Reactive sites on the surface of polycyclic aromatic hydrocarbon clusters: A numerical study

Cone-beam computed tomography (CBCT) is used to determine a patient's position in proton therapy. Its image quality is low compared to that of a conventional CT because data measured by a two-dimensional detector used in CBCT contain scattered X-ray components. Correcting for scattered X-rays using the Klein-Nishina’s formula can improve CBCT image quality, but the formula requires the atomic number and atomic number density of substances. In this work, I developed a photoncounting image reconstruction method for estimating the atomic number Z and atomic number density N using the energy information of X-rays. In this study, NZ and Z4 were calculated as variables in consideration of the convergence of the optimization algorithm. I applied the developed method to an X-ray energy spectrum of a gantry-mounted CBCT, which was simulated with a Monte Carlo simulation code. The result was possible to distinguish soft tissues from water in the simulated object, which was not possible without the energy information. An atomic number and number density obtained with our method allow calculating the stopping power of protons more accurately, which can contribute to improving dose calculation accuracy.

The surface reactivity of carbonaceous nanoparticles is revealed from the barrier height and reaction enthalpy of hydrogen abstraction reaction by H radicals computed at the M06-2X/6–311g(d,p)//B3LYP/6-311G(d,p) level of theory. Small polycyclic aromatic hydrocarbon (PAH) clusters are selected as the model system of carbonaceous nanoparticles. The PAHs considered are naphthalene, pyrene, coronene, ovalene and circumcoronene. Cluster sizes range from dimer to tetramer with a parallel or crossed configuration. All results show similar values as that of monomers, but naphthalene dimers with a crossed configuration yield a lower barrier height and reaction enthalpy by ∼2 kcal/mol. A minor size dependence is noticed in the series of naphthalene clusters where a larger cluster exhibits a smaller barrier height. Larger homogeneous PAH clusters in a size range of 1.1–1.9 nm are later generated to mimic nascent soot surface. It is found that the barrier height decreases with the increase in particle size, and the averaged values are ∼2 kcal/mol lower than that of monomers. More importantly, a larger particle shows a wider spread in barrier heights, and low barrier heights are seen in the surface shallow regions (e.g., surface pockets). The lowest barrier height of ∼8.5 kcal/mol is observed at a C-H site locating in a surface pocket. A set of model systems are built to reveal the underlying mechanism of reduction in barrier height. It is shown that the reduction is caused by local interactions between the neighboring atoms and the local curvature. Further analysis on the average localized ionization potential shows that larger particles have higher reactivity, further supporting our findings from the barrier height of hydrogen abstraction reactions. Therefore, it is concluded that the surface reactivity depends on the particle size and the most reactive sites always locate at the surface pockets.

This article presents a comprehensive treatment of the polycyclic aromatic hydrocarbon (PAH) hypothesis. The interstellar, infrared spectral features which have been attributed to emission from highly vibrationally excited PAHs are discussed in detail. These include major (most intense) bands at 3040, 1615, "1310," 1150, and 885 cm-1 (3.29, 6.2 "7.7," 8.7, and 11.3 micrometers), minor bands and broad features in the 3200-2700 cm-1 [correction of 3200-2700-1] (3.1-3.7 micrometers), 1600-1100 cm-1 (6.0-9 micrometers) and 910-770 cm-1 (11-13 micrometers) regions, as well as the vibrational quasi-continuum spanning the entire mid-IR and the electronic transitions which contribute to the high-frequency IR continuum. All the major and minor bands, as well as the quasi-continuum, can be attributed to vibrational transitions in molecular-sized PAHs. The latter two broad features probably arise from very large PAHs, PAH clusters, and amorphous carbon particles. A precise match of the interstellar spectra with laboratory spectra is not yet possible because laboratory spectra are not available of PAHs in the forms probably present in the interstellar medium (completely isolated, ionized, some completely dehydrogenated, and containing between about 20 and 40 carbon atoms). The method with which one can calculate the IR fluorescence spectrum from a vibrationally excited molecule is also described in detail. Fluorescence band intensities, relaxation rates, and dependence on molecule size and energy content are treated explicitly. Analysis of the interstellar spectra indicates that the PAHs which dominate the infrared spectra contain between about 20 and 40 carbon atoms. The results obtained with this method are compared with the results obtained using a thermal approximation. It is shown that for high levels of vibrational excitation and emission from low-frequency modes, the two methods give similar results. However, at low levels of vibrational excitation and for the high-frequency modes (for example, the 3040 cm-1, 3.3 micrometers band), the thermal approach overestimates the emission intensities. For calculations of molecular reactions (such as H-loss, deuterium enrichment, and carbon skeleton rearrangement) a thermal approximation is invalid. The relationship between PAH molecules and amorphous carbon particles is presented and their production in circumstellar shells is described. The most likely interstellar PAH molecular structures are discussed and the possibility of destructive reactions with interstellar oxygen and hydrogen atoms is considered in detailed and found to be unimportant. Interstellar PAH size and abundance estimates are made. On the order of a few percent of the available interstellar carbon is tied up in the small (20-40 carbon atom) PAHs which are responsible for the sharp features, and a similar amount is tied up in the larger (200-500 carbon atom) PAHs or PAH clusters and amorphous carbon particles which are responsible for the broad components underlying the 1600-1100 and 900-770 cm-1 (6-9 and 11-13 micrometers) regions. It is shown that the spectroscopic structure these PAHs and PAH-related materials produce in the UV portion of the interstellar extinction curve lie just below current detection limits but fall in the range detectable by the Hubble Space Telescope. Finally, the influence of PAH charge on the ultraviolet, visible, and infrared regions is described.

Context. The infrared signature of polycyclic aromatic hydrocarbons (PAHs) is present in many protostellar discs, and these species are thought to play an important role in the heating of the gas in the photosphere. Aims. We consider PAH cluster formation as one possible cause for non-detections of PAH features in protoplanetary discs. We test the necessary conditions for cluster formation and cluster dissociation by stellar optical and far-UV photons in protoplanetary discs using a Herbig Ae/Be and a T Tauri star disc model. Methods. We perform Monte Carlo and statistical calculations to determine dissociation rates for coronene, circumcoronene, and circumcoronene clusters with sizes of between 2 and 200 cluster members. By applying general disc models to our Herbig Ae/Be and T Tauri star model, we estimate the formation rate of PAH dimers and compare these with the dissociation rates. Results. We show that the formation of PAH dimers can take place in the inner 100 AU of protoplanetary discs in sub-photospheric layers. Dimer formation takes seconds to years, allowing them to grow beyond dimer size in a short time. We further demonstrate that PAH clusters increase their stability while they grow when they are located beyond a critical distance that depends on stellar properties and PAH species. The comparison with the local vertical mixing timescale allows a determination of the minimum cluster size necessary for the survival of PAH clusters. Conclusions. Considering the PAH cluster formation sites, cluster survival in the photosphere of the inner disc of Herbig stars is unlikely because of the high UV radiation. For the T Tauri stars, survival of coronene, circumcoronene, and circumcircumcoronene clusters is possible, and cluster formation should be considered as one possible explanation for low PAH detection rates in T Tauri star discs.

Revealing the optical properties of polycyclic aromatic hydrocarbon clusters with surface formyl groups

Absolute number densities of helium metastable atoms determined by atomic absorption spectroscopy in helium plasma-based discharges used as ambient desorption/ionization sources for mass spectrometry

Uptake of polycyclic aromatic hydrocarbons by Trifolium pretense L. from water in the presence of a nonionic surfactant

Ozonation has been recently proposed as a treatment option to remove toxic and recalcitrant organics from offshore produced water (OPW). In this study, experimental and modeling approaches were used to investigate the removal of polycyclic aromatic hydrocarbons (PAHs) from OPW by ozonation. It was found that ozonation can effectively remove PAHs by following the pseudo first-order kinetic model, which could cover both direct and indirect ozonation pathways. The decay rate constants of most PAHs were as low as 0.01-0.16min-1, possibly due to the interference caused by OPW matrix. The effects of ozone dose, bubble size, pH, and temperature on five representative PAHs were investigated along with their possible interactions. Based on the experimental results, a novel multi-output adaptive network-based fuzzy inference system (MO-ANFIS) was developed to model the removal of four individual PAHs and total PAHs. The overall RMSE and R between measured and modeled removal rates were 6.60% and 0.98, respectively, indicating agood model fit. This study demonstrated the effectiveness of ozonation in OPW treatment and the potential applicability of MO-ANFIS for process modeling and control.

Studies on mass attenuation coefficient, effective atomic number and electron density of some thermoluminescent dosimetric compounds

Determination of effective atomic number and electron density of heavy metal oxide glasses

This work aims to calculate the effective atomic number and electron density by Monte Carlo method. In previous studies, the most widely used solution is to use the transmission method with the narrow gamma-ray beam. In the approach of this work, the gamma-ray beam after going through material is uncollimated to recording by NaI(Tl) detector. To do this, the inner diameter of detector collimator was enlarged with the aim of decreasing the strengthen of radioactive source. The obtained results were compared with NIST data and the experimental values which yield the maximum deviation of 9.05% and 3.43%, respectively. These results show the promising approach in determining the features of material.

Attenuation-density anomalous relationship of lead alkali borosilicate glasses

Determination of mass attenuation coefficients and effective atomic numbers for Inconel 738 alloy for different energies obtained from Compton scattering

Abstract. Absolute profiles of atomic oxygen number densities with high vertical resolution have been determined in the mesosphere–lower thermosphere (MLT) region from in situ measurements by several rocket-borne solid electrolyte sensors. The amperometric sensors were operated in both controlled and uncontrolled modes and with various orientations on the foredeck and aft deck of the payload. Calibration was based on mass spectrometry in a molecular beam containing atomic oxygen produced in a microwave discharge. The sensor signal is proportional to the number flux onto the electrodes, and the mass flow rate in the molecular beam was additionally measured to derive this quantity from the spectrometer reading. Numerical simulations provided aerodynamic correction factors to derive the atmospheric number density of atomic oxygen from the sensor data. The flight results indicate a preferable orientation of the electrode surface perpendicular to the rocket axis. While unstable during the upleg, the density profiles measured by these sensors show an excellent agreement with the atmospheric models and photometer results during the downleg of the trajectory. The high spatial resolution of the measurements allows for the identification of small-scale variations in the atomic oxygen concentration.

Mass attenuation coefficient, μm, atomic cross-section, σi, electronic cross-section, σe, effective atomic number, Zeff and effective electron density, Nel, were determined experimentally and theoretically for some vitamins (retinol, beta-carotene, thiamine, riboflavin, niacinamide, pantothenic acid, pyridoxine, biotin, folic acid, cyanocobalamin, ascorbic acid, cholecalciferol, alpha-tocopherol, ketamine, hesperidin) at 30.82, 59.54, 80.99, 356.61, 661.66 and 1,408.01 keV photon energies using a NaI(Tl) scintillation detector. The theoretical mass attenuation coefficients were estimated using mixture rules. The calculated values were compared with the experimental values for all vitamins.