Exponential decay of spin-spin correlation between distant defect states produced by contour hydrogenation of polycyclic aromatic hydrocarbon molecules

The first few low-lying spin states of alternant polycyclic aromatic hydrocarbon (PAH) molecules of several shapes showing defect states induced by contour hydrogenation have been studied both by ab initio methods and by a precise numerical solution of Pariser-Parr-Pople (PPP) interacting model. In accordance with Lieb's theorem, the ground state shows a spin multiplicity equal to one for balanced molecules, and it gets larger values for imbalanced molecules (that is, when the number of π electrons on both subsets is not equal). Furthermore, we find a systematic decrease of the singlet-triplet splitting as a function of the distance between defects, regardless of whether the ground state is singlet or triplet. For example, a splitting smaller than 0.001 eV is obtained for a medium size C46H28 PAH molecule (di-hydrogenated [11]phenacene) showing a singlet ground state. We conclude that π electrons unbound by lattice defects tend to remain localized and unpaired even when long-range Coulomb interaction is taken into account. Therefore they show a biradical character (polyradical character for more than two defects) and should be studied as two or more local doublets. The implications for electron transport are potentially important since these unpaired electrons can trap traveling electrons or simply flip their spin at a very small energy cost.

Quaternary ammonium-functionalized silica sorbents for the solid-phase extraction of aromatic amines under normal phase conditions

Quaternary ammonium-functionalized silica materials were synthesized and applied for solid-phase extraction (SPE) of aromatic amines, which are classified as priority pollutants by US Environmental Protection Agency. Hexamethylenetetramine used for silica surface modification for the first time was employed as SPE sorbent under normal phase conditions. Hexaminium-functionalized silica demonstrated excellent extraction efficiencies for o-toluidine, 4-ethylaniline and quinoline (recoveries 101–107%), while for N,N-dimethylaniline and N-isopropylaniline recoveries were from low to moderate (14–46%). In addition, the suitability of 1-alkyl-3-(propyl-3-sulfonate) imidazolium-functionalized silica as SPE sorbent was tested under normal phase conditions. The recoveries achieved for the five aromatic amines ranged from 89 to 99%. The stability of the sorbent was evaluated during and after 150 extractions. Coefficients of variation between 4.5 and 10.2% proved a high stability of the synthesized sorbent. Elution was carried out using acetonitrile in the case of hexaminium-functionalized silica and water for 1-alkyl-3-(propyl-3-sulfonate) imidazolium-functionalized silica sorbent. After the extraction the analytes were separated and detected by liquid chromatography ultraviolet detection (LC-UV). The retention mechanism of the materials was primarily based on polar hydrogen bonding and π–π interactions. Comparison made with activated silica proved the quaternary ammonium-functionalized materials to offer different selectivity and better extraction efficiencies for aromatic amines. Finally, 1-alkyl-3-(propyl-3-sulfonate) imidazolium-functionalized silica sorbent was successfully tested for the extraction of wastewater and soil samples.

X-Ray Imaging of SAPO-34 Molecular Sieves at the Nanoscale: Influence of Steaming on the Methanol-to-Hydrocarbons Reaction

The effect of a severe steaming treatment on the physicochemical properties and catalytic performance of H-SAPO-34 molecular sieves during the methanol-to-hydrocarbons (MTH) reaction has been investigated with a combination of scanning transmission X-ray microscopy (STXM), catalytic testing, and bulk characterization techniques, including ammonia temperature programmed desorption and 27Al and 29Si magic angle spinning nuclear magnetic resonance. For this purpose, two samples, namely a calcined and a steamed H-SAPO-34 catalyst powder, have been compared. It has been found that calcined H-SAPO-34 displays a high selectivity towards light olefins, yet shows a poor stability as compared to a zeolite H-ZSM-5 catalyst. Moreover, in situ STXM at the carbon K-edge during the MTH reaction allows construction of nanoscale chemical maps of the hydrocarbon species formed within the H-SAPO-34 aggregates as a function of reaction time and steam post-treatment. It was found that there is an initial preferential formation of coke precursor species within the core of the H-SAPO-34 aggregates. For longer times on stream the formation of the coke precursor species is extended to the outer regions, progressively filling the entire H-SAPO-34 catalyst particle. In contrast, the hydrothermally treated H-SAPO-34 showed similar reaction selectivity, but decreased activity and catalyst stability with respect to its calcined counterpart. These variations in MTH performance are related to a faster and more homogeneous formation of coke precursor species filling up the entire steamed H-SAPO-34 catalyst particle. Finally, the chemical imaging capabilities of the STXM method at the Al and Si K-edge are illustrated by visualizing the silicon islands at the nanoscale before and after steaming H-SAPO-34.

Abatement of hydrocarbons by acid ZSM-5 and BETA zeolites under cold-start conditions

Simulated cold-start tests have been carried out to evaluate the performance of H-ZSM-5 and H-BETA zeolites as hydrocarbon traps under simulated gasoline car exhaust gases, paying special attention to the effect of water on their behaviour. It is concluded that the hydrothermal treatment of the zeolites in the acidic form contributes to the better performance of these materials as hydrocarbon traps since the stabilization of the zeolites takes place. Moreover, the decrease of the surface acidity of the zeolites results in an increase of the Si/Al ratio, which contributes to the decrease of the water affinity for adsorption sites. Thus, the competition with hydrocarbon molecules in the exhaust for the adsorption sites is reduced which increases their trap efficiency. The stabilized H-ZSM-5 is the zeolite that showed the best performance with a propene offset temperature of 240 °C, which should be high enough for the three-way catalyst to carry out its role as catalytic converter.

First aromatic ring acetamidation by anodic oxidation

Anodic oxidation of 1-(trifluoromethyl)benzene in dry acetonitrile/Bu4NBF4 under constant potential conditions led to 2-(trifluoromethyl) acetanilide in 86% yield. Other experimental conditions, as the use of constant current or the change in the supporting electrolyte were considered.

Effect of the surface chemical groups of activated carbons on their surface adsorptivity to aromatic adsorbates based on π-π interactions

Three activated carbons with different surface chemical groups were used to analyse the influence of these groups on their adsorption capacities towards aromatic-type molecules whose adsorption is based on π-π interactions with surface arene centres. The three activated carbons studied were a low-functionalized carbon (Merck), an oxygen-rich carbon obtained by HNO3 oxidation of Merck, and a nitrogen-rich carbon also prepared from Merck by mild HNO3 oxidation followed by treatment with a dicyanodiamide/dimethyl formamide mixture at 300 °C. The nature of the surface chemical groups of the three activated carbons was investigated by both physical and chemical techniques (TPD, XPS, Boehm analysis and pH potentiometric titration). A systematic study of the adsorptions of a series of analogous aromatic adsorbates on the three activated carbons was carried out to study the adsorption mechanisms. In all cases the adsorption mechanism is based on π-π interactions between the aromatic moiety of the adsorbates and the arene centres of the graphite sheets. The differences in the normalized adsorption capacities of the adsorbents for a set of adsorbates indicate that the π-donor or π-withdrawing character of the functional groups have a clear influence on the basicity of the arene centres.

Intra-population variation and geographic correlation in Canthon humectus hidalgoensis using FTIR-ATR spectroscopy

In some cases external morphology is not sufficient to discern between populations of a species, as occurs in the dung beetle Canthon humectus hidalgoensis Bates; and much less to determine phenotypic distances between them. FTIR-ATR spectroscopy show several advantages over other identification techniques (e.g. morphological, genetic, and cuticular hydrocarbons analysis) due to the non-invasive manner of the sample preparation, the relative speed of sample analysis and the low-cost of this technology. The infrared spectrum obtained is recognized to give a unique ‘fingerprint’ because vibrational spectra are specific and unique to the molecular nature of the sample. In our study, results showed that proteins, amino acids and aromatic ethers of insect exocuticle have promising discriminative power to discern between different populations of C. h. hidalgoensis. Furthermore, the correlation between geographic distances between populations and the chemical distances obtained by proteins + amino acids + aromatic ethers was statistically significant, showing that the spectral and spatial information available of the taxa together with appropriated chemometric methods may help to a better understanding of the identity, structure, dynamics and diversity of insect populations.