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91.
K. Varvell A. M. Cooper-Sarkar M. A. Parker R. A. Sansum M. Aderholz N. Armenise J. P. Baton F. W. Bullock M. Berggren D. Bertrand V. Brisson W. Burkot M. Calcchio E. F. Claytoh T. Coghen O. Erriquez P. J. Fitch G. Gerbier J. Guy P. O. Hulth G. Iaselli G. T. Jones P. Kasper H. Klein C. Kochowski P. Marage M. Mermikides R. P. Middleton D. R. O. Morrison M. M. Mobayyen S. Natali M. Neveu S. Nuzzo S. W. O'Neale P. Petiau A. Petrides F. Ruggieri J. Sacton E. Simopoulou C. Vallee A. Vayaki W. A. Venus H. Wachsmuth J. Wells W. Wittek BEBC WA Collaboration 《Zeitschrift fur Physik C Particles and Fields》1987,36(1):1-13
The isoscalar nucleon structure functionsF 2(x, Q 2) andxF 3(x, Q 2) are measured in the range 0<Q 2<64 GeV2, 1.7<W 2<250 GeV2,x<0.7 using ν and \(\bar v\) interactions on neon in BEBC. The data are used to evaluate possible higher twist contributions and to determine their impact on the evaluation of the QCD parameter Λ. In contrast to previous analyses reaching to such lowW 2 values, it is found that a low \(\Lambda _{\overline {MS} } \) value in the neighbourhood of 100 MeV describes the data adequately and that the contribution of dynamical higher twist effects is small and negative. 相似文献
92.
Dr. Romain Plais Guy Gouarin Amélie Bournier Olfa Zayene Vanessa Mussard Flavien Bourdreux Dr. Jérome Marrot Arnaud Brosseau Dr. Anne Gaucher Dr. Gilles Clavier Dr. Jean-Yves Salpin Prof. Dr. Damien Prim 《Chemphyschem》2023,24(2):e202200524
Modulation and fine-tuning of the strength of weak interactions to bind anions are described in a series of synthetic receptors. The general design of the receptors includes both a urea motif and a tetrazine motif. The synthetic sequence towards three receptors is detailed. Impacts of H-bond strength and linker length between urea and tetrazine on chloride complexation are studied. Binding properties of the chloride anion are examined in both the ground and excited states using a panel of analytical methods (NMR spectroscopy, mass spectrometry, UV/Visible spectroscopies, and fluorescence). A ranking of the receptors by complexation strength has been determined, allowing a better understanding of the structure-properties relationship on these compounds. 相似文献
93.
94.
Dr. David P. Tilly Dr. William Cullen Heng Zhong Romain Jamagne Dr. Inigo Vitórica-Yrezábal Prof. Dr. Simon J. Webb 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(9):e202104293
To investigate how remotely induced changes in ligand folding might affect catalysis by organometallic complexes, dynamic α-amino-iso-butyric acid (Aib) peptide foldamers bearing rhodium(I) N-heterocyclic carbene (NHC) complexes have been synthesized and studied. X-ray crystallography of a foldamer with an N-terminal azide and a C-terminal Rh(NHC)(Cl)(diene) complex showed a racemate with a chiral axis in the Rh(NHC) complex and a distorted 310 helical body. Replacing the azide with either one or two chiral L-α-methylvaline (L-αMeVal) residues gave diastereoisomeric foldamers that each possessed point, helical and axial chirality. NMR spectroscopy revealed an unequal ratio of diastereoisomers for some foldamers, indicating that the chiral conformational preference of the N-terminal residue(s) was relayed down the 1 nm helical body to the axially chiral Rh(NHC) complex. Although the remote chiral residue(s) did not affect the stereoselectivity of hydrosilylation reactions catalysed by these foldamers, these studies suggest a potential pathway towards remote conformational control of organometallic catalysts. 相似文献
95.
Irene Schlnvogt Stefan Pitsch Catherine Lesueur Albert Eschenmoser Bernhard Jaun Romain M. Wolf 《Helvetica chimica acta》1996,79(8):2316-2345
The solution structure of the duplex formed by self-pairing of the p-RNA octamer β-D -ribopyranosyl-(2′→4′)-(CGAATTCG) was studied by NMR techniques and, independently, by molecular-dynamics calculations. The resonances of all non-exchanging protons, H-bearing C-atoms, P-atoms, and of most NH protons were assigned. Dihedral angle and distance constraints derived from coupling constants and NOESY spectra are consistent with a single dominant conformer and corroborate the main structural features predicted by qualitative conformational analysis. The duplex displays Watson-Crick pairing with antiparallel strand orientation. The dihedral angles β and ? in the phosphodiester linkages differ considerably from the idealized values. Model considerations indicate that these deviations from the idealized model allow better interstrand stacking and lessen unfavorable interactions in the backbone. The average base-pair axis forms an angle of ca. 40° with the backbone. The resulting interstrand π-π stacking between either two purines, or a purine and a pyrimidine, but not between two pyrimidines, constitutes a characteristic structural feature of the p-RNA duplex. A 1000-ps molecular-dynamics (MD) calculation with the AMBER force field resulted in an average structure of the same conformation type as derived by NMR. For the backbone torsion angle ?, dynamically averaged coupling constants from the MD calculation agree well with the experimental values, but for the angle β, a systematic difference of ca. 25° remains. The two base pairs at the ends of the duplex are calculated to be highly labile, which is consistent with the high exchange rate of the corresponding imino protons found by NMR. 相似文献
96.
An Philippaerts Richard Ensinck Nicolas Baulu Astrid Cordier Kersten Woike Romain Berthoud Gert De Cremer John R. Severn 《Journal of polymer science. Part A, Polymer chemistry》2017,55(16):2679-2690
A highly systematic size series of Ziegler catalysts with similar porosities and surface textures are synthesized by varying the stirring speed during the MgCl2 support synthesis. Besides the mean particle size, the only substantial difference observed between the various catalysts is the size and number of nodules per particle. Varying the mean diameter of the catalyst particles between 1.5 and 11.9 µm, leads to a pronounced impact on the activity in ultra‐high molecular weight polyethylene (UHMWPE) polymerization, while the Mw capabilities are only affected to a limited extend. In addition, it is observed that both the Mws as the polymer bulk density (BD) increases during the course of the polymerization. This particularity allows to optimize the Mw and/or BD at a set polymer size, by tuning the catalyst particle size. This is particularly interesting in UHMWPE production, as control of the morphological and structural properties of the UHMWPE reactor powders are critical for efficient processing as well as the performance of the final product. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2679–2690 相似文献
97.
According to Car-Parrinello molecular dynamics simulations for [UO(2)(NO(3))(3)](-), [UO(2)(NO(3))(4)](2-), and [UO(2)(OH(2))(4-)(NO(3))](+) complexes in the gas phase and in aqueous solution, the nitrate coordination mode to uranyl depends on the interplay between ligand-metal attractions, interligand repulsions, and solvation. In the trinitrate, the eta(2)-coordination is clearly favored in water and in the gas phase, leading to a coordination number (CN) of 6. According to pointwise thermodynamic integration involving constrained molecular dynamics simulations, a change in free energy of +6 kcal/mol is predicted for eta(2)- to eta(1)-transition of one of the three nitrate ligands in the gas phase. In the gas phase, the mononitrate-hydrate complex also prefers a eta(2)-binding mode but with a CN of 5, one H(2)O molecule being in the second shell. This contrasts with the aqueous solution where the nitrate binds in a eta(1)-fashion and uranyl coordinates to four H2O ligands. A driving force of ca. -3 kcal/mol is predicted for the eta(2)- to eta(1)- transition in water. This structural preference is interpreted in terms of steric arguments and differential solvation of terminal vs uranyl-coordinated O atoms of the nitrate ligands. The [UO(2)(NO(3))(4)](2-) complex with two eta(2)- and two eta(1)- coordinated nitrates, observed in the solid state, is stable for 1-2 ps in the gas phase and in solution. In the studied series, the modulation of uranyl-ligand distances upon immersion of the complex in water is found to depend on the nature of the ligand and the composition of the complex. 相似文献
98.
Using CrCl2 in THF at room temperature, trichloromethyl carbinols and trichloromethylalkanes are readily transformed to the highly reactive α-chlorocarbenes, carbynes and α-chloro-α-chromium(III) vinylidene carbenoids. A mechanistic study is carried out to determine the nature of the intermediates. 相似文献
99.
Romain Barbe 《Tetrahedron》2007,63(10):2199-2207
The design of a new biomimetic foldamer, relying on the weak amine-carbonyl interaction for secondary structure formation, is presented. The efficient synthesis of a triply protected monomer starting from glycidol was developed. This monomer contains a dioxolane-protected keto group that will allow liberation of the ketone functionality in the backbone once construction of the oligomeric backbone is complete. This monomer contains two additional orthogonal protecting groups at its two termini, the Fmoc and the TBDMS groups. The Fmoc group in particular permits oligomerisation towards the N terminus as seen in Fmoc solid phase peptide synthesis. Construction and full characterisation of a ketone-protected dimer, trimer and tetramer are reported. 相似文献
100.
A small library of squamocin analogues has been prepared and screened biologically (cytotoxicity, inhibition of mitochondrial complex I and complex III). To centre diversity on a crucial part of the molecule (i.e., the α,β-unsaturated lactone), an original and reliable lactone opening reaction has been discovered and exploited among other efficient reactions. 相似文献