全文获取类型
收费全文 | 2247篇 |
免费 | 178篇 |
国内免费 | 138篇 |
专业分类
化学 | 1484篇 |
晶体学 | 42篇 |
力学 | 80篇 |
综合类 | 12篇 |
数学 | 259篇 |
物理学 | 686篇 |
出版年
2023年 | 25篇 |
2022年 | 49篇 |
2021年 | 31篇 |
2020年 | 56篇 |
2019年 | 50篇 |
2018年 | 41篇 |
2017年 | 43篇 |
2016年 | 82篇 |
2015年 | 54篇 |
2014年 | 88篇 |
2013年 | 123篇 |
2012年 | 149篇 |
2011年 | 153篇 |
2010年 | 88篇 |
2009年 | 86篇 |
2008年 | 107篇 |
2007年 | 126篇 |
2006年 | 103篇 |
2005年 | 104篇 |
2004年 | 71篇 |
2003年 | 59篇 |
2002年 | 62篇 |
2001年 | 49篇 |
2000年 | 53篇 |
1999年 | 40篇 |
1998年 | 22篇 |
1997年 | 39篇 |
1996年 | 44篇 |
1995年 | 32篇 |
1994年 | 33篇 |
1993年 | 26篇 |
1992年 | 29篇 |
1991年 | 18篇 |
1990年 | 20篇 |
1989年 | 18篇 |
1988年 | 15篇 |
1987年 | 15篇 |
1986年 | 24篇 |
1985年 | 17篇 |
1983年 | 16篇 |
1982年 | 17篇 |
1981年 | 10篇 |
1980年 | 15篇 |
1979年 | 16篇 |
1978年 | 11篇 |
1977年 | 23篇 |
1976年 | 13篇 |
1975年 | 18篇 |
1972年 | 9篇 |
1971年 | 9篇 |
排序方式: 共有2563条查询结果,搜索用时 15 毫秒
901.
902.
Kubát P Šebera J Záliš S Langmaier J Fuciman M Polívka T Lang K 《Physical chemistry chemical physics : PCCP》2011,13(15):6947-6954
Transient absorption spectroscopy, cyclic voltammetry, and DFT calculations were used to describe charge transfer processes in a series of 5,10,15,20-tetrakis(N-methylpyridinium-n-yl) porphyrins (TMPyPn, n = 4,3,2) and TMPyPn/p-sulfonatocalix[m]arene (clxm, m = 4,6,8) complexes. Excitation of TMPyPn is accompanied by an increasing electron density at the methylpyridinium substituents in the order TMPyP2 < TMPyP3 < TMPyP4. The quenching of the excited singlet states of the complexes increases with the number of ionized phenolic groups of clxm and can be correlated with the partial transfer of the electron density from O(-) to the peripheral methylpyridinium substituents rather than to the porphyrin ring. 相似文献
903.
We present a new method to locally apply mechanical tensile and compressive force on single cells based on integration of a microfluidic device with an optical laser tweezers. This system can locate a single cell within customized wells exposing a square-like membrane segment to a functionalized bead. Beads are coated with extracellular matrix (ECM) proteins of interest (e.g. fibronectin) to activate specific membrane receptors (e.g. integrins). The functionalized beads are trapped and manipulated by optical tweezers to apply mechanical load on the ECM-integrin-cytoskeleton linkage. Activation of the receptor is visualized by accumulation of expressed fluorescent proteins. This platform facilitates isolation of single cells and excitation by tensile/compressive forces applied directly to the focal adhesion via specific membrane receptors. Protein assembly or recruitment in a focal adhesion can then be monitored and identified using fluorescent imaging. This platform is used to study the recruitment of vinculin upon the application of external tensile force to single endothelial cells. Vinculin appears to be recruited above the forced bead as an elliptical cloud, centered 2.1 ± 0.5 μm from the 2 μm bead center. The mechanical stiffness of the membrane patch inferred from this measurement is 42.9 ± 6.4 pN μm(-1) for a 5 μm × 5 μm membrane segment. This method provides a foundation for further studies of mechanotransduction and tensile stiffness of single cells. 相似文献
904.
Xu X Zhao L Xu GF Guo YN Tang J Liu Z 《Dalton transactions (Cambridge, England : 2003)》2011,40(24):6440-6444
The reaction of Dy(NO(3))(3)·6H(2)O with the ligand 2-((1-hydroxybutan-2-ylimino)methyl)phenol (H(2)L, ) generates the nonanuclear compound [Dy(9)L(8)(μ(3)-OH)(8)(μ(4)-OH)(2)(CH(3)OH)(8)](OH)(CH(3)OH)(3) (Dy(9)), whose single-crystal X-ray structure reveals the presence of two square pyramidal pentanuclear units assembled via the apical metal center. The square pyramidal core of a previously reported [Dy(5)(μ(4)-OH)(μ(3)-OH)(4)(μ-η(2)-Ph(2)acac)(4)(η(2)-Ph(2)acac)(6)] (Dy(5); Ph(2)acac = dibenzoylmethanide), is structurally related to those herein described; however, the magnetic properties of Dy(9) and Dy(5) are drastically different. Indeed, Dy(5) shows slow relaxation of magnetization while no out-of-phase ac signal is noticed for Dy(9). The underlying mechanism is not clear due to the complexity of such systems; however, the different anisotropy of the respective structures, which is dictated by the combination of the metal topology, the ligands involved and the structural parameters of the molecule, is mostly responsible for the distinctive relaxation dynamics observed. 相似文献
905.
Jiang K Zhang HX Yang YY Mothes R Lang H Cai WB 《Chemical communications (Cambridge, England)》2011,47(43):11924-11926
Well-dispersed Ag@Pd supported on magnetite nanoparticles have been obtained through a simple colloidal impregnation method. The as-synthesised nanocomposite exhibits greatly enhanced catalytic reactivity and reusability towards 4-nitrophenol hydrogenation. 相似文献
906.
Liu LL Li HX Wan LM Ren ZG Wang HF Lang JP 《Chemical communications (Cambridge, England)》2011,47(39):11146-11148
Reactions of [H(4)L][PF(6)](4) with 4 equiv. of Mn(OAc)(2)·4H(2)O in the presence of air gave rise to a mononuclear Mn(III)-superoxo complex [Mn(III)L(O(2))(H(2)O)](PF(6))(2), which contains a bowl-shaped cationic structure with a D(4d) symmetry. It has an unprecedented linear end-on Mn(III)-O(2) unit and exhibited good efficiency and selectivity in the catalytic oxidation of alkenes with O(2) plus isobutyraldehyde under mild conditions. 相似文献
907.
Rh-catalyzed C-H carbonylation of indoles under 1 atm of CO has been achieved. Various substituted indoles and indole with free N-H could be carboxylated with linear- and/or cyclic-alcohol to give the desired indole-3-carboxylates with up to 92% yield. A mechanism involving Rh(III) initiated C-H metallation is proposed. 相似文献
908.
Schmidt CD Lang N Jux N Hirsch A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(19):5289-5299
Click reactions at the bay-position of perylenes and a new route to benzo[ghi]perylenes and coronenes are presented. Irradiation with light leads to an electrocyclic reaction of the newly formed triazole ring(s) with the neighbouring bay-positions of the perylene core and after oxidation by air, the benzo[ghi]perylenes and coronenes are obtained. By using Newkome dendrimers as substituents for perylene diimides (PDIs), water solubility can be achieved after removal of the tert-butyl protecting groups. The aggregation and optical properties of the bay-functionalised PDIs, benzo[ghi]perylenes and coronenes are investigated by absorption and fluorescence spectroscopy. 相似文献
909.
Muhammad Mufakkar Anvarhusein A. Isab Tobias Rüffer Heinrich Lang Saeed Ahmad Najma Arshad Abdul Waheed 《Transition Metal Chemistry》2011,36(5):505-512
Copper(I) complexes of thioureas having the general formulae [CuLnBr] and [CuLn]Br [where, n = 1 − 4 and L = thiourea (Tu), N-methylthiourea (Metu), N-ethylthiourea (Ettu), N,N′-dipropylthiourea (Dprtu), N,N′-dibutylthiourea (Dbtu) or N,N′-diphenylthiourea (Dphtu)] were prepared and characterized by elemental analysis, IR, and NMR (1H and 13C) spectroscopy. The crystal structure of one of them, [Cu(Metu)4]Br (1), was determined by X-ray crystallography. The X-ray structure of 1 describes a tetrahedral geometry around copper(I) with all Metu ligands binding through sulfur atoms. An upfield shift in
the 13C NMR and downfield shift in the 1H NMR spectra are consistent with the thione coordination to copper(I). Antimicrobial activities of the complexes were evaluated
by the minimum inhibitory concentration method. The results showed that only [Cu(Ettu)3Br] was effective in inhibiting the growth of all the tested organisms (gram-positive, gram-negative bacteria, and Candida sp.), while the other complexes were not effective against all the organisms. 相似文献
910.
Rafael Block SamulewskiJúlio César da Rocha Rafael StielerErnesto Schulz Lang David John EvansGiordano Poneti Otaciro Rangel NascimentoRonny Rocha Ribeiro Fábio Souza Nunes 《Polyhedron》2011,30(12):1997-2006
Herein we report on the synthesis, single crystal X-ray structure, spectroscopic and magnetic properties of [{Cu2(tidf)(H2O)}2(μ-CN)2Fe(CN)4]·6H2O (1), [Cu2(tidf)(H2O)2][Ni(CN)4] (2) and [Cu2(tidf)(H2O)2][Fe(CN)5NO]·H2O (3) (tidf = a Robson type macrocyclic ligand obtained on condensation of 2,6-diformyl-4-methylphenol and 1,3-diaminopropane). Complex (1) is pentanuclear; two paramagnetic dicopper(II) units are linked by a hexacyanoferrate(II) ion through two cyano-bridges. All compounds exhibit extensive, three-dimensional, supramolecular structures supported by classic hydrogen bonding between the coordinated aqua ligands, water molecules and cyano groups. Magnetism as a function of the temperature of complexes 1-3 is consistent with a strong antiferromagnetism with exchange parameters 2J estimated −783(29), −913(2), −905(1), respectively. 相似文献