全文获取类型
收费全文 | 5591篇 |
免费 | 892篇 |
国内免费 | 384篇 |
专业分类
化学 | 3940篇 |
晶体学 | 109篇 |
力学 | 336篇 |
综合类 | 19篇 |
数学 | 581篇 |
物理学 | 1882篇 |
出版年
2024年 | 10篇 |
2023年 | 125篇 |
2022年 | 128篇 |
2021年 | 139篇 |
2020年 | 260篇 |
2019年 | 188篇 |
2018年 | 156篇 |
2017年 | 154篇 |
2016年 | 353篇 |
2015年 | 292篇 |
2014年 | 357篇 |
2013年 | 371篇 |
2012年 | 294篇 |
2011年 | 385篇 |
2010年 | 352篇 |
2009年 | 382篇 |
2008年 | 370篇 |
2007年 | 418篇 |
2006年 | 355篇 |
2005年 | 264篇 |
2004年 | 277篇 |
2003年 | 205篇 |
2002年 | 130篇 |
2001年 | 123篇 |
2000年 | 128篇 |
1999年 | 93篇 |
1998年 | 97篇 |
1997年 | 95篇 |
1996年 | 64篇 |
1995年 | 40篇 |
1994年 | 35篇 |
1993年 | 40篇 |
1992年 | 26篇 |
1991年 | 24篇 |
1990年 | 17篇 |
1989年 | 21篇 |
1988年 | 24篇 |
1987年 | 8篇 |
1986年 | 4篇 |
1985年 | 14篇 |
1984年 | 5篇 |
1982年 | 8篇 |
1981年 | 5篇 |
1980年 | 5篇 |
1978年 | 3篇 |
1976年 | 3篇 |
1975年 | 3篇 |
1974年 | 3篇 |
1969年 | 2篇 |
1967年 | 2篇 |
排序方式: 共有6867条查询结果,搜索用时 15 毫秒
111.
Gas hydrates are non-stoichiometric crystalline compounds of water with gas at a certain temperature and pressure. Compared to the thermodynamics of hydrate formation, our knowledge on the kinetics aspect is rather immature. It is well known that the kinetics of hydrate formation/dissociation plays an important role in many industrial cases, such as the exploitation of methane hydrate underground, the storage and transportation of natural gas in solid hydrate state, the inhibition of hydrate i… 相似文献
112.
Jayshree Ramkumar 《Talanta》2007,71(3):1054-1060
The single ion transport of transition metal ions like Cu2+, Co2+, Ni2+ and Zn2+ were carried out through the H+ and alkali metal ion forms of Nafion membrane. These studies showed that the ion exchange selectivity coefficient of the permeating ion had an effect on its transport process. It was found that the diffusion coefficient values (D) were directly proportional to the selectivity coefficient (K). This shows that the initial stage of permeation is governed by ion exchange process (effect of K on D). 相似文献
113.
The study of curium iodate, Cm(IO3)3, was undertaken as part of a systematic investigation of the 4f- and 5f-elements’ iodates. The reaction of 248CmCl3 with aqueous H5IO6 under mild hydrothermal conditions results in the reduction of IO65− to IO3− anions, and the subsequent formation of Cm(IO3)3 single crystals. Crystallographic data are: (193 K, MoKα, ): monoclinic, space group P21/c, , , , β=100.142(2)°, V=811.76(14), Z=4, R(F)=2.11%, for 119 parameters with 1917 reflections with I>2σ(I). The structure consists of Cm3+ cations bound by iodate anions to form [Cm(IO3)8] units, where the local coordination environment around the curium centers can be described as a distorted dodecahedron. There are three crystallographically unique iodate anions within the structure; two iodates bridge between three Cm centers, and one iodate bridges between two Cm centers and has a terminal oxygen atom. The bridging of the curium centers by the iodate anions creates a three-dimensional structure. Three strong Raman bands with comparable intensities were observed at 846, 804, and 760 cm−1 and correspond to the I-O symmetric stretching of the three crystallographically distinct iodate ions. The Raman profile suggests a lack of inter-ionic vibrational coupling of the I-O stretching, while intra-ionic coupling provides symmetric and asymmetric components that correspond to each iodate site. Repeated collection of X-ray diffraction data for a crystal of Cm(IO3)3 over a period of time revealed a gradual expansion of the unit cell from self-irradiation. After 71 days, the new parameters were: , , , β=100.021(2)°, V=818.3(2). 相似文献
114.
Marie-Florence Grenier-Loustalot Frderic Joubert Philippe Grenier 《Journal of polymer science. Part A, Polymer chemistry》1993,31(12):3049-3063
The aim of the present work was to identify and follow the main and side reactions involved in the ring dehydration of amic acid prepared from “bridged” dianhydrides whose central substituent is an electron acceptor or donor, and an aromatic diamine. Several isomeric structures may appear as a result of the opening reactivity and selectivity of anhydride groups towards the aromatic amine. Reaction mechanisms and kinetics were thus studied in solvent phase with HPLC and 13C-NMR and in solid molten phase by FTIR and solid 13C-NMR. The experimental conditions (liquid and solid) and the structure of the products (type of central substituent) affecting the mechanisms and kinetics of the reactions were noted. © 1993 John Wiley & Sons, Inc. 相似文献
115.
Juan Manuel Ortiz-Sánchez Ricard Gelabert Miquel Moreno José M Lluch 《Chemphyschem》2007,8(8):1199-1206
The two isoelectronic bipyridyl derivatives, [2,2'-bipyridyl]-3,3'-diamine and [2,2'-bipyridyl]-3,3'-diol, are experimentally known to undergo very different excited-state double-proton-transfer processes, which result in fluorescence quantum yields that differ by four orders of magnitude. Herein, density functional theory (DFT), time-dependent DFT (TDDFT), and complete active space self-consistent field (CASSCF) calculations are used to study the double-proton-transfer processes in the ground and first singlet pi-->pi* excited state. The quantum-chemistry calculations indicate 1) the existence of only one energy minimum in the ground electronic state corresponding to reactants (thus avoiding the possibility of a fast fluorescent relaxation process from the photoproducts region), 2) an endoergic process of the complete double proton transfer, and 3) the presence of a conical intersection in the excited intermediate region of [2,2'-bipyridyl]-3,3'-diamine. These facts explain the very low fluorescence quantum yield in [2,2'-bipyridyl]-3,3'-diamine compared to [2,2'-bipyridyl]-3,3'-diol. 相似文献
116.
Szymczyk A Labbez C Fievet P Vidonne A Foissy A Pagetti J 《Advances in colloid and interface science》2003,103(1):77-94
Transport mechanisms through nanofiltration membranes are investigated in terms of contribution of convection, diffusion and migration to electrolyte transport. A Donnan steric pore model, based on the application of the extended Nernst-Planck equation and the assumption of a Donnan equilibrium at both membrane-solution interfaces, is used. The study is focused on the transport of symmetrical electrolytes (with symmetric or asymmetric diffusion coefficients). The influence of effective membrane charge density, permeate volume flux, pore radius and effective membrane thickness to porosity ratio on the contribution of the different transport mechanisms is investigated. Convection appears to be the dominant mechanism involved in electrolyte transport at low membrane charge and/or high permeate volume flux and effective membrane thickness to porosity ratio. Transport is mainly governed by diffusion when the membrane is strongly charged, particularly at low permeate volume flux and effective membrane thickness to porosity ratio. Electromigration is likely to be the dominant mechanism involved in electrolyte transport only if the diffusion coefficient of coions is greater than that of counterions. 相似文献
117.
Domenico Osella Mauro Ravera Carlo Floriani Euro Solari 《Journal of organometallic chemistry》1996,510(1-2):45-50
We describe the redox behaviour in non-aqueous solvents of some cyclopentadienyl(oxo)titanium derivatives. The derivative [Ti4{η5-C5H4(SiMe3)}4(μ-O)6] shows an electrochemically and chemically reversible le reduction process, followed by a multi-electron, chemically complicated reduction at a fairly cathodic potential. On the basis of the overall electrochemical features and the comparison with the redox behaviour of the quasi-planar compound [[Ti{η5-C5H4(SiMe3)}Cl(μ-O)]4] we propose an EECCEE mechanism for the first derivative, where the second electron-transfer induces a cascade of chemical reactions giving rise to irreversible cluster breakdown. The electrochemically induced fragmentation can be viewed as a retrosynthetic pathway. The heterometallic derivative [{Ti(η5-C5H4Me)2(μ2-MoO4)2}2] shows two consecutive reduction processes; the first is chemically reversible, and the second quasi-reversible. The molybdate bridges apparently increase the stability of the electrogenerated anions. However none of these poly-oxo clusters can be considered as good models of electron ‘sinks’. 相似文献
118.
W. Weissensteiner 《Monatshefte für Chemie / Chemical Monthly》1992,123(12):1135-1147
Summary Ground state structures and conformational interconversion mechanisms of 25 diaryl compoundsAr
2
Z (Z=CH2, CHR, CH(OH), P-CH3) were analyzed. For tetra(ortho-alkyl)substituted diaryls the cogwheeling mechanism was found as the threshold mechanism. A shift from the cogwheeling mechanism to interconversions via 2-ring flips is found in di(ortho-alkyl)substituted compounds. The ground state structures and interconversion mechanisms of diarylmethylphosphines are very similar to those of the related 1,1-diarylethanes. The interconversion barrier for correlated conrotation of the aryl rings in di(tert-butylphenyl)methanol (20) was measured by low temperature NMR and is in excellent agreement with the calculated value for the 2-ring flipT2 (G (exp.)=48 kJ mol–1; G (calc.)=54 kJ mol–1).
Korrelierte Rotation von Arylringen in Diarylmethyl-, Diarylphosphin- und verwandten Fragmenten. Eine Untersuchung mit Hilfe der empirischen Kraftfeldmethode
Zusammenfassung Die Grundzustandskonformationen und die konformativen Interkonversions-mechanismen von 25 DiarylverbindungenAr 2 Z (Z=CH2, CHR, CH(OH), P-CH3) wurden analysiert. Für tetra(ortho-alkyl)substituierte Diaryle wurde der cogwheeling-Mechanismus als der Interkonversionsmechanismus niedrigster Energie ermittelt. In di(ortho-alkyl)substituierten Verbindungen werden nicht der cogwheeling-Mechanismus sondern 2-ring flips als Interkonversionsmechanismen gefunden. Die Grundzustände und Interkonversionsmechanismen für Diarylmethylphosphine sind sehr ähnlich jenen der verwandten 1,1-Diarylethane. Die Interkonversionsbarriere für die korrelierte Bewegung der Arylringe von Di(tert-butylphenyl)methanol (20) wurde mittels Tieftemperatur-NMR-Spektroskopie ermittelt und ist in sehr guter Übereinstimmung mit dem berechneten Wert für den 2-Ring flipT2 (G (exp.)=48 kJ mol–1; G (calc.)=54 kJ mol–1).相似文献
119.
《Journal of Saudi Chemical Society》2020,24(9):673-682
A single dielectric barrier discharge (DBD) low-temperature plasma reactor was set up, and toluene was selected as the representative substance for volatile organic compounds (VOCs), to study the reaction products and degradation mechanism of VOCs degradation by low-temperature plasma. Different parameters effect on the concentration of O3 and NOx during the degradation of toluene were studied. The exhaust in the process of toluene degradation was continuously detected and analyzed, and the degradation mechanism of toluene was explored. The results showed that the concentration of O3 increased with the increase of the power density and discharge voltage of the plasma device. However, as the initial concentration of toluene increased, the concentration of O3 basically keep steady. The concentration of NOx in the by-products increased with the discharge voltage, power density, and initial concentration of toluene in the plasma device, and the concentration of NO2 was much higher than the concentration of NO. The degradation process of toluene was detected and analyzed. The results showed that the degradation mechanism of toluene by plasma includes high energy electron bombardment reaction, active radical reaction and ion molecule reaction. Among them, the effect of high-energy electrons on toluene degradation is the largest, followed by the effect of free radicals, in which oxygen radicals participated in the reaction mainly through the formation of C–O bond, CO bond, (CO)–O– bond and –OH radical, while nitrogen radicals participate in the reaction mainly through the formation of C–NH2, (CNH)- bond, CN bond and C–NO2 bond. The results can provide some data supports for the study of low-temperature plasma degradation of VOCs. 相似文献
120.
Giorgio Parisi 《Journal of statistical physics》1980,23(1):49-82
We review the physical principles which are at the basis of recent field-theoretic computations of the critical exponents in two- and three-dimensional systems. We concentrate on those points that do not show up explicitly in the more standard-expansion: they must be discussed with care if one uses a perturbative approach at fixed space dimensions (the loop expansion). We present in detail simple computations of the critical exponents, while we summarize the results of longer and more accurate computations. 相似文献