全文获取类型
收费全文 | 800篇 |
免费 | 16篇 |
国内免费 | 3篇 |
专业分类
化学 | 641篇 |
晶体学 | 2篇 |
力学 | 5篇 |
数学 | 30篇 |
物理学 | 141篇 |
出版年
2022年 | 9篇 |
2021年 | 5篇 |
2020年 | 6篇 |
2019年 | 10篇 |
2018年 | 5篇 |
2017年 | 6篇 |
2016年 | 8篇 |
2015年 | 15篇 |
2014年 | 13篇 |
2013年 | 32篇 |
2012年 | 27篇 |
2011年 | 37篇 |
2010年 | 19篇 |
2009年 | 21篇 |
2008年 | 38篇 |
2007年 | 40篇 |
2006年 | 34篇 |
2005年 | 51篇 |
2004年 | 42篇 |
2003年 | 29篇 |
2002年 | 41篇 |
2001年 | 28篇 |
2000年 | 20篇 |
1999年 | 23篇 |
1998年 | 13篇 |
1997年 | 17篇 |
1996年 | 11篇 |
1995年 | 12篇 |
1994年 | 5篇 |
1993年 | 10篇 |
1992年 | 10篇 |
1991年 | 6篇 |
1990年 | 9篇 |
1989年 | 11篇 |
1988年 | 6篇 |
1987年 | 6篇 |
1985年 | 17篇 |
1984年 | 18篇 |
1983年 | 5篇 |
1982年 | 11篇 |
1981年 | 11篇 |
1980年 | 12篇 |
1979年 | 11篇 |
1978年 | 8篇 |
1977年 | 7篇 |
1976年 | 5篇 |
1975年 | 7篇 |
1974年 | 4篇 |
1973年 | 7篇 |
1967年 | 4篇 |
排序方式: 共有819条查询结果,搜索用时 46 毫秒
41.
Summary For visual analysis of the density reorganization and distortion, the one-dimensional cut (x, y
0,z
0) and the two-dimensional cut (x, y, z
0) of the three-dimensional electron density difference function (x, y, z) are frequently employed. However, these cut functions do not satisfy any sum rules in contrast to the original difference function (x, y, z). To avoid this difficulty, the use of the marginal electron density functions
x
(x) and
xy
(x, y) and their difference functions
x
(x) and
xy
(x, y) is proposed. The marginal densities are condensation of the three-dimensional density onto a particular plane or line of our interest, and they satisfy the sum rule (i.e., the conservation of the number of electrons) exactly. Some basic properties of the marginal electron density are clarified for typical diatomic molecular orbitals. An illustrative application is given for the bonding and antibonding processes in the H2 system. 相似文献
42.
The kinetic curves at infinite temperature for the solid-state reactions of the interface shrinkage type were drawn theoretically by taking account the particle size distribution in the sample mixture. The CRTA curves for the reactions with the particle size distribution can be drawn by utilizing the universal kinetic curves at infinite temperature. The proper kinetic treatment for the CRTA curves with the particle size distribution is discussed in connection with the property of the kinetic equation with respect to the particle size distribution. The present kinetic consideration is taken as a simulation for the reactions with a certain distribution in among the reactant particles, produced preferably by the mass and heat transfer phenomena during the thermoanalytical measurements. The merit of the rate jump method by a single cyclic CRTA curve is also discussed on the basis of the present results. 相似文献
43.
The kinetics of the thermal decompositions of CaCO3, SrCO3 and BaCO3 into their oxides were studied by thermogravimetry at constant and linearly increasing temperatures. The kinetics of the isothermal decompositions of calcium and strontium carbonates were described by the lawR
n
=1–(1–)1/n
, wheren=1.8 and 1.2, respectively. The kinetics of the non-isothermal decompositions of the two carbonates, analysed by the Ozawa and Coats-Redfern methods, were in keeping with the isothermal kinetics. True kinetic compensation laws were established for each decomposition of the two carbonates, including the data under both isothermal and non-isothermal conditions.As concerns the decompositions of BaCO3, however, there was some difference between the kinetic features relating the isothermal and non-isothermal conditions. A true kinetic compensation law was not established in this case.
Zusammenfassung Die Kinetik der thermischen Zersetzung von CaCO3, SrCO3 und BaCO3 zu den Oxiden wurden durch Thermogravimetrie bei konstanter und linear ansteigender Temperatur untersucht. Die Kinetik der isothermen Zersetzung von Calcium- und Strontium-carbonat folgt dem GesetzR n =1–(1 –)1/n, won=1,8 bzw. 1,2. Die Kinetik der nichtisothermen nach den Methoden von Ozawa und Coats-Redfern analysierten Zersetzung der zwei Carbonate ist in Übereinstimmung mit der isothermen Zersetzung. Wahre kinetische Kompensationsgesetze wurden für die Zersetzung der beiden Carbonate erhalten, einschließlich der sich sowohl auf isotherme als auch auf nichtisotherme Bedingungen beziehenden Daten. Was die Zersetzung von Bariumcarbonat betrifft, so wurden einige Unterschiede im kinetischen Verhalten bei der Zersetzung unter isothermen und nichtisothermen Bedingungen festgestellt. Ein wahres kinetisches Kompensationsgesetz konnte in diesem Falle nicht ermittelt werden.
, . R n =1–(1–)1/n , , , 1,8 1,2. , -, . « » , . , , . - «» .相似文献
44.
Okuma K Koga Y Kojima K Shioji K Matsuyama H Yokomori Y 《The Journal of organic chemistry》2000,65(7):2090-2095
Selenobenzophenone reacts as a diene with dimethyl acetylenedicarboxylate (DMAD) to lead to dimethyl 1H-1-diphenylmethyl-1-phenyl-2-benzoselenopyran-3,4-dicarboxylate (5c) in moderate yield; the initial [4 + 2] cycloaddition is followed by the addition of another 1 mol equiv of selenobenzophenone. The reaction might proceed through carbene insertion of the primary cycloadduct. On the other hand, 4,4'-dimethoxyselenobenzophenone combines as a diene with DMAD furnishing dimethyl 1H-1-p-methoxyphenyl-6-methoxy-2-benzoselenopyran-3,4-dicarboxylate (4a). The reaction of benzoselenopyran derivative (4) with diaryldiazomethanes afforded another type of carbene insertion product. 相似文献
45.
Gas mixtures of methane and ethane form structure II clathrate hydrates despite the fact that each of pure methane and pure ethane gases forms the structure I hydrate. Optimization of the interaction potential parameters for methane and ethane is attempted so as to reproduce the dissociation pressures of each simple hydrate containing either methane or ethane alone. An account for the structural transitions between type I and type II hydrates upon changing the mole fraction of the gas mixture is given on the basis of the van der Waals and Platteeuw theory with these optimized potentials. Cage occupancies of the two kinds of hydrates are also calculated as functions of the mole fraction at the dissociation pressure and at a fixed pressure well above the dissociation pressure. 相似文献
46.
Reaction steps and mechanisms of the thermal dehydration of lithium metaborate dihydrate were investigated by means of thermoanalytical measurements, high temperature powder X-ray diffractometry, FT-IR spectroscopy, and microscopic observations. The first half of thermal dehydration was characterized by the melting of the sample producing viscous surface layer, the formation of bubbles on the particle surfaces, and the sudden mass-loss taking place by an opportunity of cracking and/or bursting of the bubble surface layer. The second half of the dehydration with a long-tailed mass-loss process in a wide temperature region was divided further into three distinguished reaction steps by the measurements of controlled rate thermal analysis. During the course of the thermal dehydration, four different poorly crystalline phases of intermediate hydrates were observed, in addition to an amorphous phase produced by an isothermal annealing. Just after completing the thermal dehydration, an exothermic DTA peak of the crystallization of β-LiBO2 was appeared at around 750 K. The phase transition from β-LiBO2 to α-LiBO2 was observed in the temperature range of 800-900 K, which subsequently melted by indicating a sharp endothermic DTA peak with the onset temperature at 1101.4 ± 0.6 K. 相似文献
47.
RajanBabu TV Nomura N Jin J Nandi M Park H Sun X 《The Journal of organic chemistry》2003,68(22):8431-8446
Through a systematic examination of ligand and counterion effects, new protocols for a nearly quantitative and highly selective codimerization of ethylene and various functionalized vinylarenes have been discovered. In a typical reaction, 4-bromostyrene and ethylene undergo codimerization in the presence of 0.0035 equiv each of [(allyl)NiBr]2, triphenylphosphine, and AgOTf in CH2Cl2 at -56 degrees C to give 3-(4-bromophenyl)-1-butene in >98% yield and selectivity. Corresponding reactions with [(allyl)PdX]2 are much less efficient and less selective and may require further optimization before a viable system can be identified. Another useful protocol that gives comparable yield and selectivity involves the use of a single-component catalyst prepared from allyl 2-diphenylphosphinobenzoate, Ni(COD)2, and (C6F5)3B. Recognition of a synergistic relationship between a chiral hemilabile ligand (for example, (R)-2-methoxy-2'-diphenylphosphino-1,1'-binaphthyl, MOP) and a highly dissociated counteranion (BARF or SbF6) in an enantioselective version of the Ni-catalyzed reaction raises the prospects of developing a practical route for the synthesis of 3-arylbutenes. Several pharmaceutically relevant compounds, including widely used 2-arylpropionic acids, can be synthesized from these key intermediates. This reaction appears to be quite general. Synthesis of several new 2-diphenylphosphino-1,1-binaphthyl derivatives, prepared to probe the effect of hemilabile coordination on the efficiency and selectivity of the reaction, are also described. 相似文献
48.
Nishii Y Wakasugi K Koga K Tanabe Y 《Journal of the American Chemical Society》2004,126(17):5358-5359
Chirality exchange benzannulation of optically active (1S)-aryl(aryl')-2,2-dichlorocyclopropylmethanols (>99% ee) using TiCl4 successfully proceeded to give axially chiral (M)-alpha-arylnaphthalenes with excellent levels of stereo induction (>99% ee). This unique transformation involves the single-step chirality exchange from sp3 central chirality to axial chirality, that is, a type of excellent memory effect. 相似文献
49.
Koga T Taguchi K Kobuke Y Kinoshita T Higuchi M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(5):1146-1156
The self-assembly of peptides and proteins into beta-sheet-rich high-order structures has attracted much attention as a result of the characteristic nanostructure of these assemblies and because of their association with neurodegenerative diseases. Here we report the structural and conformational properties of a peptide-conjugated graft copolymer, poly(gamma-methyl-L-glutamate) grafted polyallylamine (1) in a water-2,2,2-trifluoroethanol solution as a simple model for amyloid formation. Atomic force microscopy revealed that the globular peptide 1 self-assembles into nonbranching fibrils that are about 4 nm in height under certain conditions. These fibrils are rich in beta-sheets and, similar to authentic amyloid fibrils, bind the amyloidophilic dye Congo red. The secondary and quaternary structures of the peptide 1 can be controlled by manipulating the pH, solution composition, and salt concentration; this indicates that the three-dimensional packing arrangement of peptide chains is the key factor for such fibril formation. Furthermore, the addition of carboxylic acid-terminated poly(ethylene glycol), which interacts with both of amino groups of 1 and hydrophobic PMLG chains, was found to obviously inhibit the alpha-to-beta structural transition for non-assembled peptide 1 and to partially cause a beta-to-alpha structural transition against the 1-assembly in the beta-sheet form. These findings demonstrate that the amyloid fibril formation is not restricted to specific protein sequences but rather is a generic property of peptides. The ability to control the assembled structure of the peptide should provide useful information not only for understanding the amyloid fibril formation, but also for developing novel peptide-based material with well-defined nanostructures. 相似文献
50.
Eight new homologous series of 4-alkyl-N-(4-alkloxysalicylidene)anilines were synthesized. The phase transitions of these homologues were determined using differential scanning calorimetry and polarizing optical microscopy. The homologues began to exhibit liquid crystalline phases as the terminal alkyl or alkoxyl chains were lengthened. In addition, some members of these homologues series exhibited photochromism in the solid state. 相似文献