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261.
N. Bergeard M. G. Silly D. Krizmancic C. Chauvet M. Guzzo J. P. Ricaud M. Izquierdo L. Stebel P. Pittana R. Sergo G. Cautero G. Dufour F. Rochet F. Sirotti 《Journal of synchrotron radiation》2011,18(2):245-250
Synchrotron radiation time structure is becoming a common tool for studying dynamic properties of materials. The main limitation is often the wide time domain the user would like to access with pump–probe experiments. In order to perform photoelectron spectroscopy experiments over time scales from milliseconds to picoseconds it is mandatory to measure the time at which each measured photoelectron was created. For this reason the usual CCD camera‐based two‐dimensional detection of electron energy analyzers has been replaced by a new delay‐line detector adapted to the time structure of the SOLEIL synchrotron radiation source. The new two‐dimensional delay‐line detector has a time resolution of 5 ns and was installed on a Scienta SES 2002 electron energy analyzer. The first application has been to characterize the time of flight of the photoemitted electrons as a function of their kinetic energy and the selected pass energy. By repeating the experiment as a function of the available pass energy and of the kinetic energy, a complete characterization of the analyzer behaviour in the time domain has been obtained. Even for kinetic energies as low as 10 eV at 2 eV pass energy, the time spread of the detected electrons is lower than 140 ns. These results and the time structure of the SOLEIL filling modes assure the possibility of performing pump–probe photoelectron spectroscopy experiments with the time resolution given by the SOLEIL pulse width, the best performance of the beamline and of the experimental station. 相似文献
262.
In the present Letter several carbolactones (oxidative products) are obtained under aprotic cathodic conditions in the preparative scaled electrolysis of 1,2-quinones in a divided electrochemical cell and in the presence of oxygen. When 9,10-phenanthrenequinone is reduced 6H-dibenzo[b,d]pyran-6-one and [1,1′-biphenyl]-2,2′-dicarboxylic acid are obtained as major products. In the reduction of 1,2-naphthoquinone, 2-benzopyran-1(1H)-one, and 2-(2-carboxyethenyl)-benzoic acid were formed as main products. The proposed mechanism to explain the formation of these and other products, that involves an electron-transfer reaction to the oxygen in air, is now discussed. 相似文献
263.
Visa Thongrakard Nijsiri Ruangrungsi Maneerat Ekkapongpisit Ciro Isidoro Tewin Tencomnao 《Photochemistry and photobiology》2014,90(1):214-224
Thai traditional medicine employs a wide range of indigenous herbs in the forms of tincture or tea for the cure of skin and systemic inflammatory diseases. The protection by Thai plants extracts against UVB DNA damage and cytotoxicity was investigated in human keratinocytes. Petroleum ether, dichloromethane and ethanol extracts were prepared from 15 Thai herb species, and the total phenolic and flavonoid contents, the antioxidant and UV‐absorbing properties were assessed by standard procedures. Cytoprotective effects were evaluated on the basis of cell survival, caspase‐3 activity and pyrimidine dimers determination. High total phenolic and flavonoid contents were found in the ethanol and dichloromethane fractions. Dichloromethane extract of turmeric was shown to possess the highest antioxidant activity. The maximum UV absorptions were found in the ethanol extract of turmeric and in the dichloromethane extract of ginger. These extracts stimulated the synthesis of Thioredoxin 1, an antioxidant protein, and could protect human HaCaT keratinocytes from UV‐induced DNA damage and cytotoxicity. The present data support the utilization of turmeric and ginger extracts in anti‐UV cosmetic pharmaceuticals. 相似文献
264.
Isidoro López Dr. Mehmed Z. Ertem Dr. Somnath Maji Dr. Jordi Benet‐Buchholz Anke Keidel Dr. Uwe Kuhlmann Prof. Peter Hildebrandt Prof. Christopher J. Cramer Prof. Victor S. Batista Prof. Antoni Llobet 《Angewandte Chemie (International ed. in English)》2014,53(1):205-209
The homogeneous catalysis of water oxidation by transition‐metal complexes has experienced spectacular development over the last five years. Practical energy‐conversion schemes, however, require robust catalysts with large turnover frequencies. Herein we introduce a new oxidatively rugged and powerful dinuclear water‐oxidation catalyst that is generated by self‐assembly from a mononuclear catalyst during the catalytic process. Our kinetic and DFT computational analysis shows that two interconnected catalytic cycles coexist while the mononuclear system is slowly and irreversibly converted into the more stable dinuclear system: an extremely robust water‐oxidation catalyst that does not decompose over extended periods of time. 相似文献
265.
Syntheses of 2,5,6-trideoxy-2,5-imino-d-alditol (2, 6-deoxy-DADP) and its enantiomer (3) from tri-orthogonally protected derivatives of DADP have been developed employing lipase-mediated kinetic desymmetrization and protecting group manipulations. Thus, and as an example, the starting DADP derivative (4) was transformed into a new symmetrical 2,5-bis(hydroxymethyl)pyrrolidine (6) by sequential N-protection and bis-O-desilylation. The lipase-mediated desymmetrization of 6 was best carried out under acetylation conditions to give (2R)-acetyloxymethyl derivative 7. The absolute configuration and ee of 7 were unambiguously established by chemical correlation with a homochiral sample. Compound 7 was straightforwardly transformed into the target 2,5,6-trideoxy-2,5-iminohexitol 3. 相似文献
266.
Coste F Ober M Le Bihan YV Izquierdo MA Hervouet N Mueller H Carell T Castaing B 《Chemistry & biology》2008,15(7):706-717
Fpg is a bacterial base excision repair enzyme that removes oxidized purines from DNA. This work shows that Fpg and its eukaryote homolog Ogg1 recognize with high affinity FapydG and bulky N7-benzyl-FapydG (Bz-FapydG). The comparative crystal structure analysis of stable complexes between Fpg and carbocyclic cFapydG or Bz-cFapydG nucleoside-containing DNA provides the molecular basis of the ability of Fpg to bind both lesions with the same affinity and to differently process them. To accommodate the steric hindrance of the benzyl group, Fpg selects the adequate rotamer of the extrahelical Bz-cFapydG formamido group, forcing the bulky group to go outside the binding pocket. Contrary to the binding mode of cFapydG, the particular recognition of Bz-cFapydG leads the BER enzymes to unproductive complexes which would hide the lesion and slow down its repair by the NER machinery. 相似文献
267.
Latorre A López I Ramírez V Rodríguez S Izquierdo J González FV Vicent C 《The Journal of organic chemistry》2012,77(11):5191-5197
The mechanism of the dehydrosulfenylation of 2-arylsulfinyl esters was investigated. The reaction was found to follow a homolytic cleavage mechanism as verified by electrospray ionization tandem mass spectrometry and experimental work. Rearranged sulfoxides are obtained as byproduct during the elimination reaction. 相似文献
268.
Within the class of zero-monotonic games, we prove that a cooperative game with transferable utility is convex if and only
if the core of the game coincides with the Mas-Colell bargaining set (à la Shimomura, in Int J Game Theory 26:283–302, 1997). 相似文献
269.
Uc VH Alvarez-Idaboy JR Galano A García-Cruz I Vivier-Bunge A 《The journal of physical chemistry. A》2006,110(33):10155-10162
The OH abstraction of a hydrogen atom from both the side chain and the ring of toluene has been studied in the range 275-1000 K using quantum chemistry methods. It is found that the best method of calculation is to perform geometry optimization and frequency calculations at the BHandHLYP/6-311++G(d,p) level, followed by CCSD(T) calculations of the optimized structures with the same basis set. Four different reaction paths are considered, corresponding to the side chain and three possible ring hydrogen abstractions, and the branching ratio is determined as a function of temperature. Although negligible at low temperatures, at 1000 K ring-H abstraction is found to contribute 11% to the total abstraction reaction. The calculated rate coefficients agree very well with experimental results. Side chain abstraction is shown to occur through a complex mechanism that includes the reversible formation of a collisionally stabilized reactant complex. 相似文献
270.
T. Aguayo E. Clavijo F. Eisner C. Ossa‐Izquierdo M. M. Campos‐Vallette 《Journal of Raman spectroscopy : JRS》2011,42(12):2143-2148
Pigments and fresco‐related materials from the wall painting Historia de Concepción by Gregorio De La Fuente in Concepción, Chile were identified by Raman microscopy. The pigments were compared with those obtained from the artist's studio, and results allowed inference about subsequent interventions. Materials coming from processes such as salt efflorescence were also studied. The results contribute to the diagnosis of the current conservation state of the wall painting for its future restoration. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献