Air-saturated Solutions Research Articles

Kinetics of autoxidation of tartaric acid in presence of iron

The kinetics of the autoxidation reaction of tartaric acid in an air-saturated solution in the presence of Fe(II) show autocatalytic behavior with distinct initiation, propagation, and termination phases. The initiation phase, which involves activation of dissolved oxygen, decreases with increasing pH, over the test range of pH of 2.5-4.5, indicating that activation of oxygen is catalyzed by an Fe(II)-tartrate complex. The autocatalytic nature of this reaction indicates the presence of a catalytic intermediate that is produced during the initiation phase and regenerated during the propagation phase. The addition of catalase, as well as direct measurements, provided evidence of the presence and kinetic action of hydrogen peroxide as one of the intermediates. Direct addition of hydrogen peroxide resulted in shortening of the initiation stage and the propagation phase with similar rates as in the autoxidation reaction at low pH. The propagation is approximately a zero order reaction with respect to oxygen and iron. The kinetic analysis suggests that an intermediate catalytic complex(s) involving a ferryl ion (FeO2+) controls the rate of the propagation reaction. The Fe(III) formation shows autocatalytic behavior that mirrors the dissolved oxygen consumption patterns under all pH conditions studied. At pH values of 2.5 and 3.0, Fe(III) accumulated to a maximum, before it was partially consumed. This maximum coincided with the depletion of dissolved oxygen. The consumption of Fe(III), or the reduction of Fe(III) back to Fe(II), reflects the catalytic nature of Fe(II) and the essential role of tartaric acid in the initiation phase of Fenton's original reaction.

Evaluation of General Synthesis Procedures for Bioflavonoid-Metal Complexes in Air-Saturated Alkaline Solutions.

The general synthesis methods of bioflavonoid–metal complexes are considered to be unreliable due to the instability of flavonoids in air-saturated alkaline solutions. In this study, dihydromyricetin (DHM), as a representative bioflavonoid, was selected for complexation with various transition metal ions in an air-saturated alkaline solution to form DHM–metal(II) complexes, following the general synthetic procedure. After characterization, the metal complexes were hydrolyzed to observe the stability of DHM under acidic conditions via HPLC. The effects of synthetic conditions (metal ion, alkalinity, and reflux time) on DHM stability were then investigated by UV-vis spectroscopy and HPLC. Finally, using electron paramagnetic resonance, DHM and its analogs were observed with DMPO (5,5-dimethyl-1-pyrroline-N-oxide) to form a relatively stable free radical adduct. Multiple peaks corresponding to unknown compounds appeared in the LC spectra of the DHM–metal(II) complexes after hydrolysis, indicating that some DHM reacted during synthesis. Subsequently, the transition metal ion and solution alkalinity were found to have notable effects on the stability of free DHM. Furthermore, DHM and several of its analogs generated the superoxide-anion radical in air-saturated alkaline solutions. Their capacities for generating the superoxide anion seemed to correspond to the number and/or location of hydroxyl groups or their configurations. Interestingly, DHM can react with the superoxide anion to transform into myricetin, which involves the abstraction of a C3–H atom from DHM by O2−. Therefore, the general synthetic procedure for bioflavonoid–metal complexes in air-saturated alkaline solutions should be improved.

13C isotope enrichment of the central trityl carbon decreases fluid solution electron spin relaxation times

Electron spin relaxation times for perdeuterated Finland trityl 99% enriched in 13C at the central carbon (13C1-dFT) were measured in phosphate buffered saline (pH = 7.2) (PBS) solution at X-band. The anisotropic 13C1 hyperfine (Ax = Ay = 18 ± 2, Az = 162 ± 1 MHz) and g values (2.0033, 2.0032, 2.00275) in a 9:1 trehalose:sucrose glass at 293 K and in 1:1 PBS:glycerol at 160 K were determined by simulation of spectra at X-band and Q-band. In PBS at room temperature the tumbling correlation time, τR, is 0.29 ± 0.02 ns. The linewidths are broadened by incomplete motional averaging of the hyperfine anisotropy and T2 is 0.13 ± 0.02 µs, which is shorter than the T2 ~ 3.8 µs for natural abundance dFT at low concentration in PBS. T1 for 13C1-dFT in deoxygenated PBS is 5.9 ± 0.5 µs, which is shorter than for natural abundance dFT in PBS (16 µs) but much longer than in air-saturated solution (0.48 ± 0.04 µs). The tumbling dependence of T1 in PBS, 3:1 PBS:glycerol (τR = 0.80 ± 0.05 ns, T1 = 9.7 ± 0.7 µs) and 1:1 PBS:glycerol (τR = 3.4 ± 0.3 ns, T1 = 12.0 ± 1.0 µs) was modeled with contributions to the relaxation predominantly from modulation of hyperfine anisotropy and a local mode. The 1/T1 rate for the 1% 12C1-dFT in the predominantly 13C labeled sample is about a factor of 6 more strongly concentration dependent than for natural abundance 12C1-trityl, which reflects the importance of Heisenberg exchange with molecules with different resonance frequencies and faster relaxation rates. In glassy matrices at 160 K, T1 and Tm for 13C1-dFT are in good agreement with previously reported values for 12C1-dFT consistent with the expectation that modulation of nuclear hyperfine does not contribute to electron spin relaxation in a rigid lattice.

Relationship between oxygen consumption and neuronal activity in a defined neural circuit

BackgroundNeuronal computations related to sensory and motor activity along with the maintenance of spike discharge, synaptic transmission, and associated housekeeping are energetically demanding. The most efficient metabolic process to provide large amounts of energy equivalents is oxidative phosphorylation and thus dependent on O2 consumption. Therefore, O2 levels in the brain are a critical parameter that influences neuronal function. Measurements of O2 consumption have been used to estimate the cost of neuronal activity; however, exploring these metabolic relationships in vivo and under defined experimental conditions has been limited by technical challenges.ResultsWe used isolated preparations of Xenopus laevis tadpoles to perform a quantitative analysis of O2 levels in the brain under in vivo-like conditions. We measured O2 concentrations in the hindbrain in relation to the spike discharge of the superior oblique eye muscle-innervating trochlear nerve as proxy for central nervous activity. In air-saturated bath Ringer solution, O2 levels in the fourth ventricle and adjacent, functionally intact hindbrain were close to zero. Inhibition of mitochondrial activity with potassium cyanide or fixation of the tissue with ethanol raised the ventricular O2 concentration to bath levels, indicating that the brain tissue consumed the available O2. Gradually increasing oxygenation of the Ringer solution caused a concurrent increase of ventricular O2 concentrations. Blocking spike discharge with the local anesthetics tricaine methanesulfonate diminished the O2 consumption by ~ 50%, illustrating the substantial O2 amount related to neuronal activity. In contrast, episodes of spontaneous trochlear nerve spike bursts were accompanied by transient increases of the O2 consumption with parameters that correlated with burst magnitude and duration.ConclusionsControlled experimental manipulations of both the O2 level as well as the neuronal activity under in vivo-like conditions allowed to quantitatively relate spike discharge magnitudes in a particular neuronal circuitry with the O2 consumption in this area. Moreover, the possibility to distinctly manipulate various functional parameters will yield more insight in the coupling between metabolic and neuronal activity. Thus, apart from providing quantitative empiric evidence for the link between physiologically relevant spontaneous spike discharge in the brain and O2-dependent metabolism, isolated amphibian preparations are promising model systems to further dissociate the O2 dynamics in relation to neuronal computations.

Sources of 2,5-diaminoimidazolone lesions in DNA damage initiated by hydroxyl radical attack

The present study reports radiation-chemical yields of 2.5-diaminoimidazolone (Iz) derivatives in X-irradiated phosphate-buffered solutions of guanosine and double-stranded DNA. Various gassing conditions (air, N20/O2 (4:1), N2O, vacuum) were employed to elucidate the contribution of several alternative pathways leading to Iz in reactions initiated by hydroxyl radical attack on guanine. In all systems, Iz was identified as the second by abundance guanine degradation product after 8-oxoguanine, formed in 1:5 (guanosine) and 1:3.3 (DNA) ratio to the latter in air-saturated solutions. Experimental data strongly suggest that the addition of molecular oxygen to the neutral guanine radical G(-H)• plays a major in Iz production in oxygenated solutions of double-stranded DNA while in other systems it may compete with recombination of G(-H)• with superoxide and/or alkyl peroxyl radicals. The production of Iz through hydroxyl radical attack on 8-oxoguanine was also shown to take place although the chemical yield of Iz (ca 6%) in this process is too low to compete with the other pathways. The linearity of Iz accumulation with dose also indicates a negligible contribution of this channel to its yield in all systems.

Stable Olympicenyl Radicals and Their π-Dimers.

An olympicenyl radical, a spin 1/2 hydrocarbon radical with C2v symmetry and uneven spin distribution, remains elusive despite the considerable theoretical research interest. Herein, we report syntheses of two air-stable olympicenyl radical derivatives, OR1 and OR2, with half-life times (τ1/2) in air-saturated solution of 7 days and 34 days. The high stability was ascribed to kinetic blocking of reactive sites with high spin densities. X-ray crystallographic analysis revealed unique 20-center-2-electron head-to-tail π-dimer structures with intermolecular distances shorter than the sum of van der Waals radius of carbon. The ground state of the π-dimers was found to be singlet, with singlet-triplet energy gaps estimated to be -2.34 kcal/mol and -3.28 kcal/mol for OR1 and OR2, respectively, by variable-temperature electron spin resonance (ESR) spectroscopy. The monomeric radical species were in equilibrium with the π-dimer in solution, and the optical and electrochemical properties of the monomers and π-dimers in solution were investigated by UV-vis-NIR spectroscopy and cyclic voltammetry, revealing a concentration-dependent nature. Theoretical calculations illustrated that upon formation of a π-dimer the local aromaticity of each monomer was enhanced, and spatial ring current between the monomers was present, which resulted in an increment of aromaticity of the interior of the π-dimer.

Nano Structured and Pyrolytic Deposited Carbon Electrodes for Detection of Nitroaromates – a Comparison

IntroductionNitroaromatics like 2,4,6-trinitrotoluene (TNT) and 2,4-dinitrotoluene (DNT) are long-lasting organic pollutants in natural water and soil caused mainly by the military usage. Nano structured electrodes are established in detection of such compounds in water by linear sweep voltammetry (DP) [1]. On the other hand, it could be shown that screen printed carbon electrodes [2] and such made of pyrolytic deposited carbon are also suited for that purpose [3]. Both kind of electrodes were investigated regarding the determination of nitroaromatic compounds in aqueous solution. The aim of this paper is to compare the performance of both electrodes in comparison to commercial electrodes respecting sensitivity, selectivity and long-term stability.ExperimentalElectrodes using carbon nano-tubes and gold nano-particles on printed carbon are commercially available (DropSens, Spain DRP-110CNT-GNP). Screen printed electrodes (SPCE) of 3mm in diameter were industrially like produced on an alumina substrate with a commercial carbon ink (DuPont) carbon paste. Pyrolytic graphite layer were deposited by high temperature decomposition (1050 °C) of aromatic vapor for 15 min with high reproducibility (PyGE). Solid state analyses as XRD and SEM analysis show crystalline carbon with a sp2 hybridization (Fig. 1). The setup of the electrodes is seen in Fig. 2. All experiments were performed in a three electrode arrangement using platinum counter electrode and Ag/AgCl,Cl--reference electrode in a buffer solution. Voltammetric experiments were performed by a PalmSens potentiostate (Palm Instruments, NL). DRP-110CNT-GNP were investigated by linear sweep voltammetrie. SPCE and PyGE were measured in differential pulse voltammetry mode (DPV). The parameter for the DPV were selected as follows: scan rates of 15 mV∙s-1 to 20 mV∙s-1, amplitude of 50 mV and step height of 5 mVResults and discussionThe potentials of the single reduction peak of nitro-aromates can be clearly separated (Fig. 3) for both kind of electrodes, SPCE and PyGE. The nitroaromates trinitrotoluene (TNT) and dinitrotoluene (DNT) are reduced and dopamine is oxidized in DPV mode (Fig.4). The peak currents are proportional to the TNT concentrations with a sensitivity of 2.7 nA/ppb for SPCE (Fig.5) and 0.78 for PyGE (Fig. 6) at the characteristic peak potential of -0.59 V (R²=0.99). Commercial electrodes DRP-110CNT-GNP made of carbon with gold nano particles require a special treatment in cyclo-voltammertic mode up to stable measuring conditions. The sensitivity of 2.8 nA/ppb is high compared to PyGEs. The relative errors in measuring cycles (35 %) are very much higher than those for PyGEs (5 %). PyGE do not need a special pretreatment before use.Screen printed and pyrolytic deposited carbon electrodes can be applied in air saturated aqueous solutions like in field application. For both electrodes, SCPE and PyGE, the oxygen reduction peak do not interfere with the reduction of the nitro groups. The manufacturing tolerances become smaller in the row DRP-110CNT-GNP, SPCE, PyGE. PyGEs can be produced in few steps with very small deviations. They can stored in air or in water over years without a loss of performance. Commercial electrodes are very complex in setup and obviously not so easy to produce in proper quality. Furthermore, their signals are remarkably influenced by oxygen so that measurements in air are not possible.

Enhanced photodegradation of applied dithianon fungicides on plant leaves by dissolved substances in atmosphere under simulated sunlight

Photolysis of pesticides has been widely investigated for evaluating their environmental behavior and agricultural effectiveness after crop spraying. However, little information about the effects of the water-soluble substances in atmosphere on photodegradation of pesticides is available. In current study, we found that photolysis of applied dithianon fungicides on real plant leaves was much faster than that in sealed stock aqueous suspensions under simulated sunlight. To simulate the natural conditions, for the first time, photodegradation of dithianon in air-saturated solutions containing typical dissolved atmospheric substances (DAS) including CO2 (HCO3−/CO32−), NO2 (NO3−), Fe3+ (Fe3+-complexes), and humic-like substances (HULIS) exposed to simulated solar irradiations were carried out in lab-scale. Fulvic acid (FA) was used as a surrogate for atmospheric HULIS in this study. The dithianon photodegradation was significantly enhanced in the presence of DAS and the photo-generated reactive species such as ·OH, 1O2, CO3·- and 3FA∗ play important roles according to the results of reactive species quenching, electron spin resonance spectroscopy, and laser flash photolysis experiments. Moreover, the photodegraded intermediates and final products of dithianon on plant leaves have been identified by HPLC-MS analysis, and its possible photodegradation pathways were proposed. This work indicated that, except for direct photolysis, indirect photosensitive degradation induced by the dissolved photo-active substances in atmosphere should be considered for evaluating the degradation of the applied pesticides on crops.

Generation of hydroxyl radical during chlorination of hydroxyphenols and natural organic matter extracts

The generation of hydroxyl radicals (•OH) during the chlorination of air saturated solutions of different hydroxyphenols (hydroquinone, resorcinol, catechol, gallic and tannic acids) at pH 7 has been determined by the formation of phenol (in presence of benzene in excess) or 2-hydroxyterephthalic acid (in presence of terephthalic acid). Formation of •OH was only detected during the chlorination of o- or p-hydroxyphenols, compounds that react with chlorine by electron transfer forming the corresponding semiquinones/quinones. In aerated solutions, oxygen is reduced by the semiquinone to the superoxide radical, O2•−, which reacts with HOCl to •OH. Compared to the studied o-hydroxyphenols, the lower reactivity of hydroquinone towards chlorine favours the reaction between chlorine and O2•−, and its •OH formation potential is ∼50 times higher. The extent of •OH generated increased with the concentration of the hydroxyphenol and chlorine, but the •OH yield (moles formed per mole of hydroxyphenol eliminated), decreased due to the formation of the quinone, that acts as O2•− scavenger. The yield was almost not affected by the pH (6 ≤ pH ≤ 7.5), whereas a strong impact of dissolved O2 was observed. The •OH production was null in absence of O2 and 2.5–3 times higher at oxygen saturated conditions compared to air-saturated. Contrary to chlorination, during bromination of hydroquinone •OH was not formed, which can be attributable to a much faster consumption of the oxidant, with no chance for O2•− to react with bromine.Formation of •OH during the chlorination of different NOM extracts (SRHA, SRFA, PLFA and Nordic Lake NOM) and water from Lake Greifensee (Switzerland) was also studied using terephthalic acid as •OH scavenger. For SRHA, SRFA and Nordic Lake NOM (all of allochthonous origin and presenting high electron-donating capacity, EDC), •OH yields expressed as moles formed per mole of DOC0 (%), were between 1.1 and 2.0, similar to that of hydroquinone (∼1.5). For PLFA and Lake Greifensee water (autochthonous, lower EDC) much lower •OH yields were observed (0.1–0.3). Both chlorination rate and EDC, the later favouring the formation/stabilization of O2•−, seem to be key factors involved in •OH generation during the chlorination of NOM. A mechanism for these findings is proposed based on kinetic simulations of hydroquinone chlorination at pH 7.

Kinetic Consideration of Photochemical Formation and Decay of Superoxide Radical in Dissolved Organic Matter Solutions.

The photochemical formation and decay rates of superoxide radical ions (O2•-) in irradiated dissolved organic matter (DOM) solutions were directly determined by the chemiluminescent method. Under irradiation, uncatalyzed and catalyzed O2•- dismutation account for ∼25% of the total O2•- degradation in air-saturated DOM solutions. Light-induced O2•- loss, which does not produce H2O2, was observed. Both the O2•- photochemical formation and light-induced loss rates are positively correlated with the electron-donating capacities of the DOM, suggesting that phenolic moieties play a dual role in the photochemical behavior of O2•-. In air-saturated conditions, the O2•- quantum yields of 12 DOM solutions varied in a narrow range, from 1.8 to 3.3‰, and the average was (2.4 ± 0.5)‰. The quantum yield of O2•- nonlinearly increased with increasing dissolved oxygen concentration. Therefore, the quantum yield of one-electron reducing intermediates, the precursor of O2•-, was calculated as (5.0 ± 0.4)‰. High-energy triplets (3DOM*, ET > 200 kJ mol-1) and 1O2 quenching experiments indicate that 3DOM* and 1O2 play minor roles in O2•- production. These results are useful for predicting the photochemical formation and decay of O2•- in sunlit surface waters.

Effect of Chloride and Suwannee River Fulvic Acid on Cu Speciation: Implications to Cu Redox Transformations in Simulated Natural Waters.

Copper is a critical trace nutrient and, at higher concentrations, a toxicant in natural waters, with the relative rates of transformation between the Cu(I) and Cu(II) oxidation states being key to its speciation, bioavailability, and toxicity. While the influence of chloride (Cl-) and natural organic matter on Cu speciation and associated redox transformations has been studied separately, their combined influence on Cu speciation and Cu redox transformations has not been examined. As such, in this study, we investigate the impact of Cl- and Suwannee River fulvic acid (SRFA) on Cu(II) reduction and Cu(I) oxidation kinetics at pH 8.2. SRFA plays a dual role in providing Cu(II) reducing moieties as well as Cu ligating sites. Our results indicate that the SRFA-bound Cu(II) is less reactive than the inorganic Cu(II), and the SRFA-bound Cu(I) being much more rapidly oxidized than the inorganic Cu(I). The presence of Cl- weakens Cu(II) binding by SRFA, thereby increasing the reactivity of Cu(II). Similarly, weakening of Cu(I) binding by SRFA and concomitant binding of Cu(I) by Cl- stabilizes Cu(I). Our results further show that continuous formation of hydrogen peroxide occurs in the presence of Cu(II), SRFA, and Cl- in air-saturated solution with the presence of H2O2 enhancing the dynamic nature of the system.

Visible-to-UV triplet-triplet annihilation upconversion from a thermally activated delayed fluorescence/pyrene pair in an air-saturated solution

Despite increasing use of triplet-triplet annihilation upconversion (TTA-UC) of low-energy visible light, the generation of ultraviolet (UV) photons by TTA remains challenging because of the difficulty in finding sensitizers and acceptors with suitable energy levels. Here, we report efficient, photostable visible-to-UV TTA-UC in an air-saturated solution using a new pair with suitable energy levels: a thermally activated delayed fluorescence (TADF) molecule and pyrene. 4CzIPN, which has extremely small energy difference ΔEST (0.083 eV), was used as the TADF sensitizer to promote effective triplet energy transfer to the acceptor. When oleic acid was used as an effective singlet oxygen receptor in an air-saturated solution, the 4CzIPN/pyrene pair exhibited bright upconverted emission at 370–430 nm under 445 nm laser excitation, but no noticeable upconverted emission was observed when 4CzIPN was paired with previously reported UV-emitting acceptors [2,5-diphenyloxazole (PPO), p-terphenyl, and p-quaterphenyl]. TTA was confirmed by the quadratic dependence of the upconverted emission intensity on the 445 nm laser power density. The maximum quantum yield of the upconverted emission from the 4CzIPN/pyrene pair was 0.66%, which is considerable when compared with that of a previously reported visible-to-UV TTA-UC system with a biacetyl/PPO pair (0.58%).

Single mutation in a novel bacterial LOV protein yields a singlet oxygen generator.

Mr4511 from Methylobacterium radiotolerans is a 164 amino acid protein built of a flavin mononucleotide (FMN) binding, blue-light responsive LOV (Light, Oxygen, Voltage) core domain plus flanking regions. In contrast to the majority of LOV domains, Mr4511 lacks a tryptophan residue that was previously identified as a major quencher for the FMN triplet state in photosensitizers for singlet oxygen (SO) engineered from these photoreceptors. Here we show that for Mr4511 it is sufficient to only mutate the reactive cysteine responsible for the photocycle (Cys71) in the native protein to generate an efficient SO photosensitizer: both C71S and C71G variants exhibit SO quantum yields of formation, ΦΔ, around 0.2 in air-saturated solutions. Under oxygen saturated conditions, ΦΔ reaches ∼0.5 in deuterated buffer. The introduction of Trp112 in the canonical position for LOV domains dramatically lowers ΦΔ to values comparable to miniSOG, one of the early FMN binding proteins touted as a SO sensitizer. Besides its SO properties, Mr4511 is also exceedingly robust against denaturation with urea and is more photostable than free FMN.

Synthesis of acridone-naphthylamine derivative and its thermally-activated delayed fluorescence studies for application in OLEDs

Acridone (acceptor) and naphthylamine (donor) based Donor-Acceptor-Donor (D-A-D) compound (1) was synthesised, characterised and its thermally-activated delayed fluorescence (TADF) properties were studied in detail. Compound 1 is fluorescent and emits in the green region (550 nm). The energy gap between the ground and the lowest excited singlet (S1) state is estimated to be 2.55 eV. The energy gap between the CT singlet and triplet states (∆EST) was found to be ~0.3 eV. Small ∆ES1-T1 is one of the important criteria for TADF to take place in a molecule and thus detailed photophysics has been studied. Transient lifetime measurements showed an increase in the fluorescence lifetime (τ) on purging with N2, as compared with that in air-saturated solution, indicating the involvement of the triplet state in emission. Emission at 550 nm was also observed with a delay of 100 µs which corresponded to the delayed fluorescence in 1. The lifetime of TADF was found to be 176 µs. Applications of TADF materials in organic light-emitting devices (OLEDs) has gotten attention as TADF materials utilise the triplet excitons which helps in increasing internal quantum efficiency of device. Air-saturated based on 1 were fabricated and their intensity was found to be nearly as high as 17,000 Cd/m2 at 25 mA/cm2 which was comparable to many of the known TADF emitters. Acridone-amine derivatives was synthesized and its photophysical properties were carried out to establish TADF. It was also used in fabrication of OLEDs.

Design Optimisation of Acoustic Absorbers with Cross-Like Pores Via a Homogenisation Method

Mechanical modelling and associated numerical methods are able to improve the design of absorbing materials which are otherwise difficult to accomplish through experimental studies only. In this paper, we provide an original procedure for obtaining high acoustic absorption of single and multi-layered panels with predefined microstructure. The procedure uses the homogenisation technique for obtaining effective properties of an airsaturated material and solution to acoustic problems. We study a certain topology of the material and point out the effect of matrix material stiffness on the results of the optimisation procedure. We demonstrate that for stiff and rigid frames of a single layer, the optimal design parameters do not differ much whereas for the soft frames, the same results may significantly change. Moreover, we show that the absorption properties can be essentially improved by arrangements of different materials (soft, stiff and air) in sandwich panels. It is also possible to design a material which efficiently absorbs acoustic energy at low frequencies which is hard to achieve by means of conventional materials.

Autoradiolytic Decomposition of Radiopharmaceutical 2-[18F]Fluorodeoxyglucose

The kinetics of autoradiolytic degradation of the radiopharmaceutical drug 2-[18F]fluorodeoxyglucose ([18F]FDG) in an air-saturated normal saline solution with initial activity concentrations of 1 and 2 GBq/mL has been studied. It has been established that the only radioactive product of radiation-induced transformations of [18F]FDG is [18F]fluoride, whose contribution in the total activity of the radiopharmaceutical increases with storage. It has been shown that an increase in the initial activity concentration of the radiopharmaceutical or a decrease in the concentration of ethanol in it leads to the enhancement of autoradiolytic degradation of [18F]FDG. However, an increase in the storage temperature of the solutions from 25 to 40°C does not affect the rate of radiation-induced dehalogenation of [18F]FDG.

An improved understanding of chalcopyrite leaching kinetics and mechanisms in the presence of NaCl

Copper (Cu) extraction rate from chalcopyrite (CuFeS2) is normally slowed down by the passivation layers formed on CuFeS2 surface. Cost-effective CuFeS2 extraction strategies are therefore strongly expected in both academic and industrial worlds. This study investigated CuFeS2 leaching in the presence of NaCl and the results showed that NaCl played a significantly positive role on Cu extraction in air-saturated solution. Smaller CuFeS2 particle size led to a higher Cu recovery while pH 1.0 was optimum. In addition, the increment of NaCl concentration increased Cu extraction rate and recovery significantly. Moreover, Cu extraction from CuFeS2 was increased apparently with increased temperature, with an approximately 100% Cu recovery being achieved at 348 K and 0.1 M NaCl, within 144 h. XRD indicated that the major products formed were crystalline elemental sulfur (S0) rather than Cu–S like compounds at a NaCl concentration greater than 0.1 M, indicating that crystalline S0 did not inhibit Cu extraction. This study therefore provides a promising strategy of applying seawater in hydrometallurgical processing of chalcopyrite.

Enhanced oxygen sensing sensitivity by eliminating the protection of triplet phosphorescence.

High oxygen sensitivity (the slope of the Stern-Volmer plot reaches 0.73/μM) is achieved with a phosphorescence indicator, gadolinium-hematoporphyrin monomethyl ether (Gd-HMME), by decreasing the extent of its protection. In air-saturated solution, the phosphorescence quantum efficiency (QE) of Gd-HMME in a non-rigid microenvironment is lower than that in a rigid microenvironment. In contrast, when oxygen is removed, the QE of Gd-HMME in the non-rigid microenvironment was found to be same as that of Gd-HMME in the rigid microenvironment. This indicates that Gd-HMME is much more sensitive to oxygen in the non-rigid microenvironment. The oxygen sensitivity of Gd-HMME was found to increase as the rigidity of its microenvironment decreases. The oxygen response of Gd-HMME without any protection reaches 240 (0-374 μM oxygen), whereas that in the rigid microenvironment is only 3 in this range. The measurement precision of Gd-HMME without any protection is lower than that in the rigid microenvironment. These results indicate that the measurement of oxygen in different concentration ranges would require the rigidity of the microenvironment to be varied. Gd-HMME without any protection can be applied to detect oxygen as low as 0.1 μM. The detection limit of oxygen was evaluated to be as low as 20 nM based on Gd-HMME without any protection.

Synchrotron X-radiolysis of l-cysteine at the sulfur K-edge: Sulfurous products, experimental surprises, and dioxygen as an oxidoreductant.

In situ inventory of sulfurous products from the sulfur K-edge synchrotron X-radiolysis of l-cysteine in solid-phase and anaerobic (pH 5) and air-saturated (pH 5, 7, and 9) solutions without and with 40% glycerol is reported. Sequential K-edge X-ray Absorption Spectroscopic (XAS) spectra were acquired. l-cysteine degraded systematically in the X-ray beam. Radiolytic products were inventoried by fits using the XAS spectra of sulfur model compounds. Solid l-cysteine declined to 92% fraction after a single K-edge XAS scan. After six scans, 60% remained, accompanied by 14% cystine, 16% thioether, 5.4% elemental sulfur, and smaller fractions of more highly oxidized products. In air-saturated pH 5 solution, 73% of l-cysteine remained after ten scans, with 2% cystine and 19% elemental sulfur. Oxidation increased with 40% glycerol, yielding 67%, 5%, and 23% fractions, respectively, after ten scans. Higher pH solutions exhibited less radiolytic chemistry. All the reactivity followed first-order kinetics. The anaerobic experiment displayed two reaction phases, with sharp changes in kinetics and radiolytic chemistry. Unexpectedly, the radiolytic oxidation of l-cysteine was increased in anaerobic solution. After ten scans, only 60% of the l-cysteine remained, along with 17% cystine, 22% elemental sulfur, and traces of more highly oxidized products. A new aerobic reaction cycle is hypothesized, wherein dissolved dioxygen captures radiolytic H• or eaq -, enters HO2 •/O2 •-, reductively quenches cysteine thiyl radicals, and cycles back to O2. This cycle is suggested to suppress the radiolytic production of cystine in aerobic solution.

Photochemical Processes in Molecular Polymethine Dye Probes in the Presence of Bile Salts

Primary photochemical processes in polymethine dye probes 3,3′-di(γ-sulfopropyl)-4,5,4′,5′-dibenzo-9-ethylthiacarbocyanine betaine (DEC) and 3,3′,9-trimethylthiacarbocyanine iodide (Cyan 2) in micellar systems of bile-acid salts (BASs) sodium cholate, deoxycholate, and taurocholate and sodium dodecyl sulfate (SDS) as a reference are studied by flash photolysis. Signals due to photoisomerization of dye trans-isomers and dark reverse isomerization of the resulting cis-photoisomers are observed during pulse photolysis of air-saturated aqueous dye solutions in the presence of BAS and SDS micelles. The lifetimes of the photoisomers are 60–190 μs. Pulse photolysis of Cyan 2 and DEC solutions without oxygen and with BAS and SDS micelles induced photoisomerization and transition of the dyes into an excited triplet state followed by the reverse transition (intersystem crossing) into the initial singlet state. Triplet–triplet absorption spectra of these dyes isomers in polar (EtOH, i-PrOH) and nonpolar (dioxane) solvents were obtained for comparison using triplet–triplet energy transfer from anthracene. The conclusion was drawn that the photochemical behavior of the dyes in BAS and SDS micellar systems were similar.