全文获取类型
收费全文 | 844篇 |
免费 | 35篇 |
国内免费 | 1篇 |
专业分类
化学 | 563篇 |
晶体学 | 3篇 |
力学 | 20篇 |
数学 | 156篇 |
物理学 | 138篇 |
出版年
2023年 | 13篇 |
2022年 | 13篇 |
2021年 | 12篇 |
2020年 | 11篇 |
2019年 | 11篇 |
2018年 | 11篇 |
2017年 | 12篇 |
2016年 | 26篇 |
2015年 | 19篇 |
2014年 | 18篇 |
2013年 | 50篇 |
2012年 | 50篇 |
2011年 | 55篇 |
2010年 | 31篇 |
2009年 | 33篇 |
2008年 | 43篇 |
2007年 | 39篇 |
2006年 | 42篇 |
2005年 | 38篇 |
2004年 | 44篇 |
2003年 | 34篇 |
2002年 | 22篇 |
2001年 | 12篇 |
2000年 | 8篇 |
1999年 | 9篇 |
1998年 | 13篇 |
1997年 | 8篇 |
1996年 | 19篇 |
1995年 | 7篇 |
1994年 | 16篇 |
1993年 | 13篇 |
1992年 | 8篇 |
1991年 | 10篇 |
1990年 | 5篇 |
1989年 | 5篇 |
1987年 | 4篇 |
1986年 | 3篇 |
1985年 | 10篇 |
1984年 | 7篇 |
1983年 | 9篇 |
1982年 | 4篇 |
1981年 | 11篇 |
1980年 | 4篇 |
1979年 | 5篇 |
1978年 | 5篇 |
1976年 | 6篇 |
1969年 | 3篇 |
1968年 | 3篇 |
1957年 | 3篇 |
1956年 | 3篇 |
排序方式: 共有880条查询结果,搜索用时 250 毫秒
141.
This paper reports on the use of electrochemical surface plasmon resonance (E-SPR) for the detection of carbohydrate-binding proteins. The generation of an SPR sensor specific to lectins Arachis hypogaea (PNA) and Maackia amurensis (MAA) is based on the electrochemical polymerization of oligosaccharide derivatives functionalized by pyrrole groups. The resulting thin conducting polymer films were characterized using E-SPR and atomic force microscopy (AFM). The specific binding of PNA to polypyrrole-lactosyl and of MAA to polypyrrole-3'-sialyllactosyl films was investigated using SPR. The detection limit was 41 nM for PNA and 83 nM for MAA. Through Scatchard analysis and linear transformation of the SPR sensorgram data, association (k(ass)) and dissociation rate constants (k(diss)) could be determined. 相似文献
142.
NIR‐to‐NIR Two‐Photon Scanning Laser Microscopy Imaging of Single Nanoparticles Doped by YbIII Complexes 下载免费PDF全文
Dr. Adrien Bourdolle Dr. Anthony D'Aléo Dr. Cécile Philippot Dr. Patrice L. Baldeck Dr. Yannick Guyot Dr. Fabien Dubois Dr. Alain Ibanez Dr. Chantal Andraud Dr. Sophie Brasselet Dr. Olivier Maury 《Chemphyschem》2016,17(1):128-135
The photophysical and nonlinear optical properties of water‐soluble chromophore‐functionalised tris‐dipicolinate complexes [LnL3]3? (Ln=Yb and Nd) are thoroughly studied, revealing that only the YbIII luminescence can be sensitized by a two‐photon excitation process. The stability of the complex in water is strongly enhanced by embedding in dispersible organosilicate nanoparticles (NPs). Finally, the spectroscopic properties of [NBu4]3[YbL3] are studied in solution and in the solid state. The high brightness of the NPs allows imaging them as single objects using a modified two‐photon microscopy setup in a NIR‐to‐NIR configuration. 相似文献
143.
Dr. Subrata Kundu Prof. Dr. S. Chantal E. Stieber Dr. Maryline G. Ferrier Dr. Stosh A. Kozimor Dr. Jeffery A. Bertke Prof. Dr. Timothy H. Warren 《Angewandte Chemie (International ed. in English)》2016,55(35):10321-10325
Nitrosobenzene (PhNO) serves as a stable analogue of nitroxyl (HNO), a biologically relevant, redox‐active nitric oxide derivative. Capture of nitrosobenzene at the electron‐deficient β‐diketiminato nickel(I) complex [iPr2NNF6]Ni results in reduction of the PhNO ligand to a (PhNO)./? species coordinated to a square planar NiII center in [iPr2NNF6]Ni(η2‐ONPh). Ligand centered reduction leads to the (PhNO)2? moiety bound to NiII supported by XAS studies. Systematic investigation of structure–reactivity patterns of (PhNO)./? and (PhNO)2? ligands reveals parallels with superoxo (O2)./? and peroxo (O2)2? ligands, respectively, and forecasts reactivity patterns of the more transient HNO ligand. 相似文献
144.
Villaume S Strich A Daniel C Perera SA Bartlett RJ 《Physical chemistry chemical physics : PCCP》2007,9(46):6115-6122
The transition energies to the low-lying singlet and triplet excited states of Cr(CO)(6) are computed by equation-of-motion coupled cluster singles and doubles (EOM-CCSD) and similarity transformed equation-of-motion coupled cluster singles and doubles (STEOM-CCSD) methods with all-electrons basis sets. Both experimental and optimized geometries are used for the calculations. Calculations with various basis sets, among them one of the largest calculations performed at the EOM-CCSD level, based on atomic natural orbitals with 627 functions, were used to evaluate the basis set influence on computed transition energies. The presence of a shoulder at 3.9 eV in the experimental absorption spectrum, assigned to the (1)A(1g)-->(1)T(2u) transition, which was not reproduced by recent density functional theory (DFT) or multi-state complete active space perturbation theory (MS-CASPT2) is supported by the present STEOM-CCSD calculations with a theoretical value of 3.92 eV. In addition to this weak (1)A(1g)--> a (1)T(2u) absorption, we observe two strong absorptions corresponding to (1)A(1g)--> a (1)T(1u) at 4.37 eV (vs. an experimental value of 4.46 eV) and (1)A(1g)--> b (1)T(1u) at 5.20 eV (vs. an experimental value of 5.53 eV). Both are characterized as metal-to-ligand charge-transfer (MLCT) allowed transitions. The first metal-centered (MC) absorption at 4.37 eV in our best calculation is degenerate with the lowest MLCT absorbing state. The one-dimensional potential energy curves associated to the low-lying singlet MLCT and MC states as a function of the chromium axial carbonyl bond distance q(a) = [Cr-CO(axial)] show that an avoided crossing exists between the a (1)T(1g) (MC) and a (1)T(1u) (MLCT) states near 1.92 A, which is very close to the equilibrium Cr-CO distance. Moreover, the MC state seems to be dissociative for the CO loss. These two important features could explain the ultra-fast dissociation of CO (100 fs) observed in recent low intensity laser probed gas phase experiments. 相似文献
145.
In Combinatorica 17(2), 1997, Kohayakawa, ?uczak and Rödl state a conjecture which has several implications for random graphs. If the conjecture is true, then, for example, an application of a version of Szemerédi’s regularity lemma for sparse graphs yields an estimation of the maximal number of edges in an H-free subgraph of a random graph G n, p . In fact, the conjecture may be seen as a probabilistic embedding lemma for partitions guaranteed by a version of Szemerédi’s regularity lemma for sparse graphs. In this paper we verify the conjecture for H = K 4, thereby providing a conceptually simple proof for the main result in the paper cited above. 相似文献
146.
Thomas TD Püttner R Fukuzawa H Prümper G Ueda K Kukk E Sankari R Harries J Tamenori Y Tanaka T Hoshino M Tanaka H 《The Journal of chemical physics》2007,127(24):244309
The boron 1s photoelectron spectrum of (11)BF(3) has been measured at a photon energy of 400 eV and a resolution of about 55 meV. The pronounced vibrational structure seen in the spectrum has been analyzed to give the harmonic and anharmonic vibrational frequencies of the symmetric stretching mode, 128.1 and 0.15 meV, as well as the change in equilibrium BF bond length upon ionization, -5.83 pm. A similar change in bond length has been observed for PF(3) and SiF(4), but a much smaller change for CF(4). Theoretical calculations for BF(3) that include the effects of electron correlation give results that are in reasonable accord with the experimental values. The Lorentzian (lifetime) width of the boron 1s core hole in BF(3) is found to be 72 meV, comparable to the value of 77 meV that has been reported for CF(4). 相似文献
147.
Kosmulski M Skubiszewska-Zieba J Leboda R Marczewska-Boczkowska K Próchniak P 《Journal of colloid and interface science》2007,309(1):160-168
A new class of composite materials is introduced. Fine powders of silica, titania, Y-modified zirconia, and three types of alumina were pressed and sintered to form porous monoliths with relatively uniform pore structure. Carbon was then deposited in the pores of such monoliths by thermal decomposition of dichloromethane, cyclohexene, and glucose. The structure of the carbon deposit was studied by low-temperature nitrogen adsorption and by thermal analysis. The composite materials were used as electrodes in electrochemical capacitors with 1-ethyl-3-methylimidazolium trifluoromethylsulfonate (a low-temperature ionic liquid) as the electrolyte. High capacitances were observed for glucose-derived materials, which had high specific surface areas. 相似文献
148.
W. Seidel M. Bravin M. Bruckmayer C. Bucci S. Cooper P. DiStefano F. V. Feilitzsch T. Frank J. Jochum R. Keeling H. Kraus M. Loidl J. Marchese O. Meier P. Meunier U. Nagel D. Pergolesi F. Pröbst Y. Ramachers J. Schnagl I. Sergeyev M. Sisti L. Stodolsky S. Uchaikin L. Zerle 《Physics of Atomic Nuclei》2000,63(7):1242-1248
We discuss the short-and long-term perspectives of the CRESST (Cryogenic Rare Event Search using Superconducting Thermometers) project and present the current status of the experiment and new results concerning detector development. In the search for elementary particle dark matter, CRESST is presently the most advanced deep underground, low-background, cryogenic facility. The basic technique involved is to search for WIMPs (Weakly Interacting Massive Particles) by the measurement of nonthermal phonons, as created by WIMP-induced nuclear recoils. Combined with our newly developed method for the simultaneous measurement of scintillation light, strong background discrimination is possible, resulting in a substantial increase in WIMP detection sensitivity. This will allow a test of the reported positive evidence for a WIMP signal by the DAMA Collaboration in the near future. In the long term, the present CRESST setup permits the installation of a detector mass up to 100 kg. In contrast to other projects, CRESST technology allows the employment of a large variety of detection materials. This offers a powerful tool in establishing a WIMP signal and in investigating WIMP properties in the event of a positive signal. 相似文献
149.
Fernando P. Carvalho Jean-Pierre Villeneuve Chantal Cattini 《Trends in analytical chemistry : TRAC》1999,18(11):1005-664
A seaweed sample (Fucus sp.) was prepared, homogenised and distributed to laboratories worldwide as the IAEA-140 intercomparison material for the analysis of organochlorine compounds and petroleum hydrocarbons. A total of 80 laboratories from 51 countries reported results for this sample. The data sets reported by laboratories were evaluated statistically and the mean concentration values could be computed with 95% confidence limits for a large number of analytes. The accuracy of the analytical performance of each laboratory has been introduced by using Z-scores. The spread of results reported generally indicates that the accurate determination of many persistent organic pollutants, such as hexachlorobenzene, lindane, Aroclors or fluoranthene, is still difficult for many laboratories. The final results of this intercomparison exercise enable individual participants to assess their performance and, where necessary, to introduce appropriate modifications in their analytical procedures. Furthermore, as a series of statistical criteria was fulfilled for a number of compounds, the sample IAEA-140 can now be used as a reference material for quality control in the determination of chlorinated compounds and petroleum hydrocarbons in environmental samples. 相似文献
150.
Philippe Mongondry Chantal Bonnans‐Plaisance Martine Jean Jean Franois Tassin 《Macromolecular rapid communications》2003,24(11):681-685
The hydroxyl end groups of poly(ethylene glycol) (PEG) have been transformed easily and quantitatively into amino groups via the Mitsunobu reaction. Phthalimide was alkylated with PEGs and the hydrazinolysis of the resulting phthalimido‐PEGs gave the amino compounds in high yields. Quaternization of the amino groups leads to hydrophilic polymer chains bearing a positive charge on one or two ends, depending on the chosen PEG. Such products can be used to protect sterically, negatively charged particles such as clays.