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101.
The first example of a transition metal-catalyzed hetero-[5 + 2] cycloaddition reaction is described. Use of cyclopropyl imines as five-atom components, an alkyne as a two-carbon component, and a Rh(I) catalyst enables a new route to dihydroazepines. This new hetero-[5 + 2] cycloaddition works well with aldimines, ketimines, and with substituted cyclopropanes and affords the desired dihydroazepines in excellent yields as single regioisomers. Use of serial imine formation/aza-[5 + 2] cycloaddition generates the desired dihydroazepines in one operation from three commercially available starting materials. The reaction has been scaled to give gram quantities of dihydroazepine. 相似文献
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de Hazan Y Reuter T Werner D Clasen R Graule T 《Journal of colloid and interface science》2008,323(2):293-300
The effect of comb polyelectrolytes on the dispersion stability of colloidal alumina particles in DI water and commercial electroless nickel (EN) solutions was investigated. Adsorption of polyelectrolytes and major EN components onto colloidal alumina was assessed by TGA, chemical analysis, and zeta potential measurements. Zeta potential measurements were made during titrations of comb-polyelectrolyte-stabilized dispersions with EN solutions to full ionic strength for the first time. The compilation of titration curves made with varying amounts of comb polyelectrolytes provides high resolution and novel insight into the particle/surfactant/EN systems. Continuous decrease in particle/EN components surface interactions with the increase in comb polyelectrolyte coverage is observed. Laser diffraction measurements reveal steric stabilization of nano- and submicronmeter alumina dispersions in both DI water and EN solutions with >7 wt% and >2 wt% comb polyelectrolyte, respectively. 相似文献
104.
Torben Maack Bisgaard 《Proceedings of the American Mathematical Society》1998,126(11):3227-3237
For a certain constant (a little less than ), every function satisfying , , is a Stieltjes indeterminate Stieltjes moment sequence. For every indeterminate moment sequence there is a positive definite matrix sequence which is not of positive type and which satisfies , . For a certain constant (a little greater than ), for every function satisfying , , there is a convolution semigroup of measures on , with moments of all orders, such that , , and for every such convolution semigroup the measure is Stieltjes indeterminate for all .
105.
Huxley P Sutton DH Debnam P Matthews IR Brewer JE Rose J Trickett M Williams DD Andersen TB Classon BJ 《Chemistry & biology》2004,11(12):1651-1658
Costimulatory molecules are important regulators of T cell activation and thus favored targets for therapeutic manipulation of immune responses. One of the key costimulatory receptors is CD80, which binds the T cell ligands, CD28, and CTLA-4. We describe a set of small compounds that bind with high specificity and low nanomolar affinity to CD80. The compounds have relatively slow off-rates and block both CD28 and CTLA-4 binding, implying that they occlude the shared ligand binding site. The compounds inhibit proinflammatory cytokine release in T cell assays with submicromolar potency, and as such, they represent promising leads for the development of novel therapeutics for immune-mediated inflammatory disease. Our results also suggest that other predominantly beta proteins, such as those that dominate the cell surface, may also be accessible as potentially therapeutic targets. 相似文献
106.
Two new sensitive and selective LC-MS methods have been developed for the quantification of the total coenzyme Q(10) concentration in human blood serum. The sensitivity of the methods is based on the very efficient formation of the radical anions of CoQ(10)[M(-)[radical dot]] by negative atmospheric pressure ionisation, APCI(-). The mass detection of the [M(-)[radical dot]] ions, m/z= 862.6, was performed either in selective ion monitoring (SIM) or in MS(2) mode (m/z= 862.6 [rightward arrow]m/z= 847.6) using an LCQ-deca ion-trap mass spectrometer. Two standard serum samples with medium (0.73 [micro sign]g ml(-1)) and high (1.96 [micro sign]g ml(-1)) total CoQ(10) concentrations were analysed by LC-APCI(-)-SIM and LC-APCI(-)-MS(2) and the results compared with a HPLC literature procedure with electrochemical detection (ECD). Both the LC-MS methods were shown to be more selective and with comparable or better sensitivity than the HPLC-ECD method. The LC-MS-SIM and LC-MS(2) chromatograms of the medium concentration sample showed CoQ(10) signal to noise ratios of 25 and 625, respectively. In addition, a simple and fast serum pre-treatment procedure was developed, in which the serum CoQ(10)H(2) content was quantitatively oxidised quantitatively to CoQ(10) in less than 15 min by 1,4-benzoquinone. 相似文献
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Torben Pottgiesser Yorck Olaf Schumacher 《Analytical and bioanalytical chemistry》2013,405(30):9625-9639
During the last 30 years, the artificial increase of red blood cell volume (“blood doping”) has changed the level of performance in all endurance sports. Many doping scandals have shown the extent of the problem. The detection of blood doping relies on two different approaches: the direct detection of exogenous manipulating substances (erythropoietic stimulants) or red cells (homologous transfusion) and the indirect detection, where not the doping substance or technique itself, but its effect on certain biomarkers is measured. Whereas direct detection using standard laboratory procedures such as isoelectric focusing can identify erythropoietic stimulants, homologous blood transfusion is identified through mismatches in minor blood group antigens by flow cytometry. Indirect methods such as the athlete biological passport are the only means to detect autologous transfusion and may also be used for the detection of erythropoietic stimulants or homologous transfusion. New techniques to unmask blood doping include the use of high-throughput ‘omics’ technologies (proteomics/metabolomics) and the combination of different biomarkers with the help of mathematical approaches. Future strategies should aim at improving the use of the available data and resources by applying pattern recognition algorithms to recognize suspicious athletes and, on the basis of these findings, use the appropriate testing method. Different types of information should be combined in the quest for a forensic approach to anti-doping. 相似文献