全文获取类型
收费全文 | 400篇 |
免费 | 5篇 |
专业分类
化学 | 207篇 |
力学 | 21篇 |
数学 | 39篇 |
物理学 | 138篇 |
出版年
2019年 | 4篇 |
2018年 | 3篇 |
2016年 | 3篇 |
2014年 | 6篇 |
2013年 | 17篇 |
2012年 | 21篇 |
2011年 | 17篇 |
2010年 | 5篇 |
2009年 | 7篇 |
2008年 | 12篇 |
2007年 | 18篇 |
2006年 | 22篇 |
2005年 | 16篇 |
2004年 | 25篇 |
2003年 | 11篇 |
2002年 | 11篇 |
2001年 | 16篇 |
2000年 | 16篇 |
1999年 | 9篇 |
1998年 | 4篇 |
1997年 | 3篇 |
1996年 | 12篇 |
1995年 | 7篇 |
1994年 | 4篇 |
1993年 | 6篇 |
1992年 | 9篇 |
1990年 | 3篇 |
1989年 | 3篇 |
1988年 | 4篇 |
1987年 | 4篇 |
1986年 | 5篇 |
1985年 | 5篇 |
1984年 | 6篇 |
1983年 | 4篇 |
1982年 | 6篇 |
1981年 | 4篇 |
1980年 | 7篇 |
1979年 | 8篇 |
1978年 | 6篇 |
1977年 | 5篇 |
1976年 | 3篇 |
1974年 | 3篇 |
1973年 | 3篇 |
1966年 | 2篇 |
1965年 | 3篇 |
1940年 | 2篇 |
1933年 | 2篇 |
1928年 | 2篇 |
1894年 | 2篇 |
1888年 | 2篇 |
排序方式: 共有405条查询结果,搜索用时 15 毫秒
71.
Concise construction of novel bridged bicyclic lactams by sequenced Ugi/RCM/Heck reactions 总被引:1,自引:0,他引:1
Ribelin TP Judd AS Akritopoulou-Zanze I Henry RF Cross JL Whittern DN Djuric SW 《Organic letters》2007,9(24):5119-5122
Herein we report a concise protocol for the diastereoselective synthesis of novel bridged bicyclic lactams from commercially available components by the sequence of Ugi, ring-closing metathesis (RCM), and Heck reactions. X-ray diffraction studies revealed that the bicyclic products contain varying degrees of pyramidalization of the bridgehead nitrogen atom. 相似文献
72.
Schuster DI Li K Guldi DM Palkar A Echegoyen L Stanisky C Cross RJ Niemi M Tkachenko NV Lemmetyinen H 《Journal of the American Chemical Society》2007,129(51):15973-15982
A new group of porphyrin-fullerene dyads with an azobenzene linker was synthesized, and the photochemical and photophysical properties of these materials were investigated using steady-state and time-resolved spectroscopic methods. The electrochemical properties of these compounds were also studied in detail. The synthesis involved oxidative heterocoupling of free base tris-aryl-p-aminophenyl porphyrins with a p-aminophenylacetal, followed by deprotection to give the aldehyde, and finally Prato 1,3-dipolar azomethineylide cycloaddition to C60. The corresponding Zn(II)-porphyrin (ZnP) dyads were made by treating the free base dyads with zinc acetate. The final dyads were characterized by their 1H NMR, mass, and UV-vis spectra. 3He NMR was used to determine if the products are a mixture of cis and trans stereoisomers, or a single isomer. The data are most consistent with the isolation of only a single configurational isomer, assigned to the trans (E) configuration. The ground-state UV-vis spectra are virtually a superimposition of the spectral features of the individual components, indicating there is no interaction of the fullerene (F) and porphyrin (H2P/ZnP) moieties in the ground state. This conclusion is supported by the electrochemical data. The steady-state and time-resolved fluorescence spectra indicate that the porphyrin fluorescence in the dyads is very strongly quenched at room temperature in the three solvents studied: toluene, tetrahydrofuran (THF), and benzonitrile (BzCN). The fluorescence lifetimes of the dyads in all solvents are sharply reduced compared to those of H2P and ZnP standards. In toluene, the lifetimes of the free base dyads are 600-790 ps compared to 10.1 ns for the standard, while in THF and BzCN the dyad lifetimes are less than 100 ps. For the ZnP dyads, the fluorescence lifetimes were 10-170 ps vs 2.1-2.2 ns for the ZnP references. The mechanism of the fluorescence quenching was established using time-resolved transient absorption spectroscopy. In toluene, the quenching process is singlet-singlet energy transfer (k approximately 10(11) s-1) to give C60 singlet excited states which decay with a lifetime of 1.2 ns to give very long-lived C60 triplet states. In THF and BzCN, quenching of porphyrin singlet states occurs at a similar rate, but now by electron transfer, to give charge-separated radical pair (CSRP) states, which show transient absorption spectra very similar to those reported for other H2P-C60 and ZnP-C60 dyad systems. The lifetimes of the CSRP states are in the range 145-435 ns in THF, much shorter than for related systems with amide, alkyne, silyl, and hydrogen-bonded linkers. Thus, both forward and back electron transfer is facilitated by the azobenzene linker. Nonetheless, the charge recombination is 3-4 orders of magnitude slower than charge separation, demonstrating that for these types of donor-acceptor systems back electron transfer is occurring in the Marcus inverted region. 相似文献
73.
Glass fillers were suface modified by direct formation of a silicon-carbon non-hydrolyzable linkage between glass and coupling agent. The grafted silane monolayer was evaluated by infrared spectroscopy. Samples were subjected to hydrolytic conditions to compare their surface treatment stability with traditional surface treatment hydrolytic stability. Composite specimens were fabricated and their mechanical properties were compared with traditional aminopropylsilane coupling agent treatment. 相似文献
74.
Qian C Fu R Gor'kov P Brey WW Cross TA Gan Z 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2009,196(1):96-99
Polarization Inversion Spin Exchange at Magic Angle (PISEMA) is a powerful experiment for determining peptide orientation in uniformly aligned samples such as planar membranes. In this paper, we present (14)N-PISEMA experiment which correlates (14)N quadrupolar coupling and (14)N-(1)H dipolar coupling. (14)N-PISEMA enables the use of (14)N quadrupolar coupling tensor as an ultra sensitive probe for peptide orientation and can be carried out without the need of isotope enrichment. The experiment is based on selective spin-exchange between a proton and a single-quantum transition of (14)N spins. The spin-exchange dynamics is described and the experiment is demonstrated with a natural abundant N-acetyl valine crystal sample. 相似文献
75.
76.
Y Miao H Qin R Fu M Sharma TV Can I Hung S Luca PL Gor'kov WW Brey TA Cross 《Angewandte Chemie (International ed. in English)》2012,51(33):8383-8386
Validation: Membrane protein structures are sensitive to the environment used for structural characterization. NMR spectra of the full-length M2 proton channel from influenza?A were measured directly in E.?coli membranes and compared to spectra of the protein in synthetic lipid bilayers. The results demonstrate that these bilayers provide a native-like membrane environment. 相似文献
77.
The redox-active ligand N-(2-hydroxy-5-methylbenzyl)-N,N',N'-tris(2-pyridinylmethyl)-1,2-ethanediamine (Hptp1) was prepared and complexed to manganese(II). The isolated [Mn(Hptp1)(MeCN)](2+) serves as a magnetic resonance imaging contrast agent, with an r(1) value comparable to those of other mononuclear gadolinium(III) and manganese(II) complexes. The metal and ligand are stable in aerated aqueous solutions, but the addition of H(2)O(2) causes the complex to oxidatively couple to itself through a bimolecular reaction involving the phenol groups of two Hptp1 ligands. The binuclear product is less paramagnetic per manganese(II) than its mononuclear precursor, lowering the measured r(1) per manganese(II). The manganese(II) complex with Hptp1 can thereby serve as a sensor for oxidative stress. 相似文献
78.
Polinski MJ Wang S Cross JN Alekseev EV Depmeier W Albrecht-Schmitt TE 《Inorganic chemistry》2012,51(14):7859-7866
Reactions of LnBr(3) or LnOI with molten boric acid result in formation of Ln[B(5)O(8)(OH)(H(2)O)(2)Br] (Ln = La-Pr), Nd(4)[B(18)O(25)(OH)(13)Br(3)], or Ln[B(5)O(8)(OH)(H(2)O)(2)I] (Ln = La-Nd). Reaction of PuOI with molten boric acid yields Pu[B(7)O(11)(OH)(H(2)O)(2)I]. The Ln(III) and Pu(III) centers in these compounds are found as nine-coordinate hula-hoop or 10-coordinate capped triangular cupola geometries where there are six approximately coplanar oxygen donors provided by triangular holes in the polyborate sheets. The borate sheets are connected into three-dimensional networks by additional BO(3) triangles and/or BO(4) tetrahedra that are roughly perpendicular to the layers. The room-temperature absorption spectrum of single crystals of Pu[B(7)O(11)(OH)(H(2)O)(2)I] shows characteristic f-f transitions for Pu(III) that are essentially indistinguishable from Pu(III) in other compounds with alternative ligands and different coordination environments. 相似文献
79.
C. F. Cross E. J. Bevan und C. Beadle 《Fresenius' Journal of Analytical Chemistry》1894,33(1):751-753
Ohne Zusammenfassung 相似文献
80.