Band Intensity Research Articles

Effect of Ca co-doping on gamma-stimulated luminescence of Lu2SiO5:Ce

In order to estimate the stability of the light output of the scintillation detector, the Lu2SiO5:Ce scintillation crystals, additionally doped with Ca2+ ions at concentrations of 0 ÷ 0.4 at%, were studied. The spectra of optical absorption, gamma-luminescence, thermal luminescence, dose and temperature dependences of luminescence were measured. Gamma-luminescence in the dose range 10 - 5·107 Gy was recorded using 60Co gamma-source at the temperature range of 310–460 K. In contrast to the initial sample (non-doped with Ca), in the sample doped with 0.1 at% of Ca, an increase in the luminescence intensity was observed in the range of 390–425 nm, but further with an increase in the concentration of Ca (0.3–0.4 at%), the intensity of this band decreased to the initial level (undoped). At Ca concentrations of 0.3 and 0.4 at%, the intensity of the Ce1 center band remains practically unchanged up to a dose of 5·107 Gy. LSO crystals doped with Ce 0.1 at% and co-doped with Ca 0.1 at% can be recommended as a scintillation detector up to a gamma-dose of 105 Gy at room temperature.

Deprotonation-induced changes in π-electron systems of iridium(III) and rhodium(III) complexes with azophenine

N,N′,N′′,N′′′-Tetraphenyl-2,5-diamino-1,4-benzoquinonediimines (RAp·H2) are used as unique bridging ligands containing localized π-electron systems at each of the two NCCCNH moieties, which are susceptible to changes on coordination of the N atoms to Lewis acid(s). In this contribution, we disclose deprotonation-induced changes in the π-electron systems, spectroscopic properties, and electronic state of cationic cyclometalated iridium(III) and rhodium(III) complexes with 4-EtAp·H2, i.e., [M(ppy)2(4-EtAp·H2)]Cl (ppy: 2-phenylpyridinate; M: Ir(III) (1·H2+) and Rh(III) (2·H2+)). The cationic complexes possessed localized π-electron systems, but the NCCCNH moieties were isomerized from those in free 4-EtAp·H2. Although 4-EtAp·H2 showed no responsiveness to tetrabutylammonium hydroxide (TBAOH) as a base, the reaction of 1·H2+ and 2·H2+ with TBAOH afforded monodeprotonated neutral complexes [M(ppy)2(4-EtAp·H)] (M: Ir(III) (1·H) and Rh(III) (2·H)). UV–vis absorption spectral titrations of 1·H2+ and 2·H2+ with TBAOH revealed the occurrence of monodeprotonation even in the presence of 4 equivalents of TBAOH. The cationic complexes were regenerated from 1·H and 2·H upon addition of p-toluenesulfonic acid. X-ray crystallography of 2·H showed that the complex has localized and delocalized π-electron systems at the NCCCNH and NCCCN moieties, respectively. The UV–vis absorption spectra of 1·H2+ and 2·H2+ in CH2Cl2 present intense bands around 500 nm, and those of 1·H and 2·H exhibit intense bands around 450 nm and broad bands around 700 nm. Density functional theory (DFT), time-dependent DFT, and natural transition orbital calculations suggest that the intense bands of all complexes and the broad bands of 1·H and 2·H stem from π–π* transitions in the localized and delocalized π-electron systems, respectively, with MLCT transition.

New line list for the ν4 bands of the trans (790.117 cm–1) and cis (851.943 cm–1) conformers of nitrous acid (HONO): Accurate positions and absolute intensities

The goal of this work was to update and significantly improve the line lists that have been generated recently for 11 µm bands of the trans- and cis- conformer forms of nitrous acid (HONO) [Armante R, Perrin A, Kwabia Tchana F, Manceron L. The ν4 bands at 11 μm: linelists for the trans- and cis- conformer forms of nitrous acid (HONO) in the 2019 version of the GEISA database. Molecular Physics 2021;120:e1951860]. That 2019 version of the 11 µm line list was generated using the spectroscopic parameters that were available, at that time, in the literature. During the present study, we used high-resolution Fourier transform spectra recorded at 11 µm to perform a large investigation of line positions and intensities for the ν4 bands of the trans- and cis-conformer of HONO. The resulting set of experimental ν4 (absolute) intensities and of 41 energy levels were used to determine, by least squares fit computations, improved position and intensity parameters for the ν4 bands of the trans- and cis-conformer of HONO. For trans-HONO, the ν4 band appeared not to be perturbed, while for cis-HONO a weak high order B-type Coriolis, coupling together the 41 and 61 energy levels was evidenced for the first time. This new list is of potential interest for the IASI-NG (Infrared Atmospheric Sounding Interferometer - New Generation) instrument which will be launched on board the METOP-SG satellite in 2025.

Sr-doped CuFe2O4 nanoparticles: Exploring structural, magnetic, and blood compatibility characteristics

The aim of this study is to investigate the structural, magnetic, and blood compatibility properties of Sr2+ substituted for Cu2+ in Cu1−xSrxFe2O4 (x = 0.0 to 1 with a 0.25 increment) nanoparticles synthesized via the sol-gel auto-combustion technique. Regardless of the substitution rate, the sol-gel auto-combustion method consistently yields powders with sizes ranging from 20 to 40 nm. The specific surface area of the produced powders is determined as 12 m2/g. X-ray diffraction analysis reveals that CuFe2O4 exhibits a singular phase; however, as the Sr2+ ion substitution increases, the emergence of various secondary phases becomes apparent, with their proportions increasing with the substitution rate. The magnetic characteristics of the synthesized powders exhibit variations in magnetization, correlating with the distribution of cations in the sublattice points. Coercivities are influenced by both anisotropy and secondary phases. Saturation magnetization decreases from 31.3 (CuFe2O4) to 7.6 (SrFe2O4) emu/g with Sr replacement. The lowest observed coercivity is 429.5 Oe in powders prepared with CuFe2O4 composition, while the highest is measured at 583.8 Oe in nanopowders prepared with Cu0.5Sr0.5Fe2O4 composition. Moreover, blood compatibility experiments indicate significantly low hemolysis ratios for Cu1−xSrxFe2O4 nanoparticles. Additionally, all examined samples exhibit an increase in Soret band intensity compared to the negative control test, suggesting potential biocompatibility.

Newly developed CeO2 and Gd2O3-reinforced borosilicate glasses from municipal waste ash and their optical, structural, and gamma-ray shielding properties

From the useless municipal solid waste (MSW) ashes, CeO2, Gd2O3 and CeO2 + Gd2O3 doped borosilicate glasses were organized via melting-quenching procedure. Various optical, structural, physical and radiation shielding parameters were examined towards the influence of 100 kGy of γ-radiation. UV–visible NIR spectra revealed UV peaks at 351, 348 and 370 nm corresponding to the trivalent states of Ce3+ and Gd3+ ions, while, photoluminescence (PL) spectra displayed asymmetric broad excitations of Ce3+ and Gd3+ ions due to 4f → 5d transitions, and emission intense bands at 412, 434, and 417 nm. CIE chromaticity shows that Gd3+ ions increase the luminescence of Ce3+. FTIR absorption bands revealed an overlapping between tetrahedral groups of silicate (SiO4), with trigonal (BO3) and tetrahedral (BO4) units of borate. The influence of 100 kGy obtains quite reduction in UV–visible NIR and PL peaks, large stability in FTIR and ESR spectra, and stability of thermal expansion coefficient (CTE) as well. The whole data revealed optical, structural and physical stability of glasses after irradiation besides an enhancement in microhardness owing to more structural compactness and high bonding connectivity. Radiation shielding parameters from Phy-X/PSD program showed higher values of mass (MAC) and linear attenuation coefficients (LAC), and effective atomic number (Zeff) in the order of; glass Ce+Gd > glass Ce > glass Gd. Ce + Gd doped glass revealed also the lowest half value layer (HVL) comparing to other shielding commercial concretes. The study recommends the beneficial and economical use of the useless MSW ash to produce CeO2 and/or Gd2O3 borosilicate glasses with hopeful radiation shielding features.

The Annealing Kinetics of Defects in CVD Diamond Irradiated by Xe Ions

The radiation-induced optical absorption at 1.5–5.5 eV (up to the beginning of fundamental absorption) has been analyzed in CVD diamond disks exposed to 231-MeV 132Xe ions with four fluences from 1012 to 3.8 × 1013 cm−2. The 5 mm diameter samples (thickness 0.4 mm) were prepared by Diamond Materials, Freiburg (Germany); the average grain size at growth site was around 80 μm; and the range of xenon ions was R = 11.5 μm. The intensity of several bands grows with ion fluence, thus confirming the radiation-induced origin of the defects responsible for these bands. The recovery of radiation damage has been investigated via isochronal (stepwise) thermal annealing procedure up to 650 °C, while all spectra were measured at room temperature. Based on these spectra, the annealing kinetics of several defects, in particular carbon vacancies (GR1 centers with a broad band ~2 eV) and complementary C-interstitial-related defects (~4 eV), as well as impurity-related complex defects (narrow bands around 2.5 eV) have been constructed. The experimental kinetics have also been analyzed in terms of the diffusion-controlled bimolecular reactions. The migration energies of tentatively interstitial atoms (mobile components in recombination process) are obtained, and their dependence on the irradiation fluences is discussed.

M(TEIM) complexes with M as Co and Fe: Analogues of classic M(TIM)

The syntheses and characterization of Fe and Co complexes supported by a new tetra-imine macrocycle, TEIM (2,3,9,10-tetraethyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene), are reported. Templating with Co(OAc)2·4H2O yielded trans-[Co(TEIM)Cl2][PF6] (1a), which was converted to trans-[Co(TEIM)X2][PF6] (X = N3 (2a) and NO2 (3a)) through reactions with NaX (X = N3 or NO2). Templating with Fe generated trans-[Fe(TEIM)(NCCH3)2][PF6]2, which was oxidized to trans-[Fe(TEIM)Cl2][PF6] (1b). The reaction of 1b with NaN3 formed [Fe(TEIM)(N3)2][PF6] (2b) while the reaction with [Fe(TEIM)(NCCH3)2][PF6]2 and NaNO2 yielded trans-[Fe(TEIM)(NO2)2] (3b). Single crystal X-ray diffraction studies revealed a pseudo-octahedral geometry around the Co / Fe centers with the ethyl groups oriented above or below the plane of the TEIM ring. The absorption spectra of 1b displays weak charge transfer bands near the UV to visible region, while 2b and 3b displayed intense charge transfer bands within the visible region. Cyclic voltammograms of 1a revealed four 1 e− reductions while those of 2a and 3a display only three cathodically shifted reductions. Analogous studies of 1b and 2b revealed two 1 e- reductions while 3b displays only an oxidation event. EPR studies of ferric complexes 1b and 2b indicated a low spin d5 electronic figuration with S = ½ ground state.

Нитрозирование лигносульфонатов в условиях твердофазного катализа

Lignosulfonates are the most common commercial lignin-based product due to their unique properties. Various methods are known for modifying lignosulfonates and lignosulfonic acids. This article presents the results of the development of a new approach to the production of nitrosated lignosulfonic acids. The method is based on a reaction catalyzed by cation exchange resins in the H-form: KU-2-8 cation exchanger and wofatite. The influence of reagent consumption and reaction duration on the course of nitrosation has been studied. The dynamics of the proposed nitrosation practically coincides with the dynamics of a similar reaction using sulfuric acid by the known method. The optimal consumption of sodium nitrite equals 15 %, and the optimal consumption of cation exchanger equals 100 % by weight of lignosulfonates. During the nitrosation of lignosulfonates, significant changes in the electronic spectra occur in the region of 280...500 nm. Two overlapping absorption bands appear with maxima at 300 and 330 nm, as well as an intense absorption band at 430 nm, due to nitroso groups conjugated with the aromatic nuclei of phenylpropane units. To analyze the ionization spectra, they have been deconvoluted. The resulting spectra are well approximated by 5 Gaussians with an error of no more than 5 %. Two options for carrying out the nitrosation reaction of lignosulfonates have been proposed: under static and dynamic conditions. It has been established that under dynamic conditions, nitroso derivatives of lignosulfonic acids are formed that do not contain metal cations, and the pH of the resulting solutions does not exceed 1.4. The elemental compositions of the isolated initial and nitrosated lignosulfonic acids have been determined. The nitrogen content of lignosulfonic acids has increased from 0.32 (initial) to 2.17 % (nitrosated). In addition, under dynamic conditions, an additional stage of separating the cation exchanger from the reaction medium by filtration is not required. New bands have appeared in the IR spectrum of nitrosated lignosulfonic acids: at 1540 cm–1, which is due to the presence of nitroso groups, and a wide absorption band at 1700...1715 cm–1, which can be caused by vibrations of the carboxyl group or the quinone monooxime tautomeric form of the guaiacyl structures of lignosulfonic acids.

Chirality Sensing of Cryptochiral Guests with Prism[n]arenes.

Optical chirality sensing has gained significant attention in recent years. Within this field, the quest for stereodynamic chiroptical probes capable of detecting cryptochiral guests presents a formidable challenge. Macrocycles exhibiting planar chirality have emerged as promising candidates for amplifying the chirality of cryptochiral guests. In this study, we demonstrate that the formation of host-guest complexes between cryptochiral molecules and planar chiral prismarenes triggers electronic circular dichroism (ECD) signals via host-guest complexation-induced chirality amplification. The absolute configuration of the most stable chiral macrocyclic host-guest complex has been established by resorting to both exciton model and DFT computations. Furthermore, we demonstrated that this supramolecular chirality sensing system can be employed to determine the enantiomeric composition of scalemic mixtures by measuring the ECD bands intensity. The information described here opens the way for the use of prismarenes as stereodynamic probes for sensing of cryptochiral guests.

Tailoring of structural and optical properties of GeOx thin films using 100 MeV Si ions

In the present work, the effects of 100 MeV Si ions on the structural and optical properties of GeOx thin films have been investigated. Thin films of Germanium oxide (GeOx) were deposited onto silicon substrates using electron beam evaporation technique. Subsequently, 100 MeV Si7+ ions were used to irradiate as-deposited films at different fluences ranging from 5 × 1012 to 2 × 1013 ions/cm2. As-deposited films are amorphous as evident from XRD and Raman results. After irradiation with a fluence of 5 × 1012 ions/cm2 the films show partial crystallization. The strong photoluminescence (PL) exhibited from as-deposited and irradiated films is in ultraviolet (UV) and blue region. The blue shift was observed in PL bands after ion beam irradiation. PL band intensity was found to vary with irradiation fluence. The possible mechanism of variation in the PL emission from GeOx thin films with Si ion irradiation has been studied.

The impact of high pressure on the number of photons involved in upconversion luminescence of NaYF4:Er3+@NaYF4 and NaYF4:Yb3+,Er3+@NaYF4 core@shell nanoparticles and application as contactless pressure sensor

Inorganic nanomaterials doped with lanthanide ions and exhibiting upconversion (UC) luminescence are leading in research of nonlinear optical materials. Extreme conditions, such as high-pressure compression (in the GPa range), may influence the physicochemical properties of various compounds. In this work, we investigated the optical properties of upconverting NaYF4:Er3+@NaYF4 and NaYF4:Yb3+,Er3+@NaYF4 core@shell nanoparticles (NPs), focusing on the impact of high pressure on the number of photons involved in the UC mechanism. We measured the UC emission spectra of the synthesized NPs under high-pressure conditions, which allowed us to observe the pressure-induced intensity changes, band centroids spectral shifts, and band intensity ratios alterations. Importantly, by measuring the power-dependent UC emission spectra as a function of pressure, we determined and analyzed the number of photons (n) involved in the UC processes for the first time. It turned out that the n value changes with pressure as a result of diverse multi-phonon relaxation processes enhanced under high-pressure conditions. The results show potential adjustment of UC mechanisms with the use of high-pressure. The calculated band intensity ratios were also used for pressure sensing applications, resulting in the relative sensitivity reaching almost ≈20 % GPa−1 for the Er3+-doped core@shell NPs.

Spectroscopic detection of chromatin uncoiling and chromosome alignment in neuronal-like cells under exposure to low intensity magnetic fields

In this manuscript we reported the results of our studies concerning the response of vibration bands in deoxyribonucleic acid region in neuronal-like cells under exposure to static and 50 Hz electromagnetic fields using Fourier Transform Infrared spectroscopy. This technique was chosen because it is able to detect alteration of vibration bands of chemical compounds even induced by small stress agents. The aim of this study was to investigate the response of chromatin and chromosome to low intensity electromagnetic fields at values similar to manmade electromagnetic fields. The phosphate bands of asymmetric and symmetric stretching mode (representative of deoxyribonucleic acid spectral region) were observed to decrease after 3 h exposure at 1 mT (both static and 50 Hz magnetic field). Prolonging time exposure or increasing the intensity of applied magnetic field induced a low increasing in intensity of these vibration bands. This finding can be explaining assuming that chromatin uncoiling occurred at low intensity of the field and that increasing time exposure or magnetic field intensity caused an increasing of the torque on chromosome inducing an alignment along the direction of the field.

Deep postnatal phenotyping of a new mouse model of nonketotic hyperglycinemia.

Nonketotic hyperglycinemia due to deficient glycine cleavage enzyme activity causes a severe neonatal epileptic encephalopathy. Current therapies based on mitigating glycine excess have only limited impact. An animal model with postnatal phenotyping is needed to explore new therapeutic approaches. We developed a Gldc p.Ala394Val mutant model and bred it to congenic status in two colonies on C57Bl/6J (B6) and J129X1/SvJ (J129) backgrounds. Mutant mice had reduced P-protein and enzyme activity indicating a hypomorphic mutant. Glycine levels were increased in blood and brain regions, exacerbated by dietary glycine, with higher levels in female than male J129 mice. Birth defects were more prevalent in mutant B6 than J129 mice, and hydrocephalus was more frequent in B6 (40%) compared to J129 (none). The hydrocephalus rate was increased by postnatal glycine challenge in B6 mice, more so when delivered from the first neonatal week than from the fourth. Mutant mice had reduced weight gain following weaning until the eighth postnatal week, which was exacerbated by glycine loading. The electrographic spike rate was increased in mutant mice following glycine loading, but no seizures were observed. The alpha/delta band intensity ratio was decreased in the left cortex in female J129 mice, which were less active in an open field test and explored less in a Y-maze, suggesting an encephalopathic effect. Mutant mice showed no evidence of memory dysfunction. This partial recapitulation of human symptoms and biochemistry will facilitate the evaluation of new therapeutic approaches with an early postnatal time window likely most effective.

Dibenzothiophene Bridged Bis‐Bodipy and Bis‐Metal Dipyrrin Complexes

AbstractDibenzothiophene (DBT) bridged bis‐dipyrromethane was synthesized by treating readily available 4,6‐di(p‐formylphenyl) dibenzothophene with pyrrole under acid catalyzed conditions. The DBT bridged bis‐dipyrromethane was further oxidized with DDQ to afford the DBT bridged bis‐dipyrrin which was used as a ligand to prepare DBT bridged bis‐BODIPY, bis‐Ni(II) dipyrrin and bis‐Pd(II) dipyrrin complexes by treating the ligand with BF3 ⋅ Et2O, Ni(acac)2 and Pd(acac)2 respectively under mild reaction conditions. The DBT‐bridged bis‐BODIPY and bis‐metal dipyrrin complexes were thoroughly characterized and studied by HR‐MS, 1D & 2D NMR, absorption, fluorescence, cyclic voltammetry and DFT techniques. The bis‐BODIPY and bis‐Pd(II) dipyrrin showed highly intense absorption band at ~500 nm along with one low intense absorption band at 340 nm whereas the bis‐Ni(II) dipyrrin complex showed slightly broadened blue shifted high intense band at 490 nm along with one additional band at 426 nm. The bis‐BODIPY was fluorescent with fluorescence band at 524 nm and quantum yield of 0.031 whereas bis‐M(II) dipyrrin complexes were nonfluorescent. DFT optimized structures revealed that the BODIPY units are more planar with the dibenzophene moiety in bis‐BODIPY with an angle of ∼5.68°. However, in 3‐Pd and 3‐Ni, the M(II)‐dipyrrin units are much more deviated from the dibenzothiophene plane with an angle of 12.81°–14.23°.

Integrated Intensities of the Main Absorption Band of С2HD in the 6530–6627 cm–1 Region

Integrated Intensities of the Main Absorption Band of С2HD in the 6530–6627 cm–1 Region

Probing the mesophase formation in thermotropic liquid crystal HBDBA using temperature-dependent Raman spectroscopy and DFT method

Liquid crystalline properties of the synthesized liquid crystal (LC) N-(o-hydroxybenzylidene)-N′-(4-n-alkoxybenzylidene) azines (HBDBA) are probed thoroughly using the comprehensive array of techniques e.g. differential scanning calorimetry (DSC), differential thermal analysis (DTA), polarizing optical microscopy (POM), temperature-dependent Raman spectroscopy and density functional theory (DFT) method. In this study, intricate molecular interactions crucial for mesophase formation of liquid crystalline system HBDBA and molecular rearrangement that occurs during LC transitions are unravelled comprehensively. Remarkably, at the Cr → SmA phase transition, the peak position, linewidth, and intensity of signature Raman bands are prominently changed. A thorough analysis of Raman marker bands and DFT calculation confirm the disruption of intramolecular hydrogen bonds in HBDBA at the Cr → SmA transition. The conclusion of the present study enriches the understanding of the underlying mechanisms of mesophase formation and intricate molecular interactions and arrangement at the molecular level of the thermotropic LC.

The effect of ZnSO4 and Fe2(SO4)3 on the pyrolysis of cocoa shells: A tg-FTIR study

Pyrolysis stands out as one potential route for valorizing abundant agro-industrial cocoa residues. However, the products of this reaction, particularly bio-oil, do not possess the required quality for direct use in many applications. Thus, this study explores the use of iron sulfate and zinc sulfate as potential catalysts in the pyrolysis of these residues. In this investigation, the biomass, previously ground and dried, was impregnated with varying percentages of ferric sulfate and zinc sulfate. The TG-FTIR technique was employed to ascertain the effect of these salts on the pyrolysis of cocoa shell. The results were fitted with the DAEM model with three pseudo-components. It was determined that both salts induced alterations in the DTG profiles of the thermal decomposition of cocoa shell. In the evolved gases, compounds such as CO2, H2O, CH4, CO, HCN, and oxygenated compounds like HCOOH and CH3COOH were detected. Ferric sulfate significantly influenced the activation energies governing the reactions of the three pseudo-components. Conversely, the presence of zinc sulfate did not alter the activation energies associated with the decomposition of cocoa shell pseudo-components. Both catalysts induced alterations in the infrared spectra of the evolved gases, which is primarily evident in the relative intensities of bands corresponding to the stretching vibrations of constituent groups within CO2, CO, water, and oxygenated compounds.

Development of a low allergenic product for patients with milk allergy and assessment of its specific IgE reactivity.

Milk oral immunotherapy is the riskiest and most unpredictable form of oral immunotherapy. We aimed to produce a low allergenic product than conventional once baked-cake/muffin, to develop indirect in-house ELISA to check the tolerance status with milk products and evaluate IgE reactivity of patients' sera via western blotting (WB) and indirect in-house ELISA. A low allergenic product named biscotti-twice baked-cake was developed, and the total protein concentration was determined. The protein content was studied by SDS-PAGE and proteomics. Milk-specific IgE (sIgE) binding assays were performed by WB and indirect in-house ELISA by using patients' sera. Casein band intensity was observed to be lower in the biscotti-twice baked-cake than in the once baked-cake (p = .014). Proteomics analysis and αS1-casein measurement showed that the lowest intensity of casein was found in biscotti. The low binding capacity of milk sIgE to biscotti compared with once baked-cake was shown by WB (p = .0012) and by indirect in-house ELISA (p = .0001). In the ROC analysis, the area under the curve (AUC) of the in-house ELISA IgE was comparable with Uni-CAP milk and casein sIgE. The AUC of the in-house ELISA IgE for cake (0.96) and biscotti (1) was slightly better than Uni-CAP milk sIgE (0.94; 0.97) and casein sIgE (0.96; 0.97), respectively. The low allergenicity of the newly developed low allergenic product "biscotti-twice baked-cake" has been demonstrated by invitro experiments. Biscotti could be a safe treatment option than once baked-cake/muffin in patients who are reactive to once baked-milk products.

Role of Polycyclic Aromatic Hydrocarbons with Edge Defects in Explaining Astronomical Infrared Emission Observations

A systematic study was performed on the spectral properties of polycyclic aromatic hydrocarbons (PAHs) with edge defects using harmonic density functional theory calculations. Their potential astronomical relevance was assessed through direct comparison with NIRSpec and MIRI-MRS spectra of the atomic photodissociation region of the Orion Bar from the JWST Early Release Science PDRs4All program. It is found that the astronomical 6.2 μm PAH emission band, including its blue side, is well reproduced by PAHs with edge defects, when taking into account the effects of polarization in the computations, and without a need for PAHs that contain nitrogen. Small neutral PAHs with edge defects explain the blue wing of the 3.3 μm band. A low number of edge defects is required to reproduce the 8.6 and 11.2 μm band profiles, while the 11.0 + 11.2/12.7 μm band intensity ratio is a measure for the number of edge defects. A blind database fit to the Orion Bar spectrum reproduces the 6–15 μm region with an error of 9.9% and shows a clear delineation of charge, with the 6–10 μm PAH bands being carried by PAH cations and the 10–15 μm region by predominantly neutral PAHs. The contribution of anions is negligible. Armchair PAHs fit the 12.7 μm band, simultaneously producing a very weak broad emission feature centered at 3.225 μm. Zigzag PAHs fit the 11.2 μm band. It is concluded that PAHs with a low number of edge defects, in addition to armchair and zigzag PAHs, all contribute to the observed interstellar infrared emission.

High-pressure high-temperature synthesis and characterization of B10C

The boron-rich boron carbide materials have been traditionally synthesized by adding boron powder to B4C material and subjecting it to hot pressing sintering for materials composition containing 8.8–20 at. % carbon in boron (composition range of B10.4C to B4C). Our study explores a synthesis route for B10C starting from high-purity boron and carbon and direct conversion under high pressure and high temperature (HPHT) conditions of 2000 °C and 6–8 GPa. Synthesis was verified via x-ray diffraction analysis, showing the conversion of the high-purity boron and carbon powder mixture into a hexagonal B10C structure (R-3m space group) with lattice parameters of a = b = 5.6115 Å and c = 12.197 Å. The concentration of boron was measured through x-ray photoelectron spectroscopy, confirming the B10C ratio. The measured nanoindentation mean hardness of B10C was 40 GPa. Raman spectroscopy of the HPHT synthesized sample shows characteristic vibrational breathing modes of boron icosahedron and an additional intense band at a vibrational frequency of 380 cm−1. This Raman band, which appears notably weaker in earlier studies and B4C samples, is assigned to the linear chain of B–B–B and attributed to the maximal incorporation of boron within the hexagonal structure.