全文获取类型
收费全文 | 194篇 |
免费 | 1篇 |
专业分类
化学 | 164篇 |
力学 | 2篇 |
数学 | 3篇 |
物理学 | 26篇 |
出版年
2023年 | 1篇 |
2021年 | 2篇 |
2020年 | 2篇 |
2017年 | 1篇 |
2014年 | 1篇 |
2013年 | 2篇 |
2012年 | 9篇 |
2011年 | 17篇 |
2010年 | 3篇 |
2009年 | 3篇 |
2008年 | 14篇 |
2007年 | 4篇 |
2006年 | 9篇 |
2005年 | 10篇 |
2004年 | 10篇 |
2003年 | 10篇 |
2002年 | 8篇 |
2001年 | 10篇 |
2000年 | 10篇 |
1999年 | 4篇 |
1997年 | 1篇 |
1996年 | 7篇 |
1995年 | 2篇 |
1994年 | 3篇 |
1993年 | 7篇 |
1992年 | 10篇 |
1991年 | 4篇 |
1990年 | 3篇 |
1989年 | 4篇 |
1988年 | 4篇 |
1987年 | 1篇 |
1986年 | 3篇 |
1985年 | 1篇 |
1984年 | 3篇 |
1980年 | 3篇 |
1977年 | 2篇 |
1976年 | 1篇 |
1970年 | 5篇 |
1966年 | 1篇 |
排序方式: 共有195条查询结果,搜索用时 31 毫秒
1.
Butyltins were analyzed in waters from California river and lake marinas and were detected at the part per trillion (ppt) level in most locations. The tributyltin:dibutyltin (TBT/DBT) ratios in the fresh waters were similar to those in their saline counterparts indicating like rates of degradation in the two salinity regimes. 相似文献
2.
3.
Brel VK Belsky VK Stash AI Zavodnik VE Stang PJ 《Organic & biomolecular chemistry》2003,1(23):4220-4226
Reaction of 1-chloro-4-(diethoxyphosphonyl)alka-2,3-dienes 14,15 with purine and pyrimidine heterocyclic bases in the presence of cesium carbonate afforded new acyclic analogues of nucleotides containing a 1,2-alkadienic skeleton 18-23. Dealkylation of 18-23 furnished phosphonic acids 2a-f. In contrast, alkylation reaction with 1-chloro-4-(diethoxyphosphonyl)octa-2,3-diene 16 led to Z- and E-1,3-alkadienic phosphonates 25a,b and 26a,b. A similar reaction with 1-chloro-4-(diethoxyphosphonyl)-2-methylbuta-2,3-diene 17 led to the elimination of hydrochloride and formation of 4-(diethylphosphonyl)-2-methylbut-1-en-3-yne 24. Molecular structures of new acyclic nucleotides 18 and 2f are determined by X-ray crystallographic analysis. 相似文献
4.
Peter J. Stang 《Angewandte Chemie (International ed. in English)》1992,31(3):274-285
Compounds with highly coordinated, polyvalent main-group elements represent an interesting alternative to the many well-known transition-metal complexes. Among the oldest and best known stable examples of such organic molecules are the iodine(III) compounds. Diaryliodonium species, Ar2IX, for example, have been known for over a hundred years and play an important role in lithography. Likewise, acetylenes and olefins are among the oldest, most important, and most valuable compounds in chemistry. Besides simple hydrocarbon alkenes and alkynes, numerous functionalized derivatives are also known and widely employed in organic chemistry. Despite the ubiquity and prominance of both IIII species and olefins and acetylenes, the combination of these two types of functional groups in a single molecular unit, namely compounds with polyvalent iodine and at least one alkyne or olefin residue, was unknown until recently. The successful preparations of simple alkynyl- and alkenyl-(phenyl)iodonium species during the 1980s has resulted in a renaissance in both acetylene and IIII chemistry. These alkynyliodonium compounds readily undergo nucleophilic substitution on the alkyne moiety (SN-A reactions) which are difficult with other substrates. The application of a wide variety of nucleophiles in this reaction resulted in diverse functionalized alkynes including previously unknown acetylenic carboxylates, sulfonates, and phosphates. These are excellent substrates for cycloaddition reactions as well as numerous other interesting chemical transformations. 相似文献
5.
The intramolecular and long-range ferromagnetic coupling between p-phenylenediamine radical cations in head-to-tail coupled oligo(1, 4-phenyleneethynylene)s and oligo(1,4-phenylenvinylene)s between neighbors and next-nearest neighbors is described. UV/vis/near-IR experiments show that the radical cations are localized in the pendant p-phenylenediamine units of the conjugated oligomers. The ESR spectra of these oligo(1,4-phenyleneethynylene) and oligo(1, 4-phenylenvinylene) di(radical cation)s are consistent with those of a triplet state. A linear behavior is observed for the doubly integrated ESR intensity of the DeltaM(s) = +/-1 and DeltaM(s) = +/-2 signals with the inverse temperature (I approximately 1/T), consistent with Curie's law. This behavior indicates a triplet ground-state diradical with a large triplet-singlet energy gap or possibly a degeneracy of singlet and triplet states. 相似文献
6.
calculations were carried out for three exocyclic alkylidene carbenes. Cyclopentadienylvinyl carbene is predicted to be highly electrophilic while the cyclopropenylidenevinyl carbene may provide the first example of a nucleophilic alkylidene carbene. 相似文献
7.
8.
9.
10.
Chatterjee B Noveron JC Resendiz MJ Liu J Yamamoto T Parker D Cinke M Nguyen CV Arif AM Stang PJ 《Journal of the American Chemical Society》2004,126(34):10645-10656
The syntheses, structures, and N2 adsorption properties of six new supramolecular metallacycles are reported. Flexible ditopic linkers, 1-4, with systematically varied lengths and conformational degrees of freedom were synthesized utilizing ester linkages. They were used in combination with (dppp)M(OTf)2, where M = Pt(II) and Pd(II), and cis-(Me3P)2Pt(OTf)2 to form flexible supramolecular metallacycles 5-10 in 88-98% isolated yields. Their structures were characterized via multinuclear NMR and X-ray crystallography. The metallacycles stack to form porous structures in the crystalline state. The pore dimensions depend on both the phosphorus ligands attached to the metals and the flexible linkers. Adsorption studies on the porous materials show that 5a, 6, 8, and 9 held 11.7, 16.5, 5.7, and 6.8 cm3/g STP of N2 at 77 K, respectively. A guest-exchange study with nitromethane and toluene reveals that the nanopore in 5 is flexible, a property which was transferred from the linker to the supramolecular structure in the solid state. 相似文献