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1.
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
2.
The Mitsunobu reaction is a widely used and versatile method for the dehydrative oxidation–reduction condensation of an acid/pronucleophile usually with a primary or secondary alcohol that requires the combination of a reducing phosphine reagent together with an oxidizing azo reagent. The utility of this reaction stems from the fact that it is generally highly stereoselective and occurs with inversion of the stereochemical configuration of the alcohol starting material. Furthermore, as carboxylic acids, phenols, imides, sulfonamides, and other compounds can be used as the acid/pronucleophile, this reaction is useful for the preparation of a wide variety of functional groups. This Focus Review of the Mitsunobu reaction summarizes its origins, the current understanding of its mechanism, and recent improvements and applications. 相似文献
3.
Na Li Dr. Pengxiang Zhao Prof. Didier Astruc 《Angewandte Chemie (International ed. in English)》2014,53(7):1756-1789
Anisotropic gold nanoparticles (AuNPs) have attracted the interest of scientists for over a century, but research in this field has considerably accelerated since 2000 with the synthesis of numerous 1D, 2D, and 3D shapes as well as hollow AuNP structures. The anisotropy of these nonspherical, hollow, and nanoshell AuNP structures is the source of the plasmon absorption in the visible region as well as in the near‐infrared (NIR) region. This NIR absorption is especially sensitive to the AuNP shape and medium and can be shifted towards the part of the NIR region in which living tissue shows minimum absorption. This has led to crucial applications in medical diagnostics and therapy (“theranostics”), especially with Au nanoshells, nanorods, hollow nanospheres, and nanocubes. In addition, Au nanowires (AuNWs) can be synthesized with longitudinal dimensions of several tens of micrometers and can serve as plasmon waveguides for sophisticated optical devices. The application of anisotropic AuNPs has rapidly spread to optical, biomedical, and catalytic areas. In this Review, a brief historical survey is given, followed by a summary of the synthetic modes, variety of shapes, applications, and toxicity issues of this fast‐growing class of nanomaterials. 相似文献
4.
A method for simultaneous neutron activation determination of Al, Mg and Si using two irradiations in a nuclear reactor—the first one with epithermal and the second one with pile neutrons is proposed. The applicability of the method is demonstrated by the analysis of standard reference materials—rocks, glass, as well as of archaeological finds from medieval glass and sgraffito ceramics. 相似文献
5.
The development of antimicrobial food packaging is needed for food preservation and quality maintenance. Silver nanoparticles (AgNPs) have been widely used as an antimicrobial agent in food packaging technologies. However, the risks associated with their potential migration into foods are a major concern. This paper comprehensively reviews the use of AgNPs in food packaging technologies. The application of AgNPs in food packaging technologies has been regulated by the United States Food and Drug Administration and the European Food Safety Authority. The addition of AgNPs into food packaging can improve their barrier, mechanical, and antibacterial properties, as well as maintain the quality of foods. Migration of AgNPs from food packaging into foods is still a concern as it has implications for human health associated with their toxicity properties. A study on the toxicological properties of AgNPs released from food packaging needs to be carried out intensively to ensure their safety before being widely implemented. Moreover, comprehensive economic evaluation to implement AgNPs in food packaging is needed as such a study is missing in the literature. 相似文献
6.
Yada M Inoue Y Uota M Torikai T Watari T Noda I Hotokebuchi T 《Langmuir : the ACS journal of surfaces and colloids》2007,23(5):2815-2823
Sodium titanate nanotube/titanium metal composites were synthesized by hydrothermal treatment of titanium metals with various morphologies such as plate, wire, mesh, microsphere, and microtube at 160 degrees C in aqueous NaOH solution and by the subsequent fixation treatment by calcination at 300 degrees C. The surface of the composite was covered with sodium titanate nanotubes with a diameter of approximately 7 nm, and the core part of the composite was titanium metal phase. The raw titanium metal acts as a template or a morphology-directing agent of micrometer size or more to arrange the nanotubes as well as a titanium source for the formation of nanotubes. The concentration of titanium species increases in the reaction solution as the dissolution of titanium metal is accelerated by the reaction between titanium and OH-. Furthermore, with an increase in concentration of titanium species in the reaction solution, the titanium species are re-precipitated as sodium titanate nanotubes onto the titanium metal. Titanium metal with a large surface area and volume can form sodium titanate nanotubes on the surface of the titanium metal, though titanium metal with a small volume and surface area tends to dissolve with the hydrothermal treatment. Even in the synthesis using titanium metal with a small volume and surface area, sodium titanate nanotubes are formed and cover the surface of the titanium metal by adding another titanium metal as a source of titanium species in the reaction solution. 相似文献
7.
A polystyrenesulfonic acid resin in the hydrogen form is a useful stationary phase for chromatographic separation of adenine, caffeine, theobromine, theophylline, tannic acid, xanthine and tea components with aqueous ethanol as eluent. The results indicated that caffeine, theophylline, theobromine, adenine, xanthine and tannic acid could be separated on a column of Dowex-50W-X8(H)+ by elution with 25% ethanol as eluent. 相似文献
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9.
Measurements on chitosan, which is used as a selective chromatographic support in inorganic chromatography, show that its molecular weight is 1.2 x 10(5), the nitrogen content is 7.4%, and its crystalline structure is not lost after adsorption of metal ions, which are co-ordinated with the nitrogen atoms of the -NH(2) groups of the polymer. Chitosan treated with copper sulphate exhibits a new crystal structure and a distinctive infrared spectrum, is quite stable and does not shrink, and is proposed as a chromatographic support for ligand-exchange chromatography. 相似文献
10.
H. A. Vogel 《Journal of polymer science. Part A, Polymer chemistry》1970,8(8):2035-2047
A new class of high molecular weight polyarylsulfones is described. Polymer synthesis and structure–property relationships are discussed. The polymers are prepared by Friedel-Crafts type polycondensation of aromatic sulfonyl chlorides with aromatic hydrocarbons. A number of Lewis acids in small quantities are useful as catalysts for the polymerization. The polymerization reaction is carried out at elevated temperatures in the melt or in solution. Inert, nonbasic solvents which are compatible with the Lewis acid catalysts such as nitrobenzene and dimethyl sulfone are useful for conducting the polymerization. Many of the polyarylsulfones are amorphous, rigid thermoplastics with unusually high softening points, having glass transition temperatures in the range of 200–350°C. Outstanding resistance to air oxidation at high temperatures is derived from incorporation of the deactivating sulfone groups in the aromatic polymer backbone. Melt stability and solubility in selected solvents are emphasized as basis for processibility by conventional solution casting and molding techniques. The combination of properties, which in addition to thermal stability includes a high level of mechanical and electrical properties, chemical inertness, and hydrolysis resistance makes these new arylsulfone polymers useful over a wide temperature range and in severe and corrosive environments. 相似文献
11.
H. X. Nguyen H. Ishida F. I. Hurwitz J. P. Gorecki L. D'Amore L. H. Hyatt 《Journal of Polymer Science.Polymer Physics》1989,27(8):1611-1627
4,4′-Diethynyldiphenylmethane thermally polymerizes by a free radical mechanism to a highly crosslinked structure of interest as a high temperature composite matrix resin. The polymerization reaction was characterized by differential scanning calorimetry, Fourier-transform infrared (FTIR) spectroscopy, 1H and 13C nuclear magnetic resonance (NMR) spectroscopy, and microdi-electrometry. The predominant reaction mechanism appears to be linear polymerization through the acetylene end groups, which follows first-order kinetics. However, during the early stages of reaction a second, more rapid polymerization mechanism is evident; it is postulated that this is the formation of a cyclic trimer, which is kinetically favored but sterically prohibited as the crosslinked network grows. Formation of a liquid crystalline trimer is hyppthesized; such intermediate formation is supported by intensity increases in the aromatic region of the NMR spectra, by FTIR difference spectroscopy comparisons with model compounds, and by enhancement of conductivity as observed by microdielectrometry. 相似文献
12.
M Calvin 《Angewandte Chemie (International ed. in English)》1974,13(2):121-131
A brief statement concerning the way in which biopolymers may have originated in the nonbiological world is made, including experimental evidence. This also includes a discussion of such matters as the way in which the code might have originated, that is, the relationship between polypeptides and polynucleotides as well as the secondary and tertiary structure resulting from the primary structure determination. The importance of the interaction of biopolymers with lipids for the formation of limiting membranes, leading to the formation of cells and other self-organizing cellular type organelles, is discussed. Thus, the second critical physical-chemical problem for cellular organization, namely, the biopolymer-lipid interaction, is now coming under scrutiny, both in terms of synthetic systems as well as natural ones. 相似文献
13.
Hermann Josef Roth 《Chemie in Unserer Zeit》2005,39(3):182-187
Words and molecules are comparable. Words are a string of letters just as molecules are linked atoms. Isomers can be considered as molecular anagrams. Isosteres correspond to verbal metagrams. The linkage of identic syllables in a word is comparable with the linkage of same atomic groups in a molecule. Numerous natural substances and active compounds (drugs) correspond in their structure to a palindrom, which results in the same sense read from left to the right as in reverse. 相似文献
14.
Celik H Ekmekci G Ludvík J Pícha J Zuman P 《The journal of physical chemistry. B》2006,110(13):6785-6796
Aromatic oximes are reduced in aqueous solution in a four-electron process. The reducible species in the pH range 5-8 is a diprotonated form of the oxime. This species is generated in the course of electrolysis in the vicinity of the electrode surface from the adsorbed neutral form of the oxime. The reduction is initiated by a cleavage of the N-O bond. The diprotonation facilitates the reduction process by the preformation of OH2+ as a good leaving group and by a positive charge on the azomethine nitrogen. Diprotonation has been proven based on shapes of i = f(pH) plots, by observed shifts of half-wave potentials with pH and by comparison with the reduction of nitrones. Some observed deviations from theoretical i = f(pH) plots were attributed to the role of adsorption on the rate of protonation. Adsorption is also responsible for dips on some of the i-E curves. Adsorption plays a role at concentrations as low as 1 x 10(-5) M, when the electrode surface is still not fully covered. This indicates that catalyzed protonation occurs on islets of adsorbed materials. At pH 2-5 the studied oximes in the vicinity of the electrode are predominately present in a protonated form, which is less strongly adsorbed. In this pH range the protonation takes place in a homogeneous reaction layer of the electrode. It yields a monoprotonated form, which is reduced. The separation of two two-electron waves observed for some oximes in acidic media serves as an experimental proof of the formation of imines as reduction intermediates. This separation is caused by the differences in pKa values of protonated forms of oximes and imines. The effects of substituents in the para position on the benzene ring are characterized by correlation with the Hammett substituent constant sigmax. This has been proven at pH 1.5 for substituted benzaldehyde oximes and at pH 5.0 for substituted acetophenone oximes. 相似文献
15.
《Progress in Surface Science》1986,21(2):93-162
This paper presents systematically the surface Green function matching analysis for systems with inherently discrete structure - e.g. phonons or tight-binding electrons. The general interface problem, the free surface, the vacancy - as a particular case of an inner surface - and point defects and adsorbates - as examples of interfaces - can all be treated on the same footing. By combining ideas of scattering and matching a unified approach encompasses a variety of different problems while yielding a method which can be used in practice for calculating e.g. surface, interface or defect state eigenvalues or spectral functions of interest. This holds for any type of physical states - electrons, phonons, waves - and for any chosen model. The practical combination with transfer matrix algorithms for planar geometry is discussed and an algorithm for growing shells is presented for point defects. Phonons allow for a discussion of the long-wave limit and contract is thus established with the surface Green function matching analysis for continuous media. The analysis is extended to layered structures - quantum wells and superlaticces - both for discrete and continuous systems. 相似文献
16.
Kobayashi N Nakajima S Ogata H Fukuda T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(24):6294-6312
Tetraazaporphyrins (TAPs), phthalocyanines (Pcs), naphthalocyanines (Ncs), and anthracocyanines (Acs) with four tert-butyl groups attached at similar positions have been synthesized, and their electronic absorption, magnetic circular dichroism (MCD), IR, and voltammetric properties were studied and interpreted with the help of quantum-mechanical calculations. Through the preparation of a series of compounds with the same number of the same substituent, the effects of the increase in the size of the ring system were clearly derived. The main results may be summarized as follows. 1) The Q band shifts to longer wavelength and its intensity increases, but with decreasing degree of change with increasing molecular size. If the size of the effect of benzene directly fused to the TAP skeleton is set at unity, the effects of the second and third benzene units are roughly 0.8 and 0.5, respectively. 2) The splitting of the Q bands in metal-free compounds decreases with increasing molecular size, so that the Q bands of H2Nc and H2Ac appear as single bands. 3) The magnitude of the orbital angular momentum of the excited state of the ligand decreases with increasing molecular size. 4) Interestingly, the ring current, as judged from the positions of pyrrole proton signals in the 1H NMR spectrum, appears to decrease with increasing molecular size. 5) The first reduction potential becomes less negative, but only slightly, whereas the first oxidation potential shows a marked shift to less positive values with increasing molecular size, indicating that the HOMO destabilizes significantly as the molecule becomes larger. 6) In 5), the extent of the HOMO destabilization with molecular size differs depending on the central metal, so metals producing smaller destabilization effects can allow larger macrocycles. Of the metals studied, the most effective is cobalt, and the practical size limit is represented by the Acs. 7) The IR spectra become simpler the larger the molecule, and the main bands were assigned by DFT calculations. 8) The trend in experimentally determined redox potentials and electronic absorption and MCD spectra were reasonably reproduced by MO calculations using the ZINDO/S Hamiltonian. 9) EPR data for several metallocomplexes are also reported. 相似文献
17.
Marshall Natapoff 《Chemical physics letters》1981,78(2):375-378
The distance in an atom from the nucleus to the final node in the wavefunction of a valence electron has been defined as the nodal radius. This parameter, in conjunction with a Thomas-Fermi pseudo-potential, is used to calculate the nearest-neighbor distance in some octet compounds. Calculated values of the atomic radii are compared with the semi-empirical ionic and tetrahedral radii for atoms in these compounds. 相似文献
18.
We propose a parameter-free algorithm for the identification of nearest neighbors. The algorithm is very easy to use and has a number of advantages over existing algorithms to identify nearest-neighbors. This solid-angle based nearest-neighbor algorithm (SANN) attributes to each possible neighbor a solid angle and determines the cutoff radius by the requirement that the sum of the solid angles is 4π. The algorithm can be used to analyze 3D images, both from experiments as well as theory, and as the algorithm has a low computational cost, it can also be used "on the fly" in simulations. In this paper, we describe the SANN algorithm, discuss its properties, and compare it to both a fixed-distance cutoff algorithm and to a Voronoi construction by analyzing its behavior in bulk phases of systems of carbon atoms, Lennard-Jones particles and hard spheres as well as in Lennard-Jones systems with liquid-crystal and liquid-vapor interfaces. 相似文献
19.
A new protocol for the Ullmann-type arylation process of different aromatic heterocycles without any transition-metal catalyst, implying the use of a combination of an excess of potassium hydroxide and dimethyl sulfoxide, is described. The reaction can be performed between a broad range of starting nucleophiles including phenol, alcohols, amines, nitrogen-containing five-membered systems such as pyrazoles, imidazoles, and indoles, and amides with haloarenes, iodide and bromide derivatives giving the best results, the possible pathway involving the in situ generation of the corresponding benzyne intermediate. When the reaction was performed with 2-iodoaniline and either carboxamides or isothiocyanato derivatives, the corresponding benzoazole derivatives were obtained. 相似文献
20.
This paper reviews calibration-, uncertainty-, and recovery-related documents from 10 consensus-based organizations. The main points from each treatise are summarized. Also included is a critique of the various approaches, as well as recommendations for a statistically sound protocol that is more compatible with chromatographic data. 相似文献