Subsequent Reaction Mechanisms Research Articles

Understanding the roles of Brønsted/Lewis acid sites on manganese oxide-zeolite hybrid catalysts for low-temperature NH3-SCR

Although metal oxide-zeolite hybrid materials have long been known to achieve enhanced catalytic activity and selectivity in NOx removal reactions through the inter-particle diffusion of intermediate species, their subsequent reaction mechanism on acid sites is still unclear and requires investigation. In this study, the distribution of Brønsted/Lewis acid sites in the hybrid materials was precisely adjusted by introducing potassium ions, which not only selectively bind to Brønsted acid sites but also potentially affect the formation and diffusion of activated NO species. Systematic in situ diffuse reflectance infrared Fourier transform spectroscopy analyses coupled with selective catalytic reduction of NOx with NH3 (NH3-SCR) reaction demonstrate that the Lewis acid sites over MnOx are more active for NO reduction but have lower selectivity to N2 than Brønsted acids sites. Brønsted acid sites primarily produce N2, whereas Lewis acid sites primarily produce N2O, contributing to unfavorable N2 selectivity. The Brønsted acid sites present in Y zeolite, which are stronger than those on MnOx, accelerate the NH3-SCR reaction in which the nitrite/nitrate species diffused from the MnOx particles rapidly convert into the N2. Therefore, it is important to design the catalyst so that the activated NO species formed in MnOx diffuse to and are selectively decomposed on the Brønsted acid sites of H-Y zeolite rather than that of MnOx particle. For the physically mixed H-MnOx+H-Y sample, the abundant Brønsted/Lewis acid sites in H-MnOx give rise to significant consumption of activated NO species before their inter-particle diffusion, thereby hindering the enhancement of the synergistic effects. Furthermore, we found that the intercalated K+ in K-MnOx has an unexpected favorable role in the NO reduction rate, probably owing to faster diffusion of the activated NO species on K-MnOx than H-MnOx. This study will help to design promising metal oxide-zeolite hybrid catalysts by identifying the role of the acid sites in two different constituents.

Optimizing Gas Sensing Properties of Fe-Loaded Indium Zinc Oxide Nanocomposite for Efficient Detection of Ammonia Gas

The current study delineates the role of gas sensing properties of Fe-IZO (Iron loaded Indium Zinc oxide) a mixed metal oxide nanocomposite. The heterostructured Fe-IZO nanocomposite (NC) was synthesized via the facile co-precipitation method. The Fe-IZO NC was characterized by various experimental techniques and the results attained allowed us to suggest the mechanism for considering the connection between morphological variations and gas-sensing characteristics of Fe-IZO NC. One of the cutting-edge circumstances now-a-days is the prime use of gas sensors for environmental applications. The NC has a good selectivity for NH3 gas that has shown good stability up to 80 d. The response time (ℸres) is 64 s, recovery time (ℸrec) is 72 s for 50 ppm (parts per million) and obtained a highest response of 87% at room temperature. The Fe-IZO NC heterostructure with efficient charge transfer can enable the subsequent reaction mechanism with NH3 gas and the adsorbed oxygen ions leading to an increased response. Consequently, the results attained in this work has shown that the synthesized heterostructured NC sensor is suitable for room temperature NH3 sensing with high performance.

Degradation of Diethyl Phthalate by HO• and SO4• – in the Aqueous Phase: Mechanisms, Kinetics, and Toxicity

The chemical degradation processes of diethyl phthalate (DEP) induced by HO• and SO4• – in aqueous solution were studied in a theoretical way. Not only radical addition and H-abstraction reactions but also single-electron transfer processes of DEP were considered. The thermodynamic and kinetic results indicate that the more favorable pathways are the H abstraction occurring in aliphatic side chains for all HO•/SO4• –-initiated degradation reactions of DEP. Subsequent reaction mechanisms of crucial primary intermediates were taken into account. At 298 K, the total rate constants for DEP degradation reactions induced by HO• and SO4• – are 2.34 × 109 and 1.24 × 108 M–1 s–1, respectively. They are in accordance with the experimental data. In comparison to SO4• –, HO• has higher reactivity toward DEP in the research temperature range of 273–303 K. Considering the impact on the water eco-environment and human health, DEP and its 10 products have no bioaccumulation potential, but most products are developmentally toxic, except for (Z)-ethyl-2,5-dioxopent-3-enoate. Moreover, (Z)-ethyl-2,5-dioxopent-3-enoate is acutely toxic to fish; phthalic acid is mutagenicity positive; and we should pay more attention to them in the future.

Effects of *CO Coverage on Selective Electrocatalytic Reduction of CO2 to Ethylene over Cu2O with Undercoordinated Cu Sites

Cu2O surface with the coordinatively unsaturated Cu sites reveals advantages in the electroreduction of CO2 toward C2H4 production. Understanding the role of *CO coverage and veritable active sites is of great significance for a good command of the catalytic mechanism. Herein, based on density functional theory, the effects of *CO coverage during the reduction of CO2 to C2H4 on various active sites of Cu2O(111) surface, in terms of the adsorption and structural changes of *CO and key intermediates; the energy profiles of the C–C coupling steps; and the subsequent reaction mechanisms were investigated. Results show that CuCUS on the Cu2O(111) surface is especially reactive toward the *CO adsorption and subsequent reactions, being the preferred site owing to the unsaturated Cu atoms. The *CO coverage obviously tunes the adsorption stability of *COH and *CHO intermediates by affecting the adsorbent–adsorbent interactions. Higher coverage of *CO within 0.13–0.25 promotes the C–C coupling by lowering the energy barrier of *CH2 dimerization, favoring the C2H4 production. Due to the more facile generation of *CHO than *COH, the rate-determining step is speculated to be the C–C coupling with the highest barrier energy occurring in the *CHO pathway. Results provide a fundamental understanding of the CO2 reduction mechanism on Cu-based surfaces, favoring novel catalysts, rational design, and chemical fuel production.

The roles of HO•, ClO• and BrO• radicals in caffeine degradation: A theoretical study

ClO• and BrO• are newly discovered reactive radicals that contribute to the degradation of micropollutants. However, the research on pollutant degradation by ClO• and BrO• is still lacking. Thus, the mechanism, kinetics, and toxicity of caffeine degradation by HO•, ClO•, and BrO• were computationally studied and compared. Results showed that radical adduct formation (RAF) reaction was dominant for HO•, ClO•, and BrO• initiated reactions of caffeine. The main reaction sites were C5 and C8 of caffeine for HO•, while only the RAF reaction on C8 was prominent for ClO• and BrO•. The initiated reaction rate constants of caffeine by HO•, ClO•, and BrO• were in the order of HO• (5.29 × 109 M−1 s−1) > ClO• (1.40 × 109 M−1 s−1) > BrO• (2.17 × 108 M−1 s−1). The kinetic simulation verified that ClO• played a crucial role in the degradation of caffeine by the UV/chlorine process. In addition to HO-adducts, the subsequent reaction mechanisms of ClO- and BrO-adducts have also been investigated. The formation mechanisms of several important products, namely dimethylparabanic acid (P2), di(N-hydroxymethyl) parabanic acid (P5), 1,3,7-trimethyluric acid (P6), and 8-oxocaffeine (P11), were elucidated. Remarkably, stable chlorinated and brominated intermediates or products were not generated in ClO•- and BrO•-mediated subsequent degradations of caffeine. The assessment of aquatic toxicity and health effects showed that caffeine could penetrate the blood-brain barrier (human), and caffeine and its degradation products were potentially harmful to the aquatic environment.

Isomer‐dependent reaction mechanisms of cyclic ether intermediates: cis‐2,3‐dimethyloxirane and trans‐2,3‐dimethyloxirane

AbstractOxiranes are a class of cyclic ethers formed in abundance during low‐temperature combustion of hydrocarbons and biofuels, either via chain‐propagating steps that occur from unimolecular decomposition of β‐hydroperoxyalkyl radicals (β‐̇QOOH) or from reactions of HȮO with alkenes. The cis‐ and trans‐isomers of 2,3‐dimethyloxirane are intermediates of n‐butane oxidation, and while rate coefficients for β‐̇QOOH → 2,3‐dimethyloxirane + ̇OH are reported extensively, subsequent reaction mechanisms of the cyclic ethers are not. As a result, chemical kinetics mechanisms commonly adopt simplified chemistry to describe the consumption of 2,3‐dimethyloxirane by convoluting several elementary reactions into a single step, which may introduce mechanism truncation error—uncertainty derived from missing or incomplete chemistry.The present research examines the isomer dependence of 2,3‐dimethyloxirane reaction mechanisms in support of ongoing efforts to minimize mechanism truncation error. Reaction mechanisms are inferred via the detection of products from Cl‐initiated oxidation of both cis‐2,3‐dimethyloxirane and trans‐2,3‐dimethyloxirane using multiplexed photoionization mass spectrometry (MPIMS). The experiments were conducted at 10 Torr and temperatures of 650 K and 800 K. To complement the experiments, the enthalpies of stationary points on the ̇R + O2 surfaces were computed at the ccCA‐PS3 level of theory. In total, 28 barrier heights were computed on the 2,3‐dimethyloxiranylperoxy surfaces. Two notable aspects are low‐lying pathways that form resonance‐stabilized ketohydroperoxide‐type radicals caused by ̇QOOH ring‐opening when the unpaired electron is localized adjacent to the ether group, and cis‐trans isomerization of ̇R and ̇QOOH radicals, via inversion, which enable reaction pathways otherwise restricted by stereochemistry.Several species were identified in the MPIMS experiments from ring opening of 2,3‐dimethyloxiranyl radicals. Neither of the two conjugate alkene isomers prototypical of ̇R + O2 reactions were detected. Products were also identified from decomposition of ketohydroperoxide‐type radicals. The present work provides the first analysis of 2,3‐dimethyloxirane oxidation chemistry and reveals that consumption pathways are complex and require the expansion of submechanisms in chemical kinetics mechanisms.

Probing the surface chemistry for reverse water gas shift reaction on Pt(1 1 1) using ambient pressure X-ray photoelectron spectroscopy

Using ambient pressure XPS (APXPS), we explored carbon dioxide (CO2) adsorption and CO2 hydrogenation on Pt(111) single crystal surface to observe the activation of CO2 and the subsequent reaction mechanism. In pure CO2, we observed CO adsorbates and adsorbed oxygen on Pt(111) derived from CO2 dissociation at room temperature. The introduction of H2 (at a pressure ratio of 1:1 (H2:CO2)) increased the production of CO across all temperatures by facilitating the removal of surface oxygen. As a consequence, the surface could expose sites that could then be utilized for producing CO. Under these conditions, the reverse water–gas shift (RWGS) reaction was observed starting at 300 oC. At higher H2 partial pressure (10:1 (H2:CO2)), the RWGS reaction initiated at a lower temperature of 200 oC and continued to enhance the conversion of CO2 with increasing temperatures. Our results revealed that CO2 was activated on a clean Pt(111) surface through the dissociation mechanism to form adsorbed CO and O at room temperature and at elevated temperatures. Introducing H2 facilitated the RWGS as adsorbed oxygen was consumed continuously to form H2O, and adsorbed CO desorbed from the surface at elevated temperatures. This work clearly provides direct experimental evidence for the surface chemistry of CO2 dissociation and demonstrates how hydrogen impacts the RWGS reaction on a platinum surface.

Activation and selective oxy-functionalization of alkanes with metal complexes: Shilov reaction and some new aspects

The quest of selective catalytic reactions for direct conversion of alkanes into valued products remains to be the most important task objective of modern chemistry and metal complex catalysis. Nowadays it is adopted that the formation of metal–alkyl intermediates (MR) is a necessary condition for activation and functionalization of alkanes on metal complexes but the mechanism of subsequent reactions of metal alkyls remain obscure, so that effective catalytic systems of this kind are still rare and uncommon. Although it is widely adopted that alkane σ-complexes (M·RH) most frequently are primary hydrocarbon intermediates in these processes, low profile in the literature is given to their reactivity and these are often considered simply just as some ‘collision complexes’. Nevertheless, theoretical and experimental studies provide more and more evidence that the СН bonds in such complexes may be markedly weakened and/or polarized, thus opening wide horizons for occurrence of subsequent direct homolytic or heterolytic reactions of alkanes. This review addresses the discussion of new routes for activation and oxygenation of saturated hydrocarbons, including those via alkane σ-complexes, without formation of metal–alkyl intermediates.

Synthesis of Hydrophilic and Hydrophobic Carbon Nanoparticles from Benzene/Water Bilayer Solution with Femtosecond Laser Generated Plasma Filaments in Water

Abstract We synthesized hydrophilic and hydrophobic carbon nanoparticles (CNPs) by femtosecond laser (0.8 µm, 40 fs) irradiation of the water layer of an aerated benzene/water (B/W) bilayer solution. Focusing intense femtosecond laser pulses onto water creates a high density of reactive species such as hydroxyl radicals in a well-confined volume; i.e., plasma filament. The properties of the particle surface were controlled simply by adjusting the laser focusing position, the duration between the preparation of B/W bilayer solution and the laser irradiation. The hydrophobic CNPs appeared to be nearly identical in size and morphology to hydrophilic CNPs. Raman spectroscopy revealed that both particles had a graphitic and disordered structure; however, IR spectroscopy clearly showed that the hydroxy group is the origin of the hydrophilicity. The time evolution of particle formation, products in water, and benzene dissolution behavior in water reveals that the surface properties are determined by the concentration of benzene in water. The diluted aqueous benzene solution gave hydrophilic particles; however, the density of particles was much smaller than that formed in B/W bilayer solution. We concluded that the production of denser hydrophilic CNPs in B/W bilayer was achieved by limiting the concentration of benzene in water layer by B/W interface, and by continuously supplying benzene into water layer through B/W interface. We discuss the subsequent reaction mechanism leading to CNPs of different surface characters.

Synergistic antibacterial effects of treatments with low temperature plasma jet and pulsed electric fields

Inactivation of Staphylococcus aureus by a non-thermal argon operated plasma jet and by microsecond pulsed electric fields (PEF) was investigated. The different methods were either applied by themselves or in combination with each other. Treatments with plasma alone or pulsed electric fields alone were found to result in significant but not complete inactivation. A 2-log reduction was observed for the longest plasma exposure time of 3 min or for the application of 300 consecutive electric field pulses with 100-μs duration and 15-kV/cm amplitude. For the combined treatment with non-thermal plasma and pulsed electric fields, significant synergistic antibacterial effects were observed when samples were treated with plasma first. However, only an additive or at most a slight synergistic effect was observed when samples were first treated with pulsed electric fields instead. The acidification of the bacteria suspension after plasma treatment is likely responsible for the support of subsequent reaction mechanisms that are induced by exposures to pulsed electric fields and is hence the reason for the observed synergy.

OH-initiated AOPs degradation mechanism of ibuprofen in aqueous environments

As a common pharmaceutical and personal care product, ibuprofen (IBP) is regarded as an important pollutant in aqueous environments. In this paper, the OH-initiated advanced oxidation processes (AOPs) degradation mechanism and its subsequent reaction mechanism with IBP were studied at the M06-2x/6-311++G(2d, p)//M06-2x/6-31+G(d,p) level. The frontier electron density and bond dissociation energy were analyzed. In addition, profiles of the potential energy surface were constructed, and all the possible pathways were discussed. H-atom abstraction is the most important mechanism. The dominant products were IBAP, 2-[4-(1-hydroxyisobutyl)phenyl]propionic acid, and 1-(4-isobutylphenyl)-1-ethanol, which is in good agreement with the experimental results.

Reaction of OH radicals with 5-hydroxy-2-pentanone: formation yield of 4-oxopentanal and its OH radical reaction rate constant

Environmental context Alkanes, major constituents of vehicle exhausts, are emitted to the atmosphere where they react, chiefly by gas-phase reactions with the hydroxyl radical, to form products which can also react further. In laboratory experiments, we studied the further reactions of a model first-generation alkane reaction product. Understanding alkane reaction chains is important because the toxicity, secondary aerosol formation and other properties of vehicle emissions can change as new compounds are formed. Abstract 1,4-Hydroxycarbonyls are major products of the gas-phase reactions of alkanes with OH radicals, and in the atmosphere they will react with OH radicals or undergo acid-catalysed cyclisation with subsequent dehydration to form highly reactive dihydrofurans. 3-Oxobutanal (CH3C(O)CH2CHO) and 4-oxopentanal (CH3C(O)CH2CH2CHO) are first-generation products of the OH radical-initiated reaction of 5-hydroxy-2-pentanone (CH3C(O)CH2CH2CH2OH). The behaviours of 3-oxobutanal and 4-oxopentanal have been monitored during OH+5-hydroxy-2-pentanone reactions carried out in the presence of NO, using solid phase microextraction fibres coated with O-(2,3,4,5,6,-pentafluorobenzyl)hydroxyl amine (PFBHA) for on-fibre derivatisation of carbonyl compounds and an annular denuder coated with XAD resin and further coated with PFBHA. The time-concentration data for 4-oxopentanal during OH+5-hydroxy-2-pentanone reactions were independent of relative humidity (0–50%), and were consistent with a rate constant for OH+4-oxopentanal of (1.2±0.5)×10–11cm3 molecule–1s–1 at 296±2K, a factor of 2 lower than both literature rate constants for other aldehydes and that estimated using a structure-reactivity approach. The molar formation yield for 4-oxopentanal from OH+5-hydroxy-2-pentanone in the presence of NO was determined to be 17±5%, consistent with predictions based on a structure-reactivity relationship and current knowledge of the subsequent reaction mechanisms.

Vacuum Refining of Molten Silicon

AbstractMetallurgical fundamentals for vacuum refining of molten silicon and the behavior of different impurities in this process are studied. A novel mass transfer model for the removal of volatile impurities from silicon in vacuum induction refining is developed. The boundary conditions for vacuum refining system—the equilibrium partial pressures of the dissolved elements and their actual partial pressures under vacuum—are determined through thermodynamic and kinetic approaches. It is indicated that the vacuum removal kinetics of the impurities is different, and it is controlled by one, two, or all the three subsequent reaction mechanisms—mass transfer in a melt boundary layer, chemical evaporation on the melt surface, and mass transfer in the gas phase. Vacuum refining experimental results of this study and literature data are used to study the model validation. The model provides reliable results and shows correlation with the experimental data for many volatile elements. Kinetics of phosphorus removal, which is an important impurity in the production of solar grade silicon, is properly predicted by the model, and it is observed that phosphorus elimination from silicon is significantly increased with increasing process temperature.

Theoretical studies of the reactions of CF3CHCLOCHF2/CF3CHFOCHF2 with OH radical and Cl atom and their product radicals with OH

The mechanisms and dynamics studies of the OH radical and Cl atom with CF(3)CHClOCHF(2) and CF(3)CHFOCHF(2) have been carried out theoretically. The geometries and frequencies of all the stationary points are optimized at the B3LYP/6-311G(d,p) level, and the energy profiles are further refined by interpolated single-point energies (ISPE) method at the G3(MP2) level of theory. For each reaction, two H-abstraction channels are found and four products (CF(3)CHFOCF(2), CF(3)CFOCHF(2), and CF(3)CHClOCF(2), CF(3)CClOCHF(2)) are produced during the above processes. The rate constants for the CF(3)CHClOCHF(2)/CF(3)CHFOCHF(2) + OH/Cl reactions are calculated by canonical variational transition-state theory (CVT) within 200-2000 K, and the small-curvature tunneling is included. The total rate constants calculated from the sum of the individual rate constants and the branching ratios are in good agreement with the experimental data. The Arrhenius expressions for the reactions are obtained. Our calculation shows that the substitution of Cl by F decreases the reactivity of CF(3)CHClOCHF(2) toward OH and Cl. In addition, the mechanisms of subsequent reactions of product radicals and OH radical are further investigated at the G3(MP2)//B3LYP/6-311G(d,p) level, and the main products are predicted in the this article.

Computational Studies on the Mechanisms and Dynamics of OH Reactions with CHF2CHFOCF3 and CHF2CH2OCF3.

The dual-level direct dynamics method has been employed to investigate the multichannel hydrogen abstraction reactions of CHF2CHFOCF3 + OH (R1) and CHF2CH2OCF3 + OH (R2) theoretically. The optimized geometries and frequencies of the stationary points and the minimum energy path are calculated at the B3LYP/6-311G(d,p) level, and the energetic information is further refined by the MC-QCISD method. There are two hydrogen abstraction channels for reaction R1 and three hydrogen abstraction channels for reaction R2. And four products, CF2CHFOCF3, CHF2CFOCF3, CF2CH2OCF3, and CHF2CHOCF3, are produced during these two reactions. The enthalpies of formation for the species involved in the two reactions (CHF2CHFOCF3, CF2CHFOCF3, CHF2CFOCF3, CHF2CH2OCF3, CF2CH2OCF3, and CHF2CHOCF3) are calculated via isodesmic reaction. Furthermore, the reaction mechanisms of subsequent reactions of product radicals (CF2CHFOCF3, CHF2CFOCF3, CF2CH2OCF3, and CHF2CHOCF3) with the OH radical are studied at the same level. The rate constants of reactions R1 and R2 are evaluated by means of canonical variational transition-state theory including the small-curvature tunneling correction over a wide range of temperatures, from 250 to 1200 K. Our results show that the tunneling correction plays an important role in the rate constant calculation in the low-temperature range. Agreement between the calculated and experimental data available at 298 K is good. It is found that the fluorine substitution decreases the reactivity of the C-H bond, and as a result, reaction R2 may proceed much easier than reaction R1. The Arrhenius expressions over a wide temperature range are obtained, and the kinetic isotope effects for reactions CHF2CHFOCF3/CDF2CDFOCF3 + OH and CHF2CH2OCF3/CDF2CD2OCF3 + OH are estimated so as to provide theoretical estimation for future laboratory investigation.

Product studies of gas-phase reactions of organic compounds

Abstract

Photochemical Mechanisms Responsible for the Versatile Application of Naphthalimides and Naphthaldiimides in Biological Systems

Despite the number and variety of their biological applications, the mechanisms of action of the photoactive naphthalenic imides have not yet been fully elucidated. In order to provide mechanistic insight, the photochemistry of several N-substituted 1,8-naphthalimides (NI) and 1,4,5,8-naphthaldiimides (NDI) has been studied using absorption and fluorescence spectroscopy and by laser flash photolysis (λexc = 355 nm). The lowest singlet state (S1) is mainly ππ* in nature for NI whereas nπ* character predominates for the NDI. This difference exerts a profound effect on subsequent reaction mechanisms: upon irradiation, only the NDI molecules can undergo intramolecular γ hydrogen abstraction. In the case of NP-III, a bishydroperoxy NDI derivative, this photoprocess (Φ = 0.03) leads to concomitant formation of an oxygen-centered radical (e = 21 600 M-1 cm-1 at 465 nm in acetonitrile) and release of the hydroxyl radical (•OH). All the compounds studied produce the triplet state (in acetonitrile, eT ≈ 10 500−11 ...

STM study ofC2H2adsorption on Si(001)

We present here a scanning tunneling microscope study of the initial bonding structure and subsequent reaction mechanism of ${\mathrm{C}}_{2}{\mathrm{H}}_{2}$ with the Si(001) surface. Upon exposure of the sample at room temperature to 0.2 L of ${\mathrm{C}}_{2}{\mathrm{H}}_{2}$ (approximately 20% coverage) adsorption of the molecule on alternate dimer pairs is observed, leading to either a local $2\ifmmode\times\else\texttimes\fi{}2$ or $c(2\ifmmode\times\else\texttimes\fi{}4)$ structure. In the filled-state image, a local minimum is observed in the center of the reacted dimer pairs, while the unreacted dimer pairs maintain the normal bean-shaped contour of the clean surface. The molecule forms an overlayer with either local $2\ifmmode\times\else\texttimes\fi{}2$ or $c(4\ifmmode\times\else\texttimes\fi{}2)$ order, leading to a saturation coverage of 0.5 monolayers. Upon annealing the substrate at 775 K the surface becomes disordered and the steps are no longer visible. After further annealing at 875 K, SiC clusters are formed and the $2\ifmmode\times\else\texttimes\fi{}1$ structure is again seen between the clusters. For a starting coverage of 20%, annealing to higher temperatures around 1100 K leads to pinning of the step movement by the SiC clusters. For a starting coverage of 0.5 monolayer, annealing at 1100 K results in faceting of the surface. Further annealing at 1275 K creates anisotropic facets that are oriented along the [1\ifmmode\bar\else\textasciimacron\fi{}10] direction with a typical aspect ratio of approximately 4 to 5. These facets act as nucleation sites for subsequent carbonization and SiC growth.

On the Mechanism of Water Cluster‐Ion Formation in Carbon Dioxide

AbstractA drift chamber mass spectrometer has been used to study the formation of water cluster‐ions in carbon dioxide containing traces of water vapour. The dominant reaction sequences were identified up to the fourth generation of daughter ions starting with CO+2. The subsequent reaction mechanism remains uncertain and several possibilities are discussed. The final ions are H3O+ H2O and H3O+ (H2O)2. The significance of the reaction schemes to the radiation chemistry of carbon dioxide is pointed out.

Photoejection of electrons from flavins in polar media.

Riboflavin and 12 of its derivatives have been shown to form solvated electrons under ultraviolet irradiation (253.7 nanometers) in various water-methanol solvent mixtures. The highest quantum yield of solvated electrons (about 0.03) was obtained for flavins containing tyrosine on a side chain in the isoalloxazine N-3 or N-10 position. The splitting of hydrogen atoms from excited flavin molecules was also observed. From the results presented here, it can be determined that the semiquinone transients are formed not only by way of the flavin triplet, as usually suggested, but also by the attack of the electrons and hydrogen atoms on flavin molecules in the ground state. This is important, because the flavin radicals remaining after the electron-ejection or hydrogen-splitting processes must also be considered in the subsequent reaction mechanisms. The electron-ejection process from electronically excited flavins has important implications in the photobiology of these compounds.