全文获取类型
收费全文 | 2137篇 |
免费 | 94篇 |
国内免费 | 9篇 |
专业分类
化学 | 1785篇 |
晶体学 | 16篇 |
力学 | 28篇 |
数学 | 71篇 |
物理学 | 340篇 |
出版年
2023年 | 8篇 |
2022年 | 12篇 |
2021年 | 22篇 |
2020年 | 31篇 |
2019年 | 35篇 |
2018年 | 29篇 |
2017年 | 22篇 |
2016年 | 54篇 |
2015年 | 47篇 |
2014年 | 56篇 |
2013年 | 91篇 |
2012年 | 107篇 |
2011年 | 172篇 |
2010年 | 75篇 |
2009年 | 87篇 |
2008年 | 172篇 |
2007年 | 153篇 |
2006年 | 149篇 |
2005年 | 130篇 |
2004年 | 122篇 |
2003年 | 102篇 |
2002年 | 87篇 |
2001年 | 23篇 |
2000年 | 30篇 |
1999年 | 31篇 |
1998年 | 26篇 |
1997年 | 23篇 |
1996年 | 25篇 |
1995年 | 13篇 |
1994年 | 19篇 |
1993年 | 16篇 |
1992年 | 13篇 |
1991年 | 11篇 |
1990年 | 13篇 |
1989年 | 10篇 |
1988年 | 10篇 |
1987年 | 14篇 |
1986年 | 8篇 |
1985年 | 19篇 |
1984年 | 27篇 |
1983年 | 13篇 |
1982年 | 24篇 |
1981年 | 18篇 |
1980年 | 9篇 |
1979年 | 12篇 |
1978年 | 9篇 |
1977年 | 7篇 |
1976年 | 7篇 |
1975年 | 10篇 |
1973年 | 15篇 |
排序方式: 共有2240条查询结果,搜索用时 15 毫秒
991.
992.
993.
Kure B Matsumoto T Ichikawa K Fukuzumi S Higuchi Y Yagi T Ogo S 《Dalton transactions (Cambridge, England : 2003)》2008,(35):4747-4755
The pH-dependent hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes and hydrogenation of the carbonyl compounds have been investigated with water-soluble bis(mu-thiolate)(mu-hydride)NiRu complexes, Ni(II)(mu-SR)(2)(mu-H)Ru(II) {(mu-SR)(2) = N,N'-dimethyl-N,N'-bis(2-mercaptoethyl)-1,3-propanediamine}, as functional models for [NiFe]hydrogenases. In acidic media (at pH 4-6), the mu-H ligand of the Ni(II)(mu-SR)(2)(mu-H)Ru(II) complexes has H(+) properties, and the complexes catalyse the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes. A mechanism of the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes through a low-valent Ni(I)(mu-SR)(2)Ru(I) complex is proposed. In contrast, in neutral-basic media (at pH 7-10), the mu-H ligand of the Ni(II)(mu-SR)(2)(mu-H)Ru(II) complexes acts as H(-), and the complexes catalyse the hydrogenation of carbonyl compounds. 相似文献
994.
Ando K 《The journal of physical chemistry. B》2008,112(2):250-256
Equilibrium and nonequilibrium dynamics of a blue copper protein plastocyanin in an oxidized state are studied by molecular dynamics (MD) simulation. Potential energy functions of the lowest seven electronic states, including ligand-to-metal charge-transfer (LMCT) and copper d --> d excited states, were taken from our previous work (Ando, K. J. Phys. Chem. B 2004, 108, 3940), which employed ab initio molecular orbital and density functional calculations on the active-site model. The equilibrium MD simulations in the ground state indicate that ligand motions coupled to transition from the ground state to the LMCT state are mostly represented by stretching and bending vibrations of the Cu-S(Cys) distance, Ndelta(His)-Cu-Ndelta(His) angle, and S(Cys)-Cu-[Ndelta(His)]2 trigonal pyramid structure. The nonequilibrium dynamics on the LMCT potential exhibit rapid decays in which surface crossings to the d --> d and the first excited states occur in 70-80 fs. The crossing dynamics mostly correlate with cleavage of the Cu-S(Cys) bond and the associated response in the Ndelta(His)-Cu-Ndelta(His) moiety. The average dynamics of the vertical energy gap coordinates exhibit an overdamped decay with a recurrence oscillation in 500 fs, which shows clear coherence surviving after the ensemble averaging. This oscillation stems mostly from the recoiling motion of the Ndelta(His)-Cu-Ndelta(His) part. The dynamics of the energy gaps after this coherent oscillation are randomized such that the ensemble average yields flat profiles along time, although each single trajectory exhibits fluctuations with amplitudes large enough to reach surface crossings. These indicate that the relaxation from the LMCT state first occurs via ballistic and coherent potential crossings in 70-80 and 500 fs, followed by thermally activated random transitions. 相似文献
995.
An efficient nickel catalyst system for the carboxylation of organozinc reagents with CO(2) under very mild conditions has been developed. The catalyst system complements the conventional methods and enables the direct synthesis of various saturated carboxylic acid derivatives from the corresponding alkylzinc reagents and CO(2). 相似文献
996.
We report here on a method for preparation of precise laboratory solutions using controlled diffusion for dosing. The desired
chemical is delivered into the target solution from a stock solution through a mass-transport-limiting delivery port that
blocks convection but allows reproducible diffusive transport. Solution making with this approach involves a single step irrespective
of how low the desired concentration is. Diffusional delivery of chemicals involves no appreciable movement of water and,
thus, no addition of volume. The approach is therefore particularly suitable for standard addition. Precise solutions of usual
laboratory volumes can be made within a short time period with proper design of the delivery port or ports. Comparison with
the performance of conventional methods of routine solution preparation shows that better precision can be achieved with less
labor using this approach. 相似文献
997.
Yessi Permana Koji Nakano Dr. Makoto Yamashita Dr. Daisuke Watanabe Kyoko Nozaki Prof. Dr. 《化学:亚洲杂志》2008,3(4):710-718
Four acetyl cobalt complexes, [AcCo(CO)3P(p‐tolyl)3] ( 1 ; p‐tolyl=4‐Me‐C6H4), [AcCo(CO)3P(OPh)3] ( 2 ), [AcCo(CO)3P(NMe2)3] ( 3 ), and [AcCo(CO)2(dppp)] ( 4 ; dppp=1,3‐bis(diphenylphosphanyl)propane), were synthesized, characterized, and examined as catalysts for the unprecedented carbonylative polymerization of oxetanes. Copolymers containing ester (4‐hydroxyalkanoate) and/or ether units were obtained with complexes 1 and 2 , but not with complexes 3 and 4 either in the presence or absence of additional phosphorus ligands. The ester unit/ether unit ratio varied in the range 21:79–63:37, and the highest ester/ether ratio of 63:37 was achieved by using complex 1 in the presence of a further 5 equivalents of P(OPh)3. Although direct carbonylative polymerization is possible, preformation and ring opening of the γ‐lactone is also suggested as an alternative pathway. 相似文献
998.
Nakayama K Tachikawa T Majima T 《Langmuir : the ACS journal of surfaces and colloids》2008,24(13):6425-6428
Protein adsorption and dissociation on cell membrane surfaces is a topic of important study to reveal biological processes including signal transduction and protein trafficking. We demonstrated here the establishment of a mimic model system for the spatial control of protein adsorption/elimination on a lipid bimembrane using a photochemical technique. The novel photoeliminative linker that we synthesized here consists of three distinct components: a substrate (biotin), a photoeliminative group (4-(4-(1-hydroxyethyl)-2-methoxy-5-nitrophenoxy)butanoic acid), and a lipid bimembrane-adsorbent group (farnesyl). The photoeliminative linker was inserted on the entire surface of the lipid bimembrane and two-dimensionally eliminated by spatial UV irradiation onto the membrane to create a biotin pattern. A target protein, streptavidin was selectively immobilized on the patterned biotin, although it was almost not attached on the nonirradiated region. The streptavidin array was selectively dissociated by UV irradiation onto the entire membrane. 相似文献
999.
Sakai H Tanaka K Fukushima H Tsuchiya K Sakai K Kondo T Abe M 《Colloids and surfaces. B, Biointerfaces》2008,66(2):4022-290
Polyurea capsules have been prepared using the electrocapillary emulsification method in order to control the particle size within the submicron range. The polyurea capsules have been synthesized via the interfacial polycondensation between tetraethylenepentamine (TEP) dissolved in an aqueous phase and toluenediisocyanate (TDI) dissolved in a mixture of cyclohexane and chloroform. The oil phase contains a lipophilic nonionic surfactant (sorbitan sesquioleate, SO-15) as an emulsion stabilizer. Scanning electron microscope (SEM) observations reveal that the capsule size is decreased as (i) the amount of the aqueous phase injected into the oil phase is decreased and (ii) the dropping rate of the aqueous phase is decreased. Indeed, the mole ratio of the two monomers makes a significant impact on the capsule size. Under the best experimental condition examined in this study, we obtained polyurea capsules with a diameter of approximately 200 nm, which should be useful in developing bioreactors or carriers. 相似文献
1000.