全文获取类型
收费全文 | 2625篇 |
免费 | 98篇 |
国内免费 | 15篇 |
专业分类
化学 | 1782篇 |
晶体学 | 12篇 |
力学 | 73篇 |
数学 | 391篇 |
物理学 | 480篇 |
出版年
2023年 | 15篇 |
2022年 | 33篇 |
2021年 | 65篇 |
2020年 | 46篇 |
2019年 | 40篇 |
2018年 | 38篇 |
2017年 | 38篇 |
2016年 | 95篇 |
2015年 | 79篇 |
2014年 | 73篇 |
2013年 | 158篇 |
2012年 | 158篇 |
2011年 | 187篇 |
2010年 | 102篇 |
2009年 | 107篇 |
2008年 | 166篇 |
2007年 | 168篇 |
2006年 | 164篇 |
2005年 | 147篇 |
2004年 | 145篇 |
2003年 | 110篇 |
2002年 | 110篇 |
2001年 | 36篇 |
2000年 | 29篇 |
1999年 | 31篇 |
1998年 | 19篇 |
1997年 | 18篇 |
1996年 | 33篇 |
1995年 | 14篇 |
1994年 | 14篇 |
1993年 | 12篇 |
1992年 | 11篇 |
1991年 | 11篇 |
1990年 | 19篇 |
1989年 | 14篇 |
1988年 | 14篇 |
1987年 | 9篇 |
1986年 | 11篇 |
1985年 | 27篇 |
1984年 | 19篇 |
1983年 | 18篇 |
1982年 | 24篇 |
1981年 | 16篇 |
1980年 | 21篇 |
1979年 | 25篇 |
1977年 | 6篇 |
1976年 | 5篇 |
1975年 | 5篇 |
1974年 | 6篇 |
1973年 | 4篇 |
排序方式: 共有2738条查询结果,搜索用时 570 毫秒
221.
Pettinari R Pettinari C Marchetti F Gobetto R Nervi C Chierotti MR Chan EJ Skelton BW White AH 《Inorganic chemistry》2010,49(23):11205-11215
Novel [Rh(η-diene)Tp(x)] complexes of sterically encumbered Tp(x) ligands (Tp(x) = Tp(4Bo), diene = cod, 1; nbd, 2; Tp(x) = Tp(4Bo,5Me), diene = cod, 3; nbd, 4; Tp(x) = Tp(a,3Me), diene = cod, 5; nbd, 6; Tp(x) = Tp(a*,3Me), diene = cod, 7; nbd, 8) have been prepared by treatment of [Rh(η-diene)(μ-Cl)](2) with TlTp(x) (Tp(x) in general, in detail: Tp(4Bo) = hydrotris(indazol-1-yl)borate, Tp(4Bo,5Me) = hydrotris(5-methyl-indazol-1-yl)borate, Tp(a,3Me) = hydrotris(3-methyl-2H-benz[g]-4,5-dihydroindazol-2-y1)borate, Tp(a*,3Me) = hydrotris(3-methyl-2H-benz[g]indazol-2-yl)borate), and characterized by analytical and spectral data (IR, (1)H, (11)B, and (13)C NMR solution). The structures adopted by [Rh(nbd)Tp(4Bo)] 2, [Rh(cod)Tp(4Bo,5Me)] 3, [Rh(nbd)Tp(a,3Me)] 6, [Rh(nbd)Tp(a*,3Me)] 8, and [Rh(nbd)Tp(a*,3Me*)] 8* (incorporating a borotropomeric ligand), have been investigated. Low steric hindrance between the ligands in 2 and 3 permits κ(3) coordination of the pyrazolylborate while the high steric encumbrance present in 6, 8, and 8* results in κ(2) ligands. The coordination modes of the ligands to the metal have also been established by (15)N CPMAS studies of selected ligands and their corresponding Rh complexes. These spectroscopic data are in agreement with the (15)N chemical shifts obtained by using quantum-chemical methods to assist reliable assignments of the experimental values, affording new insights into the extraction of structural information concerning the hapticity (κ(2) or κ(3)) of the poly(pyrazolyl)borate ligands to the Rh metal. 相似文献
222.
Salassa L Borfecchia E Ruiu T Garino C Gianolio D Gobetto R Sadler PJ Cammarata M Wulff M Lamberti C 《Inorganic chemistry》2010,49(23):11240-11248
Determination of transient structures in light-induced processes is a challenging goal for time-resolved techniques. Such techniques are becoming successful in detecting ultrafast structural changes in molecules and do not require the presence of probe-like groups. Here, we demonstrate that TR-WAXS (Time-Resolved Wide Angle X-ray Scattering) can be successfully employed to study the photochemistry of cis-[Ru(bpy)(2)(py)(2)]Cl(2), a mononuclear ruthenium complex of interest in the field of photoactivatable anticancer agents. TR-WAXS is able to detect the release of a pyridine ligand and the coordination of a solvent molecule on a faster timescale than 800 ns of laser excitation. The direct measurement of the photodissociation of pyridine is a major advance in the field of time-resolved techniques allowing detection, for the first time, of the release of a multiatomic ligand formed by low Z atoms. These data demonstrate that TR-WAXS is a powerful technique for studying rapid ligand substitution processes involving photoactive metal complexes of biological interest. 相似文献
223.
Benedetto Bozzini Andreas Bund Bertrand Busson Christophe Humbert Adriana Ispas Claudio Mele Abderrahmane Tadjeddine 《Electrochemistry communications》2010,12(1):56-60
In this paper we report an SFG/DFG investigation of the adsorption of CN? – used as a probe molecule to study the electrochemical double-layer structure – at a polycrystalline Au electrode in 1-butyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl) amide ([BMP][TFSA]) room-temperature ionic liquid (RTIL). The adsorption of CN? yielded single SFG and DFG bands in the range from ca. 2125 to 2135 cm?1, exhibiting a Stark tuning of ca. 3 cm?1 V?1. Vibrational resonances – corresponding to modes of the RTIL coadsorbed with CN?, were found in the range from ca. 1200 to 1500 cm?1. The study of the double-layer structure was complemented by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements, from which the differential double-layer capacity (CDL) was estimated. 相似文献
224.
225.
Yves Noel Philippe D'arco Raffaella Demichelis Claudio M. Zicovich‐Wilson Roberto Dovesi 《Journal of computational chemistry》2010,31(4):855-862
Nanotubes can be characterized by a very high point symmetry, comparable or even larger than the one of the most symmetric crystalline systems (cubic, 48 point symmetry operators). For example, N = 2n rototranslation symmetry operators connect the atoms of the (n,0) nanotubes. This symmetry is fully exploited in the CRYSTAL code. As a result, ab initio quantum mechanical large basis set calculations of carbon nanotubes containing more than 150 atoms in the unit cell become very cheap, because the irreducible part of the unit cell reduces to two atoms only. The nanotube symmetry is exploited at three levels in the present implementation. First, for the automatic generation of the nanotube structure (and then of the input file for the SCF calculation) starting from a two‐dimensional structure (in the specific case, graphene). Second, the nanotube symmetry is used for the calculation of the mono‐ and bi‐electronic integrals that enter into the Fock (Kohn‐Sham) matrix definition. Only the irreducible wedge of the Fock matrix is computed, with a saving factor close to N. Finally, the symmetry is exploited for the diagonalization, where each irreducible representation is separately treated. When M atomic orbitals per carbon atom are used, the diagonalization computing time is close to Nt, where t is the time required for the diagonalization of each 2M × 2M matrix. The efficiency and accuracy of the computational scheme is documented. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010 相似文献
226.
Mercedes Gallego-Gallegos María Liva Garrido Riansares Muñoz Olivas Patricia Baravalle Claudio Baggiani Carmen Cámara 《Journal of chromatography. A》2010,1217(20):3400-3407
Molecular imprinting technology has been employed for the first time to prepare a specifically affinity chromatographic stationary phase for speciation purposes. Tributyltin has been chosen as the template molecule and the non-covalent approach has been applied. Three different polymerization methods have been evaluated: (i) a composite material, (ii) a polymer prepared via-Iniferter grafting; (iii) an emulsion polymer. Columns packed with different polymers have been evaluated by liquid chromatography (LC) coupled to inductively coupled plasma mass spectrometry (ICP-MS). The chromatographic conditions as well as the analytical characteristics of the developed method are discussed in this paper. Our findings have shown formation of specific cavities in the grafted Iniferter as well as in the emulsion polymers with the latter achieving resolution of four organotin compounds. Detection limits are similar to those obtained with commercial, but not specific, stationary phases (6 pg for monobutyltin, MBT; 10 pg for both tributyltin, TBT, and triphenyltin, TPhT; and 20 pg for dibutyltin, DBT). The main advantage of this proposed stationary phase is that good recovery is obtained for all species, including MBT. Baseline resolution for TBT and TPhT has also been obtained. The high selectivity of this column prevents matrix interferences. The method has been validated by analyzing two biota reference materials (ERM-CE477 mussel tissue and T-38 oyster tissue). 相似文献
227.
Rosa IL Filho PC Neri CR Serra OA de Figueiredo AT Varela JA Longo E 《Journal of fluorescence》2011,21(4):1575-1583
This work reports on the synthesis and characterization of a new complex of Eu3+ with the 3-hydroxypicolinamide ligand (Hhpa). Here we present an approach for obtaining bis[2-carbamoyl(κO)pyridin-3-olato(κO’)]
lanthanide complexes, which were characterized through elemental analysis, thermal analysis, infrared and photoluminescence
spectroscopies (emission, excitation, luminescence lifetimes, quantum efficiencies, Judd-Ofelt parameters and quantum yields).
Although hpa can act as a bidentate ligand in different conformations, the results attest for the occurrence of a unique coordination
site of low symmetry for the Eu3+ ions, in which two anionic hpa ligands coordinate the cations through an O/O chelating system. The phosphorescence of the
synthesized gadolinium complex provides the energy of the triplet state, which is determined to be at 20,830 cm-1 over the ground state. This makes the Hhpa ligand very adequate for sensitizing the Eu3+ luminescence, which leads to a very efficient antenna effect and opens a wide range of applications for the complex in light
emitting organic-inorganic devices. 相似文献
228.
229.
Airflow resistivity is a physical parameter which characterizes porous and fibrous sound absorbent materials. It is well-known that such property allows the evaluation of the acoustic behaviour of sound absorbent materials in various fields of application, including automotive noise mitigation, architectural acoustics and building acoustics. In structure-borne sound insulation, airflow resistivity is essential for the evaluation of the dynamic stiffness of porous and fibrous resilient insulating materials used as underlay in floating floors.However, an inconsistency between the dynamic stiffness and the airflow resistivity test conditions can be recognized. In order to evaluate dynamic stiffness of a resilient material, a static load of about 2 kPa is applied, while in airflow resistivity determination this condition is not explicitly required. As a result, the density of analyzed material, in dynamic stiffness and airflow measurements, is different. Since these two quantities are correlated, it is necessary to measure materials under the same conditions of applied static load.In this work the effects of static load (or density after compression) in airflow resistivity determination of various porous and fibrous resilient materials are investigated, and the consequent influence on dynamic stiffness is discussed. A simply empirical relation between density and airflow resistivity is also put forth.The main focus of this paper is to propose an harmonization among requirements of the Standards in order to prevent significant errors in dynamic stiffness determination and incorrect evaluations of the acoustic behaviour. 相似文献
230.
The degree of asphericity is estimated by determining the average radius of curvature in different sections, at various points on the surface of a sphere, and the deviation from it. We employ the vectorial shearing interferometer (VSI) as the instrument to determine the radius of curvature from two subapertures of the transparent glass sphere. We incorporate the sphere as a thick lens into the interferometric setup, illuminating it with an expanded beam. The spherical aberration, introduced by the sphere in the wave front, depends on the local sphere radius, on the refraction index of the glass, and on the cone angle of the source. The wave front aberrated by the sphere impinges on the VSI. Here, the wave front is divided in two in amplitude, it is sheared vectorially, and it is superimposed with itself. The fringe pattern is formed in the intersection of the wave fronts. The shape of the resulting fringe pattern is directly related to spherical aberration. We estimate qualitatively the degree of asphericity, comparing the phase gradients in different sections of the sphere. Here, we report on the experimental setup to test the asphericity, the results with different vectorial shearing (magnitude and direction). Finally, we perform a comparison with the theoretical predictions. 相似文献