Molecular damage in bi-isonicotinic acid adsorbed on rutile TiO2(1 1 0)

Here we present the characteristic signatures in X-ray absorption and photoemission spectroscopy for molecular damage in adsorbed monolayers of bi-isonicotinic acid on a rutile TiO₂(1 1 0) surface. Bi-isonicotinic acid is the anchor ligand through which many important inorganic complexes are bound to the surface of TiO₂ in dye-sensitized solar cells. The nature of the damage caused by excessive heating of the adsorbed monolayer is consistent with splitting the molecule into two adsorbed isonicotinic acid molecular fragments. The effect on the lowest unoccupied molecular orbitals (involved in electron transfer in the molecule) can be understood in terms of the adsorption geometry of the reaction products and their nearest neighbor interactions.     

Sulfonylation of arenes with sulfonamides

In the presence of triflic anhydride, sulfonylation of arenes with sulfonamides proceeded smoothly in Cl₂CHCHCl₂ at 80-140 °C, which gave rise to the desired products in good to excellent yields.     

Liquid–liquid equilibria for {hexane + benzene + 1-ethyl-3-methylimidazolium ethylsulfate} at (298.2, 313.2 and 328.2) K

Liquid–liquid equilibria (LLE) for the ternary system {hexane + benzene + 1-ethyl-3-methylimidazolium ethylsulfate ([emim]C₂H₅SO₄)} have been measured at the temperatures (298.2, 313.2 and 328.2) K and atmospheric pressure. The reliability of the experimental data was tested using the Othmer–Tobias correlation. For the extractive effectiveness of the solvent, the distribution ratio and separation factor curves were plotted and compared with those of sulfolane. In addition, the LLE data were also correlated with UNIQUAC and NRTL models in a satisfactory manner.     

AFM, SEM and GIXRD studies of thin films of red polycarbazolyldiacetylenes

In this paper we report the results of a morphological and structural investigation on film properties of a soluble polydiacetylene, the poly[1,6-bis(3,6-dihexadecyl-N-carbazolyl)-2,4-hexadiyne] (polyDCHD-HS). The red films of this polymer, prepared by standard spin-coating techniques, revealed absence of linear dichroism and birefringence in contrast with the ordered mesophases detected by powder X-ray studies. In order to interpret the optical behavior of this polymer, we performed AFM and SEM studies of polyDCHD-HS films spun on hydrophylic and hydrophobic glass substrates. We found the presence of surfaces organized in rod-like particles, more regularly oriented on the hydrophylic substrate. GIXRD studies, carried out on films sufficiently thick to allow the observation of the diffraction pattern, reveled the presence of a lamellar structure with a spacing of 3.22 nm. The low intensity of the diffraction peaks and the isotropic linear optical properties of the films show that the lamellar mesophases are not extended over large areas. These findings were compared with the data obtained from AFM and SEM studies on films of two other polydiacetylenes, the poly[1-(3,6-dihexadexyl-N-carbazolyl)-6-(N-carbazolyl)-2,4-hexadyine] (polya-DCHD) and the poly[1,6-bis(3,6-dipalmitoyl-N-carbazolyl)-2,4-hexadyine] (polyDPCHD), spun on hydrophylic glass substrate. The results confirmed the presence of nodular morphologies which seem to be a general characteristic of this class of materials. The particles organization appears instead related to the chemical nature of the substituents on the carbazolyl rings.     

The adsorption of toluene on V-Sb oxides. Theoretical aspects

Toluene adsorption reactions on the (1 1 0) surface of VSbO₄ have been analyzed following the changes in the electronic structure of the hydrocarbon molecule and metal cation sites of the oxide using the Just Another Extended Hückel Molecular Orbital Program (JAEHMOP) code. The bonding character of these interactions has also been studied in the same theoretical framework. The calculations indicate that the exothermic hydrocarbon parallel interaction on Sb-V sites results in the weakening of one of the C-H bonds of the methyl fragment. This leads to a H-abstraction that involves the participation of a Sb-cation. Both methyl and phenyl fragments decrease their electronic population and so does the V-cation site. Most of these electrons are transferred to other V atoms in the bulk solid. As a result the LUMO of the toluene-oxide system fully populates. The analysis reveals that methyl-Sb bonding interactions mainly involve C_2px and H_1s orbitals with Sb_5s orbital, while non-bonding phenyl-V interactions involve C_2px orbitals with V_3dx²−y² orbital. This last interaction facilitates the desorption of the benzyl species after H-abstraction.     

Interaction of indigo carmine dye with silica modified with humic acids at solid/liquid interface

Two distinct humic acids, one extracted from Brazilian peat soil, HA_PS, and another one obtained from commercial source, HA_FL, were attachment onto silica gel modified with aminopropyltrimethoxysilane, producing two material named SiHA_PS and SiHA_FL, respectively. The ability of these materials in removing indigo carmine dye from aqueous solution was followed through series of adsorption isotherms adjusted to modified Langmuir equation. The maximum number of moles adsorbed gave 6.82 ± 0.12 × 10⁻⁴ and 2.15 ± 0.17 × 10⁻⁴ mol g⁻¹ for SiHA_PS and SiHA_FL, respectively. Same interactions were calorimetrically followed and the thermodynamic data showed endothermic enthalpic values: 12.31 ± 0.55 and 24.69 ± 1.05 kJ mol⁻¹ for SiHA_PS and SiHA_FL surfaces, respectively. Gibbs free energies for two adsorption processes of indigo carmine dye presented negative values, reflecting dye/surface interactions must be accompanied by an increased in entropy values, which are 65 ± 3 and 98 ± 5 J mol⁻¹ K⁻¹ for SiHA_PS and SiHA_FL materials, respectively. The adsorption processes for both materials were spontaneous in nature although they presented an endothermic enthalpy for the interaction, resulting in an entropically favored process.     

An automatic PNA analyser for the under 200°C fraction contained in a higher boiling product

Summary We present a modified circuit for the PNA-analyser, which allows analysis for paraffins, naphthenes and aromatics in the under 200°C fraction of a sample having a final boiling point above 200°C. The modified separation scheme gives, in addition, improved type separation. By the introduction of adapted instrumentation the analyser has been suited to fully automated serial analysis. The new concept will eventually be commercialized.A glossary of abbreviations has been included at the end of this paper.     

Steric effect of methyl, methoxy, and ethyl substituents on the excimer formation of naphthalene on Al2O3(0 0 0 1)

Structural relaxation of molecules on surfaces can be monitored by observing the spectral evolution as increasing amount of thermal energy is made available. Naphthalene forms excimers in the excited state when amorphously prepared, but relaxes to a more ordered state when heated. Substituent groups on the naphthalene can substantially alter the available pathways during the thermally induced structural relaxation, and is reflected in the formation of excimer or trap fluorescence. A general correlation was determined for the naphthalene substitution with methyl, methoxy, and ethyl groups on the 1- and 2-positions with the pathway taken by the molecular adlayer.     

Structural evolution at the initial growth stage of perylene on Au(1 1 1)

We report on the structural evolution at the initial growth stage of perylene thin films on Au(1 1 1) surface. Scanning tunneling microscopy and spectroscopy have been employed to investigate the structural and electronic properties at 78 K. Rapid molecular diffusion was observed at low submonolayer coverage. Molecules form an ordered structure at monolayer coverage. For the second layer, impinging molecules nucleate into molecular islands with an ordered intermediate structure.     

汽油族组成的近红外光谱快速测定

以荧光指示剂吸附色谱法（FIA）测定汽油族组成结果为基础，采用近红外光谱和化学计量学方法建立了快速、准确测定催化裂化馏出口汽油族组成（饱和烃、烯烃和芳烃）的分析模型；试验表明，该法分析速度快、重复性好、成本低，特别适用于生产中间控制分析。