全文获取类型
收费全文 | 308篇 |
免费 | 3篇 |
国内免费 | 2篇 |
专业分类
化学 | 189篇 |
晶体学 | 6篇 |
力学 | 9篇 |
数学 | 1篇 |
物理学 | 108篇 |
出版年
2018年 | 1篇 |
2014年 | 2篇 |
2013年 | 5篇 |
2012年 | 17篇 |
2011年 | 24篇 |
2010年 | 5篇 |
2009年 | 1篇 |
2008年 | 22篇 |
2007年 | 29篇 |
2006年 | 32篇 |
2005年 | 27篇 |
2004年 | 18篇 |
2003年 | 16篇 |
2002年 | 12篇 |
2001年 | 6篇 |
2000年 | 9篇 |
1999年 | 5篇 |
1998年 | 5篇 |
1997年 | 4篇 |
1996年 | 11篇 |
1995年 | 7篇 |
1994年 | 6篇 |
1993年 | 9篇 |
1992年 | 11篇 |
1990年 | 2篇 |
1988年 | 1篇 |
1987年 | 2篇 |
1986年 | 1篇 |
1985年 | 3篇 |
1984年 | 4篇 |
1983年 | 3篇 |
1982年 | 2篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1977年 | 1篇 |
1975年 | 1篇 |
1972年 | 2篇 |
1971年 | 1篇 |
1967年 | 2篇 |
1966年 | 1篇 |
排序方式: 共有313条查询结果,搜索用时 15 毫秒
191.
Preston AJ Fraenkel G Chow A Gallucci JC Parquette JR 《The Journal of organic chemistry》2003,68(1):22-26
The synthesis and conformational properties of 2,6-bis-[2-((4S)-4-methyl-4,5-dihydro-1,3-oxazol-2-yl)phenyl]carbam oylpyridines, 2, have been described. Bisoxazoline 2a was prepared in five steps from 2-nitrobenzoyl chloride in an overall yield of 71%. In contrast to related structures such as 1, bisoxazoline 2a exhibits a highly biased P-type helical conformation in solution and in the solid state. In the crystal lattice, 2a further assembles into a left-handed helical superstructure aligned along the crystallographic c axis. The barrier to helical interconversion, as measured by line-shape analysis of the temperature-dependent (1)H NMR spectra of thiobenzyl derivative 2b, was determined to be quite low ((Delta)G(++) = 12.3 kcal/mol), indicating the presence of a highly dynamic helical chirality. 相似文献
192.
Using a microscopic theory based on the Maxwell-semiconductor Bloch equations, we investigate the feasibility of an optically pumped electrically driven terahertz (THz) quantum-cascade laser as a pathway to room-temperature THz generation. In optical conversion schemes the power conversion efficiency is limited by the Manley-Rowe relation. We circumvent this constraint by incorporating an electrical bias in a four level intersubband scheme, thereby allowing coherent recovery of the optical pump energy. The observed THz radiation is generated through both stimulated emission and automatically phase-matched quantum coherence contributions--making the proposed approach both a promising source for THz radiation and a model system for quantum coherence effects such as lasing without inversion and electromagnetically induced transparency. 相似文献
193.
Model for efficient simulation of spatially incoherent light using the Wiener chaos expansion method
We demonstrate a new and efficient technique for modeling and simulation of spatially incoherent sources using the Wiener chaos expansion method. By implementing this new model, we show that a practical-size photonic structure with a spatially incoherent input source can be analyzed more than 2 orders of magnitude faster compared with the conventional models without sacrificing the accuracy. 相似文献
194.
Three new luminescent cyclometalated Pt(II) complexes, [Pt(L)Cl] (1), [Pt2(L-)2] (2), and [Pt(L)(PPh3)]ClO4 (3.ClO4) (where HL=2-phenyl-6-(1H-pyrazol-3-yl)-pyridine), were synthesized and characterized by X-ray crystallography. HL represents a new class of C,N,Npyrazolyl cyclometalating ligands containing a Cphenyl, a Npyridyl, and a Npyrazolyl donor moiety, as well as a 1-pyrazolyl-NH, that can also be available for metal coordination and other chemical interactions. Complex 1 possesses intense intraligand transitions at 275-375 nm and moderately intense metal-to-ligand charge transfer (1MLCT) (dpi(Pt)-->pi*(L)) transition at 380-410 nm. The room temperature solid-state emission lambdamax of 1 occurs at 580 nm and is attributable to the 3MMLCT (dsigma*(Pt)-->pi*(L)) transition. It also displays strong phosphorescence in acetonitrile solutions at room temperature with an emission lambdamax at 514 nm, which can be tentatively assigned to the 3MLCT (pi*(L)-->dpi(Pt)) transition. Complex 1 can be deprotonated in organic solvents to yield a cycloplatinated dimer 2, which shows a relatively high room-temperature luminescent quantum yield of 0.59 in DMF (lambdamax=509 nm). Substitution of the ancillary chloro-ligand in 1 by triphenylphosphine yields 3, which also possesses a good room-temperature luminescent quantum yield of 0.52 in DMF (lambdamax=504 nm) and a better solubility in water. Complex 3 is synthesized to demonstrate the pH dependence of luminescent properties of this C,N,Npyrazolyl cyclometalated Pt(II) system. Such a pH response is ascribable to the protonation/deprotonation of the 1-pyrazolyl-NH on the C,N,Npyrazolyl cyclometalating ligand. The pKa of the 1-pyrazolyl-NH in 3, measured in 1:2 (v/v) aqueous DMF solutions, is approximately 4.0. 相似文献
195.
We describe a technique to synthesize DNA homopolymers on a surface using surface-initiated enzymatic polymerization (SIEP) with terminal deoxynucleotidyl transferase (TdTase), an enzyme that repetitively adds mononucleotides to the 3'-end of oligonucleotides. The thickness of the synthesized DNA layer was found to depend on the deoxymononucleotide monomer, in the order of dATP > dTTP > dGTP approximately dCTP. In addition, the composition and the surface density of oligonucleotide initiators were also important in controlling the extent of DNA polymerization. The extension of single-stranded DNA chains by SIEP was further verified by their binding to antibodies specific to oligonucleotides. TdTase-mediated SIEP can also be used to grow spatially defined three-dimensional DNA structures by soft lithography and is a new tool for bioinspired fabrication at the micro- and nanoscale. 相似文献
196.
197.
198.
Ho YM Koo CK Wong KL Kong HK Chan CT Kwok WM Chow CF Lam MH Wong WY 《Dalton transactions (Cambridge, England : 2003)》2012,41(6):1792-1800
Two new C,N,N-type ligands (HL(2) and HL(3)), containing a C(phenyl), a N(pyridyl), and a N(imidazolyl) donor, and their cycloplatinated complexes, [Pt(L(2))Cl] (1), [Pt(L(3))Cl] (2), [Pt(L(2))(PPh(3))](+) (3) and [Pt(L(3))(PPh(3))](+) (4), have been successfully synthesized and characterized. Spectroscopic and (3)MLCT luminescent properties of these Pt(II) cyclometalated complexes were found to be pH dependent. This was attributed to the protonation/deprotonation of the acidic 1-imidazolyl-NH moieties on the ligands. All the cycloplatinated complexes (both protonated and deprotonated forms) possessed two-photon excitability with two-photon absorption cross-sections ranging from 6.0 to 30.0 GM (protonated forms) and from 16.2 to 24.9 GM (deprotonated forms). 相似文献
199.
Nine dendronized poly(amide-triazole)s 2-Gm Gn (m=1-3, n=1-3), were prepared by the 1:1 copolymerization between AA-type dendritic diazides 4-Gm (m=1-3) and BB-type dendritic diacetylenes 5-Gn (n=1-3) under the copper(I)-mediated click coupling conditions. The degree of polymerization value of the polymers was found to range from 15-50, and decreased with increasing size of the dendron, suggesting steric hindrance had a retardation role on the copolymerization efficiency. Based on FT-IR and (1)H NMR studies, it was found that significantly strong, interchain hydrogen bonding between the amide units was present in the solution state after copolymerization, whereas the monomers 4-Gm and 5-Gn were devoid of any intermolecular hydrogen-bonding interaction. Hence a positive allosteric hydrogen-bonding effect was observed after polymerization, and could be rationalized by the zip effect. The strength of the interchain association in polymers 2-Gm Gn was found to decrease with increasing size of the dendron (i.e., 2-G1 G1>2-G1 G2>2-G2 G1≈2-G2 G2>2-G1 G3≈2-G3 G1>2-G2 G3≈2-G3 G2>2-G3 G3). Among the nine polymers, only 2-G1 G2 and 2-G2 G1 were good organogelators for aromatic solvents, while the 2-G2 G2 polymer, bearing the closest structural resemblance to the previously reported organogelator 1-G2 prepared from the polymerization of AB-type monomers, was devoid of gelating power. Careful analysis of structures of the present polymer series 2-Gm Gn and the previously reported series 1-Gn suggested that the polymer backbone symmetry played a subtle role in controlling their self-assembling and gelating properties. 相似文献
200.