全文获取类型
收费全文 | 306篇 |
免费 | 2篇 |
国内免费 | 5篇 |
专业分类
化学 | 152篇 |
晶体学 | 9篇 |
力学 | 23篇 |
数学 | 46篇 |
物理学 | 83篇 |
出版年
2021年 | 2篇 |
2019年 | 3篇 |
2016年 | 4篇 |
2015年 | 2篇 |
2014年 | 2篇 |
2013年 | 21篇 |
2012年 | 19篇 |
2011年 | 9篇 |
2010年 | 13篇 |
2009年 | 6篇 |
2008年 | 11篇 |
2007年 | 14篇 |
2006年 | 11篇 |
2005年 | 16篇 |
2004年 | 19篇 |
2003年 | 8篇 |
2002年 | 5篇 |
2001年 | 7篇 |
2000年 | 5篇 |
1999年 | 4篇 |
1998年 | 2篇 |
1997年 | 2篇 |
1996年 | 7篇 |
1995年 | 8篇 |
1994年 | 6篇 |
1993年 | 4篇 |
1992年 | 6篇 |
1991年 | 8篇 |
1990年 | 5篇 |
1989年 | 2篇 |
1988年 | 3篇 |
1986年 | 4篇 |
1985年 | 5篇 |
1984年 | 5篇 |
1983年 | 4篇 |
1982年 | 4篇 |
1981年 | 11篇 |
1980年 | 3篇 |
1979年 | 3篇 |
1978年 | 3篇 |
1976年 | 7篇 |
1975年 | 3篇 |
1974年 | 2篇 |
1973年 | 6篇 |
1971年 | 3篇 |
1970年 | 3篇 |
1968年 | 2篇 |
1939年 | 1篇 |
1937年 | 6篇 |
1913年 | 1篇 |
排序方式: 共有313条查询结果,搜索用时 62 毫秒
151.
Fiona A. M. Rudolph Amy L. Fuller Alexandra M. Z. Slawin Michael Bühl R. Alan Aitken J. Derek Woollins 《Journal of chemical crystallography》2010,40(3):253-265
Abstract
The X-rays structures of diphenyl sulfone 1, bis(3-aminophenyl) sulfone 2, bis(4-nitrophenyl) sulfone 3, 2-nitrophenylphenyl sulfone 4, benzylphenzyl sulfone 5, 4-nitrobenzylphenyl sulfone 6, 4-methylphenylbenzyl sulfone 7, dibenzyl sulfone 8, benzylisopropyl sulfone 9, and methylacetate,ethyl sulfone 10, are reported. B3PW91 DFT calculations were performed on selected sulfones for comparison. The S = O distances in these compounds range from 1.392(5) to 1.463(3) Å and S–C bond distances range from 1.743(7) to 1.790(3) Å. The C–S–C bond angles vary from 101.1(3)° to 106.80(14)° and the O–S–O bond angles vary from 116.7(2)° to 120.61(8)°. Using data obtained here and comparison with published structural data no evidence was found for para substituents on aryl groups influencing S–O bond distances, however, small changes on S–C bond distances were noted. Additionally, if the sulfur is flanked by an alkyl group the S–C distance is slightly larger than when it is flanked by an aryl group. Most of the sulfone compounds studied here display intermolecular soft hydrogen bonding interactions which influence their solid state packing. Furthermore, in dialkyl sulfone compounds these interactions appear to be strong enough to overcome conformational barriers calculated to be ca. 6 kJ mol−1. 相似文献152.
Jacobs EA Fuller A Coles SJ Jones GA Tizzard GJ Wright JA Lancaster SJ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(28):8647-8658
Treatment of Me(2)S·B(C(6)F(5))(n) H(3-n) (n=1 or 2) with ammonia yields the corresponding adducts. H(3)N·B(C(6)F(5))H(2) dimerises in the solid state through N-H···H-B dihydrogen interactions. The adducts can be deprotonated to give lithium amidoboranes Li[NH(2)B(C(6)F(5))(n)H(3-n)]. Reaction of the n=2 reagent with [Cp(2)ZrCl(2)] leads to disubstitution, but [Cp(2)Zr{NH(2)B(C(6)F(5))(2)H}(2)] is in equilibrium with the product of β-hydride elimination [Cp(2)Zr(H){NH(2)B(C(6)F(5))(2)H}], which proves to be the major isolated solid. The analogous reaction with [Cp(2)HfCl(2)] gives a mixture of [Cp(2)Hf{NH(2)B(C(6)F(5))(2)H}(2)] and the N-H activation product [Cp(2)Hf{NHB(C(6)F(5 )(2)H}]. [Cp(2)Zr{NH(2)B(C(6)F(5))(2)H}(2)]·PhMe and [Cp(2)Hf{NH(2)B(C(6)F(5))(2)H}(2)]·4(thf) exhibit β-B-agostic chelate bonding of one of the two amidoborane ligands in the solid state. The agostic hydride is invariably coordinated to the outside of the metallocene wedge. Exceptionally, [Cp(2)Hf{NH(2)B(C(6)F(5))(2)H}(2)]?PhMe has a structure in which the two amidoborane ligands adopt an intermediate coordination mode, in which neither is definitively agostic. [Cp(2)Hf{NHB(C(6)F(5))(2)H}] has a formally dianionic imidoborane ligand chelating through an agostic interaction, but the bond-length distribution suggests a contribution from a zwitterionic amidoborane resonance structure. Treatment of the zwitterions [Cp(2)MMe(μ-Me)B(C(6)F(5))(3)] (M=Zr, Hf) with Li[NH(2)B(C(6)F(5))(n)H(3-n)] (n=2) results in [Cp(2) MMe{NH(2)B(C(6)F(5))(2)H}] complexes, for which the spectroscopic data, particularly (1)J(B,H), again suggest β-B-agostic interactions. The reactions proceed similarly for the structurally encumbered [Cp'(2)ZrMe(μ-Me)B(C(6)F(5))(3)] precursor (Cp'=1,3-C(5)H(3)(SiMe(3))(2) , n=1 or 2) to give [Cp'(2)ZrMe{NH(2)B(C(6)F(5))(n)H(3-n)}], both of which have been structurally characterised and show chelating, agostic amidoborane coordination. In contrast, the analogous hafnium chemistry leads to the recovery of [Cp'(2)HfMe(2)] and the formation of Li[HB(C(6)F(5))(3)] through hydride abstraction. 相似文献
153.
Han S Hermans TM Fuller PE Wei Y Grzybowski BA 《Angewandte Chemie (International ed. in English)》2012,51(11):2662-2666
Chemistry in motion: a combination of confocal microscopy and reaction-diffusion modeling provided a powerful toolkit with which solution transport into metal-organic framework crystals was studied. Commonly used pure diffusion models are insufficient to describe this process and, instead, it is necessary to account for the interactions of the guest molecules and the MOF scaffold. 相似文献
154.
Lee JW Carrascón V Gallimore PJ Fuller SJ Björkegren A Spring DR Pope FD Kalberer M 《Physical chemistry chemical physics : PCCP》2012,14(22):8023-8031
Atmospheric aerosol particles are important in many atmospheric processes such as: light scattering, light absorption, and cloud formation. Oxidation reactions continuously change the chemical composition of aerosol particles, especially the organic mass component, which is often the dominant fraction. These ageing processes are poorly understood but are known to significantly affect the cloud formation potential of aerosol particles. In this study we investigate the effect of humidity and ozone on the chemical composition of two model organic aerosol systems: oleic acid and arachidonic acid. These two acids are also compared to maleic acid an aerosol system we have previously studied using the same techniques. The role of relative humidity in the oxidation scheme of the three carboxylic acids is very compound specific. Relative humidity was observed to have a major influence on the oxidation scheme of maleic acid and arachidonic acid, whereas no dependence was observed for the oxidation of oleic acid. In both, maleic acid and arachidonic acid, an evaporation of volatile oxidation products could only be observed when the particle was exposed to high relative humidities. The particle phase has a strong effect on the particle processing and the effect of water on the oxidation processes. Oleic acid is liquid under all conditions at room temperature (dry or elevated humidity, pure or oxidized particle). Thus ozone can easily diffuse into the bulk of the particle irrespective of the oxidation conditions. In addition, water does not influence the oxidation reactions of oleic acid particles, which is partly explained by the structure of oxidation intermediates. The low water solubility of oleic acid and its ozonolysis products limits the effect of water. This is very different for maleic and arachidonic acid, which change their phase from liquid to solid upon oxidation or upon changes in humidity. In a solid particle the reactions of ozone and water with the organic particle are restricted to the particle surface and hence different regimes of reactivity are dictated by particle phase. The potential relevance of these three model systems to mimic ambient atmospheric processes is discussed. 相似文献
155.
Controlling the activity of water in the reactant streams is critical both to the design of fuel–cell systems and to the useable life of membrane separators. In this study, fuel–cell durability tests were conducted under different levels of relative humidity. The emission rates of various degradation products such as HF, SO42− and TFA (trifluoroacetic acid) were determined as a function of water activity. The degradation of the membrane was accelerated as the level of water activity is reduced. The membranes become less conductive, more brittle and rigid after fuel–cell testing. ATR-FTIR investigations showed that the decomposition of the ether group in the middle of side chain corresponds well with the detection of a TFA product. Thermogravimetric analysis also showed a decrease in thermal stability after testing at lower humidity. Formation of cracks was observed in membranes degraded under conditions of low humidity. A model of membrane degradation based on the main chain unzipping process indicates that the mechanism changes with water activity. Finally, the representative reaction pathways in each degradation scheme were postulated. 相似文献
156.
C.D. Schaper K. El-Awady T. Kailath A. Tay L.L. Lee W.K. Ho S.E. Fuller 《Applied Physics A: Materials Science & Processing》2005,80(4):899-902
A thermal system is developed to rapidly characterize the linewidth sensitivity of advanced resists to process temperature variations in the photolithographic manufacturing sequence. This thermal array consists of a 7×7 grid of individually programmable heating zones distributed within a thermal cycling apparatus. It is used to improve the quality and quantity of data for determining the optimal thermal conditions by effectively producing equivalent operating conditions besides the spatially controlled temperature. The system is demonstrated for the optimization of the post-apply and post-exposure thermal-processing conditions for chemically amplified photoresists used in the fabrication of quartz photomasks . PACS 07.20.Hy; 81.16.Nd; 81.70.Pg 相似文献
157.
Linear equality systems With fuzzy parameters and crisp variables defined by the Zadeh's extension principle are called possibilistic linear equality systems. This study focuses on the problem of stability (with respect to small changes in the membership function of fuzzy parameters) of the solution in these systems. 相似文献
158.
The technique of small-angle light scattering (SALS) has been employed to investigate the time-dependent behavior of a single-phase, semidilute solution of polystyrene and polybutadiene in dioctyl phthalate under shear flow. Concentration fluctuations in the polymer blend solution are found to grow with time in the direction of flow, and their orientation angles evolve from 45° from the flow direction toward 0°, with the steady-state value being dependent on shear rate. SALS patterns are simulated using a modified Cahn-Hilliard-Cook model, with an additional collective restoring force to account for polymer elasticity. Predictions from this modified model for the orientation angles of the concentration fluctuations are in excellent agreement with the experimental results. Our model also predicts that the quiescent structure factor has a Gaussian form and that the steady-state orientation of the scattering patterns is dependent on shear rate. These predictions are also in good agreement with our experimental observations. © 1994 John Wiley & Sons, Inc. 相似文献
159.
Grubel K Ingle GK Fuller AL Arif AM Berreau LM 《Dalton transactions (Cambridge, England : 2003)》2011,40(40):10609-10620
Reaction conditions were evaluated for the preparation of [(6-PhTPA)Ni(PhC(O)C(OH)C(O)Ph)]ClO(4) (3) and [(6-Ph(2)TPA)Co(PhC(O)C(OH)C(O)Ph)]ClO(4) (7), two complexes of structural relevance to the enzyme/substrate (ES) adduct in Ni(II)- and Co(II)-containing forms of acireductone dioxygenase. The presence of water in reactions directed at the preparation of 3 and 7 was found to result in isomerization of the enolate precursor 2-hydroxy-1,3-diphenylpropane-1,3-dione to give the ester 2-oxo-2-phenylethylbenzoate. Performing synthetic procedures under dryer conditions reduced the amount of ester production and enabled the isolation of 3 in high yield. This complex was comprehensively characterized, including by X-ray crystallography. Using similar conditions for the 6-Ph(2)TPACo-containing system, the amount of ester generated was only modestly affected, but the formation of a benzoate complex ([(6-Ph(2)TPA)Co(O(2)CPh)]ClO(4), 10) resulting from ester hydrolysis was prevented. The best preparation of 7 was found to involve dry conditions and short reaction times. The approach outlined herein toward determining appropriate reaction conditions for the preparation of 3 and 7 involved the preparation and characterization of several air-stable (6-PhTPA)Ni- and (6-Ph(2)TPA)Co-containing analog complexes having enolate, solvent, and benzoate ligands. These complexes were used as paramagnetic (1)H NMR standards for evaluation of reaction mixtures containing 3 and 7. 相似文献
160.
Drops and jets of liquids that are miscible with the surrounding bulk liquid are present in many processes from cleaning surfaces with the aid of liquid soaps to the creation of biocompatible implants for drug delivery. Although the interactions of immiscible drops and jets show similarities to miscible systems, the small, transient interfacial tension associated with miscible systems create distinct outcomes such as intricate droplet shapes and breakup resistant jets. Experiments have been conducted to understand several basic multiphase flow problems involving miscible liquids. Using high-speed imaging of the morphological evolution of the flows, we have been able to show that these processes are controlled by interfacial tensions. Further multiphase flows include investigating miscible jets, which allow the creation of fibers from inelastic materials that are otherwise difficult to process due to capillary breakup. This work shows that stabilization from the diminishing interfacial tensions of the miscible jets allows various elongated morphologies to be formed. 相似文献