全文获取类型
收费全文 | 2549篇 |
免费 | 105篇 |
国内免费 | 6篇 |
专业分类
化学 | 1915篇 |
晶体学 | 33篇 |
力学 | 45篇 |
数学 | 188篇 |
物理学 | 479篇 |
出版年
2023年 | 14篇 |
2022年 | 54篇 |
2021年 | 90篇 |
2020年 | 56篇 |
2019年 | 57篇 |
2018年 | 46篇 |
2017年 | 57篇 |
2016年 | 102篇 |
2015年 | 78篇 |
2014年 | 82篇 |
2013年 | 157篇 |
2012年 | 138篇 |
2011年 | 186篇 |
2010年 | 123篇 |
2009年 | 104篇 |
2008年 | 168篇 |
2007年 | 127篇 |
2006年 | 110篇 |
2005年 | 118篇 |
2004年 | 84篇 |
2003年 | 64篇 |
2002年 | 55篇 |
2001年 | 33篇 |
2000年 | 41篇 |
1999年 | 18篇 |
1998年 | 21篇 |
1997年 | 27篇 |
1996年 | 24篇 |
1995年 | 32篇 |
1994年 | 28篇 |
1993年 | 35篇 |
1992年 | 30篇 |
1991年 | 10篇 |
1990年 | 13篇 |
1989年 | 21篇 |
1988年 | 19篇 |
1987年 | 16篇 |
1986年 | 7篇 |
1985年 | 14篇 |
1984年 | 15篇 |
1983年 | 10篇 |
1982年 | 11篇 |
1981年 | 12篇 |
1980年 | 20篇 |
1979年 | 17篇 |
1978年 | 14篇 |
1977年 | 10篇 |
1976年 | 9篇 |
1974年 | 6篇 |
1973年 | 9篇 |
排序方式: 共有2660条查询结果,搜索用时 15 毫秒
91.
Strong cation-exchange chromatography (SCX-HPLC) was used in conjunction with inductively coupled plasma mass spectrometry (ICP-MS) to investigate cationic selenium species present in leaf extract of wild-type Brassica juncea supplemented with selenite. Total amount of Se accumulated by the leaves was found to be 352 microg g(-1). Cation-exchange solid-phase extraction (SCX-SPE) was used to pre-concentrate the cationic species present in the leaf extract. Methylselenomethionine (MeSeMet) and dimethylselenoniumproprionate (DMSeP) were synthesized and characterized by electrospray quadrupole time-of-flight MS (ESI-QTOF-MS). Laboratory synthesized and commercially available standards were used in chromatographic studies to identify the Se species in the leaf extract through retention time comparisons and standard addition method. Major cationic selenium species identified in the present study were MeSeMet and methylselenocysteine (MeSeCys) while selenomethionine (SeMet) was found in minor quantities. 相似文献
92.
Jörg Rethmeier Andreas Rabenstein Monika Langer Ulrich Fischer 《Journal of chromatography. A》1997,760(2):637-302
Depending on the sulfur species, picomoles of different inorganic sulfur compounds can be detected and separated by HPLC in one arrangement in a sample volume less than 50 μl. The combination of fluorescence labelling of reduced inorganic sulfur compounds such as sulfide (S2−), sulfite(SO32− and thiosulfate (S2O32−) with monobromobimane followed by an extraction of elemental sulfur (S°) by chloroform treatment enables the detection of all mentioned sulfur compounds as well as sulfate (remaining aqueous phase) in the same sample. While the derivatized sulfur compounds could be detected by their fluorescence emission at 480 nm, elemental sulfur is identified by its UV absorption at 263 nm. Sulfate in the remaining aqueous phase is detected by HPLC with indirect UV detection at 254 nm. Detection ranges for the different sulfur compounds examined are as follows: sulfide (5 μM to 1.5 mM), sulfite (5 μM to 1.0 mM), thiosulfate (1 μM to 1.5 mM), elemental sulfur (2 μM to 32 mM) and sulfate (5 μM to >1 mM). 相似文献
93.
Mendoza SM Whelan CM Jalkanen JP Zerbetto F Gatti FG Kay ER Leigh DA Lubomska M Rudolf P 《The Journal of chemical physics》2005,123(24):244708
Thin films of fumaramide [2]rotaxane, a mechanically interlocked molecule composed of a macrocycle and a thread in a "bead and thread" configuration, were prepared by vapor deposition on both Ag(111) and Au(111) substrates. X-ray photoelectron spectroscopy (XPS) and high-resolution electron-energy-loss spectroscopy were used to characterize monolayer and bulklike multilayer films. XPS determination of the relative amounts of carbon, nitrogen, and oxygen indicates that the molecule adsorbs intact. On both metal surfaces, molecules in the first adsorbed layer show an additional component in the C 1s XPS line attributed to chemisorption via amide groups. Molecular-dynamics simulation indicates that the molecule orients two of its eight phenyl rings, one from the macrocycle and one from the thread, in a parallel bonding geometry with respect to the metal surfaces, leaving three amide groups very close to the substrate. In the case of fumaramide [2]rotaxane adsorption on Au(111), the presence of certain out-of-plane phenyl ring and Au-O vibrational modes points to such bonding and a preferential molecular orientation. The theoretical and experimental results imply that the three-dimensional intermolecular configuration permits chemisorption at low coverage to be driven by interactions between the three amide functions of fumaramide [2]rotaxane and the Ag(111) or Au(111) surface. 相似文献
94.
A guanine-rich PNA dodecamer having the sequence H-G4T4G4-Lys-NH2 (G-PNA) hybridizes with a DNA dodecamer of homologous sequence to form a four-stranded quadruplex (Datta, B.; Schmitt, C.; Armitage, B. A. J. Am. Chem. Soc. 2003, 125, 4111-4118). This report describes quadruplex formation by the PNA alone. UV melting curves and fluorescence resonance energy transfer experiments reveal formation of a multistranded structure stabilized by guanine tetrads. The ion dependency of these structures is analogous to that reported for DNA quadruplexes. Electrospray ionization mass spectrometry indicates that both dimeric and tetrameric quadruplexes are formed by G4-PNA, with the dimeric form being preferred. These results have implications for the use of G-rich PNA for homologous hybridization to G-rich targets in chromosomal DNA and suggest additional applications in assembling quadruplex structures within lipid bilayer environments. 相似文献
95.
Hybridization of PNA to structured DNA targets: quadruplex invasion and the overhang effect 总被引:4,自引:0,他引:4
Peptide nucleic acid (PNA) probes have been synthesized and targeted to quadruplex DNA. UV-vis and CD spectroscopy reveal that the quadruplex structure of the thrombin binding aptamer (TBA) is disrupted at 37 degrees C by a short PNA probe. The corresponding DNA probe fails to bind to the stable secondary structure at this temperature. Thermal denaturation experiments indicate surprisingly high thermal and thermodynamic stabilities for the PNA-TBA hybrid. Our results point to the nonbonded nucleobase overhangs on the DNA as being responsible for this stability. This "overhang effect" is found for two different PNA-DNA sequences and a variety of different overhang lengths and sequences. The stabilization offered by the overhangs assists the PNA in overcoming the stable secondary structure of the DNA target, an effect which may be significant in the targeting of biological nucleic acids, which will always be much longer than the PNA probe. The ability of PNA to invade a structured DNA target expands its potential utility as an antigene agent or hybridization probe. 相似文献
96.
Monika S. K. Fuchs Alexey M. Shor Notker Rsch 《International journal of quantum chemistry》2002,86(5):487-501
The parallel density functional program PARA GAUSS has been extended by a tool for computing solvent effects based on the conductor‐like screening model (COSMO). The molecular cavity in the solvent is constructed as a set of overlapping spheres according to the GEPOL algorithm. The cavity tessellation scheme and the resulting set of point charges on the cavity surface comply with the point group symmetry of the solute. Symmetry is exploited to reduce the computational effort of the solvent model. To allow an automatic geometry optimization including solvent effects, care has been taken to avoid discontinuities due to the discretization (weights of tesserae, number of spheres created by GEPOL). In this context, an alternative definition for the grid points representing the tesserae is introduced. In addition to the COSMO model, short‐range solvent effects are taken into account via a force field. We apply the solvent module to all‐electron scalar‐relativistic density functional calculations on uranyl, UO22+, and its aquo complexes in aqueous solution. Solvent effects on the geometry are very small. Based on the model [UO2(H2O)5]2+, the solvation energy of uranyl is estimated to be about ?400 kcal/mol, in agreement with the range of experimental data. The major part of the solvation energy, about ?250 kcal/mol, is due to a donor–acceptor interaction associated with a coordination shell of five water ligands. One can interpret this large solvation energy also as a compounded effect of an effective reduction of the uranyl moiety plus a solvent polarization. The energetic effect of the structure relaxation in the solution is only about 8 kcal/mol. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001 相似文献
97.
ZnS nanoparticles of diameters of 3–4 nm were self-assembled to form dense nanospheres of sizes 100 nm by a colloidal precipitation method using PVP as the stabilizing agent. Studies indicated that the ZnS nanoparticles maintained their individual properties inside the nanospheres. Optical absorption spectra of the samples demonstrated the effect of quantum confinement in the ZnS nanocrystals. Room temperature photoluminescence measurements showed a sharp UV emission at 370 nm, attributed to sulfur vacancies. 相似文献
98.
99.
Bimetallic Gold(I) Complexes with Ethynyl‐Helicene and Bis‐Phosphole Ligands: Understanding the Role of Aurophilic Interactions in their Chiroptical Properties 下载免费PDF全文
Dr. Mehdi El Sayed Moussa Dr. Hui Chen Zuoyong Wang Dr. Monika Srebro‐Hooper Dr. Nicolas Vanthuyne Dr. Soizic Chevance Prof. Christian Roussel Prof. J. A. Gareth Williams Prof. Jochen Autschbach Prof. Régis Réau Prof. Zheng Duan Dr. Christophe Lescop Dr. Jeanne Crassous 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(17):6075-6086
Monometallic gold(I)‐alkynyl‐helicene complexes ( 1 a , b ) and bimetallic gold(I)‐alkynyl‐helicene architectures featuring the presence ( 2 a , b ) or absence ( 3 a , b ) of aurophilic intramolecular interactions were prepared by using different types of phosphole ligands (mono‐phosphole L1 or bis‐phospholes L2 , 3 ). The influence of the AuI d10 metal center(s) on the electronic, photophysical, and chiroptical properties of these unprecedented phosphole‐gold(I)‐alkynyl‐helicene complexes was examined. Experimental and theoretical results highlight the importance of ligand‐to‐ligand‐type charge transfers and the strong effect of the presence or absence of AuI–AuI interactions in 2 a , b . 相似文献
100.
C. B. Vijaya Vittala Sunirmal Ray S. Chaterjee T. Dharmavir Singh Kaushik Datta 《实验传热》2013,26(4):221-228
The heat transfer coefficient for condensation of steam has been determined experimentally for a cyclone surface. Ambient air is used as the coolant and the outer surface is maintained in a free-convection condition. A twofold increase in heat transfer coefficient is observed over a cyclone surface in comparison with a vertical tube. 相似文献