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61.
Dmytro I. Sierov Illia V. Dzhulai Kateryna I. Siryk Kostiantyn V. Shvydenko Tetiana I. Shvydenko Prof. Dr. Kostiantyn Nazarenko Prof. Dr. Aleksandr Kostyuk Oleksandr S. Liashuk Prof. Dr. Oleksandr O. Grygorenko 《European journal of organic chemistry》2023,26(34):e202300538
A systematic study on the SnAr reaction of halogenated fluoropyridines and (hetero)aliphatic nitrile anions as an approach to the synthesis of functionalized pyridines bearing a (cyclo)alkyl or saturated heterocyclic substituent by is described. The scope of the method was demonstrated on a wide range of (hetero)aliphatic nitriles (including three- to six-membered cycloalkane derivatives and N-, O-, S-containing saturated heterocycles) and all isomeric halogenated 2-and 4-fluoropyridines. High chemo- and regioselectivity (i. e., exclusive substitution of the fluorine atom), as well as excellent scalability of the proposed reaction sequence were demonstrated (up to 450 g for the arylation step or up to 77 g of cycloalkylpyridine over two steps in a single run). The utility of the synthesized products was illustrated in the additional functional group transformations resulting in synthetically valuable pyridine-containing building blocks. 相似文献
62.
Anton Shatskiy Konstantin D. Litasov Igor S. Sharygin Ilya A. Egonin Aleksandr M. Mironov Yuri N. Palyanov 《高压研究》2016,36(1):23-41
In order to constrain the Na2CO3–CaCO3–MgCO3 T–X diagram at 6?GPa in addition to the binary and pseudo-binary systems we conducted experiments along the Na2CO3–Ca0.5Mg0.5CO3 join. At 900–1000°C, melting does not occur and isothermal sections are presented by one-, two- and three-phase regions containing Ca-bearing magnesite, aragonite, Na2CO3 (Na2) and Na2(Ca1–0.9Mg0-0.1)3-4(CO3)4-5 (Na2Ca3-4), Na4(Ca1–0.6Mg0–0.4)(CO3)3 (Na4Ca), Na2(Ca0-0.08Mg1–0.92)(CO3)2 (Na2Mg) phases with intermediate compositions. The minimum melting point locates between 1000°C and 1100°C. This point would resemble that of three eutectics: Mgs–Na2Ca3–Na2Mg, Na2Mg–Na2Ca3–Na4Ca or Na2Mg–Na4Ca–Na2, in the compositional interval of [45Na2CO3·55(Ca0.6Mg0.4)CO3]–[60Na2CO3·40Ca0.6Mg0.4CO3]. The liquidus projection has seven primary solidification phase regions for Mgs, Dol, Arg, Na2Ca3, Na4Ca, Na2 and Na2Mg. The results suggest that extraction of Na and Ca from silicate to carbonate components has to decrease minimum melting temperature of carbonated mantle rocks to 1000–1100°C at 6?GPa and yields Na-rich dolomitic melt with a Na# (Na2O/(Na2O?+?CaO?+?MgO))?≥?28?mol%. 相似文献
63.
Dr. Michael S. Klenov Alexey A. Guskov Dr. Oleg V. Anikin Prof. Dr. Aleksandr M. Churakov Dr. Yurii A. Strelenko Dr. Ivan V. Fedyanin Dr. Konstantin A. Lyssenko Prof. Dr. Vladimir A. Tartakovsky 《Angewandte Chemie (International ed. in English)》2016,55(38):11472-11475
This study presents the first synthesis and characterization of a new high energy compound [1,2,3,4]tetrazino[5,6‐e][1,2,3,4]tetrazine 1,3,6,8‐tetraoxide (TTTO). It was synthesized in ten steps from 2,2‐bis(tert‐butyl‐NNO‐azoxy)acetonitrile. The synthetic strategy was based on the sequential closure of two 1,2,3,4‐tetrazine 1,3‐dioxide rings by the generation of oxodiazonium ions and their intramolecular coupling with tert‐butyl‐NNO‐azoxy groups. The TTTO structure was confirmed by single‐crystal X‐ray. 相似文献
64.
Back Cover: Synthesis of Tetrazino‐tetrazine 1,3,6,8‐Tetraoxide (TTTO) (Angew. Chem. Int. Ed. 38/2016) 下载免费PDF全文
65.
We used UV resonance Raman (UVRR) to examine the spatial dependence of the T-jump secondary structure relaxation of an isotopically labeled 21-residue mainly Ala peptide, AdP. The AdP penultimate Ala residues were perdeuterated, leaving the central residues hydrogenated, to allow separate monitoring of melting of the middle versus the end peptide bonds. For 5 to 30 degrees C T-jumps, the central peptide bonds show a approximately 2-fold slower relaxation time (189 +/- 31 ns) than do the exterior peptide bonds (97 +/- 15 ns). In contrast, for a 20 to 40 degrees C T-jump, the central peptide bond relaxation appears to be faster (56 +/- 6 ns) than that of the penultimate peptide bonds (131 +/- 46 ns). We show that, if the data are modeled as a two-state transition, we find that only exterior peptide bonds show anti-Arrhenius folding behavior; the middle peptide bonds show both normal Arrhenius-like folding and unfolding. This anti-Arrhenius behavior results from the involvement of pi-bulges/helices and 3(10)-helix states in the melting. The unusual temperature dependence of the (un)folding rates of the interior and exterior peptide bonds is due to the different relative (un)folding rates of 3(10)-helices, alpha-helices, and pi-bulges/helices. Pure alpha-helix unfolding rates are approximately 12-fold slower (approximately 1 micros) than that of pi-bulges and 3(10)-helices. In addition, we also find that the alpha-helix is most stable at the AdP N-terminus where eight consecutive Ala occur, whereas the three hydrophilic Arg located in the middle and at the C-terminus destabilize the alpha-helix in these regions and induce defects such as pi-bulges and 3(10)-helices. 相似文献
66.
We consider d-fold branched coverings of the projective plane \(\mathbb {RP}^2\) and show that the hypergeometric tau function of the BKP hierarchy of Kac and van de Leur is the generating function for weighted sums of the related Hurwitz numbers. In particular, we get the \(\mathbb {RP}^2\) analogues of the \(\mathbb {CP}^1\) generating functions proposed by Okounkov and by Goulden and Jackson. Other examples are Hurwitz numbers weighted by the Hall–Littlewood and by the Macdonald polynomials. We also consider integrals of tau functions which generate Hurwitz numbers related to base surfaces with arbitrary Euler characteristics \(\textsc {e}\), in particular projective Hurwitz numbers \(\textsc {e}=1\). 相似文献
67.
Leonid Mochalov Aleksey Nezhdanov Askold Strikovskiy Mikhail Gushin Giuseppe Chidichimo Giovanni De Filpo Aleksandr Mashin 《Optical and Quantum Electronics》2017,49(8):274
AsxTe100?x chalcogenide films (where x = 30–80 at.%) were synthesized via direct interaction of arsenic and tellurium vapors into low-temperature non-equilibrium RF (40 MHz) plasma discharge at reduced pressure. Phase and structural evolution of AsxTe100?x films were implemented by gradual changing of the ratio of the initial substances in the gas phase. The dependence of the films structure, surface morphology and optical properties on phase and chemical content has been studied. 相似文献
68.
69.
We used UV resonance Raman (UVRR) spectroscopy exciting at approximately 200 nm within the peptide bond pi --> pi* transitions to selectively study the amide vibrations of peptide bonds during alpha-helix melting. The dependence of the amide frequencies on their Psi Ramachandran angles and hydrogen bonding enables us, for the first time, to experimentally determine the temperature dependence of the peptide bond Psi Ramachandran angle population distribution of a 21-residue mainly alanine peptide. These Psi distributions allow us to easily discriminate between alpha-helix, 3(10)-helix and pi-helix/bulge conformations, obtain their individual melting curves, and estimate the corresponding Zimm and Bragg parameters. A striking finding is that alpha-helix melting is more cooperative and shows a higher melting temperature than previously erroneously observed. These Psi distributions also enable the experimental determination of the Gibbs free energy landscape along the Psi reaction coordinate, which further allows us to estimate the free energy barriers along the AP melting pathway. These results will serve as a benchmark for the numerous untested theoretical studies of protein and peptide folding. 相似文献
70.
Georgiy B. Shul’pin Aleksandr R. Kudinov Elena A. Petrovskaya 《Journal of organometallic chemistry》2006,691(5):837-845
A carbonyl osmium(0) complex with π-coordinated olefin, (2,3-η-1,4-diphenylbut-2-en-1,4-dione)undecacarbonyl triangulotriosmium (1), efficiently catalyzes oxygenation of alkanes (cyclohexane, cyclooctane, n-heptane, isooctane, etc.) with hydrogen peroxide, as well as with tert-butyl hydroperoxide and meta-chloroperoxybenzoic acid in acetonitrile solution. Alkanes are oxidized to corresponding alcohols, ketones (aldehydes) and alkyl hydroperoxides. Thus, heating cyclooctane with the 1-H2O2 combination at 70 °C gave products with turnover number as high as 2400 after 6 h. The maximum obtained yield of all products was equal to 20% based on cyclohexane and 30% based on H2O2. The oxidation of linear and branched alkanes exhibits very low regio- and bond-selectivity parameters and this testifies that the reaction proceeds via attack of hydroxyl radicals on C-H bonds of the alkane. The oxygenation products were not formed when the reaction was carried out under argon atmosphere and it can be thus concluded that the oxygenation occurs via the reaction between alkyl radicals and atmospheric oxygen. In summary, the Os(0) complex is much more powerful generator of hydroxyl radicals than any soluble derivative of iron (which is an analogue of osmium in the Periodic System). 相似文献