全文获取类型
收费全文 | 595篇 |
免费 | 9篇 |
国内免费 | 4篇 |
专业分类
化学 | 331篇 |
晶体学 | 26篇 |
力学 | 12篇 |
数学 | 84篇 |
物理学 | 155篇 |
出版年
2022年 | 5篇 |
2021年 | 11篇 |
2020年 | 5篇 |
2019年 | 10篇 |
2018年 | 9篇 |
2017年 | 4篇 |
2016年 | 7篇 |
2015年 | 9篇 |
2014年 | 16篇 |
2013年 | 23篇 |
2012年 | 32篇 |
2011年 | 38篇 |
2010年 | 11篇 |
2009年 | 21篇 |
2008年 | 23篇 |
2007年 | 35篇 |
2006年 | 49篇 |
2005年 | 28篇 |
2004年 | 11篇 |
2003年 | 18篇 |
2002年 | 22篇 |
2001年 | 12篇 |
2000年 | 18篇 |
1999年 | 9篇 |
1998年 | 4篇 |
1997年 | 4篇 |
1996年 | 10篇 |
1995年 | 8篇 |
1994年 | 7篇 |
1992年 | 6篇 |
1989年 | 3篇 |
1987年 | 3篇 |
1986年 | 3篇 |
1985年 | 6篇 |
1984年 | 5篇 |
1983年 | 7篇 |
1982年 | 6篇 |
1981年 | 8篇 |
1980年 | 11篇 |
1979年 | 8篇 |
1978年 | 5篇 |
1977年 | 5篇 |
1975年 | 7篇 |
1974年 | 3篇 |
1971年 | 3篇 |
1960年 | 3篇 |
1947年 | 6篇 |
1946年 | 5篇 |
1944年 | 4篇 |
1943年 | 7篇 |
排序方式: 共有608条查询结果,搜索用时 15 毫秒
131.
Kirubakaran Ramachandran Sharma Pratibha Manisekaran Ahilan Bijwe Jayashree Nebhani Leena 《Journal of Thermal Analysis and Calorimetry》2020,142(3):1233-1242
Journal of Thermal Analysis and Calorimetry - The present work demonstrates the synthesis of new bio-based benzoxazine monomers via Mannich-like condensation of naturally occurring raw materials,... 相似文献
132.
Kanmani S. S. Rajamanickam N. Ramachandran K. 《Journal of Solid State Electrochemistry》2020,24(10):2499-2509
Journal of Solid State Electrochemistry - In the present work, Eosin yellowish (EY) dye–sensitized and CdS-sensitized TiO2 photoanodes prepared by doctor blade technique, for dye (DSSC)- and... 相似文献
133.
A. K. Balasubramanian N. Sankar S. K. Ramakrishnan K. Ramachandran 《Crystal Research and Technology》2004,39(6):558-563
Molecular dynamics simulation using the new fit of the empirical Tersoff Potential is applied to study the thermal properties of ZnSe at and below the room temperature. The resulting diffusivity and thermal conductivity are compared with the photoacoustic measurements on the grown ZnSe crystal. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
134.
L‐valine (C5H11NO2), an essential amino acid of monoclinic space group P21, Z = 4 and lattice parameters a = 9.688 (2) Å, b = 5.267 (1) Å, c = 11.980 (2) Å and β = 90.75 (1)° and of size: 6.0 mm across and 0.5 mm thick was crystallized in silica gel under suitable pH conditions by reduction of solubility method. Density measurement and single crystal X‐ray diffraction were used to characterize the grown crystals. Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and scanning electron microscopic (SEM) studies were made and crystal packing also discussed. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
135.
The strength of the Lewis or Br?nsted acids controls the formation of either beta,gamma-disubstituted-alpha-methylene-gamma-butyrolactones or gamma-substituted-alpha-alkylidene-gamma-butyrolactones via the lactonization or oxonia cope rearrangement-lactonization, respectively, of the borate intermediates resulting from the crotylboration of aliphatic aldehydes with ester-containing crotylboronates, such as (E)-methyl 2-boramethyl-2-butenoates. 相似文献
136.
D. Ramachandran L. Rü schendorf 《Proceedings of the American Mathematical Society》1996,124(7):2223-2228
Given probability spaces let denote the set of all probabilities on the product space with marginals and and let be a measurable function on Continuous versions of linear programming stemming from the works of Monge (1781) and Kantorovich-Rubin\v{s}tein (1958) for the case of compact metric spaces are concerned with the validity of the duality
(where is the collection of all probability measures on with and as the marginals). A recently established general duality theorem asserts the validity of the above duality whenever at least one of the marginals is a perfect probability space. We pursue the converse direction to examine the interplay between the notions of duality and perfectness and obtain a new characterization of perfect probability spaces.
137.
Benial AM Ichikawa K Murugesan R Yamada K Utsumi H 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2006,182(2):273-282
DNP parameters relevant to Overhauser-enhanced magnetic resonance imaging (OMRI) are reported for a few nitroxyl radicals and their corresponding (15)N and (2)H enriched analogues, used in simultaneous imaging by OMRI. DNP enhancement was measured at 14.529 mT, using a custom-built scanner operating in a field-cycled mode, for different concentrations, ESR irradiation times and RF power levels. DNP enhancements increased with agent concentration up to 2.5 mM and decreased above 3 mM, in tune with ESR line broadening measured at X-band as a function of the agent concentration. The proton spin-lattice relaxation times (T(1)) measured at very low Zeeman field (14.529 mT) and the longitudinal relaxivity parameters were estimated. The relaxivity parameters were in good agreement with those independently computed from the linear region of the concentration dependent enhancement. The leakage factor showed an asymptotic increase with increasing agent concentration. The coupling parameters of (14)N- and (15)N-labeled carbamoyl-PROXYL showed the interaction between the electron and nuclear spins to be mainly dipolar in origin. Upon (2)H labeling, about 70% and 40% increases in enhancement for (15)N- and (14)N-labeled nitroxyl agents were observed, respectively. It is envisaged that the results reported here may enable better understanding of the factors determining DNP enhancement to design suitable 'beacons' for simultaneous molecular imaging by OMRI. 相似文献
138.
Chandrasekhar V Krishnan V Azhakar R Senapati T Dey A Suriya Narayanan R 《Inorganic chemistry》2011,50(6):2568-2579
Carbophosphazene-based coordination ligands [{NC(NMe(2))}(2){NP(3,5-Me(2)Pz)(2)}] (1), [{NC(NEt)(2)}{NC(3,5-Me(2)Pz)}{NP(3,5-Me(2)Pz)(2)}] (2), [NC(3,5-Me(2)Pz)](2)[NP(3,5-Me(2)Pz)(2)] (3), [{NCCl}(2){NP(NC(NMe(2))(2))(2)}] (4), and [{NC(p-OC(5)H(4)N)}(2){NP(NC(NMe(2))(2))(2)}] (5) were synthesized and structurally characterized. In these compounds, the six-membered C(2)N(3)P ring is perfectly planar. The reaction of 1 with CuCl(2) afforded [{NC(NMe(2))}(2){NHP(O)(3,5-Me(2)Pz)}·{Cu(3,5-Me(2)PzH)(2)(Cl)}][Cl] (6). The ligand binds to Cu(II) utilizing the geminal [P(O)(3,5-Me(2)Pz)] coordinating unit. Similarly, the reaction of 2 with PdCl(2) afforded, after a metal-assisted P-N hydrolysis, [{NC(NEt)(2)}{NC(3,5-Me(2)Pz)}{NP(O)(3,5-Me(2)Pz)}·{Pd(3,5-Me(2)PzH)(Cl)}] (7). In the latter, the [P(O)(3,5-Me(2)Pz)] unit does not coordinate; in this instance, the Pd(II) is bound by a ring nitrogen atom and a carbon-tethered pyrazolyl nitrogen atom. The reaction of 3 with PdCl(2) also results in P-N bond hydrolysis affording [{NC(3,5-Me(2)Pz)(2)}{NP(O)(3,5-Me(2)Pz)}{Pd(Cl)}] (8). In contrast to 7, however, in 8, the Pd(II) elicits a nongeminal η(3) coordination from the ligand involving two carbon-tethered pyrazolyl groups and a ring nitrogen atom. Metalated products could not be isolated in the reaction of 3 with K(2)PtCl(4). Instead, a P-O-P bridged carbodiphosphazane dimer, [{NC(3,5-Me(2)Pz)NHC(3,5-Me(2)Pz)}{NP(O)}](2) (9), was isolated as the major product. Finally, the reaction of 5 with PdCl(2) resulted in [{NC(OC(5)H(4)N)}(2){NP(NC(NMe(2))(2))(2)}·{PdCl(2)}] (10). In the latter, the exocyclic P-N bonds are quite robust and are involved in binding to the metal ion. Compounds 6-10 have been characterized by a variety of techniques including X-ray crystallography. In all of the compounds, the bond parameters of the inorganic heterocyclic rings are affected by metalation. 相似文献
139.
Pasumansky L Collins CJ Pratt LM Nguyên NV Ramachandran B Singaram B 《The Journal of organic chemistry》2007,72(3):971-976
The influence of temperature and solvent effects on the reduction and amination mechanisms of iodomethane by lithium N,N-diisopropylaminoborohydride (iPr-LAB) was examined in varying concentrations of THF and dioxane. The reactions of benzyl chloride and trimethylsilyl chloride with iPr-LAB in THF were also studied. The amination of iodomethane is favored over reduction at low and room temperatures in pure THF and with increasing the amount of dioxane in THF. At higher temperatures, the reduction reaction appears to compete with the amination. In dioxane solvent, however, iodomethane yields exclusively the amination product regardless of temperature. On the other hand, reduction by iPr-LAB to the aminoborane is the only product observed in THF when benzyl chloride and trimethylsilyl chloride are used. To understand the solvent effects on the product distribution, ab initio and density functional theory (DFT) calculations were used to examine the mechanisms of reduction and amination of chloromethane and bromomethane by lithium dimethylaminoborohydride (LAB) in THF and dioxane. The results of these calculations show that the relative reaction barrier heights are significantly affected by the nature of the coordinated solvent molecule and thus lend support to the experimental observations. 相似文献
140.
Ramachandran PV Rudd MT Burghardt TE Ram Reddy MV 《The Journal of organic chemistry》2003,68(24):9310-9316
A modified hydroalumination protocol for the preparation of [alpha-(ethoxycarbonyl)vinyl]diisobutylaluminum and its beta-methyl or -phenyl analogues was developed. These vinylaluminum reagents react with aldehydes and ketones to provide the corresponding functionalized allyl alcohols in good to excellent yields. Perfluoroalkyl and -aryl carbonyl compounds, alpha-keto esters, alpha-acyl cyanides, and alpha-acetylenic ketones provide the corresponding alpha-hydroxyalkenes in high yields. The allyl alcohol product ratios from the vinylalumination of unsymmetrical alpha-diketones with [alpha-(ethoxycarbonyl)vinyl]diisobutylaluminum and its beta-methyl or -phenyl analogues depend on the steric and electronic environments of the ketones as well as the reagents. The products from the vinylalumination of alpha-bromoaldehydes and -ketones were cyclized with K2CO3 or KF under nonaqueous conditions to provide functionalized vinylepoxides in high yields. Vinylaluminations of keto-protected pyruvaldehyde provided the products, which were converted to alpha-alkylidene-beta-hydroxy-gamma-lactones. 相似文献