全文获取类型
收费全文 | 2788篇 |
免费 | 157篇 |
国内免费 | 8篇 |
专业分类
化学 | 2123篇 |
晶体学 | 15篇 |
力学 | 33篇 |
数学 | 286篇 |
物理学 | 496篇 |
出版年
2023年 | 37篇 |
2022年 | 76篇 |
2021年 | 88篇 |
2020年 | 97篇 |
2019年 | 68篇 |
2018年 | 41篇 |
2017年 | 50篇 |
2016年 | 110篇 |
2015年 | 109篇 |
2014年 | 99篇 |
2013年 | 150篇 |
2012年 | 195篇 |
2011年 | 244篇 |
2010年 | 132篇 |
2009年 | 105篇 |
2008年 | 172篇 |
2007年 | 139篇 |
2006年 | 135篇 |
2005年 | 115篇 |
2004年 | 103篇 |
2003年 | 81篇 |
2002年 | 62篇 |
2001年 | 44篇 |
2000年 | 23篇 |
1999年 | 19篇 |
1998年 | 14篇 |
1997年 | 13篇 |
1996年 | 26篇 |
1995年 | 15篇 |
1994年 | 25篇 |
1993年 | 25篇 |
1992年 | 27篇 |
1991年 | 23篇 |
1990年 | 22篇 |
1989年 | 18篇 |
1988年 | 17篇 |
1987年 | 11篇 |
1986年 | 13篇 |
1985年 | 19篇 |
1984年 | 18篇 |
1982年 | 20篇 |
1981年 | 9篇 |
1980年 | 13篇 |
1979年 | 13篇 |
1978年 | 13篇 |
1977年 | 11篇 |
1976年 | 18篇 |
1975年 | 7篇 |
1974年 | 9篇 |
1973年 | 11篇 |
排序方式: 共有2953条查询结果,搜索用时 31 毫秒
1.
Dr. Jordan Donat Mr. Patrick Dubourdeaux Dr. Martin Clémancey Dr. Julia Rendon Clara Gervasoni Mr. Morgan Barbier Jessica Barilone Dr. Jacques Pécaut Prof. Dr. Serge Gambarelli Prof. Dr. Pascale Maldivi Prof. Dr. Jean-Marc Latour 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(70):e202201875
Nitrene transfer reactions have emerged as one of the most powerful and versatile ways to insert an amine function to various kinds of hydrocarbon substrates. However, the mechanisms of nitrene generation have not been studied in depth albeit their formation is taken for granted in most cases without definitive evidence of their occurrence. In the present work, we compare the generation of tosylimido iron species and NTs transfer from FeII and FeIII precursors where the metal is embedded in a tetracarbene macrocycle. Catalytic nitrene transfer to reference substrates (thioanisole, styrene, ethylbenzene and cyclohexane) revealed that the same active species was at play, irrespective of the ferrous versus ferric nature of the precursor. Through combination of spectroscopic (UV-visible, Mössbauer), ESI-MS and DFT studies, an FeIV tosylimido species was identified as the catalytically active species and was characterized spectroscopically and computationally. Whereas its formation from the FeII precursor was expected by a two-electron oxidative addition, its formation from an FeIII precursor was unprecedented. Thanks to a combination of spectroscopic (UV-visible, EPR, Hyscore and Mössbauer), ESI-MS and DFT studies, we found that, when starting from the FeIII precursor, an FeIII tosyliodinane adduct was formed and decomposed into an FeV tosylimido species which generated the catalytically active FeIV tosylimide through a comproportionation process with the FeIII precursor. 相似文献
2.
Synthesis,Electronic Properties and WOLED Devices of Planar Phosphorus‐Containing Polycyclic Aromatic Hydrocarbons 下载免费PDF全文
Dr. François Riobé Rózsa Szűcs Dr. Pierre‐Antoine Bouit Dr. Denis Tondelier Bernard Geffroy Fátima Aparicio Julia Buendía Prof. Luis Sánchez Prof. Régis Réau Prof. László Nyulászi Prof. Muriel Hissler 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(17):6547-6556
We describe the synthesis and the physical properties of polyaromatic hydrocarbons (PAHs) containing a phosphorus atom at the edge. In particular, the impact of the successive addition of aromatic rings on the electronic properties was investigated by experimental (UV/Vis absorption, fluorescence, cyclic voltammetry) and theoretical studies (DFT). The physical properties recorded in solution and in the solid state showed that the P‐containing PAHs exhibit properties expected for an emitter in white organic light‐emitting diodes (WOLEDs). 相似文献
3.
Julia K Pruns Jens-Peter Vietzke Manfred Strassner Claudius Rapp Ulrich Hintze Wilfried A K?nig 《Rapid communications in mass spectrometry : RCM》2002,16(3):208-211
A new solvent-free sample preparation method using silver trifluoroacetate (AgTFA) was developed for the analysis of low molecular weight paraffins and microcrystalline waxes by laser desorption/ionization time-of-flight mass spectrometry (LDI-TOFMS). Experiments show that spectral quality can be enhanced by dispersing AgTFA directly in liquid paraffins without the use of additional solvents. This preparation mixture is applied directly to the MALDI probe. Solid waxes could be examined by melting prior to analysis. The method also provides sufficiently reproducible spectra that peak area ratios between mono- and bicyclic alkane peaks indicated variations in the cycloalkane content of paraffin samples. Dehydrogenation of hydrocarbons observed during the desorption/ionization process was studied by analysis of alkane standards. 相似文献
4.
S. Heinze P. Kurz D. Wortmann G. Bihlmayer S. Blügel 《Applied Physics A: Materials Science & Processing》2002,75(1):25-36
In this paper we present a density functional theory investigation of complex magnetic structures in ultra-thin films. The
focus is on magnetically frustrated antiferromagnetic Cr and Mn monolayers deposited on a triangular lattice provided by a
Ag (111) substrate. This involves non-collinear magnetic structures, which we treat by first-principles calculations on the
basis of the vector spin-density formulation of the density functional theory. We find for Cr/Ag (111) a coplanar non-collinear
periodic 120° Néel structure, for Mn/Ag (111) a row-wise antiferromagnetic structure, and for Fe/Ag (111) a ferromagnetic
structure as magnetic ground states. The spin-polarized scanning tunneling microscope (SP–STM) operated in the constant-current
mode is proposed as a powerful tool to investigate complex atomic-scale magnetic structures of otherwise chemically equivalent
atoms. We discuss a recent application of this operation mode of the SP–STM on Mn/W (110), which led to the first observation
of a two-dimensional antiferromagnet on a non-magnetic metal. The future potential of this approach is demonstrated by calculating
SP–STM images for different magnetic structures of Cr/Ag (111). The results show that the predicted non-collinear magnetic
ground state structure can clearly be discriminated from competing magnetic structures. A general discussion of the application
of different operation modes of the SP–STM is presented on the basis of the model of Tersoff and Hamann.
Received: 07 May 2001 / Accepted: 23 July 2001 / Published online: 3 April 2002 相似文献
5.
V Ravindran Pankaj Agrawal Rahul Basu Satyaki Bhattacharya J Blümlein V Del Duca R Harlander D Kosower Prakash Mathews Anurag Tripathi 《Pramana》2006,67(5):983-992
This is the report of the subgroup QCD of Working Group-4 at WHEPP-9. We present the activities that had taken place in the
subgroup and report some of the partial results arrived at following the discussion at the working group meetings. 相似文献
6.
An acoustic pulse propagating on a two-mode fiber can act as a beam splitter in a scanning interferometer. When this device
is employed in white-light interferometry, the effects of distributed coupling and dispersive interferometer arms need to
be considered. A theory suitable for treating acousto-optic interaction of partially coherent light in a moving interaction
region was developed. It was found that differential optical dispersion should be negligible and the acoustic pulse length
short. Also the coherence time should be short but long compared to the intermodal group delay difference over a pulse length.
Experiments with long acoustic pulses were performed, and fairly good agreement with theory was obtained. 相似文献
7.
Damien P. Foster Carlo Vanderzande Julia Yeomans 《Journal of statistical physics》1992,69(3-4):857-868
We study the zero-temperature behavior of several simple models for randomly self-interacting polymers in one and 1+1 dimensions. Results are based on exact enumeration and closed-form expressions. 相似文献
8.
The theory for the calculation of the frequency-dependent hyperpolarizabilities β(?2ω; 0, ω), β(?ω; 0, ω), and β(0; ω, ?ω) is discussed. New relations between these tensors are derived for those wave functions that obey the time-dependent Hellmann–Feynman theorem (e.g., the self-consistent field [SCF] or the exact wave function). Using second-order Møller–Plesset perturbation theory (MP2), expressions are obtained for the hyperpolarizabilities in terms of derivatives of appropriately defined linear polarizability tensors with respect to a static electric field. Results are presented for ammonia and formaldehyde for the optical Kerr effect and for secondharmonic generation. These results indicate that it is desirable to determine the frequency-dependent contribution to the hyperopolarizability at the MP2 rather than the SCF level of theory, in cases where the static hyperpolarizability has a large contribution from electron correlation and/or where the frequency-dependent contribution may be more significant, such as for secondharmonic generation. 相似文献
9.
The complex morphology of high-speed melt-spun nylon-6 fibres hydrated with D2O was investigated using 1H double-quantum-filtered spin-diffusion NMR experiments. The magnetisation exchange from selected crystalline domains along the fibrils and interfibrils was simulated with the help of a three-dimensional solution of a spin-diffusion equation approximated by a product of one-dimensional analytical NMR signals, which correspond to a lamellar morphology. This allows to measure the sizes of crystalline and less-mobile amorphous domains along the fibrils, as well as the diameter of the fibrils and interfibril distances. A series of nylon-6 fibres with extreme values of winding speed and draw ratio was investigated. The changes detected in the domain size along the fibrils and interfibrils show the same trend in the data obtained from wide-angle X-ray diffraction and small-angle X-ray scattering. 相似文献
10.
Solichová D Melichar B Klejna M Jurašková B Královská L Bláha V Zd'ánský P Zadák Z 《Talanta》2003,60(2-3):459-465
Twelve self-sustaining nonagenarians, 10 women and two men, aged 94+/-3 years, and eight institutionalised nonagenarians, eight women, aged 91+/-1 year as well as 11 control subjects, seven women and four men, aged 84+/-5 years entered the study. Urinary neopterin, an indicator of systemic immune activation, and serum thiobarbituric acid reactive substances (TBARS), a marker of lipoperoxidation, were determined initially, and collection of the blood and urine samples was repeated at 3-month interval. Neopterin was measured in the urine specimens by reversed-phase high performance liquid chromatography. A C(18) reversed-phase column 3.3x150 mm, 5 mum-diameter packing Separon SGX was used. Potassium phosphate buffer (15 mmol l(-1), pH 6.4) at flow rate of 0.8 ml min(-1) was used as mobile phase. After centrifugation (5 min, 1300xg) and diluting 100 mul of urine specimens with 1.0 ml of mobile phase containing 2 g of disodium-EDTA per litre, a 20 mul sample was injected on a column. Neopterin was identified by its native fluorescence (353 nm excitation, 438 nm emission). Creatinine was determined by Jaffé kinetic reaction after dilution of sample 1:50 (v/v). The concentration of neopterin in urine was expressed as neopterin/creatinine ratio (mumol mol(-1) creatinine). TBARS were determined spectrofluorometrically using LS-5 spectrofluorimeter (excitation wavelength 528 nm, emission wavelength 558 nm) after extraction with n-butanol treatment with thiobarbituric acid. The significance of differences between nonagenarians and control group was examined by ANOVA-Kruskal-Wallis tests, using statistical software NCSS 6.0.21 (Kaysville, UT, 1996). The decision on significance was based on P=0.05. Urinary neopterin was significantly higher in institutionalised compared to self-sustaining subjects and controls (625+/-565 vs. 203+/-63 mumol mol(-1) creatinine, and 198+/-128 mumol mol(-1) creatinine, respectively, P=0.006). The serum TBARS were higher in both groups of nonagenarians (3.23+/-1.16 mumol l(-1) and 2.69+/-0.39 vs. 2.12+/-0.83 mumol l(-1) for the self-sustaining, institutionalised and controls, respectively, P=0.023). We conclude that the fluorimetric determinations of urinary neopterin and serum TBARS can be useful for the monitoring health status in the elderly patients. 相似文献