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41.
《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(2):352-362
Coenzyme B12 initiates radical chemistry in two types of enzymatic reactions, the irreversible eliminases (e.g., diol dehydratases) and the reversible mutases (e.g., methylmalonyl‐CoA mutase). Whereas eliminases that use radical generators other than coenzyme B12 are known, no alternative coenzyme B12 independent mutases have been detected for substrates in which a methyl group is reversibly converted to a methylene radical. We predict that such mutases do not exist. However, coenzyme B12 independent pathways have been detected that circumvent the need for glutamate, β‐lysine or methylmalonyl‐CoA mutases by proceeding via different intermediates. In humans the methylcitrate cycle, which is ostensibly an alternative to the coenzyme B12 dependent methylmalonyl‐CoA pathway for propionate oxidation, is not used because it would interfere with the Krebs cycle and thereby compromise the high‐energy requirement of the nervous system. In the diol dehydratases the 5′‐deoxyadenosyl radical generated by homolysis of the carbon–cobalt bond of coenzyme B12 moves about 10 Å away from the cobalt atom in cob(II )alamin. The substrate and product radicals are generated at a similar distance from cob(II )alamin, which acts solely as spectator of the catalysis. In glutamate and methylmalonyl‐CoA mutases the 5′‐deoxyadenosyl radical remains within 3–4 Å of the cobalt atom, with the substrate and product radicals approximately 3 Å further away. It is suggested that cob(II )alamin acts as a conductor by stabilising both the 5′‐deoxyadenosyl radical and the product‐related methylene radicals. 相似文献
42.
A. A. Tyshchenko O. F. Filatova S. M. Khodzhibaeva K. D. Davranov 《Chemistry of Natural Compounds》2004,40(1):75-78
The ability to bind reversibly molecular oxygen was established for a free-radical product of gossypol oxidation. Conversion of dianhydrogossypol into the stable biradical dioxodianhydrogossypol was viewed as the reason for interruption of the gossypol redox conversion cycle in the extracellular milieu of cotton steles. 相似文献
43.
辣根过氧化物酶对心肌线粒体过氧化损伤的保护作用 总被引:1,自引:0,他引:1
以黄嘌呤氧化酶/次黄嘌呤自由基诱生系统建立了稳定的离体心肌线粒体的损伤模型,并应用此模型研究辣根过氧化物酶对心肌线粒体自由基氧化损伤的保护作用,结果表明,辣根过氧化物酶能抑制心肌线粒体中氧自由基的形成,降低膜脂的过氧水平,保护了线粒体膜酶活性,有效地防止自由基对线粒体结构和功能的损伤。 相似文献
44.
Tretyakov E. V. Romanenko G. V. Shvedenkov Yu. G. Ovcharenko V. I. Sagdeev R. Z. 《Russian Chemical Bulletin》2004,53(6):1301-1304
Esters of 4,5-dihydro-1H-imidazole-1-oxyl-3-oxide-carboximidic acid were synthesized. Their structures and magnetic properties were investigated. 相似文献
45.
O. I. Dyubchenko V. V. Nikulina E. I. Terakh A. E. Prosenko I. A. Grigor’ev 《Russian Chemical Bulletin》2007,56(6):1149-1155
The reaction of ω-(4-hydroxyaryl)haloalkanes with various nitrogen-containing agents afforded primary, secondary, and tertiary
amino derivatives of 2,6-dialkylphenols. For the compounds synthesized, the reaction rate constants with peroxide radicals
were measured for cumene and methyl oleate oxidation. The total inhibitory activity in the model reactions of thermal autooxidation
of lard and hexadecane was studied. The rate constants of alkyl(hydroxylaryl)amines are the same as those of the corresponding
alkylphenols, whereas the total inhibitory activity of some alkyl(hydroxylaryl)amines exceeds substantially that for alkylphenols.
Dedicated to the memory of Academician N. N. Vorozhtsov on the 100th anniversary of his birth.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1107–1112, June, 2007. 相似文献
46.
S. V. Fokin G. V. Romanenko M. Baumgarten V. I. Ovcharenko 《Journal of Structural Chemistry》2003,44(5):864-869
The organomercury biradical HgL2 (L is deprotonated 4,4,5,5-tetramethyl-2-imidazoline-3-oxide-1-oxyl) is capable of performing the bridging function for design of multinuclear heterospin systems. This paper describes synthesis and crystal structure of HgL2 and the first multinuclear complexes of Cu(hfac)2 with HgL2. 相似文献
47.
W. Russell Bowman Anthony J. Fletcher Peter J. Lovell Elena Hernández López Graeme B.S. Potts 《Tetrahedron》2007,63(1):191-203
Amides have been successfully used as precursors of imidoyl radicals for radical cyclisation. The amides have been converted to imidoyl selanides via reaction with phosgene to yield imidoyl chlorides followed by reaction with potassium phenylselanide. Imidoyl selanides were reacted with tributyltin hydride (Bu3SnH) as the radical mediator with triethylborane or AIBN as initiators to yield imidoyl radicals for cyclisation reactions. Imidoyl radicals have been cyclised onto alkenes to yield 2,3-substituted-indoles and -quinolines and also onto pyrroles and indoles to give bi- and tricyclic heteroarenes. 相似文献
48.
Rondeau D Martineau C Blanchard P Roncali J 《Journal of mass spectrometry : JMS》2002,37(10):1081-1085
Oligothienylenevinylenes/C(60) dyads n-C and triads n-C(2) are studied by electrospray mass spectrometry. A clear correlation is observed between the nature of the charged species detected by mass spectrometry, i.e. protonated molecule [M + H], (+) cation radical M(+.) and dication M(++), and the oxidation potentials of the molecules. Moreover, under defined solubility conditions, mass spectrometry provides conclusive evidences for the reversible dimerization of cation-radicals of n-C(2) compounds. 相似文献
49.
Cataldo L Dutan C Misra SK Loss S Grützmacher H Geoffroy M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(11):3463-3468
The EPR spectrum of the novel radical Mes*(CH3)P--PMes* (Mes*=2,4,6-(tBu)3C6H2) was measured in the temperature range 100-300 K, and was found to be drastically temperature dependent as a result of the large anisotropy of the 31P hyperfine tensors. Below 180 K, a spectrum of the liquid solution is accurately simulated by calculating the spectral modifications due to slow tumbling of the radical. To achieve this simulation, an algorithm was developed by extending the well-known nitroxide slow-motion simulation technique for the coupling of one electron spin to two nuclear spins. An additional dynamic process responsible for the observed line broadening was found to occur between 180 K and room temperature; this broadening is consistent with an exchange between two conformations. The differences between the isotropic 31P couplings associated with the two conformers are shown to be probably due to an internal rotation about the P--P bond. 相似文献
50.
R. G. Bulgakov Yu. G. Ponomareva Z. S. Muslimov F. G. Valyamova R. A. Sadykov R. F. Tuktarov 《Russian Chemical Bulletin》2007,56(2):211-219
Fullerenyl radicals (FR) RC60
· and chemiluminescence (CL) are generated in the presence of O2 in C60—R3Al (R = Et, Bui) solutions in toluene (T = 298 K). The FR are formed due to the addition of the R· radical, which is an intermediate of R3Al autooxidation, to C60. Mass spectroscopy and HPLC were used to identify EtnC60Hm (n, m = 1–6), EtpC60 (p = 2–6), and dimer EtC60C60Et as stable products of FR transformations. As found by ESR, the EtC60
· radical (g = 2.0037) is also generated by photolysis of solutions obtained after interaction in the (C60— R3Al)—O2 system. In the presence of dioxygen, the FR is not oxidized but yields complexes with O2, which appear as broadening of the ESR signals. Chemiluminescence arising in the (C60—R3Al)—O2 system is much brighter (I
max = 1.86·108 photon s−1 mL−1) than the known background CL (I
max = 6.0·106 photon s−1 mL−1) for the autooxidation of R3Al and is localized in a longer-wavelength spectral region (λmax = 617 and 664 nm). This CL is generated as a result of energy transfer from the primary emitter 3CH3CHO* to the products of FR transformation: RnC60Hm, RpC60, and EtC60C60Et.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 205–213, February, 2007. 相似文献