全文获取类型
收费全文 | 189篇 |
免费 | 10篇 |
专业分类
化学 | 169篇 |
晶体学 | 3篇 |
数学 | 2篇 |
物理学 | 25篇 |
出版年
2023年 | 1篇 |
2022年 | 5篇 |
2021年 | 6篇 |
2020年 | 3篇 |
2019年 | 5篇 |
2018年 | 1篇 |
2016年 | 4篇 |
2015年 | 4篇 |
2014年 | 7篇 |
2013年 | 8篇 |
2012年 | 21篇 |
2011年 | 8篇 |
2010年 | 5篇 |
2009年 | 4篇 |
2008年 | 16篇 |
2007年 | 17篇 |
2006年 | 10篇 |
2005年 | 13篇 |
2004年 | 13篇 |
2003年 | 13篇 |
2002年 | 6篇 |
2001年 | 3篇 |
2000年 | 3篇 |
1998年 | 2篇 |
1997年 | 2篇 |
1996年 | 4篇 |
1995年 | 2篇 |
1994年 | 1篇 |
1993年 | 1篇 |
1991年 | 2篇 |
1989年 | 1篇 |
1986年 | 1篇 |
1982年 | 1篇 |
1981年 | 2篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1977年 | 1篇 |
排序方式: 共有199条查询结果,搜索用时 0 毫秒
1.
Guldi DM Hirsch A Scheloske M Dietel E Troisi A Zerbetto F Prato M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(20):4968-4979
Control over the interchromophore separation, their angular relationship, and the spatial overlap of their electronic clouds in several ZnP-C(60) dyads (ZnP=zinc porphyrin) is used to modulate the rates of intramolecular electron transfer. For the first time, a detailed analysis of the charge transfer absorption and emission spectra, time-dependent spectroscopic measurements, and molecular dynamics simulations prove quantitatively that the same two moieties can produce widely different electron-transfer regimes. This investigation also shows that the combination of ZnP and C(60) consistently produces charge recombination in the inverted Marcus region, with reorganization energies that are remarkably low, regardless of the solvent polarity. The time constants of electron transfer range from the mus to the ps regime, the electronic couplings from a few tens to several hundreds of cm(-1), and the reorganization energies remain below 0.54 eV and can be as low as 0.16 eV. 相似文献
2.
Gian Paolo Chiusoli Mirco Costa Luciano Pallini Giuliana Terenghi 《Transition Metal Chemistry》1982,7(6):304-306
Summary In presence of nickel or palladium catalysts, nucleophiles can attack vinylcyclopropanes with concomitant ring cleavage. With palladium catalysts in presence of appropriate substituents the terminal carbon atom of the resulting open chain is able to add to two molecules of a conjugated diene giving rise to long-chain unsaturated compounds. 相似文献
3.
Free-energy-perturbation theory from molecular dynamics calculations has been used to obtain the DeltaG of adjoining cavities' formation in water. The DeltaGs for systems with three, five and seven cavities are compared with that of a single cavity of the same volume, and found to be in good agreement. The conditions under which the analytical formulation of the energy of cavity formation proposed by Pierotti holds are discussed. The data for a single cavity have been tabulated and can lend themselves to a simple numerical implementation in standard quantum chemical packages, which can be used when high accuracy for DeltaG(cav) is required. 相似文献
4.
Mendoza SM Whelan CM Jalkanen JP Zerbetto F Gatti FG Kay ER Leigh DA Lubomska M Rudolf P 《The Journal of chemical physics》2005,123(24):244708
Thin films of fumaramide [2]rotaxane, a mechanically interlocked molecule composed of a macrocycle and a thread in a "bead and thread" configuration, were prepared by vapor deposition on both Ag(111) and Au(111) substrates. X-ray photoelectron spectroscopy (XPS) and high-resolution electron-energy-loss spectroscopy were used to characterize monolayer and bulklike multilayer films. XPS determination of the relative amounts of carbon, nitrogen, and oxygen indicates that the molecule adsorbs intact. On both metal surfaces, molecules in the first adsorbed layer show an additional component in the C 1s XPS line attributed to chemisorption via amide groups. Molecular-dynamics simulation indicates that the molecule orients two of its eight phenyl rings, one from the macrocycle and one from the thread, in a parallel bonding geometry with respect to the metal surfaces, leaving three amide groups very close to the substrate. In the case of fumaramide [2]rotaxane adsorption on Au(111), the presence of certain out-of-plane phenyl ring and Au-O vibrational modes points to such bonding and a preferential molecular orientation. The theoretical and experimental results imply that the three-dimensional intermolecular configuration permits chemisorption at low coverage to be driven by interactions between the three amide functions of fumaramide [2]rotaxane and the Ag(111) or Au(111) surface. 相似文献
5.
Permanently fixed noisily recorded refractive index gratings are discovered in single crystals of LiNbO(3):Fe upon long-term exposure to a single laser beam with high intensities of I=100 kW/m(2) and ambient temperature. The fixing process is explained by considering the effect of laser-induced heating of the sample and the well-known simultaneous thermal fixing procedure. 相似文献
6.
Giuseppina La Ganga Fausto Puntoriero Enza Fazio Mirco Natali Francesco Nastasi Antonio Santoro Maurilio Galletta Sebastiano Campagna 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(68):16904-16911
The luminophore Ru(bpy)2(dcbpy)2+ (bpy=2,2’-bipyridine; dcbpy=4,4’-dicarboxy-2,2’-bipyridine) is covalently linked to a chitosan polymer; crosslinking by tripolyphosphate produced Ru-decorated chitosan fibers (NS-RuCh), with a 20 : 1 ratio between chitosan repeating units and RuII chromophores. The properties of the RuII compound are unperturbed by the chitosan structure, with NS-RuCh exhibiting the typical metal-to-ligand charge-transfer (MLCT) absorption and emission bands of RuII complexes. When crosslinks are made in the presence of IrO2 nanoparticles, such species are encapsulated within the nanofibers, thus generating the IrO2⊂NS-RuCh system, in which both RuII photosensitizers and IrO2 water oxidation catalysts are within the nanofiber structures. NS-RuCh and IrO2⊂NS-RuCh have been characterized by dynamic light scattering, scanning electronic microscopy, and energy-dispersive X-ray analysis, which indicated a 2 : 1 ratio between RuII chromophores and IrO2 species. Photochemical water oxidation has been investigated by using IrO2⊂NS-RuCh as the chromophore/catalyst assembly and persulfate anions as the sacrificial species: photochemical water oxidation yields O2 with a quantum yield (Φ) of 0.21, definitely higher than the Φ obtained with a similar solution containing separated Ru(bpy)32+ and IrO2 nanoparticles (0.05) or with respect to that obtained when using NS-RuCh and “free” IrO2 nanoparticles (0.10). A fast hole-scavenging process (rate constant, 7×104 s−1) involving the oxidized photosensitizer and the IrO2 catalyst within the IrO2⊂NS-RuCh system is behind the improved photochemical quantum yield of IrO2⊂NS-RuCh. 相似文献
7.
Javier Mateos Francesco Rigodanza Alberto Vega‐Pealoza Andrea Sartorel Mirco Natali Tommaso Bortolato Giorgio Pelosi Xavier Company Marcella Bonchio Luca Dell'Amico 《Angewandte Chemie (International ed. in English)》2020,59(3):1302-1312
Twelve naphthochromenone photocatalysts (PCs) were synthesized on gram scale. They absorb across the UV/Vis range and feature an extremely wide redox window (up to 3.22 eV) that is accessible using simple visible light irradiation sources (CFL or LED). Their excited‐state redox potentials, PC*/PC.? (up to 1.65 V) and PC.+/PC* (up to ?1.77 V vs. SCE), are such that these novel PCs can engage in both oxidative and reductive quenching mechanisms with strong thermodynamic requirements. The potential of these bimodal PCs was benchmarked in synthetically relevant photocatalytic processes with extreme thermodynamic requirements. Their ability to efficiently catalyze mechanistically opposite oxidative/reductive photoreactions is a unique feature of these organic photocatalysts, thus representing a decisive advance towards generality, sustainability, and cost efficiency in photocatalysis. 相似文献
8.
G. Carelli N. Ioli A. M. Messina A. Moretti F. Strumia S. Zerbetto 《Applied physics. B, Lasers and optics》1991,52(1):32-35
We report new FIR laser lines from 13CH2F2 molecules optically pumped by a waveguide CO2 laser. The increased tunability (300 MHz) with respect to a conventional CO2 laser allows the pumping of 13CH2F2 vibrational transitions of large offset. 34 new laser lines have been discovered, ranging from 113.1 m to 491.4 m in wavelength, thus increasing the number of known FIR laser lines from this important molecule to 99. For all the new lines and many (36) of those known previously, precise offset measurements through the transferred Lamb-dip technique were performed. The frequency of six new laser lines was also directly measured by heterodyne detection with known laser lines. 相似文献
9.
E. C. C. Vasconcellos S. C. Zerbetto L.-H. Xu R. M. Lees L. R. Zink K. M. Evenson 《International Journal of Infrared and Millimeter Waves》1998,19(5):719-726
Eight far-infrared laser lines have been obtained by optically pumping acetaldehyde (CH3CHO) and nine by pumping vinyl fluoride (CH2CHF) with a cw CO2 laser. The far-infrared laser structure used a metal-dielectric waveguide cavity. This is the first reported observation of four of the laser lines in acetaldehyde. In this work, we measure the frequency, optimum pressure of operation, relative intensity, relative polarization, and pump offset from CO2 laser-line center. 相似文献
10.
Marta Catellani Gian Paolo Chiusoli Mirco Costa 《Journal of organometallic chemistry》1995,500(1-2):69-80
Chelating or metallacycle-forming substrates are very useful for directing organometallic reactions. This review covers the more recent research that has been carried out in the authors' laboratory. Rhodium(I)- and (III)-catalysed reactions of C---C coupling of butadiene with N-allylamides or N-alkylbutenamides are described. These reactions are controlled by the size and strength of the chelate ring formed by double-bond insertion into the crotyl-rhodium bond (formed from butadiene) and their regioselectivity can change with the oxidation state of the metal. Rhodium(I)-catalysed reactions of butadiene with enamides are also chelation controlled and lead to different products, depending on the substituents at nitrogen. Cobalt(II) metallacycles have been utilized for promoting some organic reactions. It has been shown that alkenes can be catalytically incorporated into cobaltacyclopentadiene rings, that spirocycles can be obtained from diynes, carbon monoxide and acrylic esters and that a Pauson-Khand-type reaction can be combined with a Michael-type reaction to prepare catalytically new cyclopentenones. The use of palladacycles, derived from norbornene insertion into aryl-palladium bonds, followed by cyclization, has allowed the selective functionalization of either end of the metallacycle and the formation of condensed rings. Conversion of a palladium(II) into a palladium(IV) metallacycle, and catalytic processes involving these intermediates, have been achieved. The formation of alkylaromatic palladacycles has also been exploited for the selective meta functionalization of the aromatic moiety by means of alkyl groups, accompanied by expulsion of the norbornene molecule. 相似文献