全文获取类型
收费全文 | 652篇 |
免费 | 30篇 |
国内免费 | 2篇 |
专业分类
化学 | 417篇 |
晶体学 | 4篇 |
力学 | 8篇 |
数学 | 55篇 |
物理学 | 200篇 |
出版年
2023年 | 6篇 |
2022年 | 5篇 |
2021年 | 6篇 |
2020年 | 15篇 |
2019年 | 15篇 |
2018年 | 7篇 |
2017年 | 4篇 |
2016年 | 14篇 |
2015年 | 19篇 |
2014年 | 12篇 |
2013年 | 44篇 |
2012年 | 38篇 |
2011年 | 48篇 |
2010年 | 24篇 |
2009年 | 27篇 |
2008年 | 45篇 |
2007年 | 57篇 |
2006年 | 49篇 |
2005年 | 27篇 |
2004年 | 22篇 |
2003年 | 30篇 |
2002年 | 20篇 |
2001年 | 16篇 |
2000年 | 6篇 |
1999年 | 5篇 |
1998年 | 3篇 |
1997年 | 6篇 |
1996年 | 4篇 |
1995年 | 6篇 |
1994年 | 13篇 |
1993年 | 2篇 |
1992年 | 6篇 |
1990年 | 3篇 |
1989年 | 7篇 |
1988年 | 4篇 |
1987年 | 4篇 |
1986年 | 7篇 |
1985年 | 5篇 |
1984年 | 3篇 |
1982年 | 2篇 |
1981年 | 5篇 |
1980年 | 8篇 |
1979年 | 6篇 |
1977年 | 5篇 |
1976年 | 4篇 |
1975年 | 6篇 |
1974年 | 2篇 |
1972年 | 2篇 |
1933年 | 2篇 |
1865年 | 1篇 |
排序方式: 共有684条查询结果,搜索用时 234 毫秒
111.
Synthetic,Optical and Theoretical Study of Alternating Ethylenedioxythiophene–Pyridine Oligomers: Evolution from Planar Conjugated to Helicoidal Structure towards a Chiral Configuration
下载免费PDF全文
![点击此处可从《Chemphyschem》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Floris Chevallier Marina Charlot Florence Mongin Benoît Champagne Edith Franz Koen Clays Mireille Blanchard‐Desce 《Chemphyschem》2016,17(24):4090-4101
A series of alternating 3,4‐ethylenedioxythiophene–alkynylpyridine oligomers (DA)n with increased solubility are synthesized and their photophysical properties and nonlinear optical properties are investigated. Their quadratic polarizabilities are determined from hyper‐Rayleigh scattering experiments to obtain information on their conformations in solution. These chromophores, based on the alternation of electron‐rich (D) and electron‐deficient (A) moieties, exhibit optical properties that arise from the combination of dipolar and helicoidal features in the (DA)n homologue series where n=1–4. The transition from dipolar conjugated planar structures (n=1, 2) to helicoidal structures (n=3, 4) is clearly evidenced by results from symmetry‐sensitive second‐order nonlinear optical experiments. This suggests an approach towards highly efficient chiral chromophores for second‐order nonlinear optics. Interestingly, this structural evolution also has significant impact on the photophysical properties: both absorption and fluorescence emission show bathochromic and hyperchromic shifts with increasing number of repeating units in the dipolar planar derivatives (n=1–2) but show saturation effects in the helicoidal structures (n=2–4). In addition, the helicoidal structures show sizeable two‐photon absorption at 700–750 nm (40–100 GM) for compounds lacking either electron‐donating or electron‐withdrawing substituents. 相似文献
112.
Pozo OJ Van Eenoo P Deventer K Delbeke FT 《Analytical and bioanalytical chemistry》2007,389(4):1209-1224
A screening method for the urinary detection of 34 exogenous anabolic steroids has been developed. The method involves an
enzymatic hydrolysis, liquid-liquid extraction and detection by liquid chromatography-tandem mass spectrometry. The use of
some adducts such as [M+NH4]+, [M+CH3COO]− and [M+H+MeOH]+ was necessary in order to detect some analytes at the required level (lower than 10 ng/ml). Two transitions were selected
for each analyte. Different concentration factors have been studied in order to increase the sensitivity. A concentration
factor of 50 was selected for the screening method although the high ion suppression observed under these conditions can hamper
its application as a quantitative method. The method was validated and limits of detection were obtained by spiking ten different
blank urine samples at five different concentration levels. Up to 29 analytes were detected in all spiked urines at the required
level. Limits of detection between 1 and 10 ng/ml were obtained for most analytes which fulfil current requirements. The applicability
of the method was shown by analysing positive samples. 相似文献
113.
The ionization of 46 anabolic steroids has been studied. The absence of basic or acidic moieties in most of these analytes makes their direct ionization as [M + H]+ by atmospheric pressure interfaces difficult. The formation of adducts with different components of the mobile phase has been found to be an efficient way to ionize anabolic steroids by electrospray. Different mobile phases using methanol (MeOH) or acetonitrile as organic solvent and HCOOH, Na+ or NH4+ as additives have been tested to favor the adduct formation. A direct correlation between the chemical structure of the anabolic steroid and the possibility to ionize it in a particular chromatographic condition has been found. According to their ionization, anabolic steroids can be divided into seven different groups depending on both the nature and the relative position of their functional groups. The formation of different adducts such as [M + Na + MeOH]+ or [M + H + CH3 CN - H2O]+ is required in order to ionize some of these groups and the optimal mobile phase composition for each group of anabolic steroids is proposed. Despite the ionization limitations due to their chemical structure, most of tested anabolic steroids could be ionized using the adduct formation approach. 相似文献
114.
Deventer K Pozo OJ Van Eenoo P Delbeke FT 《Rapid communications in mass spectrometry : RCM》2007,21(18):3015-3023
A new screening procedure for 18 narcotics in urine for anti-doping purposes has been developed using liquid chromatography/triple quadrupole mass spectrometry (LC/MS). Electrospray ionization (ESI) was used as interface. Infusion experiments were performed for all substances to investigate their mass spectrometric behaviour in terms of selecting product specific ions. These product ions were then used to develop a tandem mass spectrometric method using selected reaction monitoring (SRM). For the LC/MS analysis, chromatography was performed on an octadecylsilane column. The total run time of the chromatographic method was 5.5 min. For the sample preparation prior to LC/MS analysis, the urine samples were liquid-liquid extracted at pH 9.5 after overnight enzymatic hydrolysis. Two extraction solvents were evaluated: dichloromethane/methanol 9/1 (v/v), which is currently used for the extraction of narcotics, and diethyl ether, used for the extraction of steroids. With diethyl ether the detection limits for all compounds ranged between 0.5 and 20 ng/mL and with the mixture containing dichloromethane the detection limits ranged between 0.5 and 10 ng/mL. Taking into account the minimum required performance limits of the World Anti-Doping Agency of 200 ng/mL for narcotics, diethyl ether can also be considered as extraction solvent for narcotics. Finally, the described method was applied to the analysis of urine samples previously found to contain narcotics by our routine gas chromatography/mass spectrometry (GC/MS) method. 相似文献
115.
Determination of polydimethylsiloxane-air partition coefficients using headspace sorptive extraction
Polydimethylsiloxane-air partition coefficients (K(PDMS-A)) were determined using direct headspace analysis and headspace sorptive extraction (HSSE) with polydimethylsiloxane-coated (PDMS) stir bars. The partition coefficients were investigated for three compounds, p-dichlorobenzene (PDCB), naphthalene and camphor, all of which sublimate at room temperature and find use as moth repellents. In order to determine the K(PDMS-A) values of these compounds, the air concentration and the concentration present on PDMS, both at equilibrium, were measured. The results indicate that PDMS-air partition coefficients are proportional to octanol-air partition coefficients. Thus, the latter could be used to estimate the extraction efficiency of PDMS for these compounds in air. Alternatively, octanol-air partition coefficients for organic compounds could be estimated from the PDMS-air partition coefficient values. As expected, the PDMS-air (or octanol-air) partition coefficient increased with decreasing temperature. Importantly, the partition coefficients determined at saturated vapor pressures were lower than the values determined at lower analyte concentrations, with the differences being greater for compounds with larger partition coefficients. Consequently, caution should be exercised when applying K(PDMS-A) values determined at high analyte concentrations to measurements at lower concentrations, especially when the partition coefficients are large. 相似文献
116.
Zrig S Koeckelberghs G Verbiest T Andrioletti B Rose E Persoons A Asselberghs I Clays K 《The Journal of organic chemistry》2007,72(15):5855-5858
The synthesis of a new series of Lambda-type, D-Pi-A regioregular oligothiophenes is described. The simultaneous presence of the chiral centers and the Lambda-type structure disfavored the formation of centro-symmetrical dimeric assemblies. Hence, enhanced first hyperpolarizabilities betaHRS were measured in comparison with those of the corresponding monomers. 相似文献
117.
Numerical computation of stability and detection of Hopf bifurcations of steady state solutions of delay differential equations 总被引:3,自引:0,他引:3
The characteristic equation of a system of delay differential equations (DDEs) is a nonlinear equation with infinitely many
zeros. The stability of a steady state solution of such a DDE system is determined by the number of zeros of this equation
with positive real part. We present a numerical algorithm to compute the rightmost, i.e., stability determining, zeros of
the characteristic equation. The algorithm is based on the application of subspace iteration on the time integration operator
of the system or its variational equations. The computed zeros provide insight into the system’s behaviour, can be used for
robust bifurcation detection and for efficient indirect calculation of bifurcation points.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
118.
H. Watanabe G. J. Lane G. D. Dracoulis A. P. Byrne P. Nieminen F. G. Kondev K. Ogawa M. P. Carpenter R. V. F. Janssens T. Lauritsen D. Seweryniak S. Zhu P. Chowdhury 《The European Physical Journal A - Hadrons and Nuclei》2009,42(2):163-169
The nucleus $\ensuremath {\rm ^{127}Sb}$ , which is on the neutron-rich periphery of the $\ensuremath \beta$ -stability region, has been populated in complex nuclear reactions involving deep-inelastic and fusion-fission processes with $\ensuremath {\rm {}^{136}Xe}$ beams incident on thick targets. The previously known isomer at 2325 keV in $\ensuremath {\rm {}^{127}Sb}$ has been assigned spin and parity $\ensuremath 23/2^+$ , based on the measured $\ensuremath \gamma$ - $\ensuremath \gamma$ angular correlations and total internal conversion coefficients. The half-life has been determined to be 234(12) ns, somewhat longer than the value reported previously. The 2194 keV state has been assigned $\ensuremath J^{\pi} = 19/2^+$ and identified as an isomer with $\ensuremath T_{1/2} = 14(1) {\rm ns}$ , decaying by two $\ensuremath E2$ branches. The observed level energies and transition strengths are compared with the predictions of a shell model calculation. Two $\ensuremath 15/2^+$ states have been identified close in energy, and their properties are discussed in terms of mixing between vibrational and three-quasiparticle configurations. 相似文献
119.
Wout De Nolf Jakub Jaroszewicz Roberto Terzano Ole Christian Lind Brit Salbu Bart Vekemans Koen Janssens Gerald Falkenberg 《Spectrochimica Acta Part B: Atomic Spectroscopy》2009,64(8):775
The performance of a combined microbeam X-ray fluorescence/X-ray powder diffraction (XRF/XRPD) measurement station at Hamburger Synchrotronstrahlungslabor (HASYLAB) Beamline L is discussed in comparison to that at European Synchrotron Radiation Facility (ESRF) ID18F/ID22. The angular resolution in the X-ray diffractograms is documented when different combinations of X-ray source, optics and X-ray diffraction detectors are employed. Typical angular resolution values in the range 0.3–0.5° are obtained at the bending magnet source when a ‘pink’ beam form of excitation is employed. A similar setup at European Synchrotron Radiation Facility beamlines ID18F and ID22 allows to reach angular resolution values of 0.1–0.15°. In order to document the possibilities and limitations for speciation of metals in environmental materials by means of Hamburger Synchrotronstrahlungslabor Beamline L X-ray fluorescence/X-ray powder diffraction setup, two case studies are discussed, one involved in the identification of the crystal phases in which heavy metals such as chromium, iron, barium and lead are present in polluted soils of an industrial site (Val Basento, Italy) and another involved in the speciation of uranium in depleted uranium particles (Ceja Mountains, Kosovo). In the former case, the angular resolution is sufficient to allow identification of most crystalline phases present while in the latter case, it is necessary to dispose of an angular resolution of ca. 0.2° to distinguish between different forms of oxidized uranium. 相似文献
120.
Peter Nockemann Dr. Ben Thijs Dr. Kyra Lunstroot Dr. Tatjana N. Parac‐Vogt Prof. Dr. Christiane Görller‐Walrand Prof. Dr. Koen Binnemans Prof. Dr. Kristof Van Hecke Dr. Luc Van Meervelt Prof. Dr. Sergey Nikitenko John Daniels Dr. Christoph Hennig Dr. Rik Van Deun Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(6):1449-1461
The dissolution process of metal complexes in ionic liquids was investigated by a multiple‐technique approach to reveal the solvate species of the metal in solution. The task‐specific ionic liquid betainium bis(trifluoromethylsulfonyl)imide ([Hbet][Tf2N]) is able to dissolve stoichiometric amounts of the oxides of the rare‐earth elements. The crystal structures of the compounds [Eu2(bet)8(H2O)4][Tf2N]6, [Eu2(bet)8(H2O)2][Tf2N]6?2H2O, and [Y2(bet)6(H2O)4][Tf2N]6 were found to consist of dimers. These rare‐earth complexes are well soluble in the ionic liquids [Hbet][Tf2N] and [C4mim][Tf2N] (C4mim=1‐butyl‐3‐methylimidazolium). The speciation of the metal complexes after dissolution in these ionic liquids was investigated by luminescence spectroscopy, 1H, 13C, and 89Y NMR spectroscopy, and by the synchrotron techniques EXAFS (extended X‐ray absorption fine structure) and HEXS (high‐energy X‐ray scattering). The combination of these complementary analytical techniques reveals that the cationic dimers decompose into monomers after dissolution of the complexes in the ionic liquids. Deeper insight into the solution processes of metal compounds is desirable for applications of ionic liquids in the field of electrochemistry, catalysis, and materials chemistry. 相似文献