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541.
Construction of tricyclic enone, a common precursor for aphidicolane and stemodane B/C/D-ring system
Tanaka T Yamamoto S Hiramatsu K Murakami K Yoshino H Patra D Iwata C Ohno H 《Chemical & pharmaceutical bulletin》2006,54(8):1138-1143
Synthesis of a tricyclic enone (B/C/D ring system), a common key precursor for the aphidicolane- and stemodane-type diterpene, is described. The key reaction for the construction of the quaternary carbon center is allylation of epoxide at the more substituted carbon with an organotitanium reagent. Asymmetric reduction with DIP-Cl followed by stereoselective cyclization of spirocyclic ketone and the functional group modification gave the desired tricyclic enone in good yield. 相似文献
542.
Franzini RM Watson RM Patra GK Breece RM Tierney DL Hendrich MP Achim C 《Inorganic chemistry》2006,45(24):9798-9811
Substitution of natural nucleobases in PNA oligomers with ligands is a strategy for directing metal ion incorporation to specific locations within a PNA duplex. In this study, we have synthesized PNA oligomers that contain up to three adjacent bipyridine ligands and examined the interaction with Ni2+ and Cu2+ of these oligomers and of duplexes formed from them. Variable-temperature UV spectroscopy showed that duplexes containing one terminal pair of bipyridine ligands are more stable upon metal binding than their nonmodified counterparts. While binding of one metal ion to duplexes that contain two adjacent bipyridine pairs makes the duplexes more stable, additional metal ions lower the duplex stability, with electrostatic repulsions being, most likely, an important contributor to the destabilization. UV titrations showed that the presence of several bipyridine ligands in close proximity of each other in PNA oligomers exerts a chelate effect. A supramolecular chelate effect occurs when several bipyridines are brought next to each other by hybridization of PNA duplexes. EPR spectroscopy studies indicate that even when two Cu2+ ions coordinate to a PNA duplex in which two bipyridine pairs are next to each other, the two metal-ligand complexes that form in the duplex are far enough from each other that the dipolar coupling is very weak. EXAFS and XANES show that the Ni2+-bipyridine bond lengths are typical for [Ni(bipy)2]2+ and [Ni(bipy)3]2+ complexes. 相似文献
543.
T. J. Jaison A. K. Patra P. C. Verma A. G. Hegde 《Journal of Radioanalytical and Nuclear Chemistry》2010,285(3):573-578
During operation and maintenance of Pressurised Heavy Water Reactors (PHWRs) at Kakrapar Atomic Power Station (KAPS), low level radioactive liquid waste is generated and released to the aquatic ecosystem (Moticher lake). The silt and aquatic weed (Hydrilla verticillata) samples collected from different locations in Moticher lake were analysed for 137Cs, 134Cs, 65Zn, 60Co, 54Mn and 40K during 2007–2008. A wide variation in activity levels of 137Cs, 134Cs, 65Zn, 60Co, 54Mn and 40K in silt and weed samples were observed in aquatic system of KAPS. The activity buildup in the silt is confined to a small area in the Moticher lake. The activity levels were found to be insignificant at 1 km away from discharge point (upstream and downstream). An attempt was made to evaluate the radiological dose to aquatic weed (Hydrilla verticillata), which was found to be well within the dose limit prescribed by US DOE. The total radiological dose due to the naturally occurring radionuclide (40K) is comparatively higher than that of other reactor released gamma emitting radionuclides. 相似文献
544.
Here, we demonstrate an ionic liquid-assisted hydrothermal method for preparing Tb3+ and Eu3+ doped LaF3 hierarchical microstructures and the morphology is modified by hydrothermal reaction time, temperature of heating and ionic liquid concentration. The mechanism related to morphology control is proposed and discussed. It is also found that PL intensity, decay time and quantum efficiency are sensitive to the morphology. The average decay times are 2.9 ms and 4.8 ms for Eu3+ doped LaF3 microstructures prepared at 10 min and 3 h reaction time, respectively. The average decay time is increased from 4.8 ms to 5.8 ms after heating the sample at 500 °C. The quantum efficiency varies from 34% to 67% with changing morphology. Analysis suggests that morphology plays an important role on efficiency of rare-earth doped materials. 相似文献
545.
The photophysical properties of novel cyclic azacyanine derivatives have been investigated in acetonitrile, N-butyronitrile,
methanol, ethanol, DMF and water. Introduction of electron donating or accepting groups on the cyclic azacyanine has a direct
impact on the spectroscopic and photophysical properties. Irrespective of the nature of the substitution, azacyanine shows
a general solvent relaxation in accordance with Lippert-Mataga’s prediction; however, in protic solvent, specific interactions
are encountered. Fluorescence lifetime decay suggests a relaxation in the nanosecond time scale with monoexponential decay
in polar solvents and biexponential decay in non polar solvents. The fluorescence lifetime of azacyanines are found to be
longer than popular cy3 dyes. An electron donating substituent increases the fluorescence lifetime and influences the radiative
process, whereas an electron withdrawing group marginally increases the excited state lifetime but remarkably enhances the
radiative process. The fluorescence quantum yield of substituted cyclic azacyanine in water is noted to be at least five fold
higher than the popular cy3 dye. 相似文献
546.
Subrata Patra Ivan Mosiagin Rahul Giri Dr. Thomas Nauser Prof. Dr. Dmitry Katayev 《Angewandte Chemie (International ed. in English)》2023,62(28):e202300533
Herein, we introduce an electrochemically assisted generation of nitryl radicals from ferric nitrate under mild reaction conditions using a simple setup with inexpensive graphite and stainless-steel electrodes. The mechanism of the reaction is supported by detailed spectroscopic and experimental studies. Powered by electricity and driven by electrons, the synthetic diversity of this reaction has been demonstrated through the development of highly efficient nitration protocols of various unsaturated hydrocarbons. In addition to a broad application area, these protocols are easy to scale for decagram quantities, and exhibit exceptional substrate generality and functional-group compatibility. 相似文献
547.
Arkaprabha Giri G. Shreeraj Tapas Kumar Dutta Abhijit Patra 《Angewandte Chemie (International ed. in English)》2023,62(23):e202219083
Dynamic covalent chemistry (DCC) opens up a fascinating route for the construction of well-organized supramolecular architectures, starting from organic molecular cages to crystalline macromolecular covalent organic frameworks (COFs). Herein, for the first time, we have manifested a facile room-temperature DCC-directed transformation of discrete organic imine cage-to-COF film at the liquid–liquid interface. The unfolding of the cage leading to the generation of imine intermediates, followed by their interface-assisted preorganization and subsequent growth of the COF film, are elucidated through detailed spectroscopic and microscopic investigations. The interfacial cage-to-COF transformation provides a facile route for the faster fabrication of free-standing COF films with high porosity and crystallinity, demonstrating excellent performance towards molecular sieving and high solvent permeance. Thus, the current study opens up a new route for structural interconversion between two crystalline entities with diverse dimensionality employing DCC at the confined interface. 相似文献
548.
Sitaram Ramakrishnan Shidaling Matteppanavar Andreas Schönleber Bikash Patra Birender Singh Arumugam Thamizhavel Bahadur Singh Srinivasan Ramakrishnan Sander van Smaalen 《Annalen der Physik》2023,535(6):2200611
Temperature-dependent electronic and magnetic properties are reported for nickel-deficient NiV2Se4. Single-crystal X-ray diffraction shows it to crystallize in the monoclinic Cr3S4 structure type with space group and vacancies on the Ni site, resulting in the composition Ni0.85V2Se4 in agreement with our electron-probe microanalysis. Structural distortions are not observed down to 1.5 K. Nevertheless, the electrical resistivity shows metallic behavior with a broad anomaly around 150–200 K that is also observed in the heat capacity data. This anomaly indicates a change of state of the material below 150 K. It is believed that this anomaly could be due to spin fluctuations or charge-density-wave fluctuations, where the lack of long-range order is caused by vacancies at the Ni site of Ni0.85V2Se4. The non-linear temperature dependence of the resistivity as well as an enhanced value of the Sommerfeld coefficient mJ mol−1 K−2 suggest strong electron–electron correlations in this material. First-principles calculations performed for NiV2Se4, which are also applicable to Ni0.85V2Se4, classify this material as a topological metal with and coexisting electron and hole pockets at the Fermi level. The phonon spectrum lacks any soft phonon mode, consistent with the absence of periodic lattice distortion in the present experiments. 相似文献
549.
Shilpi Jaiswal Arkaprabha Giri Dipendranath Mandal Madhurima Sarkar Abhijit Patra 《Angewandte Chemie (International ed. in English)》2023,62(49):e202312910
Photocatalysts capable of harvesting a broad range of the solar spectrum are essential for sustainable chemical transformations and environmental remediation. Herein, we have integrated NIR-absorbing upconversion nanoparticles (UCNP) with UV-Vis absorbing conjugated porous organic polymer (POP) through the in situ multicomponent C−C coupling to fabricate a UC−POP nanocomposite. The light-harvesting ability of UC−POP is further augmented by loading plasmonic gold nanoparticles (AuNP) into UC−POP. A three-times enhancement in the upconversion luminescence is observed upon the incorporation of AuNP in UC−POP, subsequently boosting the photocatalytic activity of UC−POP−Au. The spectroscopic and photoelectrochemical investigations infer the enhanced photocatalytic oxidation of thioethers, including mustard gas simulant by UC−POP−Au compared to POP and UC−POP due to the facile electron-hole pair generation, suppressed exciton recombination, and efficient charge carrier migration. Thus, the unique design strategy of combining plasmonic and upconversion nanoparticles with a conjugated porous organic polymer opens up new vistas towards artificial light harvesting. 相似文献