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91.
In this work, the modulation of the diffusion potential formed at the microfluidic aqueous-aqueous boundary by a pharmaceutical substance is presented. Co-flowing aqueous streams in a microchannel were used to form the stable boundary between the streams. Measurement of the open circuit potential between two silver/silver chloride electrodes enabled the diffusion potential at the boundary to be determined, which is concentration dependent. Experimental results for protonated propranolol as well as tetrapropylammonium are presented. This concept may be useful as a strategy for the detection of drug substances. 相似文献
92.
93.
The irradiation of pure molecular oxygen (O(2)) and carbon dioxide (CO(2)) ices with 5 keV H(+) and He(+) ions was investigated experimentally to simulate the chemical processing of oxygen rich planetary and interstellar surfaces by exposure to galactic cosmic ray (GCR), solar wind, and magnetospheric particles. Deposited at 12 K under ultra-high vacuum conditions (UHV), the irradiated condensates were monitored on-line and in situ in the solid-state by Fourier transform infrared spectroscopy (FTIR), revealing the formation of ozone (O(3)) in irradiated oxygen ice; and ozone, carbon monoxide (CO), and cyclic carbon trioxide (c-CO(3)) in irradiated carbon dioxide. In addition to these irradiation products, evolution of gas-phase molecular hydrogen (H(2)), atomic helium (He) and molecular oxygen (O(2)) were identified in the subliming oxygen and carbon dioxide condensates by quadrupole mass spectrometry (QMS). Temporal abundances of the oxygen and carbon dioxide precursors and the observed molecular products were compiled over the irradiation period to develop reaction schemes unfolding in the ices. These reactions were observed to be dependent on the generation of atomic oxygen (O) by the homolytic dissociation of molecular oxygen induced by electronic, S(e), and nuclear, S(n), interaction with the impinging ions. In addition, the destruction of the ozone and carbon trioxide products back to the molecular oxygen and carbon dioxide precursors was promoted over an extended period of ion bombardment. Finally, destruction and formation yields were calculated and compared between irradiation sources (including 5 keV electrons) which showed a surprising correlation between the molecular yields (~10(-3)-10(-4) molecules eV(-1)) created by H(+) and He(+) impacts. However, energy transfer by isoenergetic, fast electrons typically generated ten times more product molecules per electron volt (~10(-2)-10(-3) molecules eV(-1)) than exposure to the ions. Implications of these findings to Solar System chemistry are also discussed. 相似文献
94.
Duckworth BP Geders TW Tiwari D Boshoff HI Sibbald PA Barry CE Schnappinger D Finzel BC Aldrich CC 《Chemistry & biology》2011,18(11):1432-1441
The mycobacterial biotin protein ligase (MtBPL) globally regulates lipid metabolism in Mtb through the posttranslational biotinylation of acyl coenzyme A carboxylases involved in lipid biosynthesis that catalyze the first step in fatty acid biosynthesis and pyruvate coenzyme A carboxylase, a gluconeogenic enzyme vital for lipid catabolism. Here we describe the design, development, and evaluation of a rationally designed bisubstrate inhibitor of MtBPL. This inhibitor displays potent subnanomolar enzyme inhibition and antitubercular activity against multidrug resistant and extensively drug resistant Mtb strains. We show that the inhibitor decreases in?vivo protein biotinylation of key enzymes involved in fatty?acid biosynthesis and that the antibacterial activity is MtBPL dependent. Additionally, the gene encoding BPL was found to be essential in M.?smegmatis. Finally, the X-ray cocrystal structure of inhibitor bound MtBPL was solved providing detailed insight for further structure-activity analysis. Collectively, these data suggest that MtBPL is a promising target for further antitubercular therapeutic development. 相似文献
95.
96.
R Smith D Huskens D Daelemans RE Mewis CD Garcia AN Cain TN Freeman C Pannecouque ED Clercq D Schols TJ Hubin SJ Archibald 《Dalton transactions (Cambridge, England : 2003)》2012,41(37):11369-11377
Tetraazamacrocyclic complexes of transition metals provide useful units for incorporating multiple coordination interactions into a single protein binding molecule. They can be designed with available sites for protein interactions via donor atom-containing amino acid side chains or labile ligands, such as H(2)O, allowing facile exchange. Three configurationally restricted nickel(ii) cyclam complexes with either one or two macrocyclic rings were synthesised and their ability to abrogate the CXCR4 chemokine receptor signalling process was assessed (IC(50) = 8320, 194 and 14 nM). Analogues were characterised crystallographically to determine the geometric parameters of the acetate binding as a model for aspartate. The most active nickel(ii) compound was tested in several anti-HIV assays against representative viral strains showing highly potent EC(50) values down to 13 nM against CXCR4 using viruses, with no observed cytotoxicity (CC(50) > 125 μM). 相似文献
97.
P. F. Hodnett C. Courtney 《International Journal of Mathematical Education in Science & Technology》2013,44(8):1029-1049
This paper uses a partial differential equation which occurs in a reduced model of large scale circulation in an ocean basin as an educational vehicle through which to demonstrate the usefulness of a set of mathematical techniques in analysing the equation. A parameter occurring in the equation does in reality vary from very small through intermediate to very large values. Therefore separate solutions are required for (a) very small, (b) very large and (c) intermediate values of the parameter. This allows for the demonstration of how when the parameter is very small the method of characteristics and the singular perturbation method are useful. When the parameter is very large the regular perturbation method is useful. At intermediate values of the parameter numerical methods must be used and in this case it is a helpful check to have available the asymptotic results for both small and large values of the parameter. 相似文献
98.
The octol of a new rigid, tetraarylene-bridged cavitand was investigated for self-assembly behaviour in solution. 1H and DOSY NMR spectroscopic experiments show that the cavitand readily dimerizes through an unusual seam of interdigitated hydrogen-bonds that is resistant to disruption by polar co-solvents. The well-defined cavity encapsulates small cationic guests, but not their neutral counterparts, restricting the conformation of sequestered tetraethylammonium in solution and the solid state.A robust, dimeric capsule forms quantitatively in low-polarity solvents via a seam of 8 hydrogen bonds. The resulting electron-rich cavity selectively binds small organic cations over neutral counterparts. 相似文献
99.
Courtney H. Lanier Ann N. Chiaramonti Laurence D. Marks Kenneth R. Poeppelmeier 《Surface science》2009,603(16):2574-2579
The so-called Biphase termination on α-Fe2O3 has been widely accepted to be a structure with a 40 Å unit supercell composed of coexisting islands of Fe1−xO and α-Fe2O3. Based on thermodynamic arguments and experimental evidence, including transmission electron diffraction, imaging, magnetic and spectroscopic information, it is found that the previously proposed structure model is inaccurate. The actual Biphase structure is instead a layered structure related to the reduction of α-Fe2O3 to Fe3O4. A model for the Biphase termination is proposed which does not contain islands of Fe1−xO but instead consists of bulk α-Fe2O3 and a Fe3O4-derived overlayer. The proposed model is consistent with all current and previously reported experimental findings. 相似文献
100.
In the presence of a phosphine oxide cocatalyst, a bimetallic aluminium(salen) complex was found to catalyse the asymmetric addition of trimethylsilyl cyanide to aldehydes. Under optimised conditions, enantioselectivities of 53-96% were obtained using 2 mol % of the catalyst. An analysis of the reaction kinetics showed that the reactions exhibited first-order kinetics, with the rate of reaction being independent of the aldehyde concentration. 相似文献