全文获取类型
收费全文 | 547篇 |
免费 | 15篇 |
国内免费 | 3篇 |
专业分类
化学 | 365篇 |
晶体学 | 2篇 |
力学 | 11篇 |
数学 | 96篇 |
物理学 | 91篇 |
出版年
2022年 | 8篇 |
2021年 | 8篇 |
2020年 | 2篇 |
2019年 | 7篇 |
2018年 | 7篇 |
2017年 | 4篇 |
2016年 | 20篇 |
2015年 | 16篇 |
2014年 | 17篇 |
2013年 | 39篇 |
2012年 | 36篇 |
2011年 | 35篇 |
2010年 | 23篇 |
2009年 | 24篇 |
2008年 | 31篇 |
2007年 | 29篇 |
2006年 | 31篇 |
2005年 | 28篇 |
2004年 | 26篇 |
2003年 | 26篇 |
2002年 | 16篇 |
2001年 | 6篇 |
2000年 | 7篇 |
1999年 | 9篇 |
1998年 | 5篇 |
1997年 | 6篇 |
1996年 | 6篇 |
1995年 | 9篇 |
1994年 | 8篇 |
1993年 | 5篇 |
1992年 | 8篇 |
1991年 | 4篇 |
1990年 | 3篇 |
1989年 | 3篇 |
1988年 | 4篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1985年 | 6篇 |
1984年 | 5篇 |
1983年 | 2篇 |
1982年 | 4篇 |
1981年 | 3篇 |
1980年 | 5篇 |
1979年 | 4篇 |
1978年 | 4篇 |
1976年 | 2篇 |
1974年 | 2篇 |
1973年 | 2篇 |
1966年 | 1篇 |
1940年 | 1篇 |
排序方式: 共有565条查询结果,搜索用时 15 毫秒
31.
Sylvia Pulmannová 《International Journal of Theoretical Physics》2003,42(7):1413-1423
A noncommutative version of generalized Sasaki projections in pseudoeffect algebras is introduced. It is proved that an ideal in a pseudoeffect algebra is Riesz if and only if it is closed under the right and left Sasaki projections. In lattice ordered pseudoeffect algebras, it is shown that generalized Sasaki projections are one-element sets, and their explicit form is found. It is shown that if a supremum of a normal Riesz ideal in a lattice ordered pseudoeffect algebra exists, it is a central element. These results extend those obtained recently by Avallone and Vitolo for effect algebras. 相似文献
32.
Gejza Jenca Sylvia Pulmannová 《Proceedings of the American Mathematical Society》2003,131(9):2663-2671
We prove that for every orthocomplete effect algebra the center of forms a complete Boolean algebra. As a consequence, every orthocomplete atomic effect algebra is a direct product of irreducible ones.
33.
Schön P Görlich M Coenen MJ Heus HA Speller S 《Langmuir : the ACS journal of surfaces and colloids》2007,23(20):9921-9923
Liquid tapping atomic force microscopy was used to study the nonspecific adsorption of horse spleen ferritin at a bare gold surface at single molecule resolution. The majority of ferritin molecules adsorbed irreversible on gold surfaces in accordance with the random sequential adsorption (RSA) mechanism frequently used to describe irreversible adsorption processes. However, the time-resolved data also reveal events that go beyond the RSA model, i.e., lateral mobility and fragility of some molecules, resulting in desorption, chain formation, and subunit dissociation. Scanning effects of the AFM tip were observed, resulting in diminished protein coverage in the scanned area. 相似文献
34.
Feliciano J Xu S Guan X Lehmler HJ Bachas LG Daunert S 《Analytical and bioanalytical chemistry》2006,385(5):807-813
Polychlorinated biphenyls (PCBs) are a group of organic pollutants that are persistent when released into the environment. Among the metabolites of PCBs, dihydroxylated PCBs are also considered as toxic compounds. Various studies have shown that dihydroxylated PCBs affect the reproductive, immune, nervous, and endocrine systems. Detection of these chemicals in environmental and biological samples could provide first-hand information about their levels and lead to a better understanding of their role in toxicity. To that end, we developed a sensing system for the detection of dihydroxylated PCBs based on the clc operon. The Pseudomonas putida clc operon encodes a catabolic pathway for degradation of chlorocatechols, which are major metabolites of a large number of chlorinated compounds. In P. putida, the expression of these genes is regulated by a protein encoded by the gene clcR located upstream from the clcABD genes. We demonstrate here for the first time that dihydroxy PCBs can also induce the clc operon. Our sensing system employs P. putida bacteria harboring a plasmid in which the reporter gene, lacZ, is under the control of the regulatory protein ClcR. Consequently, when exposed to dihydroxy PCBs, the bacteria express β-galactosidase in an amount related to the concentration of the corresponding dihydroxy PCB. Various dihydroxylated PCBs, differing in the number and position of chlorines and in the position of hydroxyls, were tested for their ability to induce expression of β-galactosidase. Detection limits as low as 1×10−6 mol L−1 were obtained for various dihydroxylated PCBs.
Electronic Supplementary Material Supplementary material is available for this article at and is accessible for authorized users. 相似文献
35.
Sylvia Jeney Ernst H K Stelzer Helmut Grubmüller Ernst-Ludwig Florin 《Chemphyschem》2004,5(8):1150-1158
A new method combining three-dimensional (3D) force measurements in an optical trap with the analysis of thermally induced (Brownian) position fluctuations of a trapped probe was used to investigate the mechanical properties of a single molecule, the molecular motor kinesin. One kinesin molecule attached to the probe was bound in a rigorlike state to one microtubule. The optical trap was kept weak to measure the thermal forces acting on the probe, which were mainly counterbalanced by the kinesin tether. The stiffness of kinesin during stretching and compression with respect to its backbone axis were measured. Our results indicate that a section of kinesin close to the motor domain is the dominating element in the flexibility of the motor structure. The experiments demonstrate the power of 3D thermal fluctuation analysis to characterize mechanical properties of individual motor proteins and indicate its usefulness to study single molecule in general 相似文献
36.
Anne Techen Sylvia Czapla Kristian Möllnitz Dennis Budach Pablo Wessig Michael U. Kumke 《Helvetica chimica acta》2013,96(11):2046-2067
Fluorescence probes consisting of well‐established fluorophores in combination with rigid molecular rods based on spirane‐type structures were investigated with respect to their fluorescence properties under different solvent conditions. The attachment of the dyes was accomplished by 1,3‐dipolar cycloaddition between alkynes and azides (‘click’ reaction) and is a prime example for a novel class of sensor constructs. Especially, the attachment of two (different) fluorophores on opposite sides of the molecular rods paves the way to new sensor systems with less bulky (compared to the conventional DNA‐ or protein‐based concepts), nevertheless rigid spacer constructs, e.g., for FRET‐based sensing applications. A detailed photophysical characterization was performed in MeOH (and in basic H2O/MeOH mixtures) for i) rod constructs containing carboxyfluorescein, ii) rod constructs containing carboxyrhodamine, iii) rod constructs containing both carboxyfluorescein and carboxyrhodamine, and iv) rod constructs containing both pyrene and perylene parts. For each dye (pair), two rod lengths with different numbers of spirane units were synthesized and investigated. The rod constructs were characterized in ensemble as well as single‐molecule fluorescence experiments with respect to i) specific rod? dye and ii) dye? dye interactions. In addition to MeOH and MeOH/NaOH, the rod constructs were also investigated in micellar systems, which were chosen as a simplified model for membranes. 相似文献
37.
The hydration of the phosphocholine headgroup in 1,2-dipropionyl-sn-glycero-3-phosphocholine (C(3)-PC) in solution has been determined by using neutron diffraction enhanced with isotopic substitution in combination with computer simulation techniques. The atomic scale hydration structure around this head group shows that both the -N(CH(3))(3) and -CH(2) portions of the choline headgroup are strongly associated with water, through a unique hydrogen bonding regime, where specifically a hydrogen bond from the C-H group to water and a strong association between the water oxygen and N(+) atom in solution have both been observed. In addition, both PO(4) oxygens (P=O) and C=O oxygens are oversaturated when compared to bulk water in that the average number of hydrogen bonds from water to both X=O oxygens is about 2.5 for each group. That water binds strongly to the glycerol groups and is suggestive that water may bind to these groups when phosophotidylcholine is embedded in a membrane bilayer. 相似文献
38.
Continuous flow hydroformylation of alkenes in supercritical fluid-ionic liquid biphasic systems 总被引:1,自引:0,他引:1
Webb PB Sellin MF Kunene TE Williamson S Slawin AM Cole-Hamilton DJ 《Journal of the American Chemical Society》2003,125(50):15577-15588
A process for the hydroformylation of relatively low volatility alkenes (demonstrated for 1-dodecene) in a continuous flow system is described. The catalyst is dissolved in an ionic liquid while the substrate and gaseous reagents are transported into the reactor dissolved in supercritical CO(2), which simultaneously acts as a transport vector for aldehyde products. Decompression of the fluid mixture downstream yields products which are free of both reaction solvent and catalyst. The use of rhodium complexes of triaryl phosphites leads to ligand degradation through reaction of the ionic liquid with water and subsequent attack of the released HF on the phosphite. Sodium salts of sulfonated phosphines are insufficiently soluble in the ionic liquids to obtain acceptable rates, but replacing the sodium by a cation similar to that derived from the ionic liquid, allows good solubility and activity to be obtained. The nature of the ionic liquid is very important in achieving high rates, with 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amides giving the best activity if the alkyl chain is at least C(8). Catalyst turnover frequencies as high as 500 h(-1) have been observed, with the better rates at higher substrate flow rates. Rhodium leaching into the product stream can be as low as 0.012 ppm, except at low partial pressures of CO/H(2), when it is significantly higher. Oxygen impurities in the CO(2) feed can lead to oxidation of the phosphine giving higher rates, lower selectivities to the linear aldehyde, increased alkene isomerization and greater leaching of rhodium. However, it is found that under certain process conditions, the supercritical fluid-ionic liquid (SCF-IL) system can be operated continuously for several weeks without any visible sign of catalyst degradation. Comparisons with commercial hydroformylation processes are provided. 相似文献
39.
Katarzyna Raulin Odile Cristini-Robbe Patrice Baldeck Olivier Stéphan Christophe Kinowski Sylvia Turrell Bruno Capoen Mohamed Bouazaoui 《Journal of nanoparticle research》2010,12(4):1459-1467
A novel method for direct laser writing of two-dimensional cadmium sulfide (CdS) semiconductor nanoparticle microstructures
is reported. A two photon or a higher-order multiphoton absorption process, originating from femtosecond laser pulses, was
used to decompose CdS precursors dispersed in a zirconia thin film previously dip-coated on a glass substrate. The kinetics
of nanoparticle formation as a function of laser power were monitored in situ by photoluminescence spectroscopy. Raman spectroscopy
was also performed to characterize the structural changes of the zirconia matrix under irradiation and to verify the formation
of CdS nanoparticles. Results show that CdS nanoparticles were formed by two-photon absorption (TPA) with or without the help
of an additional carbazole photoinitiator. 相似文献
40.