The direction of the dipole moments of furan,thiophen, and pyrrole: A controversial question

The report that the dipole moment in the five-membered heterocyclic rings, furan, thiophene, and pyrrole has the positive pole on the heteroatom is contradicted with arguments based on reactivity data, theoretical calculations and moment values of substituted derivatives. In actuality, the dipole moment in furan and thiophene is directed from the ring (positive pole) to the heteroatom (negative pole).     

Optical Anisotropy of Porphyrin Nanocrystals Modified by the Electrochemical Dissolution

Reflectance anisotropy spectroscopy (RAS) coupled to an electrochemical cell represents a powerful tool to correlate changes in the surface optical anisotropy to changes in the electrochemical currents related to electrochemical reactions. The high sensitivity of RAS in the range of the absorption bands of organic systems, such as porphyrins, allows us to directly correlate the variations of the optical anisotropy signal to modifications in the solid-state aggregation of the porphyrin molecules. By combining in situ RAS to electrochemical techniques, we studied the case of vacuum-deposited porphyrin nanocrystals, which have been recently observed dissolving through electrochemical oxidation in diluted sulfuric acid. Specifically, we could identify the first stages of the morphological modifications of the nanocrystals, which we could attribute to the single-electron transfers involved in the oxidation reaction; in this sense, the simultaneous variation of the optical anisotropy with the electron transfer acts as a precursor of the dissolution process of porphyrin nanocrystals.     

The water-silicas interfacial interaction energies

The water-silicas interfacial interaction energies were calculated for samples of quartz, silicas and silicas outgassed at high temperatures using own and published data of the spreading pressure of water, its surface tension, its contact angle and using formulas obtained by the combination of the Young equation with a general equation of pair interaction. The values obtained for 18 different samples were in the range 7.80-6.92 kJ mol⁻¹. Lower values of energies are for samples that contain relatively less amounts of water at P/P₀ = 0.25 and are characterized also by relatively low values of surface pressures.     

Driving Organic Nanocrystals Dissolution Through Electrochemistry

We have recently discussed how organic nanocrystal dissolution appears in different morphologies and the role of the solution pH in the crystal detriment process. We also highlighted the role of the local molecular chemistry in porphyrin nanocrystals having comparable structures: in water-based acid solutions, protonation of free-base porphyrin molecules is the driving force for crystal dissolution, whereas metal (Zn^II) porphyrin nanocrystals remain unperturbed. However, all porphyrin types, having an electron rich π-structure, can be electrochemically oxidized. In this scenario, a key question is: does electrochemistry represent a viable strategy to drive the dissolution of both free-base and metal porphyrin nanocrystals? In this work, by exploiting electrochemical atomic force microscopy (EC-AFM), we monitor in situ and in real time the dissolution of both free-base and metal porphyrin nanocrystals, as soon as molecules reach the oxidation potential, showing different regimes according to the applied EC potential.     

A Stable Porphyrin Functionalized Graphite Electrode Used at the Oxygen Evolution Reaction Potential

Many researches have been devoted to rechargeable power generators that can store (but also release) energy. This availability is ensured through (e. g.) the oxygen evolution reaction (OER). However, (i) large values of the overpotentials and (ii) a progressive detriment of the anode (graphite) electrode limit the ultimate device. In view of enhancing the electrode performances, graphite was protected by following different strategies, which oblige to follow precise preparation protocols. Here, we prove that a thin layer of free-base porphyrin molecules is able to protect the underneath graphite electrode from detriment even if many (about 100) electrochemical cycles are performed.     

Growth-related properties and postgrowth phenomena in organic molecular thin films

The problem of monitoring the structural and morphological evolutions of thin films of organic molecular materials during their growth by organic molecular beam epitaxy and in the postgrowth stage is addressed here by a combination of in situ optical reflectance anisotropy measurements, ex situ optical and morphological investigations, and theoretical simulation of the material optical response. For alpha-quaterthiophene, a representative material in the class of organic molecular semiconductors, the results show that molecules crystallize in the first stage of growth in metastable structures, even when deposition is carried out at room temperature. In the postdeposition stage, the film structure evolves within a few days to the known equilibrium structure of the low temperature polymorph. When deposition is carried out at low substrate temperatures, an evolution of the film morphology is also demonstrated.     

Compared EC-AFM Analysis of Laser-Induced Graphene and Graphite Electrodes in Sulfuric Acid Electrolyte

Flexible and economic sensor devices are the focus of increasing interest for their potential and wide applications in medicine, food analysis, pollution, water quality, etc. In these areas, the possibility of using stable, reproducible, and pocket devices can simplify the acquisition of data. Among recent prototypes, sensors based on laser-induced graphene (LIGE) on Kapton represent a feasible choice. In particular, LIGE devices are also exploited as electrodes for sensing in liquids. Despite a characterization with electrochemical (EC) methods in the literature, a closer comparison with traditional graphite electrodes is still missing. In this study, we combine atomic force microscopy with an EC cell (EC-AFM) to study, in situ, electrode oxidation reactions when LIGE or other graphite samples are used as anodes inside an acid electrolyte. This investigation shows the quality and performance of the LIGE electrode with respect to other samples. Finally, an ex situ Raman spectroscopy analysis allows a detailed chemical analysis of the employed electrodes.     

The surface energy of talc

The determination of an average value for the surface energy of talc (gammaS) via solid-water interfacial interactions is described. It is based on a formula obtained by the combination of the Young equation with a general equation of pair interaction. Important features of the method are (a) the use of the Young equation to determine the range where the value of the surface energy lies and (b) the determination of the mean value within this range using a probability function. The value found is 217.31 mJ m(-2) in the range 193.36-257.43 mJ m(-2).     

Partial specific adsorption of organic molecules in binary mixtures of adsorbents: 2,2'-bipyridine on kaolinite and hematite and 1,10-phenanthroline on montmorillonite and hydroxy-Al montmorillonite

The adsorption of 2,2'-bipyridyl in binary mixtures of sodium kaolinite and hematite at pH 6.6 and of 1,10-phenanthroline in binary mixtures of sodium montmorillonite and hydroxy-Al montmorillonite at pH 7.5 was studied as a function of the equilibrium concentration and composition of the mixture. A model is presented for determining the partial specific adsorption of two adsorbents by each component of the mixture, based on the graphic method for determining partial quantities. The partial specific adsorption values obtained for binary mixtures of Na-kaolinite with hematite and Na-montmorillonite with hydroxy-Al montmorillonite are strongly influenced by the concentration of adsorbates and adsorbents in the mixtures.