RESUMO
Heteroditopic monomers containing an arylboronate ester and a dialkyl-4-aminopyridine group aggregate via dative boron-nitrogen bonds to give main chain supramolecular polymers. The degree of polymerization can be tuned by changing the electronic and steric properties of the boronate ester.
RESUMO
Dative boron-nitrogen bonds were found to be a useful binding motif in structural supramolecular chemistry. Crystalline cages were formed using a diboronate ester and 2,4,6-tri(4-pyridyl)-1,3,5-triazine. These cages can act as hosts for electron-rich planar aromatic systems such as triphenylene. Further, crystalline two-dimensional polymers were formed via dative B-N bonds between a triboronic ester and a ditopic pyridyl ligand. Use of an extended triboronate ester resulted in formation of a gel in toluene with a minimum gelation concentration of 0.5 wt%.
RESUMO
We present an experimental and computational study of the reaction of aryl substituted benzyl 1-alkynyl sulfides with potassium alkoxide in acetonitrile, which produces 2-aryl 2,3-dihydrothiophenes in poor to good yields. The cyclization is most efficient with electron withdrawing groups on the aromatic ring. Evidence indicates there is rapid exchange of protons and tautomerism of the alkynyl unit prior to cyclization. Theoretical calculations were also conducted to help rationalize the base induced 5-endo cyclization of benzyl 1-propynyl sulfide (1a). The potential energy surface was calculated for the formation of 2,3-dihydrothiophene in a reaction of benzyl 1-propynyl sulfide (1a) with potassium methoxide. Geometries were optimized with CAM-B3LYP/6-311+G(d,p) in acetonitrile with the CPCM solvent model. It is significant that the benzyl propa-1,2-dien-1-yl sulfane (6) possessed a lower benzylic proton affinity than the benzyl prop-2-yn-1-yl sulfane (8) thus favoring the base induced reaction of the former. From benzyl(propa-1,2-dien-1-yl sulfane (6), 2,3-dihydrothiophene can be formed via a conjugate base that undergoes 5-endo-trig cyclization followed by a protonation step.
RESUMO
A procedure to evaluate the surface dipole potential chi of thiol and disulfide self-assembled monolayers (SAMs) is described. The procedure consists of self-assembling the monolayers on a hanging mercury drop electrode and of measuring the charge involved in a progressive expansion of the mercury drop. This measurement is then combined with an estimate of the charge density q experienced by diffuse layer ions, obtained by measuring the diffuse layer capacitance of the SAM at different electrolyte concentrations by electrochemical impedance spectroscopy. These chi measurements, combined with chronocoulometric measurements of the total charge density sigma(M) against potential, indicate that SAMs of tetraoxyethylene glycol-D,L-alpha-lipoic acid ester (TEGL), 2,3-di-O-phytanyl-sn-glycerol-1-tetraoxyethylene glycol-D,L-alpha-lipoic ester (DPTL), and trioxyethyleneoxythiol (EO3) on mercury may undergo a reversal in the surface dipole potential of their polyoxyethylene chain with a change in the interfacial electric field. Moreover, TEGL and EO3 form stable SAMs without electron transfer to the metal, while no such conclusion can be drawn for DPTL.
RESUMO
Atomic force microscopy (AFM) has been used to characterize the formation of a phospholipid bilayer composed of 1,2-dimyristyl-sn-glycero-3-phosphocholine (DMPC) at a Au(111) electrode surface. The bilayer was formed by one of two methods: fusion of lamellar vesicles or by the combination of Langmuir-Blodgett (LB) and Langmuir-Schaefer (LS) deposition. Results indicate that phospholipid vesicles rapidly adsorb and fuse to form a film at the electrode surface. The resulting film undergoes a very slow structural transformation until a characteristic corrugated phase is formed. Force-distance curve measurements reveal that the thickness of the corrugated phase is consistent with the thickness of a bilayer lipid membrane. The formation of the corrugated phase may be explained by considering the elastic properties of the film and taking into account spontaneous curvature induced by the asymmetric environment of the bilayer, in which one side faces the gold substrate and the other side faces the solution. The effect of temperature and electrode potential on the stability of the corrugated phase has also been described.
Assuntos
Eletroquímica/métodos , Ouro/química , Microscopia de Força Atômica/métodos , Adsorção , Físico-Química/métodos , Dimiristoilfosfatidilcolina/química , Eletrodos , Eletrólitos , Cinética , Bicamadas Lipídicas/química , Modelos Biológicos , Propriedades de Superfície , TemperaturaRESUMO
The adsorption behavior of the cationic surfactant N-decyl-N,N,N-trimethylammonium triflate (DeTATf) on the Au(111) electrode surface was characterized using cyclic voltammetry, differential capacity, and chronocoulometry. The thermodynamics of the ideally polarized electrode have been employed to determine the Gibbs excess and the Gibbs energy of adsorption. The results show that the adsorption of DeTATf has a multistate character. At low bulk DeTATf concentrations, the adsorption state is consistent with the formation of an adsorbed film of nearly flat molecules. At higher concentrations this film may represent a three-dimensional aggregated state. At negative potentials and charge densities close to 0 microC cm-2, the data suggest the formation of a film of tilted molecules oriented with the hydrocarbon tail toward the metal surface and the polar head toward the solution. A surprising result of this study is that DeTATf displays adsorption characteristics of a zwitterionic rather than a cationic surfactant. This behavior indicates that the adsorbed species is an ion pair.