全文获取类型
收费全文 | 448篇 |
免费 | 35篇 |
国内免费 | 1篇 |
专业分类
化学 | 475篇 |
物理学 | 9篇 |
出版年
2022年 | 4篇 |
2021年 | 1篇 |
2020年 | 12篇 |
2019年 | 3篇 |
2018年 | 1篇 |
2017年 | 6篇 |
2016年 | 19篇 |
2015年 | 13篇 |
2014年 | 16篇 |
2013年 | 18篇 |
2012年 | 50篇 |
2011年 | 60篇 |
2010年 | 19篇 |
2009年 | 9篇 |
2008年 | 48篇 |
2007年 | 25篇 |
2006年 | 31篇 |
2005年 | 26篇 |
2004年 | 25篇 |
2003年 | 30篇 |
2002年 | 20篇 |
2001年 | 20篇 |
2000年 | 6篇 |
1999年 | 4篇 |
1998年 | 2篇 |
1997年 | 2篇 |
1996年 | 3篇 |
1995年 | 2篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
排序方式: 共有484条查询结果,搜索用时 15 毫秒
411.
412.
413.
S Itoh H Bandoh M Nakagawa S Nagatomo T Kitagawa K D Karlin S Fukuzumi 《Journal of the American Chemical Society》2001,123(45):11168-11178
Bis(mu-oxo)dinickel(III) complexes supported by a series of bis[2-(2-pyridyl)ethyl]amine ligands have been successfully generated by treating the corresponding bis(mu-hydroxo)dinickel(II) complexes or bis(mu-methoxo)dinickel(II) complex with an equimolar amount of H(2)O(2) in acetone at low temperature. The bis(mu-oxo)dinickel(III) complexes exhibit a characteristic UV-vis absorption band at approximately 410 nm and a resonance Raman band at 600-610 cm(-1) that shifted to 570-580 cm(-1) upon (18)O-substitution. Kinetic studies and isotope labeling experiments using (18)O(2) imply the existence of intermediate(s) such as peroxo dinickel(II) in the course of formation of the bis(mu-oxo)dinickel(III) complex. The bis(mu-oxo)dinickel(III) complexes supported by the mononucleating ligands (L1(X) = para-substituted N,N-bis[2-(2-pyridyl)ethyl]-2-phenylethylamine; X = OMe, Me, H, Cl) gradually decompose, leading to benzylic hydroxylation of the ligand side arm (phenethyl group). The kinetics of the ligand hydroxylation process including kinetic deuterium isotope effects (KIE), p-substituent effects (Hammett plot), and activation parameters (Delta H(H)(*) and Delta S(H)(*)) indicate that the bis(muxo)dinickel(III) complex exhibits an ability of hydrogen atom abstraction from the substrate moiety as in the case of the bis(mu-oxo)dicopper(III) complex. Such a reactivity of bis(mu-oxo)dinickel(III) complexes has also been suggested by the observed reactivity toward external substrates such as phenol derivatives and 1,4-cyclohexadiene. The thermal stability of the bis(mu-oxo)dinickel(III) complex is significantly enhanced when the dinucleating ligand with a longer alkyl strap is adopted instead of the mononucleating ligand. In the m-xylyl ligand system, no aromatic ligand hydroxylation occurred, showing a sharp contrast with the reactivity of the (mu-eta(2):eta(2)-peroxo)dicopper(II) complex with the same ligand which induces aromatic ligand hydroxylation via an electrophilic aromatic substitution mechanism. Differences in the structure and reactivity of the active oxygen complexes between the nickel and the copper systems are discussed on the basis of the detailed comparison of these two systems with the same ligand. 相似文献
414.
Self-promoted electron transfer from a cobalt(II) porphyrin [Co(II)OEP] to p-fluoranil (F4Q) occurs, exhibiting a second-order dependence of the electron-transfer rate with respect to the F4Q concentration due to the formation of a strong complex between the dimer radical anion [(F4Q)2*-] and the resulting Co(III)OEP+. 相似文献
415.
The products and kinetics for the reactions of ketone silyl acetals with a series of p-methoxy-substituted trityl cations have been examined, and they are compared with those of outer-sphere electron transfer reactions from 10,10'-dimethyl-9,9', 10, 10'- tetrahydro-9,9'-biacridine [(AcrH)2] to the same series of trityl cations as well as other electron acceptors. The C-C bond formation in the reaction of beta,beta-dimethyl-substituted ketene silyl acetal (1: (Me2C=C(OMe)OSiMe3) with trityl cation salt (Ph3C+ClO4-) takes place between 1 and the carbon of para-positon of phenyl group of Ph3C+, whereas a much less sterically hindered ketene silyl acetal (3: H2C=C(OEt)OSiEt3) reacts with Ph3C+ at the central carbon of Ph3C+. The kinetic comparison indicates that the nucleophilic reactivities of ketene silyl acetals are well correlated with the electron transfer reactivities provided that the steric demand at the reaction center for the C-C bond formation remains constant. 相似文献
416.
Exciplex intermediates in photoinduced electron transfer of porphyrin-fullerene dyads 总被引:1,自引:0,他引:1
Kesti TJ Tkachenko NV Vehmanen V Yamada H Imahori H Fukuzumi S Lemmetyinen H 《Journal of the American Chemical Society》2002,124(27):8067-8077
The photoinduced electron transfer in differently linked zinc porphyrin-fullerene dyads and their free-base porphyrin analogues was studied in polar and nonpolar solvents with femto- to nanosecond absorption and emission spectroscopies. A new intermediate state, different from the locally excited (LE) chromophores and the complete charge-separated (CCS) state, was observed. It was identified as an exciplex. The exciplex preceded the CCS state in polar benzonitrile and the excited singlet state of fullerene in nonpolar toluene. The behavior of the dyads was modeled by using a common kinetic scheme involving equilibria between the exciplex and LE chromophores. The scheme is suitable for all the studied porphyrin-fullerene compounds. The rates of reaction steps depended on the type of linkage between the moieties. The scheme and Marcus theory were applied to calculate electronic couplings for sequential reactions, and consistent results were obtained. 相似文献
417.
Nakanishi I Uto Y Ohkubo K Miyazaki K Yakumaru H Urano S Okuda H Ueda J Ozawa T Fukuhara K Fukuzumi S Nagasawa H Hori H Ikota N 《Organic & biomolecular chemistry》2003,1(9):1452-1454
Hydrogen transfer from artepillin C to cumylperoxyl radical proceeds via one-step hydrogen atom transfer rather than via electron transfer, the rate constant of which is comparable to that of (+)-catechin, indicating that artepillin C can act as an efficient antioxidant. 相似文献
418.
Kato S Yang HJ Ueno T Ozaki S Phillips GN Fukuzumi S Watanabe Y 《Journal of the American Chemical Society》2002,124(29):8506-8507
The H64D/V68A and H64D/V68S mutants of Myoglobin are found to oxidize thioanisole with high enantioselectivity and reactivity. These mutants are also capable of enantioselective binding of alpha-methylbenzylamine, which mimics an expected sulfoxidation intermediate. The kinetic study of the amine binding shows that the Fe-O bond cleavage in the intermediate may be the chiral discrimination step of the sulfoxidation. 相似文献
419.
Imahori H Kimura M Hosomizu K Sato T Ahn TK Kim SK Kim D Nishimura Y Yamazaki I Araki Y Ito O Fukuzumi S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(20):5111-5122
Systematic series of indium tin oxide (ITO) electrodes modified covalently with self-assembled monolayers (SAMs) of ferrocene-porphyrin-fullerene triads and porphyrin-fullerene dyads were designed to gain valuable insight into the development of molecular photovoltaic devices. The structures of SAMs on ITO have been investigated by UV/Vis absorption spectroscopy, atomic force microscopy, and cyclic voltammetry. The photoelectrochemical and photophysical (fluorescence lifetime and time-resolved transient absorption) properties were also determined. The highest quantum yield of photocurrent generation (11 %) among donor-acceptor linked systems which are covalently attached to the surface of ITO electrodes was achieved with SAMs of ferrocene-zinc porphyrin-fullerene linked triad on ITO electrodes. The quantum yields of photocurrent generation correlate well with the charge-separation efficiency and the lifetime of the charge-separated state of the porphyrin-fullerene linked systems in solution. These results provide valuable information for the construction of photonic molecular devices and artificial photosynthetic systems on ITO electrodes. 相似文献
420.
Semiquinone radical anion (Q(*-)) forms a stable pi-dimer with neutral p-benzoquinone (Q), bridged by two or three scandium ions (Sc(3+)) to afford Q(*-)-nSc(3+)-Q (n= 2,3), which is in disproportionation equilibrium with Q and hydroquinone (QH(2)). The number of binding scandium ions changes depending on temperature, causing a remarkable color change associated with the change in the ESR spectra. 相似文献