全文获取类型
收费全文 | 2433篇 |
免费 | 105篇 |
国内免费 | 9篇 |
专业分类
化学 | 1609篇 |
晶体学 | 13篇 |
力学 | 87篇 |
数学 | 356篇 |
物理学 | 482篇 |
出版年
2023年 | 20篇 |
2022年 | 48篇 |
2021年 | 52篇 |
2020年 | 62篇 |
2019年 | 73篇 |
2018年 | 52篇 |
2017年 | 38篇 |
2016年 | 111篇 |
2015年 | 68篇 |
2014年 | 83篇 |
2013年 | 148篇 |
2012年 | 162篇 |
2011年 | 171篇 |
2010年 | 109篇 |
2009年 | 91篇 |
2008年 | 161篇 |
2007年 | 135篇 |
2006年 | 116篇 |
2005年 | 110篇 |
2004年 | 115篇 |
2003年 | 77篇 |
2002年 | 94篇 |
2001年 | 31篇 |
2000年 | 35篇 |
1999年 | 21篇 |
1998年 | 25篇 |
1997年 | 23篇 |
1996年 | 16篇 |
1995年 | 14篇 |
1994年 | 10篇 |
1993年 | 12篇 |
1992年 | 12篇 |
1991年 | 18篇 |
1990年 | 9篇 |
1989年 | 14篇 |
1988年 | 8篇 |
1986年 | 7篇 |
1985年 | 9篇 |
1984年 | 22篇 |
1983年 | 8篇 |
1982年 | 15篇 |
1981年 | 13篇 |
1980年 | 15篇 |
1979年 | 18篇 |
1978年 | 20篇 |
1977年 | 7篇 |
1976年 | 8篇 |
1974年 | 11篇 |
1973年 | 8篇 |
1972年 | 5篇 |
排序方式: 共有2547条查询结果,搜索用时 15 毫秒
191.
The azine bridged dicatechol ligand (E,E)-benzaldehyde azine (H4L) was fully characterized by X-ray analysis. The reaction of [ReCl6]2− with this compound was studied and the novel Re(IV) complex (HNEt3)(NBu4)[ReCl4(H2L)] was prepared and characterized. The structure and spectroscopy of the compound H4L and its Re(IV) complex were studied experimentally and by means of density functional calculations. 相似文献
192.
Tomáš Šmejkal Denis Gribkov Jens Geier Manfred Keller Bernhard Breit 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(8):2470-2478
A library of monodentate phosphane ligands, each bearing a guanidine receptor unit for carboxylates, was designed. Screening of the library gave some excellent catalysts for regioselective hydroformylation of β,γ‐unsaturated carboxylic acids. A terminal alkene, but‐3‐enoic acid, was hydroformylated with a linear/branched (l/b) regioselectivity up to 41. An internal alkene, pent‐3‐enoic acid was hydroformylated with regioselectivity up to 18:1. Further substrate selectivity (e.g., acid vs. methyl ester) and reaction site selectivity (monofunctionalization of 2‐vinylhept‐2‐enoic acid) were also achieved. Exploration of the structure–activity relationship and a practical and theoretical mechanistic study gave us an insight into the nature of the supramolecular guanidinium–carboxylate interaction within the catalytic system. This allowed us to identify a selective transition‐state stabilization by a secondary substrate–ligand interaction as the basis for catalyst activity and selectivity. 相似文献
193.
Vladislav Ganine Denis Laxalde Christophe Pierre 《Journal of sound and vibration》2011,330(3):445-460
Light and flexible rotating parts of modern turbine engines operating at supercritical speeds necessitate application of more accurate but rather computationally expensive 3D FE modeling techniques. Stacked disks misalignment due to manufacturing variability in the geometry of individual components constitutes a particularly important aspect to be included in the analysis because of its impact on system dynamics. A new parametric model order reduction algorithm is presented to achieve this goal at affordable computational costs. It is shown that the disks misalignment leads to significant changes in nominal system properties that manifest themselves as additional blocks coupling neighboring spatial harmonics in Fourier space. Consequently, the misalignment effects can no longer be accurately modeled as equivalent forces applied to a nominal unperturbed system. The fact that the mode shapes become heavily distorted by extra harmonic content renders the nominal modal projection-based methods inaccurate and thus numerically ineffective in the context of repeated analysis of multiple misalignment realizations. The significant numerical bottleneck is removed by employing an orthogonal projection onto the subspace spanned by first few Fourier harmonic basis vectors. The projected highly sparse systems are shown to accurately approximate the specific misalignment effects, to be inexpensive to solve using direct sparse methods and easy to parameterize with a small set of measurable eccentricity and tilt angle parameters. Selected numerical examples on an industrial scale model are presented to illustrate the accuracy and efficiency of the algorithm implementation. 相似文献
194.
Stephen R. Williams Denis J. Evans Debra J. Searles 《Journal of statistical physics》2011,145(4):831-840
We review the theoretical underpinning of nonequilibrium umbrella sampling. We provide its historical context and show how it relates to other important results in nonequilibrium statistical mechanics. Its relationships to the generalised Yamada-Kawasaki distribution function is explored. A new functional version of the Crooks Fluctuation Theorem is also presented. 相似文献
195.
Merlet D Béguin L Courtieu J Giraud N 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2011,209(2):315-322
The application of the G-SERFph pulse sequence is presented on enantiomeric mixtures dissolved in a chiral liquid crystal. It aims at editing, within one single 2D spectrum, every proton coupling which is experienced by a given proton site in the molecule, and leads to real phased T-edited spectroscopy (T=J+2D). This NMR experiment is based on the combination of homonuclear semi-selective refocusing techniques with a spatial frequency encoding of the sample. This approach, which consists in handling selectively each coupling in separate cross sections of the sample, is applied to the visualization of enantiomers dissolved in a chiral liquid crystalline phase. Advantages and limits of this methodology are widely discussed. 相似文献
196.
The use of chiral liquid crystals as NMR solvent is a powerful tool to visualize and quantify enantiomers. This technique is much more robust than traditional liquid state techniques. Recent developments have been performed to simplify proton spectra obtained in these solvents which are usually complex to analyze. In the different published sequences the enantiomeric differentiation can be visualized but none of them rely the different (1)H-(1)H couplings to have a coherent set for each enantiomer especially in cases of racemic mixtures. In this work to overcome such limitations, we present a new NMR pulse sequence using semi-selective pulses to assign for each enantiomer the different (1)H-(1)H couplings. The aim is to obtain the signal of only one enantiomer, through a first Selective ReFocussing (SERF) filtering block implemented for the enantio-selection followed by a second SERF block for measuring a chosen coupling. The whole sequence is called (1)H SERF-filtered-SERF. These techniques permit for the first time to assign all dipolar couplings to each enantiomer of racemic mixtures dissolved in chiral oriented media. We demonstrate that using this experiment it is possible to visualize enantio-differentiation even in the case where the multiplets are not resolved in the SERF experiments, pushing back the limits of the enantiomeric visualization. 相似文献
197.
Saro Memarzadeh Erik D. Tolmachoff Denis J. Phares Hai Wang 《Proceedings of the Combustion Institute》2011,33(2):1917-1924
The properties of TiO2 nanoparticles synthesized using the flame stabilized on a rotating surface method (FSRS) are investigated. The method uses a laminar, premixed, stagnation flame, combining particle synthesis and film deposition in a single step. The current study examines the effects of flame properties on particle characteristics. Synthesized particles were characterized using X-ray diffractometry, Transmission Electron Microscopy and UV–vis spectrometry in order to quantify the effects of equivalence ratio and precursor loading on particle size, crystallinity and optical band-gap. Results show that flame stoichiometry significantly affects crystal phase, but it has little to no effect on particle size and light absorption band edge. In addition, precursor loading impacts both the particle size and the crystal phase. The study demonstrates the potential of the FSRS method for producing tailored nanoscale TiO2 particles for a variety of applications. 相似文献
198.
Donlagic D 《Optics letters》2011,36(16):3148-3150
This Letter presents an open-path, all-fiber microcell and a micromachining method for its production. The proposed micromachining method utilizes the selective etching of a purposely designed phosphorus-doped fiber that is spliced in between two standard lead-in fibers. Microcells with various open optical-path lengths were successfully demonstrated. The proposed microcell can be used as a transmission cell or as a miniature Fabry-Perot resonator. The transmission losses and fringe contrast were experimentally investigated over a range of prototype microcells with different lengths. For example, the insertion losses below 1 dB were demonstrated for 50 μm or shorter open path prototype microcells, when immersed in dematerialized water. 相似文献
199.
We report on what we believe is the first experimental demonstration of the linear precompensation of a nonlinear transfer function due to frequency conversion. As a proof of principle, we show the effective precompensation with an interferometric filter of FM-to-AM conversion due to second-harmonic generation in a potassium titanyl phosphate crystal. 相似文献
200.
Peruzzo D Zanderigo F Bertoldo A Pillonetto G Cosottini M Cobelli C 《Magnetic resonance imaging》2011,29(7):927-936
Dynamic susceptibility contrast magnetic resonance imaging (DSC-MRI) allows the noninvasive assessment of brain hemodynamics alterations by quantifying, via deconvolution, the cerebral blood flow (CBF) and mean transit time (MTT). Singular value decomposition (SVD) and block-circulant SVD (cSVD) are the most widely adopted deconvolution method, although they bear some limitations, including unphysiological oscillations in the residue function and bias in the presence of delay and dispersion between the tissue and the arterial input function. A nonlinear stochastic regularization (NSR) has been proposed, which performs better than SVD and cSVD on simulated data both in the presence and absence of dispersion. Moreover, NSR allows to quantify the dispersion level. Here, cSVD and NSR are compared for the first time on a group of nine patients with severe atherosclerotic unilateral stenosis of internal carotid artery before and after carotid stenting to investigate the effect of arterial dispersion. According to region of interest-based analysis, NSR characterizes the pathologic tissue more accurately than cSVD, thus improving the quality of the information provided to physicians for diagnosis. In fact, in 7 (78%) of the 9 subjects, CBF and MTT maps provided by NSR allow to correctly identify the pathologic hemisphere to the physician. Moreover, by emphasizing the difference between pathologic and healthy tissues, NSR may be successfully used to monitor the subject's recovery after the treatment and/or surgery. NSR also generates dispersion level and non-dispersed CBF and MTT maps. The dispersion level provides information on CBF and MTT estimates reliability and may also be used as a clinical indicator of pathological tissue state complementary to CBF and MTT, thus increasing the clinical information provided by DSC-MRI analysis. 相似文献