Time-resolved luminescence and singlet oxygen formation under illumination of hypericin in acetone

We present time- and spectral-resolved phosphorescence study of hypericin as well as evolution of singlet oxygen formation and elimination under the illumination of hypericin in acetone solution. The obtained time-resolved hypericin phosphorescence can be satisfactorily fitted by using a two-exponential decay curve. The value of shorter component is about 0.29 μs and is independent of the hypericin concentration in the studied range (2–200 μM). The rise time of singlet oxygen production matches this value perfectly. It confirms that singlet oxygen formation represents the significant channel of hypericin triplet state deactivation under aerobic conditions at room temperature. The total phosphorescence intensity of hypericin is linearly proportional to the hypericin concentration within the studied concentration range, but the singlet oxygen phosphorescence intensity exhibits saturation behavior. This observation is a result of at least two effects: quenching of singlet oxygen by hypericin, as well as quenching of singlet oxygen by singlet oxygen.     

Room temperature phosphorescence lifetime and quantum yield of erythrosine B and rose bengal in aerobic alkaline aqueous solution

The room-temperature phosphorescence behavior of erythrosine B (ER) and rose bengal (RB) in aerobic aqueous solution at pH 10 (10^?4 M NaOH) is investigated. The samples were excited with sliced second harmonic pulses of a Q-switched Nd:glass laser. A gated photomultiplier tube was used for instantaneous fluorescence signal discrimination and a digital oscilloscope was used for signal recording. For phosphorescence lifetime measurement the oscilloscope response time was adjusted to appropriate time resolution and sensitivity by the ohmic input resistance. In the case of phosphorescence quantum yield determination the gated photomultiplier – oscilloscope arrangement was operated in integration mode using 10 MΩ input resistance. Phosphorescence quantum yield calibration was achieved with erythrosine B and rose bengal doped starch films of known quantum yields. The determined phosphorescence lifetimes (quantum yields) of ER and RB in 0.1 mM NaOH are τ_P=1.92±0.1 μs (?_P=(1.5±0.3)×10^?5) and 2.40±0.1 μs ((5.7±0.9)×10^?5), respectively. The results are discussed in terms of triplet state deactivation by dissolved molecular oxygen.     

Spectroscopic characterization of Tm3+:TeO2–K2O–Nb2O5 glasses for 2-μm lasing applications

We have performed detailed experiments to investigate the spectroscopic properties of a new type of tellurite based host doped with thulium: Tm₂O₃:(0.70)TeO₂–(0.15)K₂O–(0.15)Nb₂O₅ having Tm₂O₃ concentrations of 0.125, 0.25, 0.5, and 1.0 mol%. By performing a Judd–Ofelt analysis of the absorption bands, we obtained average radiative lifetimes of 2.57±0.20 and 0.35±0.01 ms for the ³H₄ and ³F₄ levels, respectively. Furthermore, we also observed that an increase in the Tm₂O₃ concentration from 0.125 to 1.0 mol% results in a decrease of the measured fluorescence lifetime from 814 to 439 μs and from 258 to 47 μs for the ³H₄ and ³F₄ levels, respectively, due to efficient non-radiative decay. The highest quantum efficiency of 32% was obtained for the sample doped with 0.125 mol% Tm₂O₃ for the ³H₄ level. Results show that cross relaxation becomes important as the ion concentration is increased, leading to the quenching of the 1460-nm band and enhancement of the 1860-nm emission. The highest emission cross section of 6.85×10^?21 cm² measured for the 1860-nm band reveals the potential of this host for the development of 2-μm lasers in bulk glass as well as fiber media.     

Proton transfer in water–hydroxyl mixed overlayers on Pt(1 1 1): Combined approach of laser desorption and spatially-resolved X-ray photoelectron spectroscopy

Proton transfer in water–hydroxyl mixed overlayers on a Pt(1 1 1) surface was studied by a combination of laser induced thermal desorption (LITD) method and spatially-resolved X-ray photoelectron spectroscopy (micro-XPS). The modulated pattern OH + H₂O/H₂O/OH + H₂O was initially prepared by the LITD method; vacant area with a 400 μm width was first formed in the mixed OH + H₂O overlayer by irradiation of focused laser pulses, and followed by refilling the vacant area with pure H₂O. Spatial distribution changes of OH and H₂O were measured as a function of time with the micro-XPS technique, which indicated that H₂O molecules in the central region flow into the OH + H₂O region. From quantitative analyses using a diffusion equation, we found that the proton transfer in the mixed overlayer consists of at least two pathways: direct proton transfer from H₂O to OH in the nearest site and the proton transfer to the next-nearest site via H₃O⁺ formation. The time scale of first and second path was estimated to be 5.2 ± 0.9 ns and 48 ± 12 ns at 140 K, respectively. In the presence of water capping layer, however, the rate of proton transfer is reduced by an order of magnitude, which would be explained by peripatetic behavior of proton into H₂O capping layer.     

Conversion between different forms of LET

Measurement of linear energy transfer (LET) spectra by detectors such as CR-39 PNTD or Si diodes for purposes of determining dose and dose equivalent in tissue often requires the conversion of LET as measured in the detector medium (e.g. LET₂₀₀CR-39 or LET_∞Si) to LET in water (LET_∞H₂O). Traditionally this conversion is carried out by multiplying values of LET in the form measured by a single numerical constant. Here we present an alternative conversion method wherein the single constant is replaced by a mathematical function obtained from a least squares fit of LET values for heavy ions of Z ranging from 1 to 54 over an energy interval ranging from 0.8 to 2000 MeV/amu. For conversion of LET₂₀₀CR-39 to LET_∞H₂O in units of keV/μm, a fitted function of Log(LET_∞H₂O) = 0.1689 + 0.984Log(LET₂₀₀CR-39) was obtained. For conversion of LET_∞Si to LET_∞H₂O, a fitted function of Log(LET_∞H₂O) = ?0.2902 + 1.025Log(LET_∞Si) was obtained.     

Multi-species time-history measurements during n-hexadecane oxidation behind reflected shock waves

Species concentration time-histories were measured during oxidation for the large, normal-alkane, diesel-surrogate component n-hexadecane. Measurements were performed behind reflected shock waves in an aerosol shock tube, which allowed for high fuel loading without pre-test heating and possible decomposition and oxidation. Experiments were conducted using near-stoichiometric mixtures of n-hexadecane and 4% oxygen in argon at temperatures of 1165–1352 K and pressures near 2 atm. Concentration time-histories were recorded for five species: C₂H₄, CH₄, OH, CO₂, and H₂O. Methane was monitored using DFG laser absorption near 3.4 μm; OH was monitored using UV laser absorption at 306.5 nm; C₂H₄ was monitored using a CO₂ gas laser at 10.5 μm; and CO₂ and H₂O were monitored using tunable DFB diode laser absorption at 2.7 and 2.5 μm, respectively. These time-histories provide critically needed kinetic targets to test and refine large reaction mechanisms. Comparisons were made with the predictions of two diesel-surrogate reaction mechanisms (Westbrook et al. [1]; Ranzi et al. [9]) that include n-hexadecane, and areas of needed improvement in the mechanisms were identified. Comparisons of the intermediate product yields of ethylene for n-hexadecane with those found for other smaller n-alkanes, show that an n-hexadecane mechanism derived from a simple hierarchical extrapolation from a smaller n-alkane mechanism does not properly simulate the experimental measurements.     

Infrared spectra of acetylene–water complexes: C2D2–H2O,C2D2–HDO,and C2D2–D2O

Infrared spectra of C₂D₂–water complexes are studied in the 4.1 μm region of the C₂D₂ ν₃ fundamental band using a tunable diode laser source to probe a pulsed supersonic slit jet. Relatively large vibrational red shifts (?27.7 to ?28.0 cm^?1) are observed which are more easily interpretable than for the analogous C₂H₂ vibration thanks to the absence of Fermi resonance effects for C₂D₂. Noticeable homogeneous line broadening leads to estimates of upper state predissociation lifetimes of about 0.5, 0.9 and 1.1 ns for C₂D₂–H₂O, –HDO, and –D₂O, respectively. Transitions involving K_a = 0 and 1 levels are observed for C₂D₂–HDO, but there is a puzzling absence of K_a = 1 for C₂D₂–H₂O and C₂D₂–D₂O.     

The structure and extinction of nonpremixed methane/nitrous oxide and ethane/nitrous oxide flames

Knowledge of combustion of hydrocarbon fuels with nitrogen-containing oxidizers is a first step in understanding key aspects of combustion of hypergolic and gun propellants. Here an experimental and kinetic-modeling study is carried out to elucidate aspects of nonpremixed combustion of methane (CH₄) and nitrous oxide (N₂O), and ethane (C₂H₆) and N₂O. Experiments are conducted, at a pressure of 1 atm, on flames stabilized between two opposing streams. One stream is a mixture of oxygen (O₂), nitrogen (N₂), and N₂O, and the other a mixture of CH₄ and N₂ or C₂H₆ and N₂. Critical conditions for extinction are measured. Kinetic-modeling studies are performed with the San Diego Mechanism. Experimental data and results of kinetic-modeling show that N₂O inhibits the flame by promoting extinction. Analysis of the flame structure shows that H radicals are produced in the overall chain-branching step 3H₂ + O₂ ? 2H₂O + 2H, in which molecular hydrogen is consumed. Hydrogen is also consumed in the overall step N₂O + H₂ ? N₂ + H₂O where stable products are formed. Inhibition of the flames by N₂O is attributed to competition between these two overall steps.     

Photocatalytic water splitting of La2AlTaO7 and the effect of aluminum on the electronic structure

A new photocatalyst La₂AlTaO₇ with orthorhombic structure was synthesized by the solid-state reaction method. The formation rate of H₂ evolution from CH₃OH/H₂O solution under the irradiation of a 350 W high-pressure Hg lamp is about 108.9 μmol h^?1 for La₂AlTaO₇ (0.1 g). It also showed activity leading to the decomposition of pure water into H₂ and O₂ even in the absence of co-catalysts under UV light irradiation. The photocatalyst loaded with 0.2 wt% NiO co-catalyst was found to have the highest activity. It was found from the electronic band structure study, using the density functional theory (DFT) with plane-wave basis, that the valence band top mainly consists of O 2p orbitals and the conduction band bottom is mainly constructed of Al 3s3p. The effect of aluminum on electronic structure was discussed in close connection with the UV–vis absorption spectrum.     

Defect structure analysis of B-site doped perovskite-type proton conducting oxide BaCeO3 Part 1: The defect concentration of BaCe0.9M0.1O3−δ (M = Y and Yb)

By means of a high-temperature gravimetry, the defect chemical relationships between oxygen nonstoichiometry and water content in BaCe_0.9M_0.1O_3?δ (M = Y and Yb) were investigated as functions of partial pressure of oxygen, P(O₂), partial pressure of water vapor, P(H₂O), and temperature. Concentrations of protonic defect and that of oxygen vacancy strongly depend on P(H₂O) and temperature, while the dependences on P(O₂) were weak. The equilibrium constants of the water vapor incorporation reaction H₂O + V_O^??? + O_O^× = 2OH_O^? were determined. Concentrations of hole, [h^?], in the dry-atmospheres were determined by the weight gain by the incorporation of oxygen from the gas atmospheres. The [h^?] values increased with decreasing temperature. The [h^?] values were estimated to be about 2 to 3 orders of magnitude less than [OH_O^?] values measured in the wet-atmospheres.     

Vibration spectroscopy of water on stepped gold surfaces

The vibration spectrum of H₂O (ice) adsorbed at low temperatures on Au(1 0 0), Au(1 11 1), and Au(1 1 5) is studied using electron energy loss spectroscopy. On the Au(1 0 0) surface, the spectra show the presence of the typical H-bonded network of water molecules for all coverages from the submonolayer into the multilayer range. The absence of a non-H-bonded OH-stretching mode is indicative for the “H-down bilayer”. On stepped surfaces, on the other hand, a considerable fraction of the H-atoms remains in the non-H-bonded state; surprisingly even in the multilayer range, and even after annealing. The fraction of non-H-bonded hydrogen atoms scales with the step density. Spectral features of water adsorbed at step-sites are isolated after annealing a surface exposed to small doses of H₂O. The results are discussed in the context of recent theoretical studies as well as in conceivable relation to the experimentally found reduction of the Helmholtz-capacitance on stepped Au(1 1 n) electrodes.     

Tunable fiber laser based photoacoustic gas sensor for early fire detection

A photoacoustic gas sensor using a near-infrared tunable fiber laser and based on wavelength modulation spectroscopy technique is developed. This sensor is capable of quasi-simultaneous quantification of water vapour, acetylene, carbon dioxide, and carbon monoxide (H₂O, C₂H₂, CO and CO₂) concentrations in the fire emulator. The feasibility of using this sensor as an early fire detector was demonstrated. The fire warning gases from smoldering paper were measured. The peak concentrations of gases from smoldering paper were 20,300 ppm H₂O, 2.1 ppm C₂H₂, 756 ppm CO, and 1612 ppm CO₂ after 400 s.     

CO and H2O adsorption and reaction on Au(310)

We have studied desorption of ¹³CO and H₂O and desorption and reaction of coadsorbed, ¹³CO and H₂O on Au(310). From the clean surface, CO desorbs mainly in, two peaks centered near 140 and 200 K. A complete analysis of desorption spectra, yields average binding energies of 21 ± 2 and 37 ± 4 kJ/mol, respectively. Additional desorption states are observed near 95 K and 110 K. Post-adsorption of H₂O displaces part of CO pre-adsorbed at step sites, but does not lead to CO oxidation or significant shifts in binding energies. However, in combination with electron irradiation, ¹³CO₂ is formed during H₂O desorption. Results suggest that electron-induced decomposition products of H₂O are sheltered by hydration from direct reaction with CO.     

Modeled quenching limits of spherical hydrogen diffusion flames

Hydrogen–air diffusion flames were modeled with an emphasis on kinetic extinction. The flames were one-dimensional spherical laminar diffusion flames supported by adiabatic porous burners of various diameters. Behavior of normal (H₂ flowing into quiescent air) and inverse (air flowing into quiescent H₂) configurations were considered using detailed H₂/O₂ chemistry and transport properties with updated light component diffusivities. For the same heat release rate, inverse flames were found to be smaller and 290 K hotter than normal flames. The weakest normal flame that could be achieved before quenching has an overall heat release rate of 0.25 W, compared to 1.4 W for the weakest inverse flame. There is extensive leakage of the ambient reactant for both normal and inverse flames near extinction, which results in a premixed flame regime for diffusion flames except for the smallest burners with radii on the order of 1 μm. At high flow rates H + OH(+M) → H₂O(+M) contributes nearly 50% of the net heat release. However at flow rates approaching quenching limits, H + O₂(+M) → HO₂(+M) is the elementary reaction with the largest heat release rate.     

Ho:LaF3 single crystal as potential material for 2 μm and 2.9 μm lasers

Optical properties of a Ho-doped LaF₃ single crystal have been detailed investigated as a promising material for 2 μm and 2.9 μm lasers for the first time. Judd–Ofelt theory was applied to analyze the absorption spectrum to determine the J–O intensity parameters Ω_t(t=2,4,6), based on which the emission probabilities, branching ratio and radiative lifetime for the as-grown crystal were all calculated. The stimulated emission cross-sections of the ⁵I₇ → ⁵I₈ and ⁵I₆ → ⁵I₇ transitions were obtained by using the Fuchtbauer–Ladenburg method. The gain cross-section for 2 μm emission becomes positive once the population inversion level reaches 30%. The Ho:LaF₃ crystal shows long fluorescence lifetime of ⁵I₇ manifold (25.81 ms) as well as ⁵I₆ manifold (10.37 ms) compared with other Ho³⁺-doped crystals. It can be proposed that the Ho:LaF₃ crystal may be a promising material for 2 μm and 2.9 μm laser applications.     

Chemical diffusion of water in the double perovskites Ba4Ca2Nb2O11 and Sr6Ta2O11

The mechanism and kinetics of water incorporation in the double perovskites Ва₄Ca₂Nb₂O₁₁ and Sr₆Ta₂O₁₁ has been investigated (T = 300÷500 °C and aH₂O = 1 · 10^− 3÷2.2 · 10^− 2). The formation of hydration products Ba₄Ca₂Nb₂O₁₁·xH₂O and Sr₆Ta₂O₁₁·xH₂O (0.2 < x < 0.50) was limited by the diffusion of H₂O. It has been found that the concentration dependences of D˜_H2O are the same for both samples: small increasing of D˜_H2O with increasing x. The temperature dependences of the chemical diffusion coefficients of water for compositions of Ba₄Ca₂Nb₂O₁₁·0.35H₂O and Sr₆Ta₂O₁₁·0.35H₂O could be described with close activation energies of E_a = 0.38 ± 0.03 eV and E_a = 0.49 ± 0.03 eV, respectively. The chemical diffusion coefficients of water are nearly one order of magnitude smaller for tantalate Sr₆Ta₂O₁₁. This result correlates with lower oxygen and proton conductivities in Sr₆Ta₂O₁₁ as the consequence of lower mobilities.     

The in-situ solid-state NMR spectroscopy investigation of alcoholic lactose suspensions

The polymorphic forms of lactose in alcoholic suspensions have been determined by ¹³C CP-MAS NMR spectroscopy, employing hand-made glass inserts. Suspensions of alpha lactose monohydrate (Lα·H₂O) with particle size between 2 and 200 μm were prepared by 24 h reflux or by storage for 28 d in anhydrous ethanol without agitation. These suspensions were compared to an ethanolic sub-micron lactose suspension provided by a 3 M Health Care (Loughborough). The ¹³C CP-MAS NMR spectra indicated that Lα·H₂O dehydrated to stable anhydrous alpha lactose polymorph (Lα_S) whilst suspended in ethanol. In addition, strong ethanol ¹³C resonances were observed for some samples, indicating a liquid–solid interaction between the ethanol and lactose surface. Replacement of ethanol with anhydrous methanol, n-butanol and 3-methylbutan-2-ol implied that the solvent mediated dehydration of Lα·H₂O to Lα_S occurs as a result of sterically controlled interactions.     

Adsorption of O2 and CO2 on the Si(111)-7 × 7 surfaces

The interaction of O₂ and CO₂ with the Si(111)-7 × 7 surface has been studied with X-ray photoelectron spectroscopy (XPS). It was found that both O₂ and CO₂ molecules can readily oxidize the Si(111)-7 × 7 surface to form thin oxide films. Two oxygen species were identified in the oxide film: oxygen atoms binding to on-top sites of adatom/rest atoms with an O 1s binding energy of ~ 533 eV as well as to bridge sites of adatom/rest atom backbonds at ~ 532 eV. These two oxygen species can be interconverted thermally during the annealing process. Due to the low oxidation capability, the silicon oxide film formed by CO₂ has a lower O/Si ratio than that of O₂.     

Surface modification of Ni and Co metal nanowires through MeV high energy ion irradiation

Nickel (Ni) and cobalt (Co) metal nanowires were fabricated by using an electrochemical deposition method based on an anodic alumina oxide (Al₂O₃) nanoporous template. The electrolyte consisted of NiSO₄ · 6H₂O and H₃BO₃ in distilled water for the fabrication of Ni nanowires, and of CoSO₄ · 7H₂O with H₃BO₃ in distilled water for the fabrication of the Co ones. From SEM and TEM images, the diameter and length of both the Ni and Co nanowires were measured to be ∼ 200 nm and 5–10 μm, respectively. We observed the oxidation layers in nanometer scale on the surface of the Ni and Co nanowires through HR–TEM images. The 3 MeV Cl²⁺ ions were irradiated onto the Ni and Co nanowires with a dose of 1 × 10¹⁵ ions/cm². The surface morphologies of the pristine and the 3 MeV Cl²⁺ ion-irradiated Ni and Co nanowires were compared by means of SEM, AFM, and HR–TEM experiments. The atomic concentrations of the pristine and the 3 MeV Cl²⁺ ion-irradiated Ni and Co nanowires were investigated through XPS experiments. From the results of the HR–TEM and XPS experiments, we observed that the oxidation layers on the surface of the Ni and Co nanowires were reduced through 3 MeV Cl²⁺ ion irradiation.