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131.
Recent synthesis of sp-hybridized cyclo[18]carbon allotrope has attracted immense curiosity. Since then, a generous amount of theoretical studies concerning aromaticity, adsorption, and spectra of the molecule have been performed. However, very few stuides have been carried out concerning its reactivities and catalytic behaviour. In this article, a DFT-based inquisition has been reported regarding the reactivity of Si substituted cyclo[18]carbon molecule towards molecular N2. Results show that the Si substituted derivative is effective in producing adducts with molecular nitrogen. Charge calculations and IRC trapping methods indicate that only the Si center of C17Si and its (HOMO-1) level participate in N2 addition. The N-adduct so formed, is then found to spontaneously react with molecular H2. The addition of two H2 molecules to the activated nitrogen molecule to give respective amine derivatives have also been studied. The successful generation of the precursor of NH3 by C17Si lays a clear emphasis on its potentiality. 相似文献
132.
Herein, we report a detailed periodic DFT investigation of Mn(II)-based [(Mn4Cl)3(BTT)8]3− (BTT3−=1,3,5-benzenetristetrazolate) metal-organic framework (MOF) to explore various hydrogen binding pockets, nature of MOF…H2 interactions, magnetic coupling and, H2 uptake capacity. Earlier experiments found an uptake capacity of 6.9 wt % of H2, with the heat of adsorption estimated to be ∼10 kJ/mol, which is one among the highest for any MOFs reported. Our calculations unveil different binding sites with computed binding energy varying from −6 to −15 kJ/mol. The binding of H2 at the Mn2+ site is found to be the strongest (site I), with H2 found to bind Mn2+ ion in a η2 fashion with a distance of 2.27 Å and binding energy of −15.4 kJ/mol. The bonding analysis performed using NBO and AIM reveal a strong donation of σ (H2) to the dz2 orbital of the Mn2+ ion responsible for such large binding energy. The other binding pockets, such as −Cl (site II) and BTT ligands (site III and IV) were found to be weaker, with the binding energy decreasing in the order I>II>III>IV. The average binding energy computed for these four sites put together is 9.6 kJ/mol, which is in excellent agreement with the experimental value of ∼10 kJ/mol. We have expanded our calculations to compute binding energy for multiple sites simultaneously, and in this model, the binding energy per site was found to decrease as we increased the number of H2 molecules suggesting electronic and steric factors controlling the overall uptake capacity. The calculated adsorption isotherm using the GCMC method reproduces the experimental observations. Further, the magnetic coupling computed for the unbound MOF reveals moderate ferromagnetic and strong antiferromagnetic coupling within the tetrameric {Mn4} unit leading to a three-up-one-down spin configuration as the ground state. These were then coupled ferromagnetically to other tetrameric units in the MOF network. The magnetic coupling was found to alter only marginally upon gas binding, suggesting that both exchange interaction and the spin-states are unlikely to play a role in the H2 uptake. This is contrary to the O2 uptake studied lately, where strong dependence on exchange-coupling/spin state was witnessed, suggesting exchange-coupling/magnetic field dependent binding as a viable route for gas separation. 相似文献
133.
Sucheta Mondal Subhasree Pal Subhankar Khanra Santana Chakraborty Dr. Nanda D. Paul 《欧洲无机化学杂志》2023,26(29):e202300263
Herein we report a cobalt-catalyzed sustainable approach for C−N cross-coupling reaction between amines and alcohols. Using a well-defined Co-catalyst 1 a bearing 2-(phenyldiazenyl)-1,10-phenanthroline ligand, various N-alkylated amines were synthesized in good yields. 1 a efficiently alkylates diamines producing N, N′-dialkylated amines in good yields and showed excellent chemoselectivity when oleyl alcohol and β-citronellol, containing internal carbon-carbon double bond were used as alkylating agents. 1 a is equally compatible with synthesizing N-heterocycles via dehydrogenative coupling of amines and alcohols. 1H-Indole was synthesized via an intramolecular dehydrogenative N-alkylation reaction, and various substituted quinolines were synthesized by coupling of 2-aminobenzyl alcohol and secondary alcohols. A few control reactions and spectroscopic experiments were conducted to illuminate the plausible reaction mechanism, indicating that the 1 a -catalyzed N-alkylation proceeds through the borrowing hydrogen pathway. The coordinated arylazo ligand participates actively throughout the reaction; the hydrogen eliminated during dehydrogenation of alcohols was set aside in the ligand backbone and subsequently gets transferred in the reductive amination step to imine intermediates yielding N-alkylated amines. On the other hand, 1 a -catalyzed quinoline synthesis proceeds through dehydrogenation followed by successive C−C and C−N coupling steps forming H2O2 as a by-product under air. 相似文献
134.
Dr. Manju P. Maman Dr. Tamilselvi Gurusamy Dr. Arun K. Pal Dr. Rajkumar Jana Dr. Kothandaraman Ramanujam Dr. Ayan Datta Dr. Sukhendu Mandal 《Angewandte Chemie (International ed. in English)》2023,62(27):e202305462
The fixing of N2 to NH3 is challenging due to the inertness of the N≡N bond. Commercially, ammonia production depends on the energy-consuming Haber-Bosch (H−B) process, which emits CO2 while using fossil fuels as the sources of hydrogen and energy. An alternative method for NH3 production is the electrochemical nitrogen reduction reaction (NRR) process as it is powered by renewable energy sources. Here, we report a tiara-like nickel-thiolate cluster, [Ni6(PET)12] (where, PET=2-phenylethanethiol)] as an efficient electro-catalyst for the electrochemical NRR at ambient conditions. Ammonia (NH3: 16.2±0.8 μg h−1 cm−2) was the only nitrogenous product over the potential of −2.3 V vs. Fc+/Fc with a Faradaic efficiency of 25%±1.7. Based on theoretical calculations, NRR by [Ni6(PET)12] proceeds through both the distal and alternating pathways with an onset potential of −1.84 V vs. RHE (i.e., −2.46 V vs. Fc+/Fc) which corroborates with the experimental findings. 相似文献
135.
Palá-Paúl J Pérez-Alonso MJ Velasco-Negueruela A Sanz J 《Journal of chromatography. A》2002,947(2):327-331
The essential oil of Ageratina adenophora Spreng., growing in the Canary Islands was analyzed by GC-MS. A total of 78 volatile compounds was identified and p-cymene (11.6%) was the major component in the oil. The sesquiterpene fraction (44.3%) was higher than the monoterpene one (32.1%). 相似文献
136.
Summary The energy spectrum of sea level muons in the range (102÷104) GeV has been calculated from the latest directly measured JACEE primary spectrum using Fermilab results on pp→π± X and pp→K± X inclusive reactions. The conventional pion atmospheric diffusion equation after Bugaevet al. has been used in this analysis to account the flux of muons emerged from the multiple generation of mesons in air. The derived
muon spectrum has been compared with the earlier magnetic spectrograph data of Durham and Kiel groups. The latest BAKSAN scintillator
telescope data is well in agreement with the calculated integral spectrum originated from the meson decays in the range (1÷104) GeV. 相似文献
137.
Warm plasma theory is used to investigate the propagation of electromagnetic waves in a plasma filled parallel plate waveguide with one boundary plate corrugated. Dispersion relations for TE- and TM-modes are derived and it is found that the propagation of TE-modes is unaffected by corrugation of one boundary plane while the propagation of TM-modes is affected by it. For TM-modes the wave numberk depends on the frequency ta as well as on the distance through which the wave is propagated.The authors take the opportunity to thank Professor M. L. Ghosh, Department of Mathematics, North Bengal University for suggesting the problem and one of the authors (S. K. Ghosh) wishes to express his thanks to the University of North Bengal for financial support. 相似文献
138.
A simple method for the amperometric estimation of N-cyclohexyl-2-benzothiazole sulphenamide, N-dicyclohexyl-2-benzothiazole sulphenamide, 2-(morpholinothio)benzothiazole and N-tert.-butyl-2-benzothiazole sulphenamide is reported. The results are obtained within 5 min and are correct within +/- 2.0%. 相似文献
139.
140.
W.E. Cleland A. Delfosse P.-A. Dorsaz J.-L. Gloor M.N. Kienzle-Focacci G. Mancarella A.D. Martin M. Martin P. Muhlemann C. Nef T. Pal J. Rutschmann H. Zeidler 《Nuclear Physics B》1982,208(2):228-261
The mass and momentum transfer spectra of the charged system produced in the reaction π±p→Ks0K±p are analyzed. The data have been collected at the CERN SPS with the Geneva-Lausanne two-arm, non-magnetic spectrometer at 30 and 50 GeV/c incident momenta. The general features of the reactions at these energies and the results of partial-wave analyses of the two kaon system are presented.The channel is dominated by the diffractive production of even spin resonances. The spin 4 recurrence of the A2(1320) is clearly observed at 2040 MeV (Γ=380 MeV. A new resonance is observed with a mass M=2450MeV and a width Γ=400 MeV; the quantum numbers of this state are found to be IG(JPC)=1?(6++). The analysis also shows the decay of the decay of the meson ?′(1600) through the channel at both energies.The production amplitudes are determined both as a function of the effective mass and of the momentum transfer. Isoscalar natural parity exchange is dominant. The energy dependence between 10 and 50 GeV/c is shown to be well described by a Regge pole model based on the f-dominated pomeron hypothesis. We compare the production mechanisms of the 2+ resonances A2(1320) and K1(1430). Finally, we estimate the branching ratios of the spin 4 A2(2040) and spin 6 A2(2450) resonances. 相似文献