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61.
全内反射荧光显微镜技术是当今最灵敏的生物成像和检测方法之一,可以直接探测单个荧光分子。这种方法已成功地用于生命科学、化学、物理学等研究领域,获得了常规方法无法得到的重要信息。本文介绍了全内反射荧光显微镜的工作原理和实验技术,总结了近年来这种单分子检测方法在生命科学、化学等领域的重要应用,并对其发展前景进行了展望。 相似文献
62.
An important goal in single molecule fluorescence correlation spectroscopy is the theoretical simulation of the fluorescence signal stemming from individual molecules and its autocorrelation function. The simulation approaches developed up to now are based exclusively on continuous-wave (cw) illumination and consequently on cw-excitation. However, this approximation is no longer valid in the case of two-photon excitation, for which pulsed illumination is usually employed. We present a novel theoretical model for the simulation of the fluorescence signal of single molecules and its autocorrelation function with consideration of the time dependence of the excitation flux and thus of all illumination-dependent photoprocesses: two-photon excitation, induced emission and photobleaching. Further important characteristics of our approach are the consideration of the dependence of the photobleaching rate on illumination and the low intersystem-crossing rates of the studied coumarins. Moreover, using our approach, we can predict quantitatively the effect of the laser pulse width on the fluorescence signal of a molecule, that is, the contributions of the photobleaching and saturation effects, and thus we can calculate the optimal laser pulse width. The theoretical autocorrelation functions were fitted to the experimental data, and we could ascertain a good agreement between the resulting and the expected parameters. The most important parameter is the photobleaching constant sigma, the cross section of the transition Sn<--S1, which characterises the photostability of the molecules independent of the experimental conditions. Its value is 1.7 x 10(-23) cm2 for coumarin 153 and 5 x 10(-23) cm2 for coumarin 314. 相似文献
63.
Baumgartner T Bergmans W Kárpáti T Neumann T Nieger M Nyulászi L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(16):4687-4699
To explore their suitability for applications in molecular optoelectronics and as sensory materials, novel dithieno[3,2-b:2',3'-d]phospholes have been synthesized and their reactivity and properties investigated. An efficient two-step synthesis allowed for a modular assembly of differently functionalized compounds. The dithieno[3,2-b:2',3'-d]phosphole system exhibits extraordinary optoelectronic properties with respect to wavelength, intensity, and tunability. Owing to the nucleophilic nature of the central phosphorus atom, its significant electronic influence on the conjugated pi system can be altered selectively by chemically facile modifications such as oxidation or complexation with Lewis acids or transition metals. All the dithienophosphole species presented show very strong blue photoluminescence with excellent quantum yield efficiencies supporting their potential utility as blue-light emitting components in organic light emitting diodes (OLEDs). Furthermore, depending on the electronic nature of the phosphorus center, the materials exhibit distinctive optoelectronic properties suggesting that the dithieno[3,2-b:2',3'-d]phosphole system may be useful as sensory material. Theoretical calculations, including time-dependent DFT methods, revealed the excellent predictability of the structures and optoelectronic properties of the functionalized dithienophospholes allowing the design of future dithieno[3,2-b:2',3'-d]phosphole-based materials to be "stream-lined". By using tin-functionalized dithienophosphole monomers, a strategy, which involves Stille coupling, towards extended pi-conjugated materials with significantly redshifted optoelectronic properties is also presented. 相似文献
64.
65.
The title compound N'-tert-butylaminocarbonyl-N-2-chlorophenoxyacetylthiou- rea has been synthesized for the first time. Complete assignments were achieved by IR, 1H NHR and single-crystal X-ray diffraction analyses. The inhibitory rate of the cellular growth of K562 cells (chronic myeloid 1eukemic cells) was measured using MTT [3-(4,5-dimethylthiazo-2-y1)-2,5-di- phenyltetra-zolium bromide] assay. The cell apoptosis was assessed by agarose gel electrophoresis to find that the title compound has antiproliferation and apoptosis inducing effects on K562 cells. In order to investigate the relationship between structure and activity of the target compound, we report its crystal structure and biological behavior in the present paper. Crystallographic data: C14H18- ClN3O3S, Mr = 343.82, orthorhombic, space group Pnma, a = 19.786(6), b = 6.789(2), c = 12.938(4) , V = 1738.0(9) 3, Z = 4, Dc = 1.314 g/cm3, F(000) = 720, μ(MoKα) = 0.354 mm-1, R = 0.0378 and wR = 0.0941. The molecule is a planar structure. 相似文献
66.
采用传统水分子力场模型(SPC, TIPnP(n=3-5))和极化模型(POL3, AMOEBA, SPC-FQ, TIP4P-FQ)对水分子二聚体团簇性质进行了比较和研究. 以从头计算和实验数据为依据, 分析水分子在外场作用下体系的静电极化, 电荷转移和分子结构变化. 通过水分子二聚体结合能和各分解能量项评价极化静电势能在双分子结合能中的地位和作用, 以及各水分子力场的适用性. 通过水分子团簇多体相互作用能的计算,展示不同极化水分子力场定量计算极化能量的实际能力. 通过对力场模型结果的对比和分析, 为进一步发展极化力场模型, 并应用到其他体系提供借鉴和依据. 相似文献
67.
过渡金属配合物催化剂及其分子设计构思的发展与相互作用 总被引:4,自引:2,他引:4
讨论了某些不对称合成和α-烯烃定向配位聚合及α-烯烃氢甲酰化的过渡金属配合物向络合催化剂的发展与催化剂分子设计构思的发展及相互促进作用,并藉以说明过渡金属配合物定向络合物催化剂的分子设计已具备向计算机辅助设计发展的科学基础。 相似文献
68.
T. Hondoh H. Anzai A. Goto S. Mae A. Higashi C. C. Langway Jr. 《Journal of inclusion phenomena and macrocyclic chemistry》1990,8(1-2):17-24
We have carried out X-ray diffraction studies on single crystals of natural air-hydrate in deep ice cores recovered at Dye-3 Greenland. Integrated intensities for 470 diffracting planes were measured by an automated four-circle diffractometer. The space group determined is cubicFd3m and the lattice constant is 17.21(3) Å. These results indicate that the crystallographic structure is the Stackelberg's structure II, in contrast to the previously anticipated structure. This finding agrees with the recent results on the synthetic air-hydrate by Davidsonet al. It was also found by difference Fourier synthesis for guest molecules that electron density in a 16-hedral cage has multiple maxima displaced from the center of the cage while that in the 12-hedron was approximately spherical.Dedicated to Dr D. W. Davidson in honor of his great contributions to the sciences of inclusion phenomena. 相似文献
69.
Nicolai Stuhr-Hansen Jakob Kryger Srensen Kasper Moth-Poulsen Jrn Bolstad Christensen Thomas Bjrnholm Mogens Brndsted Nielsen 《Tetrahedron》2005,61(52):12288-12295
Simple and readily accessible aryl bromides are useful building blocks for thiol end-capped molecular wires. Thus, 4-bromophenyl tert-butyl sulfide and 1-bromo-4-(methoxymethyl)benzene serve as precursors for a variety of oligo(phenylenevinylene) and oligo(phenyleneethynylene) wires via efficient synthetic transformations as presented in this paper. 相似文献
70.
John D. Watts Miroslav Urban Rodney J. Bartlett 《Theoretical chemistry accounts》1995,90(5-6):341-355
Summary This paper reports a series of coupled-cluster (CC) calculations through CCSDT on the theoretically challenging ground state of the BeO molecule. Along with CC methods, quadratic configuration interaction (QCI) approximations to CC theory have been used (QCISD and QCISD(T)), which show several dramatic failings. Equilibrium electrical properties (,
xx
, and
zz
) and basic spectroscopic properties (r
e, e,D
e, and infrared intensity (I)) have been computed. Basis set and electron correlation effects are analyzed in order to arrive at accurate values of the dipole moment and polarizability, which are not known experimentally. For the dipole moment, we obtain a value of 6.25 D, with an uncertainty of about 0.1 D. For
xx
and
zz
, we suggest respective values of 32 and 36 atomic units (a.u.) and error bars of about 1 and 2 a.u. With extended basis sets, the spectroscopic propertiesr
e, e, andD
e are reproduced to high accuracy, which is the first time this has been achieved for this species byab initio methods. At the highest calculation levels,I is predicted to be very small. AlthoughI has not been measured, some support for this prediction comes from a recent infrared study of BeO-rare gas complexes. The QCI methods are shown to be much more sensitive to basis set, and even with large basis sets yield values of
zz
andI which differ from CC results by an order of magnitude and three orders of magnitude, respectively. These differences doubtless arise from the importance of single excitations (T
1) for this molecule, as several terms involvingT
1 are neglected in the QCISD approximation compared with CCSD. We also report CC calculations with Brueckner orbitals, which yield results similar to those obtained with restricted Hartree-Fock orbitals. 相似文献