to the formation of 3 , 4 and 8 starting from 2 are supported by DFT calculations. In particular, the pathway from 2 to 3 revealed the deprotonation by the amine of the dihydride species [Rh(H)2(CO)2{(R,R)‐Ph? BPE}]BF4 ( 6 ), resulting from the oxidative addition of H2 on 2 . 相似文献
96.
Lukas AS Bushard PJ Weiss EA Wasielewski MR 《Journal of the American Chemical Society》2003,125(13):3921-3930
The spin-spin exchange interaction, 2J, in a radical ion pair produced by a photoinduced electron transfer reaction can provide a direct measure of the electronic coupling matrix element, V, for the subsequent charge recombination reaction. We have developed a series of dyad and triad donor-acceptor molecules in which 2J is measured directly as a function of incremental changes in their structures. In the dyads the chromophoric electron donors 4-(N-pyrrolidinyl)- and 4-(N-piperidinyl)naphthalene-1,8-dicarboximide, 5ANI and 6ANI, respectively, and a naphthalene-1,8:4,5-bis(dicarboximide) (NI) acceptor are linked to the meta positions of a phenyl spacer to yield 5ANI-Ph-NI and 6ANI-Ph-NI. In the triads the same structure is used, except that the piperidine in 6ANI is replaced by a piperazine in which a para-X-phenyl, where X = H, F, Cl, MeO, and Me(2)N, is attached to the N' nitrogen to form a para-X-aniline (XAn) donor to give XAn-6ANI-Ph-NI. Photoexcitation yields the respective 5ANI(+)-Ph-NI(-), 6ANI(+)-Ph-NI(-), and XAn(+)-6ANI-Ph-NI(-) singlet radical ion pair states, which undergo subsequent radical pair intersystem crossing followed by charge recombination to yield (3)NI. The radical ion pair distances within the dyads are about 11-12 A, whereas those in the triads are about approximately 16-19 A. The degree of delocalization of charge (and spin) density onto the aniline, and therefore the average distance between the radical ion pairs, is modulated by the para substituent. The (3)NI yields monitored spectroscopically exhibit resonances as a function of magnetic field, which directly yield 2J for the radical ion pairs. A plot of ln 2J versus r(DA), the distance between the centroids of the spin distributions of the two radicals that comprise the pair, yields a slope of -0.5 +/- 0.1. Since both 2J and k(CR), the rate of radical ion pair recombination, are directly proportional to V(2), the observed distance dependence of 2J shows directly that the recombination rates in these molecules obey an exponential distance dependence with beta = 0.5 +/- 0.1 A(-)(1). This technique is very sensitive to small changes in the electronic interaction between the two radicals and can be used to probe subtle structural differences between radical ion pairs produced from photoinduced electron transfer reactions. 相似文献
97.
Shaakov S Galili T Stavitski E Levanon H Lukas A Wasielewski MR 《Journal of the American Chemical Society》2003,125(21):6563-6572
We have synthesized a series of structurally related, covalently linked electron donor-acceptor triads having highly restricted conformations to study the effects of radical ion pair (RP) structure, energetics, and solvation on charge recombination. The chromophoric electron acceptor in these triads is a 4-aminonaphthalene-1,8-dicarboximide (6ANI), in which the 4-amine nitrogen atom is part of a piperazine ring. The second nitrogen atom of the piperazine ring is part of a para-substituted aniline donor, where the para substituents are X = H, OMe, and NMe(2). The imide group of 6ANI is linked to a naphthalene-1,8:4,5-bis(dicarboximide) (NI) electron acceptor across a phenyl spacer in a meta relationship. The triads undergo two-step photoinduced electron transfer to yield their respective XAn(*)(+)-6ANI-Ph-NI(*)(-) RP states, which undergo radical pair intersystem crossing followed by charge recombination to yield (3)NI. Time-resolved electron paramagnetic resonance experiments on the spin-polarized RPs and triplet states carried out in toluene and in E-7, a mixture of nematic liquid crystals (LCs), show that for all three triads, the XAn(*)(+)-6ANI-Ph-NI(*)(-) RPs are correlated radical pairs and directly yield values of the spin-spin exchange interaction, J, and the dipolar interaction, D. The values of J are all about -1 mT and show that the LC environment most likely enforces the chair conformation at the piperazine ring, for which the RP distance is larger than that for the corresponding boat conformation. The values of D yield effective RP distances that agree well with those calculated earlier from the spin distributions of the radical ions. Within the LC, changing the temperature shows that the CR mechanism can be changed significantly as the energy levels of the RPs change relative to that of the recombination triplet. 相似文献
98.
Aaron C. West Joseph D. Lynch Bernhard Sellner Hans Lischka William L. Hase Theresa L. Windus 《Theoretical chemistry accounts》2012,131(10):1-14
Extensive density functional theory (DFT) calculations have been performed to develop a force field for the classical molecular dynamics (MD) simulations of various azobenzene derivatives. Besides azobenzene, we focused on a thiolated azobenzene’s molecular rod (4′-{[(1,1′-biphenyl)-4-yl]diazenyl}-(1,1′-biphenyl)-4-thiol) that has been previously demonstrated to photoisomerize from trans to cis with high yields on surfaces. The developed force field is an extension of OPLS All Atoms, and key bonding parameters are parameterized to reproduce the potential energy profiles calculated by DFT. For each of the parameterized molecule, we propose three sets of parameters: one best suited for the trans configuration, one for the cis configuration, and finally, a set able to describe both at a satisfactory degree. The quality of the derived parameters is evaluated by comparing with structural and vibrational experimental data. The developed force field opens the way to the classical MD simulations of self-assembled monolayers (SAMs) of azobenzene’s molecular rods, as well as to the quantum mechanics/molecular mechanics study of photoisomerization in SAMs. 相似文献
99.
The reaction of pyridyl functionalized porphyrins with Re(CO)(5)Cl in THF results in the formation of porphyrin dimers which, despite incorporation of rhenium into the assemblies, remain fluorescent. The rigid compounds provide an efficient geometry and/or orbital pathway for singlet energy transfer, rendering these compounds suitable, in principle, for the study of both through-bond and through-space energy transfer. Derivatives containing both metallated and freebase porphyrins connected via the metal corners display efficient porphyrin-porphyrin energy transfer. The photophysical properties of the assemblies have been studied by both steady-state and time-resolved fluorescence techniques, yielding approximate rates and efficiencies for porphyrin-porphyrin energy transfer. 相似文献
100.
[reaction: see text] Two readily prepared catalysts have been developed for the hydroamination of alkynes by 1,1-disubstituted hydrazines. The catalyses are facile with terminal alkynes and some internal alkynes. If the hydrazine bears an aryl group, Fischer cyclization can occur in a one-pot procedure. In addition, reactions with acetylene to produce a plethora of hydrazones are described. Catalytic reactions involving acetylene and substituted hydrazines are complete in less than 2 h at room temperature and 1 atm of pressure. 相似文献