全文获取类型
收费全文 | 2312篇 |
免费 | 144篇 |
国内免费 | 3篇 |
专业分类
化学 | 1876篇 |
晶体学 | 17篇 |
力学 | 39篇 |
数学 | 117篇 |
物理学 | 410篇 |
出版年
2023年 | 20篇 |
2022年 | 36篇 |
2021年 | 44篇 |
2020年 | 61篇 |
2019年 | 75篇 |
2018年 | 40篇 |
2017年 | 49篇 |
2016年 | 89篇 |
2015年 | 90篇 |
2014年 | 93篇 |
2013年 | 166篇 |
2012年 | 200篇 |
2011年 | 238篇 |
2010年 | 139篇 |
2009年 | 102篇 |
2008年 | 148篇 |
2007年 | 142篇 |
2006年 | 123篇 |
2005年 | 141篇 |
2004年 | 101篇 |
2003年 | 86篇 |
2002年 | 80篇 |
2001年 | 34篇 |
2000年 | 26篇 |
1999年 | 16篇 |
1998年 | 18篇 |
1997年 | 16篇 |
1996年 | 11篇 |
1995年 | 9篇 |
1994年 | 11篇 |
1993年 | 8篇 |
1992年 | 6篇 |
1991年 | 2篇 |
1990年 | 6篇 |
1989年 | 4篇 |
1988年 | 7篇 |
1987年 | 4篇 |
1986年 | 2篇 |
1985年 | 1篇 |
1984年 | 3篇 |
1981年 | 4篇 |
1980年 | 1篇 |
1979年 | 3篇 |
1978年 | 2篇 |
1977年 | 2篇 |
排序方式: 共有2459条查询结果,搜索用时 233 毫秒
41.
Lee KB Kim DJ Lee ZW Woo SI Choi IS 《Langmuir : the ACS journal of surfaces and colloids》2004,20(7):2531-2535
The micropatterns of biological ligands (biotin and RGD peptides) were generated on a flat surface of biodegradable polymer, poly(glycolic acid) (PGA). The immobilization of biological ligands onto the surface of biodegradable polymers (especially aliphatic polyesters) is usually hampered by the absence of functionalizable groups on the polymer backbone. We demonstrate herein that PGA polymer films were modified by surface hydrolysis to introduce carboxylic acid groups on the film surfaces, which were subsequently used for patterning amine-terminated ligands by microcontact printing. Fluorescence microscopy was used to verify the pattern of biotin on the surface of the PGA films after complexation with fluorescein-conjugated streptavidin. In addition, the cellular micropatterns were obtained from micropatterns of RGD peptides on the surface-hydrolyzed PGA films. 相似文献
42.
Izaskun Bustero García Ainara Obieta Isabel Muñoz Roberto Rincón Inés Arteche Amaya 《Mikrochimica acta》2006,152(3-4):239-247
Interest in carbon nanotubes (CNT) has grown at a very rapid rate in the last decade. Their interesting physical and chemical
properties open attractive possibilities in many application areas. These properties depend on the process conditions during
synthesis and on subsequent purification steps. Recent studies have demonstrated that CNT can promote the electron transfer
of biomolecules. These exceptional properties make them attractive for use in electrochemical biosensors.
Multi walled nanotubes have been synthesized by the Chemical Vapor Deposition (CVD) method using methane as a carbon source
and Ni–Al2O3–SiO2 as the catalyst. The influence of the variation of certain reaction parameters such as feed gas composition, catalyst mass,
temperature and reaction time in the yield of the CVD process has been established. In addition, the structural and chemical
characteristics of the CNTs have been studied and a purification process to eliminate the catalyst and amorphous carbon has
been developed that involves a gaseous oxidative process and acid treatment. The efficiency of the purification step has been
determined by analytical techniques.
Atomic force microscopy, Raman scattering, thermogravimetric analysis, inductively coupled plasma atomic spectroscopy are
the characterization techniques employed in this work. 相似文献
43.
Cheikhousman R Zude M Bouveresse DJ Léger CL Rutledge DN Birlouez-Aragon I 《Analytical and bioanalytical chemistry》2005,382(6):1438-1443
The potential of fluorescence spectroscopy for characterizing the deterioration of extra virgin olive oil (EVOO) during heating was investigated. Two commercial EVOO were analysed by HPLC to determine changes in EVOO vitamin E and polyphenols as a result of heating at 170°C for 3 h. This thermal oxidation of EVOO caused an exponential decrease in hydroxytyrosol and vitamin E (R2=0.90 and 0.93, respectively) whereas the tyrosol content was relatively stable. At the same time, amounts of preformed hydroperoxides (ROOH), analysed by an indirect colorimetric method, decreased exponentially during the heating process (R2=0.94), as a result of their degradation into secondary peroxidation products. Fluorescence excitation spectra with emission at 330 and 450 nm were recorded to monitor polyphenols and vitamin E evolution and ROOH degradation, respectively. Partial least-squares calibration models were built to predict these indicators of EVOO quality from oil fluorescence spectra. A global approach was then proposed to monitor the heat charge from the overall fluorescence fingerprint. Different data pretreatment methods were tested. This study indicates that fluorescence spectroscopy is a promising, rapid, and cost-effective approach for evaluating the quality of heat-treated EVOO, and is an alternative to time-consuming conventional analyses. In future work, calibration models will be developed using a wide range of EVOO samples. 相似文献
44.
Thiam Seong Chong 《Journal of organometallic chemistry》2006,691(4):687-692
The rate constant for the methyl abstraction reaction of CpFe(CO)2Me has been measured with the benzyl radical clock as (1.1 ± 0.2) × 105 M−1 s−1 at room temperature. Time-resolved Fourier-transform Infrared (FTIR) absorption spectroscopy pointed towards the formation of the CpFe(CO)2 radical upon benzyl abstraction. The main stable product has been established by a linear scan of the reaction mixture as Cp2Fe2(CO)4 produced by the dimerization of the CpFe(CO)2 radicals. The transition state structure for the abstraction process was also found at UB3LYP/6-311+G* level of theory to contain a planar CH3 group. 相似文献
45.
The self-assembly of metallosupramolecules from reactions of flexible 2-pyridyl ligands and silver salts is described. When 1,3-bis(2-pyridyl)propane (L1), tris[(2-pyridyl)methyl]methane (L2), and 1,3-bis(2-pyridyl)-2-tolylpropane (L3) are used in combination with silver ions, novel discrete metallocyclic complexes are formed in crystals. Moreover, the self-assembly of 1,3-bis(2-pyridyl)-2-phenylpropane (L4) with silver nitrate yields a coordination polymer. The examination of its solution shows that this coordination polymer is formed via the solution-based discrete metallocyclic species. 相似文献
46.
The structures of hydrated 1-hydroxyanthraquinone complexes (1-HAQ), 1-HAQ(H2O)n=1,2, with intramolecular and intermolecular hydrogen bonding interactions were studied using laser spectroscopic methods such as laser induced fluorescence, fluorescence-detected infrared, infrared-visible hole burning, and visible-visible hole burning spectroscopy. In the 1:1 complex 1-HAQ(H2O)1, the water binds to the free carbonyl group of 1-HAQ not associated with intramolecular hydrogen bond. The second water in the 1:2 complex, 1-HAQ(H2O)2, binds to the first water of the 1:1 complex rather than other hydrogen bonding sites of 1-HAQ. A pair of two geometric isomers was produced in a supersonic jet for each of the 1:1 and 1:2 complexes. Both isomers of each complex have the same vibrational spectra in the region of the OH stretching vibration of water, but have different energies for the 0-0 band of vibronic transition due to the asymmetry of the two phenyl rings in 1-HAQ. The 0-0 bands for all four species of 1-HAQ(H2O)n=1,2 were unambiguously assigned by comparing with the results of ab initio calculations, which yielded the structures, vibrational frequencies, and relative energies of the frontier molecular orbitals. 相似文献
47.
Kim SH Tamrazi A Carlson KE Daniels JR Lee IY Katzenellenbogen JA 《Journal of the American Chemical Society》2004,126(15):4754-4755
We present the first example of a nuclear hormone receptor microarray, using for illustration the ligand-binding domains of the two estrogen receptors, ERalpha-LBD and ERbeta-LBD. The proteins are printed and allowed to attach to aldehyde slides; the efficiency of attachment depends on whether the LBD is liganded with agonists (low attachment) versus liganded with antagonists or unliganded (high attachment). This suggests that attachment is orientation specific and involves principally a single lysine residue. The attached ERs retain good ligand-binding activity that can be assessed using an estradiol-fluorophore conjugate, and specific and ER subtype-selective binding of ligands can be determined conveniently in competitive binding assays. This powerful new, high-throughput technique to study ligand binding to ER-LBDs can be extended to other nuclear hormone receptors and adapted to assay the recruitment of coregulator proteins. 相似文献
48.
Won Young Jung Seung Hee Baek Seong Soo Park Gun-Dae Lee Euh Duck Jeong Hyun Gyu Kim Seong-Soo Hong 《Reaction Kinetics and Catalysis Letters》2007,91(2):233-240
The nanosized titania and TiO2/SiO2 particles were prepared by the microwave-hydrothermal method. The effect of physical properties TTIP/TEOS ratio and calcination
temperature has been investigated. The major phase of the pure TiO2 particle is of the anatase structure, and a rutile peak was observed above 800°C. In TiO2/SiO2 particles, however, no significant rutile phase was observed, although the calcination temperature was 900°C. No peaks for
the silica crystal phase were observed at either silica/titania ratio. The crystallite size of TiO2/SiO2 particles decreases as compared to pure TiO2 at high calcination temperatures. The TiO2/SiO2 particles show higher activity on the photocatalytic decomposition of orange II as compared to pure TiO2 particles. 相似文献
49.
We report the use of capillary gel electrophoresis (CGE) based on a rfbS allele-specific polymerase chain reaction (PCR) for the analysis and simultaneous detection of Salmonella pullorum and Salmonella gallinarum, which are the major bacterial pathogens in poultry. rfbS allele-specific PCR was used to concurrently amplify two specific 147- and 187-bp DNA fragments for the simultaneous detection of S. pullorum and S. gallinarum at an annealing temperature of 54 ± 1 °C and an MgCl2 concentration of 2.8-5.6 mM. Under an electric field of 333.3 V/cm and a sieving matrix of 1.0% poly(ethyleneoxide) (Mr 600 000), the amplified PCR products were analyzed within 6 min by CGE separation. This CGE assay could be translated to microchip format using programmed field strength gradients (PFSG). In the microchip gel electrophoresis with PFSG, both of the Salmonella analyses were completed within 30 s, without decreasing the resolution efficiency. rfbS allele-specific PCR-microchip gel electrophoresis with the PFSG technique might be a new tool for the simultaneous detection of both S. pullorum and S. gallinarum, due to its ultra-speed and high efficiency. 相似文献
50.
Aromatic molecular "clips" bearing two symmetrically bound platinum moieties have been prepared. The molecular "clip" 4 readily self-assembled with linear linkers such as 4,4'-bipyridyl, 1,4-bis[2-(4-isocyano-3,5-diisopropylphenyl)ethynyl]benzene, and nicotinic acid to form molecular rectangles. The overall dimensions of the rectangle 7 were 7.3 Angstroms x 15.3 Angstroms. The molecular "clip" also self-assembled with tritopic pyridyl and isocyanide ligands to form trigonal prismatic frameworks. The characterization of the supramolecules by multinuclear NMR, electrospray mass spectrometry, and X-ray crystal structures is also reported. 相似文献