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71.
E. J. Ansaldo J. Boyle Ch. Niedermayer G. D. Morris J. H. Brewer C. E. Stronach R. S. Cary 《Zeitschrift für Physik B Condensed Matter》1992,86(3):317-318
Three distinct electronic states were detected for positive muons (+) after implantation into a C60 powder sample. About 40% of the + remained in the bare (diamagnetic) state, essentially an interstitial charged point particle. The rest of the muons were found to thermalize predominantly in two muonium (Mu=+ e–) atomic species. A vacuum Mu state, with hyperfine coupling close to that of free Mu, most likely at the molecular center, and a muonic substituted radical, i.e. a hydrogen-like Mu addition to double bonds on the carbon rings. This opens up a rich subfield of fullerene spectroscopy using muons. 相似文献
72.
We present a study of finite-size effects in a model exhibiting a first-order temperature-driven symmetry-breaking structural phase transition in theL
× cylindrical geometry in theL
limit. Exact studies demonstrate the applicability of our scaling ansatz even in the one-dimensional limit, making this model ideal for studying finite-size effects. The scaling ansatz, similar to the previously developed ansatz for field-driven transitions, demonstrates that latent heat is crucial in driving these transitions. This ansatz is supported by a 2×2 phenomenological transfer matrix based upon the symmetries of the system; this produces an analytic free energy which has the scaling form. Order parameter probability distributions show that the high- and low-temperature phases coexist only in a small finite-size-affected regime near the bulk transition temperature; this regime vanishes exponentially fast asL
diverges. 相似文献
73.
Ronald Grigg Anne HodgsonJames Morris Visuvanathar Sridharan 《Tetrahedron letters》2003,44(5):1023-1026
A novel sequential palladium/ruthenium-catalysed four component process is described involving carbonylation of an aryl/heteroaryl iodide followed by allenylation to generate (π-allyl) palladium species which are intercepted by nitrogen nucleophiles to afford 1,6-dienes. Subsequent Ring-Closing Metathesis (RCM) affords C-acyl-N-heterocycles in good yield. These heterocycles proved to be active dipolarophiles in sequential and cascade 1,3-dipolar cycloaddition reactions (1,3-DC) as exemplified by reactions with nitrones and azomethine ylides. 相似文献
74.
Joy Md. Tuhinur R. Uddin Md. Miaz Bhoumik Nikhil C. Ghosh Shishir Kabir Shariff E. 《Transition Metal Chemistry》2021,46(2):149-157
Reactions of unsaturated [HOs3(CO)8{µ3-Ph2PCH(R)P(Ph)C6H4}] (R?=?H, Me) with Bu3SnH are examined. [HOs3(CO)8{µ3-Ph2PCH(R)P(Ph)C6H4}] reacts with Bu3SnH at room temperature to afford [H2Os3(CO)8(SnBu3){µ3-Ph2PCH(R)P(Ph)C6H4}] (1) via oxidative addition of the Sn?H bond to the parent cluster. Heating 1 in refluxing toluene leads to the formation of [H2Os3(CO)7(SnBu3){µ3-Ph2PCH(R)P(Ph)C6H4}] (2) through decarbonylation. Cluster 2 exists in two isomeric forms in solution which has been probed by VT NMR spectroscopy. The new Os-Sn bimetallic clusters have been characterized by a combination of analytical and spectroscopic data together with single-crystal X-ray diffraction analysis.
Graphic abstract 相似文献75.
William J. Patterson Donald E. Morris 《Journal of polymer science. Part A, Polymer chemistry》1972,10(1):169-178
The synthesis and polymerization of several silphenylene siloxane polymer precursors containing a perfluoroalkylsegment in the backbone was carried out. The molecular weight characteristics of polymers from 1,3-bis[p(-hydroxydimethylsilyl)phenyl]hexafluoropropane and 1,3-bis[p(-dimethylaminodimethylsilyl)phenyl]hexafluoropropane were studied as a function of polymerization conditions. Polymers containing the dodecafluorohexane chain segment were also prepared. Polymers having inherent viscosities of 0.55 to 0.9 were obtained. The polymers crosslinked at room temperature to thermoset elastomers which were characterized by improved thermal and oxidative stability over dimethylsilicones. Room temperature swelling of the experimental polymers hydrocarbon solvents was also much lower than that of dimethylsilicones. The polymers containing the (CF2)3 and (CF2)6 linkages had glass transition points of ?12°C and ?34°C, respectively. 相似文献
76.
Phosphorescence has been simultaneously observed from both a 3π, π* and a 3n,π* level of 5-methylbicyclo-[4.3.01,5non-1-en-3-one. The emission from the higher energy 3n,π* state, which is in thermal equilibrium with the 3π,π* state, is quenched by lowering the temperature and also quenched by increasing the solvent polarity so as to raise the energy of the 3n,π* state relative to the 3π,π* state. 相似文献
77.
V. L. Spate M. M. Mason C. L. Reams C. K. Baskett J. S. Morris D. S. Mills 《Journal of Radioanalytical and Nuclear Chemistry》1994,179(2):315-322
In this study we report on the comparison between the total selenium in serum (total Se) with that which is apparently bound to high molecular weight (>12,000 D) species, presumably proteins (bound Se). Nine hundred seventy seven (977) serum samples arising out of a population-based epidemiological study were prepared in duplicate for the determination of total Se by pipeting directly into irradiation vials; and separate duplicate aliquots were dialyzed against DI water for the determination of bound Se. All samples were analyzed by neutron activation analysis via77mSe (17.4 s). A small dialyzable Se component (6%) (free Se), defined as the difference between the total Se minus the bound Se, was identified. 相似文献
78.
Thermolysis of a 2'-[(16)O]-O-benzoyl-[(17)O]-5'-O-(tert-butyldimethylsilyl)-O(2),3'-cyclouridine derivative gave the more stable 3'-[(17)O]-O-benzoyl-[(16)O]- 5'-O-(tert-butyldimethylsilyl)-O(2),2'-cyclouridine isomer, which was converted into 3'-[(17)O]-2'-azido-2'-deoxyuridine by deprotection and nucleophilic ring opening at C2' with lithium azide. The 5'-diphosphate was prepared by nucleophilic displacement of the 5'-O-tosyl group with tris(tetrabutylammonium) hydrogen pyrophosphate. Model reactions gave (16)O and (18)O isotopomers, and base-promoted hydrolysis of an O(2),2'-cyclonucleoside gave stereodefined access to 3'-[(18)O]-1-(beta-D-arabinofuranosyl)uracil. Inactivation of ribonucleoside diphosphate reductase with 2'-azido-2'-deoxynucleotides results in appearance of EPR signals for a nitrogen-centered radical derived from azide, and 3'-[(17)O]-2'-azido-2'-deoxyuridine 5'-diphosphate provides an isotopomer to perturb EPR spectra in a predictable manner. 相似文献
79.
[structure: see text] Alpha-phosphonozirconacyclopentenes or alpha-borylzirconacyclopentenes react by bromination, iodination, allylation, and propargylation to generate unique vinyl boronates and vinyl phosphonates not obtainable by other methods. The reaction proceeds in two steps, with both high regio- and stereoselectivity. With the vinyl boronates, the Zr-Csp2 bond is initially cleaved by 1 equiv of electrophile. With the phosphonates, either the Zr-Csp2 bond (allyl bromide, Br(2)) or the Zr-Csp3 bond (I(2), propargyl bromide) may be initially cleaved. The addition of a second equivalent of an electrophile results in disubstitution. 相似文献
80.
Da Re RE Kuehl CJ Brown MG Rocha RC Bauer ED John KD Morris DE Shreve AP Sarrao JL 《Inorganic chemistry》2003,42(18):5551-5559
The novel charge-transfer ground state found in alpha,alpha'-diimine adducts of ytterbocene (C(5)Me(5))(2)Yb(L) [L = 2,2'-bipyridine (bpy) and 1,10-phenanthroline (phen)] in which an electron is spontaneously transferred from the f(14) metal center into the lowest unoccupied (pi*) molecular orbital (LUMO) of the diimine ligand to give an f(13)-L(*)(-) ground-state electronic configuration has been characterized by cyclic voltammetry, UV-vis-near-IR electronic absorption, and resonance Raman spectroscopies. The voltammetric data demonstrate that the diimine ligand LUMO is stabilized and the metal f orbital is destabilized by approximately 1.0 V each upon complexation for both bpy and phen adducts. The separation between the ligand-based oxidation wave (L(0/-)) and the metal-based reduction wave (Yb(3+/2+)) in the ytterbocene adducts is 0.79 V for both bpy and phen complexes. The UV-vis-near-IR absorption spectroscopic data for both the neutral adducts and the one-electron-oxidized complexes are consistent with those reported recently, but previously unreported bands in the near-IR have been recorded and assigned to ligand (pi*)-to-metal (f orbital) charge-transfer (LMCT) transitions. These optical electronic excited states are the converse of the ground-state charge-transfer process (e.g., f(13)-L(*-) <--> f(14)-L(0)). These new bands occur at approximately 5000 cm(-1) in both adducts, consistent with predictions from electrochemical data, and the spacings of the resolved vibronic bands in these transitions are consistent with the removal of an electron from the ligand pi* orbital. The unusually large intensity observed in the f --> f intraconfiguration transitions for the neutral phenanthroline adduct is discussed in terms of an intensity-borrowing mechanism involving the low-energy LMCT states. Raman vibrational data clearly reveal resonance enhancement for excitation into the low-lying pi* --> pi* ligand-localized excited states, and comparison of the vibrational energies with those reported for alkali-metal-reduced diimine ligands confirms that the ligands in the adducts are reduced radical anions. Differences in the resonance enhancement pattern for the modes in the bipyridine adduct with excitation into different pi* --> pi* levels illustrate the different nodal structures that exist in the various low-lying pi* orbitals. 相似文献