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41.
Claudio Baggiani Gianfranco Giraudi Cristina Giovannoli Cinzia Tozzi Laura Anfossi 《Analytica chimica acta》2004,504(1):43-52
The current opinion about molecular imprinted polymers (MIPs) is that their molecular recognition properties are due to the presence of nanocavities formed during a polymerization process developed in the presence of a template molecule. According to this principle, the shape of these nanocavities is complementary to that of the template and non-covalent interactions are established between the binding site and a single template molecule. Nevertheless, there are some experimental indications that the real molecular recognition mechanism involves clusters of template molecules being packed into the binding site. Recently, it has been proposed that template molecules covalently linked to the binding site can act as nucleation points, enhancing the formation of these molecular clusters.We have tested this hypothesis by studying the adsorption isotherms of polymers prepared by imprinting them with 2,4,5-trichlorophenoxyacetic acid (2,4,5-T). Three different polymers were considered: P0, prepared without the template, P1, whose template was represented by 2,4,5-T molecules, and P2, whose template was 1/3 constituted by the polymerisable 2-(2,4,5-trichlorophenoxyacetoxy)-ethylmethacrylate (2,4,5-TEMA) and 2/3 by 2,4,5-T. The polymers were prepared by thermoinduced polymerization of template mixtures, 4-vinylpyridine and ethylene dimethacrylate. The crushed polymers were packed into HPLC columns and frontal chromatographic runs were performed by eluting the columns with a mobile phase containing variable amounts of 2,4,5-T.The experimental adsorption isotherms were fitted by using several isotherm models, and the Freundlich-Langmuir model was found to give the best fitting in terms of F-test. All the models considered showed a significant difference between the affinity constant values measured for the polymer P1 and P2, with a higher value for the polymer P2 (for Freundlich-Langmuir model: polymer P1, k=(2.00±0.43)×104 M−1; polymer P2, k=(1.93±0.0535)×105 M−1; ratio P2/P1, 9.65±2.09). Such experimental results support the hypothesis that a polymer prepared with a limited amount of template covalently attached to the binding site shows an increased affinity for the template itself. 相似文献
42.
An expeditious synthesis of t-butyldimethylsilyl triflate is described from triflic acid and t-butyldimethylsilane. Reaction between trichloromethyltrimethylsilane and triflic acid is also reported. 相似文献
43.
Huang X Margulis CJ Li Y Berne BJ 《Journal of the American Chemical Society》2005,127(50):17842-17851
When supercritical CO2 is dissolved in an ionic liquid, its partial molar volume is much smaller than that observed in most other solvents. In this article we explore in atomistic detail and explain in an intuitive way the peculiar volumetric behavior experimentally observed when supercritical CO2 is dissolved in 1-butyl-3-methylimidazolium hexafluorophosphate ([Bmim+] [PF6(-)]). We also provide physical insight into the structure and dynamics occurring across the boundary of the CO2 ionic liquid interface. We find that the liquid structure of [Bmim+] [PF6(-)] in the presence of CO2 is nearly identical to that in the neat ionic liquid (IL) even at fairly large mole fractions of CO2. Our simulations indicate, in agreement with experiments, that partial miscibilities of one fluid into the other are very unsymmetrical, CO2 being highly soluble in the ionic liquid phase while the ionic liquid is highly insoluble in the CO2 phase. We interpret our results in terms of the size and shape of spontaneously forming cavities in the ionic liquid phase, and we propose that CO2 occupies extremely well-defined locations in the IL. Even though our accurate prediction of cavity sizes in the neat IL indicates that these cavities are small compared with the van der Waals radius of a single carbon or oxygen atom, CO2 appears to occupy a space that was for the most part a priori "empty". 相似文献
44.
Magnani A Marchettini N Ristori S Rossi C Rossi F Rustici M Spalla O Tiezzi E 《Journal of the American Chemical Society》2004,126(37):11406-11407
The present work deals with the spatially extended oscillatory Belousov Zhabotinsky reaction-diffusion system carried out in an anisotropic environment of phosphatidylcholines/water binary system, which presents layered aqueous domains separated by lipid bilayers. We report the occurrence of stable Turing patterns, spiral waves, and other exotic structures in phospholipids bilayers that are generally used as a models for cell plasma membranes. 相似文献
45.
Quassinoids from Picrasma crenata 总被引:1,自引:0,他引:1
From woods of Picrasma crenata, a new stereoisomer dihydronorneoquassin was obtained together with others well knowns dihydronorneoquassin, parain, alpha-neoquassin, beta-neoquassin and quassin. The structures were determined by spectroscopic data and chemical evidence. 相似文献
46.
A series of acyclic vinyl ethers have been prepared and treated with Grubbs' ruthenium catalyst ((Cy3P)2RuCl2=CHPh). Contrary to previous findings, it has been shown that certain vinyl ethers are excellent substrates for the ring closing metathesis with ruthenium based catalysts. 相似文献
47.
Marco Vincenti Claudio Minero Stefania Lago Costanza Rovida 《Journal of separation science》1995,18(6):359-362
A rapid and effective procedure, developed for the determination of polar compounds in water, has been applied to hydroxycarbamates. In few minutes, it is possible to perform a catalyzed derivatization of such compounds directly in the aqueous medium, using n-hexyl chloroformate. Extraction with n-hexane and injection into a benchtop GC-MS system are the only two further steps to complete the analysis. Chemical ionization proved to be more effective than electron impact to produce valuable mass spectra in terms of selectivity and sensitivity. Linear quantitative responses were demonstrated over a two-order-of-magnitude range. The minimum detectable concentration was 3 ppb for acetohydroxamic acid and 10 ppb for hydroxyurethane, obtained from Po river water samples spiked with the two hydroxycarbamate standards. 相似文献
48.
Calorimetric measurements were carried out on ester-solvent systems where the esters were H(CH2)xCOO(CH2)yH, with x and y varying from 1 to 5, and the solvents were n-hexane and 1,2-dichloroethane. Calculation of the enthalpies of cavity formation enabled the enthalpies of interaction to be determined. Both enthalpies correlated with number of carbon atoms N, equal to x+y in the esters, giving for 1,2-dichloroethane
相似文献
49.
Carlo Bruno Eleonora Ussano Gianni Barucca Davide Vanossi Giovanni Valenti Edward A. Jackson Andrea Goldoni Lucio Litti Simona Fermani Luca Pasquali Moreno Meneghetti Claudio Fontanesi Lawrence T. Scott Francesco Paolucci Massimo Marcaccio 《Chemical science》2021,12(23):8048
The presence of non-hexagonal rings in the honeycomb carbon arrangement of graphene produces rippled graphene layers with valuable chemical and physical properties. In principle, a bottom-up approach to introducing distortion from planarity of a graphene sheet can be achieved by careful insertion of curved polyaromatic hydrocarbons during the growth of the lattice. Corannulene, the archetype of such non-planar polyaromatic hydrocarbons, can act as an ideal wrinkling motif in 2D carbon nanostructures. Herein we report an electrochemical bottom-up method to obtain egg-box shaped nanographene structures through a polycondensation of corannulene that produces a new conducting layered material. Characterization of this new polymeric material by electrochemistry, spectroscopy, electron microscopy (SEM and TEM), scanning probe microscopy, and laser desorption-ionization time of flight mass spectrometry provides strong evidence that the anodic polymerization of corannulene, combined with electrochemically induced oxidative cyclodehydrogenations (Scholl reactions), leads to polycorannulene with a wavy graphene-like structure.A bottom-up synthesis of wavy graphene structures obtained through an anodic polymerization process, combined with an electrochemically triggered oxidative cyclodehydrogenation, of the bowl-shaped polyaromatic hydrocarbon corannulene. 相似文献
50.
Sia dato uno spazio topologicoE con azione di un monoide topologicoH e siaE→B una funzione continue che, su ogni apertoU di una partizione dell'unità diB, sia, a meno di omotopia, la proiezioneU×H→U (ovvero una fibrazione numerabile). Un classico risultato di A. Dold e R. Lashof (1959) permette di costruire, a partire
daE→B, una funzione continuaE
∞→B∞, conE
∞ debolmente contraibile e munito di azione diH: laH-fibrazione universale associata daH. Tale funzione, in generale, non è purtroppo numerabile e quindi non si presta alla classificazione delleH-fibrazioni numerabili. Successivamente (1971), M. Fuchs ha trovato un modo di modificare la costruzione di Dold-Lashof per
recuperare la numerabilità. La costruzione di Dold-Lashof-Fuchs è, da allora, uno dei principali strumenti nella teoria degli
spazi classificanti di monoidi topologici, anche se vi è un uso di topologie alquanto complesse e quindi poco maneggevoli.
In questo lavoro ci proponiamo di mostrare come, lavorando nella categoria conveniente deik-spazi, sia possibile descrivere la costruzione di Dold-Lashof-Fuchs in modo estremamente semplificato ed adattarla anche
alla classificazione delleF-fibrazioni numerabili.
Conferenza tenuta da R. Piccinini il 15 maggio 1995 相似文献 |