Generation of nitrogen functionalities on activated carbons by amidation reactions and Hofmann rearrangement: Chemical and electrochemical characterization

Nitrogen functionalization of a highly microporous activated carbon (BET surface area higher than 3000 m2/g) has been achieved using the following sequence of treatments: (i) chemical oxidation using concentrated nitric acid, (ii) amidation by acyl chloride substitution with NH4NO3 and (iii) amination by Hoffman rearrangement. This reaction pathway yielded amide and amine functional groups, and a total nitrogen content higher than 3 at.%. It is achieved producing only a small decrease (20%) of the starting microporosity, being most of it related to the initial wet oxidation of the activated carbon. Remarkably, nitrogen aromatic rings were also formed as a consequence of secondary cyclation reactions. The controlled step-by-step modification of the surface chemistry allowed to assess the influence of individual nitrogen surface groups in the electrochemical performance in 1 M H2SO4 of the carbon materials. The largest gravimetric capacitance was registered for the pristine activated carbon due to its largest apparent surface area. The nitrogen-containing activated carbons showed the highest surface capacitances. Interestingly, the amidated activated carbon showed the superior capacitance retention due to the presence of functional groups (such as lactams, imides and pyrroles) that enhance electrical conductivity through their electron-donating properties, showing a capacitance of 83 F/g at 50 A/g.

Polarized–unpolarized ground state of small polycyclic aromatic hydrocarbons

Do polyacenes, circumacenes, periacenes, nanographenes, and graphene nanoribbons show a spin polarized ground state? In this work, we present monodeterminantal (Hartree–Fock (HF) and density functional theory (DFT) types), and multideterminantal calculations (Møller–Plesset and Coupled Cluster), for several families of unsaturated organic molecules (n-Acenes, n-Periacenes and n-Circumacenes). All HF calculations and many DFT show a spin-polarized (antiferromagnetic) ground state, in agreement with previous calculations. Nevertheless, the multideterminantal calculations, carried out with perturbative and variational wavefunctions, show that the more stable state is obtained starting from the unpolarized HF wavefunction. The trend of the stabilization of wavefunctions (polarized or unpolarized) with respect to exchange and correlation potentials, and to the number of benzene rings, has been analyzed. A study of the spin (〈Ŝ2〉) and the spin density on the carbon atoms has also been carried out.

Video of the labelling of projected Placido rings through the scanning annulus

The Elliptical Scanning Algorithm is an effective method to individually detect and label the projected rings. It consecutively defines an elliptical annulus of one pixel wide which grows pixel by pixel and sweeps the image, from centre to periphery, until it detects and labels each whole ring. In a way, it works like a snake-annealing algorithm. Active contour models (snakes) are energy-minimising curves that deform to fit image features. Elliptical Scanning Algorithm changes its geometry in order to label reflected rings.

Corneal topography reinterpretation through separate analysis of the projected rings

Póster presentado en SPIE Photonics Europe, Brussels, 16-19 April 2012.

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.

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.

Emissions of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) and polycyclic aromatic hydrocarbons (PAHs) from a cement kiln using a continuous monitoring system

Resumen de la comunicación presentada en PIC2015 – the 14th International Congress on Combustion By-Products and Their Health Effects, Umeå, Sweden, 14-17 June 2015.

Emissions of Gases, Polycyclic Aromatic Hydrocarbons and Brominated Pollutants during Thermal Degradation of Waste Printed Circuit Boards

Resumen del póster presentado en Symposium on Renewable Energy and Products from Biomass and Waste, CIUDEN (Cubillos de Sil, León, Spain), 12-13 May 2015

Missing Rings in Pinus halepensis – The Missing Link to Relate the Tree-Ring Record to Extreme Climatic Events

Climate predictions for the Mediterranean Basin include increased temperatures, decreased precipitation, and increased frequency of extreme climatic events (ECE). These conditions are associated with decreased tree growth and increased vulnerability to pests and diseases. The anatomy of tree rings responds to these environmental conditions. Quantitatively, the width of a tree ring is largely determined by the rate and duration of cell division by the vascular cambium. In the Mediterranean climate, this division may occur throughout almost the entire year. Alternatively, cell division may cease during relatively cool and dry winters, only to resume in the same calendar year with milder temperatures and increased availability of water. Under particularly adverse conditions, no xylem may be produced in parts of the stem, resulting in a missing ring (MR). A dendrochronological network of Pinus halepensis was used to determine the relationship of MR to ECE. The network consisted of 113 sites, 1,509 trees, 2,593 cores, and 225,428 tree rings throughout the distribution range of the species. A total of 4,150 MR were identified. Binomial logistic regression analysis determined that MR frequency increased with increased cambial age. Spatial analysis indicated that the geographic areas of south-eastern Spain and northern Algeria contained the greatest frequency of MR. Dendroclimatic regression analysis indicated a non-linear relationship of MR to total monthly precipitation and mean temperature. MR are strongly associated with the combination of monthly mean temperature from previous October till current February and total precipitation from previous September till current May. They are likely to occur with total precipitation lower than 50 mm and temperatures higher than 5°C. This conclusion is global and can be applied to every site across the distribution area. Rather than simply being a complication for dendrochronology, MR formation is a fundamental response of trees to adverse environmental conditions. The demonstrated relationship of MR formation to ECE across this dendrochronological network in the Mediterranean basin shows the potential of MR analysis to reconstruct the history of past climatic extremes and to predict future forest dynamics in a changing climate.