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141.
Randolph K. Belter 《Journal of fluorine chemistry》2011,132(11):961-964
At temperatures around 400 °C, nitrogen trifluoride (NF3) readily reacts with alkanes and benzene as well as ethers. In all cases, products were N,N-difluoroamines. This is in contrast to difluoroamination of benzylic substrates where the initial N,N-difluoroamines underwent eliminations or rearrangements and were not isolated. Cyclic and acyclic alkanes generated N,N-difluoroaminoalkanes. Benzene substituted on the ring to form N,N-difluoroaniline. Ethers reacted to generate α-N,N-difluoroamino ethers. Little direct fluorination was observed. 相似文献
142.
Mihaela RomanBruno Andrioletti Marc Lemaire Jean-Marie BernardJohannes Schwartz Philippe Barbeau 《Tetrahedron》2011,67(7):1506-1510
Using HMDS as catalyst for the trimerization of isocyanates presents many advantages as the expected isocyanurate is not contaminated by the catalyst or other side-products resulting from its degradation. In addition, HMDS presents a low toxicity, and is compatible with industrial applications. This article describes the hexamethyldisilazane (HMDS)-catalyzed trimerization of octylisocyanate. Experimental investigations and mechanistic considerations indicate that the true catalyst of the trimerization is trimethylsilyloctylamine, which results from the preliminary condensation of HMDS with octylisocyanate. 相似文献
143.
Jack Halpern 《Angewandte Chemie (International ed. in English)》1985,24(4):274-282
Stable organometallic compounds, notably of the later transition metals (groups VI–VIII), usually are characterized by closed shell electron configurations (typically 18-electron valence shells) which are destabilized by electron addition or removal. One-electron oxidation of such compounds results in the formation of unstable radical ions, whose characteristic reactivity patterns include susceptibility to nucleophilic attack, disproportionation, and metal-carbon bond dissociation. Two-electron oxidation may result in dissociation or oxidation of the organic ligand. In this review studies on the chemical and electrochemical oxidations of metal carbonyls, metal-olefin complexes, and alkyl transition-metal compounds are described. The studies encompass the following themes: (1) The kinetics and thermodynamics of the initial redox steps; (2) The characterization and reactivity patterns of the resulting oxidation products; (3) The synthetic and catalytic applications of organometallic redox processes. 相似文献
144.
Ooms KJ Feindel KW Willans MJ Wasylishen RE Hanna JV Pike KJ Smith ME 《Solid state nuclear magnetic resonance》2005,28(2-4):125-134
Results from a solid-state 139La NMR spectroscopic investigation of the anhydrous lanthanum(III) halides (LaX3; X=F, Cl, Br, I) at applied magnetic fields of 7.0, 9.4, 11.7, 14.1, and 17.6 T are presented and highlight the advantages of working at high applied magnetic field strengths. The 139La quadrupolar coupling constants are found to range from 15.55 to 24.0 MHz for LaCl3 and LaI3, respectively. The lanthanum isotropic chemical shifts exhibit an inverse halogen dependence with values ranging from −135 ppm for LaF3 to 700 ppm for LaI3, which represents nearly half of the total lanthanum chemical shift range. The spans of the magnetic shielding tensors also vary widely, from 35 to 650 ppm for the solid LaF3 through LaI3. DFT calculations of the 139La electric field gradient and magnetic shielding tensors have been performed and provide a qualitative interpretation of the trends observed experimentally. 相似文献
145.
146.
147.
Arun Kumar Gupta 《Tetrahedron letters》2004,45(21):4113-4116
1-(2-Iodophenyl)-1H-tetrazole 2 was synthesized by the reaction of 2-iodoaniline, sodium azide and triethyl orthoformate in acetic acid. The newly synthesized ligand 2 was successfully used in Heck reaction to give the cross-coupled products in excellent yields. 相似文献
148.
Issa?YavariEmail author Hoorieh?Djahaniani Farough?Nasiri 《Monatshefte für Chemie / Chemical Monthly》2004,135(5):543-548
Summary. The 1:1 reactive intermediate generated by the addition of alkyl isocyanides to dialkyl acetylenedicarboxylates was trapped by fairly strong NH-acids such as carbazole, indole, or pyrrole to yield highly functionalized 1-azadienes and ketenimines. 相似文献
149.
150.
F
A1:Ag+ color center at the low coordination (100) and (110) surface sites of KCl and KBr thin films play an important role in providing
tunable laser oscillation and adsorbatesubstrate interactions. Double-well potentials at this site are investigated using
ab initio molecular electronic structure calculations. The calculated Stokes shifted (optical transition bands), opticaloptical
conversion efficiencies, the probability of orientational destruction, exciton (energy) transfer and Glasner-Tompkins empirical
rule suggest that laser light generation is sensitive to (i) the lattice anion, (ii) the coordination number of surface ions,
and (iii) the choice of the basis set centered on the anion vacancy. The adsorbate-substrate interactions were found to be
dependent on the electronegativity of the adatom and on the lattice anion. Optimised geometries and the coadsorption of CO
and (F, Cl, Br, I) on KCl and KBr (100) crystals are presented. Calculated chemisorption energies for CO on the (halogen atom/defect
free sites of KCl and KBr (100) crystals) showed that the coadsorption of halogen atom tends to block other adsorbate-substrate
interactions at the nearest neighbour sites. Thus if halogen atom coverage increases, the CO prefers to be adsorbed on the
K+ site of the KCl and KBr (100) surfaces and on KBr relative to KCl.
相似文献