全文获取类型
收费全文 | 341篇 |
免费 | 4篇 |
专业分类
化学 | 205篇 |
晶体学 | 28篇 |
力学 | 7篇 |
数学 | 22篇 |
物理学 | 83篇 |
出版年
2023年 | 2篇 |
2022年 | 3篇 |
2021年 | 6篇 |
2020年 | 1篇 |
2019年 | 3篇 |
2018年 | 2篇 |
2017年 | 2篇 |
2016年 | 8篇 |
2015年 | 2篇 |
2014年 | 11篇 |
2013年 | 14篇 |
2012年 | 32篇 |
2011年 | 31篇 |
2010年 | 23篇 |
2009年 | 19篇 |
2008年 | 24篇 |
2007年 | 23篇 |
2006年 | 19篇 |
2005年 | 10篇 |
2004年 | 11篇 |
2003年 | 8篇 |
2002年 | 5篇 |
2001年 | 7篇 |
2000年 | 7篇 |
1999年 | 6篇 |
1998年 | 6篇 |
1997年 | 2篇 |
1996年 | 7篇 |
1995年 | 2篇 |
1994年 | 2篇 |
1993年 | 3篇 |
1992年 | 3篇 |
1991年 | 1篇 |
1990年 | 2篇 |
1989年 | 6篇 |
1988年 | 6篇 |
1987年 | 3篇 |
1986年 | 3篇 |
1984年 | 3篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 2篇 |
1979年 | 3篇 |
1978年 | 1篇 |
1977年 | 2篇 |
1976年 | 1篇 |
1975年 | 4篇 |
1974年 | 1篇 |
1883年 | 1篇 |
排序方式: 共有345条查询结果,搜索用时 15 毫秒
61.
Matthew L. Milling Jermaine Cooley Dmitriy V. Liskin Edward J. Valente 《Structural chemistry》2009,20(6):969-973
Abstract
Oxidation of 1,4-bis(4′-oxo-2′,2′-dimethylpent-2-yl)benzene with hypochlorite produces 1,4-bis(3′-carboxy-2′-methylbut-2-yl)benzene and 3-(4′-carboxyphenyl)-3,3-dimethylpropanoic acid. Cyclization of this mixture forms 3,3,7,7-tetramethyl-1,2,3,5,6,7-hexahydro-s-indacen-1,5-dione, 3,3,7,7-tetramethyl-1,2,3,5,6,7-hexahydro-as-indacen-1,5-dione (5) and 6-carboxy-3,3-dimethyl-1-indanone (6). Ketoacid (6) is converted to the arylpyran pseudoacid 7-carboxy-3-hydroxy-4,4-dimethylisobenzopyran-1-one (7). In the crystal structure of (7), carboxylic acid and the pseudoacid groups each form complementary dimer hydrogen bonds linking the molecules in chains. Contact O···O distances reflect their differing energetics, with pseudoacyl O···O at 2.78(1)Å and carboxylic O···O at 2.62(1)Å. 相似文献62.
Mark G. Epstein Edward J. Valente Warren J. L. Wood 《Journal of chemical crystallography》2011,41(7):1060-1063
Abstract
Two cycloaddition reactions were conducted with 5-(diphenylamino)-3-phenylimino-3H-1,2,4-dithiazole and the unsymmetrical alkenes, methyl acrylate and acrylonitrile, to produce thiazolidines 6 and 7, respectively. X-ray crystal structures of both compounds were obtained. The crystal of 6 is orthorhombic and space group Pbca with crystallographic parameters: a = 10.7090(14) ?, b = 19.612(4) ?, c = 21.353(3) ?, α = 90°, β = 90°, γ = 90°, V = 4484.7 (14) ?3, Z = 8, Dc = 1.326 Mg/m3, F(000) = 1872. The crystal of 7 is monoclinic and space group P2(1)/c with crystallographic parameters: a = 13.4143(5) ?, b = 16.1088(6) ?, c = 10.1644(6) ?, α = 90°, β = 107.282(5)°, γ = 90°, V = 2097.25(17) ?3, Z = 4, Dc = 1.313 Mg/m3, F(000) = 864. The crystal structures confirmed the thiazolidine structure and the predicted regiochemistry of the cycloaddition based on the electronics of the imino-1,2,4-dithiazole and the alkenes. 相似文献63.
Valente AJ Burrows HD Pereira RF Ribeiro AC Costa Pereira JL Lobo VM 《Langmuir : the ACS journal of surfaces and colloids》2006,22(13):5625-5629
The effect of EuCl3 on the aggregation processes of sodium dodecyl sulfate was investigated. Electrical conductivity data, combined with Eu(III) luminescence measurements, suggest that the formation of micelles involving EuCl3 and SDS occurs at low SDS concentration; the formation of these mixed aggregates was also monitored by light scattering, which indicates that the addition of EuCl3 to SDS concentration at values below the critical micelle concentration of the pure surfactant results in a much higher light scattering than that found just with SDS micelles. It was also found that the Eu(III)/DS- complexes are formed with a binding ratio which varies between 20 and 4, depending on the initial concentration of Eu(III). As the concentration increases, turbidity occurs initially, but solutions become clear subsequently. In contrast to the behavior of SDS in the presence of aluminum(III), no flocculation was observed. From the analysis of electrical conductivity data and comparison with other systems, it is suggested that growth of aggregates happens, probably with formation of nonspherical systems. At the highest concentrations these may involve just Eu(III) and DS- ions. The effect of temperature on the SDS micellization process was studied. The calculated free energy of SDS micellization is not dependent on the initial EuCl3 but is dependent on the final balance between the presence of counterions in solution (ionic strength) and the temperature. 相似文献
64.
Organ MG Avola S Dubovyk I Hadei N Kantchev EA O'Brien CJ Valente C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(18):4749-4755
We have developed the first user-friendly Negishi protocol capable of routinely cross-coupling all combinations of alkyl and aryl centers. The use of an easily synthesized, air stable, highly active, well-defined precatalyst PEPPSI-IPr (1; PEPPSI=pyridine-enhanced precatalyst preparation, stabilization and initiation; IPr=diisopropylphenylimidazolium derivative) substantially increases the scope, reliability, and ease-of-use of the Negishi reaction. All organohalides and routinely used pseudohalides were excellent coupling partners, with the use of chlorides, bromides, iodides, triflates, tosylates, and mesylates resulting in high yield of the coupled product. Furthermore, all reactions were performed by using general laboratory techniques, with no glove-box necessary as the precatalyst was weighed and stored in air. Utilization of this methodology allowed for the easy synthesis of an assortment of sterically encumbered biaryls and druglike heteroaromatics, demonstrating the value of the PEPPSI-IPr system. Furthermore, this is also the first time Pd-NHC (NHC=N-heterocyclic carbene) methodology has surpassed the related phosphine-ligated Negishi processes both in activity and use. 相似文献
65.
O'Brien CJ Kantchev EA Valente C Hadei N Chass GA Lough A Hopkinson AC Organ MG 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(18):4743-4748
The synthesis of NHC-PdCl(2)-3-chloropyridine (NHC=N-heterocyclic carbene) complexes from readily available starting materials in air is described. The 2,6-diisopropylphenyl derivative was found to be highly catalytically active in alkyl-alkyl Suzuki and Negishi cross-coupling reactions. The synthesis, ease-of-use, and activity of this complex are substantial improvements over in situ catalyst generation and all current Pd-NHC complexes. The utilization of complex 4 led to the development of a reliable, easily employed Suzuki-Miyama protocol. Employing various reaction conditions allowed a large array of hindered biaryl and drug-like heteroaromatic compounds to be synthesized without difficulty. 相似文献
66.
Rodolfo G. Figueroa Mauro Valente Jaime Guarda Jorge Leiva Eduardo Quilaguilque Bryan Casanelli Fernando Leyton 《X射线光谱测定》2022,51(3):251-261
A novel and suitable energy-dispersive X-ray fluorescent (EDXRF) device, currently at the prototype stage, the Project OXIRIS (Orthovoltage X-Ray–Induced Radiation System), is presented for the simultaneous detection and treatment of cancer diseases. Monte Carlo simulation and experimental results of EDXRF signals from a small deep artificial tumor consisting of a solution of gold nanoparticles bio-targeted and immersed in a tissue-bioequivalent matrix are presented and compared. Briefly, the device consists of a dynamic orthovoltage X-ray fluence concentration coupled to confocal with an EDXRF system along with a sample holder for 3D scanning; all integrated and controlled by a dedicated software capable of controlling the whole operation functionalities: the X-ray source, the rotating arm, the sample holder, and the detection system. The software also includes dedicated subroutines for X-ray fluorescent spectra processing to correlate K-lines signal at each acquisition position with the corresponding high atomic number elements' concentration to produce a 3D distribution according to the user-defined grid. The confocal configuration ensures that the detected signal comes exclusively from the excited volume as defined by the bulk of the focal spot. Hence, the 3D image is achieved by scanning the sample holder through the movement of the sample-carrier stretcher moved by step motors in the 3 coordinated axes. The feasibility of the proposed methodology and the design of the prototype have been successfully demonstrated experimentally, targeting gold nanoparticles in water-equivalent phantoms. 相似文献
67.
Valente C Calimsiz S Hoi KH Mallik D Sayah M Organ MG 《Angewandte Chemie (International ed. in English)》2012,51(14):3314-3332
Palladium‐catalyzed cross‐coupling reactions enable organic chemists to form C? C bonds in targeted positions and under mild conditions. Although phosphine ligands have been intensively researched, in the search for even better cross‐coupling catalysts attention has recently turned to the use of N‐heterocyclic carbene (NHC) ligands, which form a strong bond to the palladium center. PEPPSI (pyridine‐enhanced precatalyst preparation, stabilization, and initiation) palladium precatalysts with bulky NHC ligands have established themselves as successful alternatives to palladium phosphine complexes. This Review shows the success of these species in Suzuki–Miyaura, Negishi, and Stille–Migita cross‐couplings as well as in amination and sulfination reactions. 相似文献
68.
Pereira RF Valente AJ Fernandes M Burrows HD 《Physical chemistry chemical physics : PCCP》2012,14(20):7517-7527
The interaction of sodium octanoate, decanoate or dodecanoate with calcium(ii) in aqueous solutions has been studied using turbidity, conductivity and potentiometric measurements. These show a marked alkyl chain length dependence on the behaviour. At the calcium concentration used (1.0 mM), there is little interaction with the octanoate, the decanoate shows initially formation of a 1:1 complex, followed by precipitation, while the dodecanoate precipitates at low surfactant concentrations. The solid calcium carboxylates were prepared, and show lamellar, bilayer structures with planes of calcium(II) ions coordinated to carboxylate groups through bidentate chelate linkages. Thermogravimetry and elemental analyses indicate the presence of coordinated water with the calcium decanoate but not with longer chain carboxylates. The results of both the solution and solid state studies suggest that precipitation of long-chain carboxylates depends on a balance between hydration effects and hydrophobic (largely van der Waals') interactions. Electrostatic effects make little energetic contribution but play the important structural role of ordering the carboxylate anions before precipitation. Differences are observed in the interactions between calcium(II) and long chain alkylcarboxylates and alkylsulfates, and are interpreted in terms of stronger binding to the metal of the carboxylate group. A general mechanism is proposed for calcium carboxylate precipitation from aqueous solution based on this and previous studies. 相似文献
69.
Zwergel C Gaascht F Valente S Diederich M Bagrel D Kirsch G 《Natural product communications》2012,7(3):389-394
Aurones [2-benzylidenebenzofuran-3(2H)-ones] are either natural or synthetic compounds, belonging to the flavonoid family. They are isomeric to flavones and provide a bright yellow color to the plants in which they occur. Today, a literature survey indicates that the related flavonoids have been studied not only for their physiological properties and effects on Nature, but also for their therapeutic potential. Aurones are recently attracting the interest of an increasing number of research groups, and, since the last review, some interesting advances have been made in understanding the aurones. In this review, we report the recent advances made on the synthetic routes towards aurones. We also highlight their activity in different biological areas, as well as applied genetic plant modifications to produce these colored compounds. Their synthesis, structure-activity relationships and the importance of the substitution pattern will also be mentioned. Finally, some aspects regarding the possible development of aurones will be discussed briefly. 相似文献
70.
Amarante TR Neves P Tomé C Abrantes M Valente AA Paz FA Pillinger M Gonçalves IS 《Inorganic chemistry》2012,51(6):3666-3676
The reaction of [MoO(2)Cl(2)(di-tBu-bipy)] (1) (di-tBu-bipy = 4,4'-di-tert-butyl-2,2'-bipyridine) with water at 100-120 °C in a Teflon-lined stainless steel autoclave, in an open reflux system, or in a microwave synthesis system gave the octanuclear complex [Mo(8)O(22)(OH)(4)(di-tBu-bipy)(4)] (2) as a microcrystalline powder in good yields. Single crystals of 2 suitable for X-ray diffraction were obtained by the reaction of MoO(3) and di-tBu-bipy in water at 160 °C for 3 days. The molecular structure of 2 comprises a purely inorganic core, Mo(4)O(8)(μ(3)-OH)(2)(μ(2)-O)(2), attached to two peripheral oxo-bridged binuclear units, Mo(2)O(4)(μ(2)-O)(2)(OH)(di-tBu-bipy)(2). The inorganic core is composed of a unique assembly of four {MoO(5)} distorted square pyramids connected to each other via edge-sharing. Overall, the octanuclear complex adopts a highly distorted form strongly resembling an "S"-shaped molecular unit. Complex 2 was applied in the catalytic epoxidation of the biorenewable olefins DL-limonene (Lim) and methyl oleate (Ole), using tert-butylhydroperoxide (TBHP) as an oxygen donor, under mild reaction conditions (55 °C, air). The reactions of Lim and Ole gave the respective epoxide monomers in fairly high selectivities at high conversions (89% 1,2-epoxy-p-menth-8-ene selectivity at 96% Lim conversion; 99% methyl 9,10-epoxystearate selectivity at 94% Ole conversion, reached within 24 h reaction). Iodometric titrations revealed no measurable "non-productive" decomposition of TBHP. 相似文献