全文获取类型
收费全文 | 472篇 |
免费 | 21篇 |
国内免费 | 2篇 |
专业分类
化学 | 369篇 |
晶体学 | 2篇 |
力学 | 15篇 |
数学 | 54篇 |
物理学 | 55篇 |
出版年
2023年 | 6篇 |
2022年 | 4篇 |
2021年 | 14篇 |
2020年 | 13篇 |
2019年 | 6篇 |
2018年 | 5篇 |
2017年 | 7篇 |
2016年 | 20篇 |
2015年 | 15篇 |
2014年 | 16篇 |
2013年 | 39篇 |
2012年 | 35篇 |
2011年 | 39篇 |
2010年 | 20篇 |
2009年 | 13篇 |
2008年 | 22篇 |
2007年 | 24篇 |
2006年 | 19篇 |
2005年 | 20篇 |
2004年 | 19篇 |
2003年 | 14篇 |
2002年 | 21篇 |
2001年 | 6篇 |
2000年 | 6篇 |
1999年 | 5篇 |
1998年 | 5篇 |
1997年 | 4篇 |
1996年 | 2篇 |
1995年 | 3篇 |
1994年 | 3篇 |
1993年 | 6篇 |
1992年 | 2篇 |
1991年 | 5篇 |
1990年 | 2篇 |
1989年 | 6篇 |
1988年 | 2篇 |
1987年 | 5篇 |
1986年 | 2篇 |
1985年 | 5篇 |
1984年 | 3篇 |
1982年 | 6篇 |
1981年 | 2篇 |
1980年 | 7篇 |
1979年 | 7篇 |
1978年 | 2篇 |
1976年 | 1篇 |
1975年 | 3篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有495条查询结果,搜索用时 15 毫秒
61.
Molecular-mechanics calculations for strain of carbenium ions are tested using Bentley's unified reactivity scale for bridgehead solvolysis as reference. Excellent correlations are obtained for solvolytic bridgehead reactivity with the calculated steric-energy difference (ΔEst) between substrate (R? H or R? OH) and cation (R+). After adjustment of appropriate force-field parameters, the approach is successfully extended to the rigid, but planar cations derived from structures 15 – 20 ; however, the general set of parameters cannot be applied to highly strained systems such as the cation formed from 17 . With all of the 18 sets of parameters tested, the 2-endo-norbornyl derivative 16 , is adequately correlated, while the exo isomer 15 exhibits enhanced reactivity by a factor of ca. 102 to 103. 相似文献
62.
Optical lens systems that are characterized by a chromatic aberration of a predefined form are called hyperchromats. Our work describes a theory of hyperchromats with a linear dependence of longitudinal chromatic aberration on wavelength. The equations are derived for calculation of basic design parameters of these optical systems and some examples of hyperchromatic optical systems are shown. Mentioned optical systems can be used especially in 3D imaging systems and confocal microscopy. 相似文献
63.
Jiri Müller 《International journal of quantum chemistry》1982,21(2):465-473
CI calculations were performed on the energies and relative intensities of the outer and inner valence levels of the CS molecule. Breakdown of the one-particle model is discussed in terms of CI, and the results are compared with the analogous investigations using the Green's function technique. 相似文献
64.
The vibrational excitations in the core and valence ESCA bands of CO and N2 have been investigated by means of Franck—Condon (FC) analysis. FC factors obtained from optimized geometries and from the force constants of the neutral ground and ionized states are compared with those obtained from calculated ionized-state energy gradients. Geometries, force constants, and energy gradients are calculated both from frozen-orbital energies and from OS RHF wavefunctions. The differences between the results of the methods employed are discussed in the light of experimental data. 相似文献
65.
Jiri Kos Tomas Gonec Michal Oravec Izabela Jendrzejewska Josef Jampilek 《Molecules (Basel, Switzerland)》2021,26(14)
A set of twenty-four 3-hydroxynaphthalene-2-carboxanilides, disubstituted on the anilide ring by combinations of methoxy/methyl/fluoro/chloro/bromo and ditrifluoromethyl groups at different positions, was prepared. The compounds were tested for their ability to inhibit photosynthetic electron transport (PET) in spinach (Spinacia oleracea L.) chloroplasts. N-(3,5-Difluorophenyl)-, N-(3,5-dimethylphenyl)-, N-(2,5-difluorophenyl)- and N-(2,5-dimethylphenyl)-3-hydroxynaphthalene-2-carboxamides showed the highest PET-inhibiting activity (IC50 ~ 10 µM) within the series. These compounds were able to inhibit PET in photosystem II. It has been found that PET-inhibiting activity strongly depends on the position of the individual substituents on the anilide ring and on the lipophilicity of the compounds. The electron-withdrawing properties of the substituents contribute towards the PET activity of these compounds. 相似文献
66.
Jiri Benovsky 《Acta Analytica》2013,28(2):223-227
In this paper, I argue that (non-presentist) endurantism is incompatible with the view that properties are universals. I do so by putting forward a very simple objection that forces the endurantist to embrace tropes, rather than universals. I do not claim that this is bad news for the endurantist—trope theory seems to me by all means more appealing than universals—rather, I would like to see this result as a further motivation to embrace tropes. I then also put forward a (more controversial) reason to believe that at least some versions of perdurantism also require tropes rather than universals. 相似文献
67.
Dr. Yingjie Zhao Dr. Guangxi Huang Dr. Celine Besnard Dr. Jiri Mareda Dr. Naomi Sakai Prof. Stefan Matile 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(16):6202-6207
General synthetic access to expanded π‐acidic surfaces of variable size, topology, chirality, and π acidity is reported. The availability of π surfaces with these characteristics is essential to develop the functional relevance of anion–π interactions with regard to molecular recognition, translocation, and transformation. The problem is that, with expanded π surfaces, the impact of electron‐withdrawing substituents decreases and the high π acidity needed for strong anion–π interactions can be more difficult to obtain. To overcome this problem, it is herein proposed to build large surfaces from smaller fragments and connect these fragments with bridges that are composed only of single atoms. Two central surfaces for powerful anion–π interactions, namely, perfluoroarenes and naphthalenediimides (NDIs), were selected as fragments and coupled with through sulfide bridges. Their oxidation to sulfoxides and sulfones, as well as fluorine substitution in the peripheral rings, provides access to the full chemical space of relevant π acidities. According to cyclic voltammetry, LUMO levels range from ?3.96 to ?4.72 eV. With sulfoxide bridges, stereogenic centers are introduced to further enrich the intrinsic planar chirality of the expanded surfaces. The stereoisomers were separated by chiral HPLC and characterized by X‐ray crystallography. Their topologies range from chairs to π boats, and the latter are reminiscent of the cation–π boxes in operational neuronal receptors. With pentafluorophenyl acceptors, the π acidity of NDIs with two sulfoxide groups in the core reaches ?4.45 eV, whereas two sulfone moieties give a value of ?4.72 eV, which is as low as with four ethyl sulfone groups, that is, a π superacid near the limit of existence. Beyond anion–π interactions, these conceptually innovative π‐acidic surfaces are also of interest as electron transporters in conductive materials. 相似文献
68.
A new approach to the selective comparative metabolite profiling of carboxylic acids in rat urine was established using CE‐MS and a method for positively pre‐charged and 2H‐coded derivatization. Novel derivatizing reagents, N‐alkyl‐4‐aminomethyl‐pyridinum iodide (alkyl=butyl, butyl‐d9 or hexyl), containing quaternary amine and stable‐isotope atoms (deuterium), were introduced for the derivatization of carboxylic acids. CE separation in positive polarity showed high reproducibility (0.99–1.32% RSD of migration time) and eliminated problems with capillary coating known in CE‐MS anion analyses. Essentially complete ionization and increased hydrophobicity after the derivatization also enhanced MS detection sensitivity (e.g. formic acid was detected at 0.5 pg). Simultaneous derivatization of one sample using two structurally similar reagents, N‐butyl‐4‐aminomethyl‐pyridinum iodide (BAMP) and N‐hexyl‐4‐aminomethyl‐pyridinum iodide, provided additional information for recognizing a carboxylic acid in an unknown sample. Moreover, characteristic fragmentation acquired by online CE‐MS/MS allowed for identification and categorization of carboxylic acids. Applying this method on rat urine, we found 59 ions matching the characteristic patterns of carboxylic acids. From these 59, 32 ions were positively identified and confirmed with standards. For comparative analysis, 24 standard carboxylic acids were derivatized by chemically identical but isotopically distinct BAMP and N‐butyl‐d9‐4‐aminomethyl‐pyridinium iodide, and their derivatization limits and linearity ranges were determined. Comparative analysis was also performed on two individual urine samples derivatized with BAMP and N‐butyl‐d9‐4‐aminomethyl‐pyridinium iodide. The metabolite profiling variation between these two samples was clearly visualized. 相似文献
69.
Lanthanide nitrates and bis(diphenylphosphino)hexane dioxide (dpphO2) formed under solvothermal conditions a series of coordination polymers [Ln(dpphO2)2(NO3)2](NO3) (Ln = Pr (1), Nd (2), Sm (3), Dy (4), Lu (5)), featuring two-dimensional network structure of the (4, 4) topology. The compounds [Ln(dpphO2)2Cl2]Cl (Ln = Pr (6), Nd (7), Gd (8)) were obtained from corresponding chlorides. Coordination polymer 7 formed regular single crystals of the orthorhombic Pna21 space group. The nitrate complexes crystallized in the orthorhombic Aea2 space group, however, the crystals were pseudo-merohedral twins simulating a tetragonal diffraction pattern. Unlike our previously characterized neutral polymers with bis(diphenylphosphino)ethane dioxide, all present coordination networks are cationic, with anions located between or within the two-dimensional layers. 相似文献
70.
Hagihara S Gremaud L Bollot G Mareda J Matile S 《Journal of the American Chemical Society》2008,130(13):4347-4351
Synthetic ion channels and pores attract current attention as multicomponent sensors in complex matrixes. This application requires the availability of reactive signal amplifiers that covalently capture analytes and drag them into the pore. pi-Basic 1,5-dialkoxynaphthalenes (1,5-DAN) are attractive amplifiers because aromatic electron donor-acceptor (AEDA) interactions account for their recognition within pi-acidic naphthalenediimide (NDI) rich synthetic pores. Focusing on amplifier design, we report here the synthesis of a complete collection of DAN and dialkoxyanthracene amplifiers, determine their oxidation potentials by cyclic voltammetry, and calculate their quadrupole moments. Blockage experiments reveal that subtle structural changes in regioisomeric DAN amplifiers can be registered within NDI pores. Frontier orbital overlap in AEDA complexes, oxidation potentials, and, to a lesser extent, quadrupole moments are shown to contribute to isomer recognition by synthetic pores. Particularly important with regard to practical applications of synthetic pores as multianalyte sensors, we further demonstrate that application of the lessons learned with DAN regioisomers to the expansion to dialkoxyanthracenes provides access to privileged amplifiers with submicromolar activity. 相似文献