BACKGROUND: Ultrahigh dose-rate radiation (UHDR) produces less hydrogen peroxide (H2O2) in pure water, as suggested by some experimental studies, and is used as an argument for the validity of the theory that FLASH spares the normal tissue due to less reactive oxygen species (ROS) production. In contrast, most Monte Carlo simulation studies suggest the opposite.
OBJECTIVE: We aim to unveil the effect of UHDR on H2O2 production in pure water and its underlying mechanism, to serve as a benchmark for Monte Carlo simulation. We hypothesized that the reaction of solvated electrons ( e aq - ${\\mathrm{e}}_{{\\mathrm{aq}}}^ - $ ) removing hydroxyl radicals (•OH), the precursor of H2O2, is the reason why UHDR leads to a lower G-value (molecules/100 eV) for H2O2 (G[H2O2]), because: 1, the third-order reaction between e aq - ${\\mathrm{e}}_{{\\mathrm{aq}}}^ - $ and •OH is more sensitive to increased instantaneous ROS concentration by UHDR than a two-order reaction of •OH self-reaction producing H2O2; 2, e aq - ${\\mathrm{e}}_{{\\mathrm{aq}}}^ - $ has two times higher diffusion coefficient and higher reaction rate constant than that of •OH, which means e aq - ${\\mathrm{e}}_{{\\mathrm{aq}}}^ - $ would dominate the competition for •OH and benefit more from the inter-track effect of UHDR. Meanwhile, we also experimentally verify the theory of long-lived radicals causing lower G(H2O2) in conventional irradiation, which is mentioned in some simulation studies.
METHODS: H2O2 was measured by Amplex UltraRed assay. 430.1 MeV/u carbon ions (50 and 0.1 Gy/s), 9 MeV electrons (600 and 0.62 Gy/s), and 200 kV x-ray tube (10 and 0.1 Gy/s) were employed. For three kinds of water (real hypoxic: 1% O2; hypoxic: 1% O2 and 5% CO2; and normoxic: 21% O2), unbubbled and bubbled samples with N2O, the scavenger of e aq - ${\\mathrm{e}}_{{\\mathrm{aq}}}^ - $ , were irradiated by carbon ions and electrons with conventional and UHDR at different absolute dose levels. Normoxic water dissolved with sodium nitrate (NaNO3), another scavenger of e aq - ${\\mathrm{e}}_{{\\mathrm{aq}}}^ - $ , and bubbled with N2O was irradiated by x-ray to verify the results of low-LET electron beam.
RESULTS: UHDR leads to a lower G(H2O2) than conventional irradiation. O2 and CO2 can both increase G(H2O2). N2O increases G(H2O2) of both UHDR and conventional irradiation and eliminates the difference between them for carbon ions. However, N2O decreases G(H2O2) in electron conventional irradiation but increases G(H2O2) in the case of UHDR, ending up with no dose-rate dependency of G(H2O2). Three-spilled carbon UHDR does not have a lower G(H2O2) than one-spilled UHDR. However, the electron beam shows a lower G(H2O2) for three-spilled UHDR than for one-spilled UHDR. Normoxic water with N2O or NaNO3 can both eliminate the dose rate dependency of H2O2 production for x-ray.
CONCLUSIONS: UHDR has a lower G(H2O2) than the conventional irradiation for both high LET carbon and low LET electron and x-ray beams. Both scavengers for e aq - ${\\mathrm{e}}_{{\\mathrm{aq}}}^ - $ , N2O and NaNO3, eliminate the dose-rate dependency of G(H2O2), which suggests e aq - ${\\mathrm{e}}_{{\\mathrm{aq}}}^ - $ is the reason for decreased G(H2O2) for UHDR. Three-spilled UHDR versus one-spilled UHDR indicates that the assumption of residual radicals reducing G(H2O2) of conventional irradiation may only be valid for low LET electron beam.

The efficient dispersion of single-walled carbon nanotubes (SWCNTs) has been the subject of extensive research over the past decade. Despite these efforts, achieving individually dispersed SWCNTs at high concentrations remains challenging. In this study, we address the limitations associated with conventional methods, such as defect formation, excessive surfactant use, and the use of corrosive solvents. Our novel dispersion method utilizes the spontaneous charging of SWCNTs in a solvated electron system created by dissolving potassium in hexamethyl phosphoramide (HMPA). The resulting charged SWCNTs (c-SWCNTs) can be directly dispersed in the charging medium using only magnetic stirring, leading to defect-free c-SWCNT dispersions with high concentrations of up to 20 mg/mL. The successful dispersion of individual c-SWCNT strands is confirmed by their liquid-crystalline behavior. Importantly, the dispersion medium for c-SWCNTs exhibits no reactivity with metals, polymers, or other organic solvents. This versatility enables a wide range of applications, including electrically conductive free-standing films produced via conventional blade coating, wet-spun fibers, membrane electrodes, thermal composites, and core-shell hybrid microparticles.

Precise defect engineering of photocatalysts is highly demanding but remains a challenge. Here, we developed a facile and controllable γ-ray radiation strategy to assemble dual-vacancies confined MoS2-CdS-γ nanocomposite photocatalyst. We showed the solvated electron induced homogeneous growth of defects-rich CdS nanoparticles, while the symbiotic •OH radicals etched flower-like 1T/2H MoS2 substrate surfaces. The optimal MoS2-CdS-γ exhibited a H2 evolution rate of up to 37.80 mmol/h/g under visible light irradiation, which was 36.7 times higher than that of bare CdS-γ, and far superior to those synthesized by hydrothermal method. The microscopic characterizations and theoretical calculations revealed the formation of such unprecedented dual-sulfur-vacancies ensured the tight interfacial contact for fast charge separation. Besides, the existence of 1T-MoS2 phase further improved the conductivity and strengthened the adsorption interaction with H+ intermediate. Therefore, the radiolytic radical chemistry offered a facile, ambient and effective synthetic strategy to improve the catalytic performances of photocatalytic materials.

The removal of per- and polyfluoroalkyl substance (PFAS) pollution from the environment is a globally pressing issue, due to some PFAS\' recalcitrant, bioaccumulative, and carcinogenic nature. Destruction via ultrasonic waves (sonolysis) is a promising contender for industrialisation due to; moderate power consumption, applicability to several PFAS and sample types, and limited by-products. Liquid flow rate through an ultrasonic reactor can affect the size, shape, and spatial distribution of ultrasonic cavities and hence their chemical activity. Such effects have not been studied during PFAS sonolysis, and temporal effects have not been studied much beyond the reactant concentration. Here, the effects of varying recirculating flow rate on the ultrasonic defluorination of perfluorooctane sulfonic acid (PFOS) and implications for industrial scale up are presented. Under the ultrasonic power (200 W L-1, 2.27 W cm-2) and frequency (410 kHz) used, flow rates of 79 and 214 ml min-1 enhanced defluorination up to 14 % during 30 min of treatment. However, these effects were temporal and most significant in the initial minutes of treatment. This indicated a dynamic bubble size distribution which stabilised after around 15 min. Defluorination rates of PFOS were compared with measured potassium iodide dosimetry, calorimetry, sonoluminescence (SL), and sonochemiluminescence (SCL). Flow rates which enhanced defluorination correlated moderately with enhanced SCL and negatively impacted SL, calorimetry, and dosimetry. Effects were attributed to perturbed cavity surfaces, leading to asymmetric cavity collapse, and the possibility of enhanced solvated electron production/interaction. SL, SCL, dosimetry, and calorimetric measurements were also temporal, and each showed different times to equilibrate. Flow rates of 439 and 889 ml min-1 returned all sonochemical measurements to the levels without flow, likely due to continued collapse temperature quenching by furthered bubble asymmetry. Flow also enhanced reactor cooling, which is significant for industrial temperature control. The pump energy consumed was small (≈1.9 %) compared to that of the amplifier and chiller, hence, PFOS defluorination was more cost-effective using flow. However, the effect may be limited for the longer treatment times needed for environmental remediation.

Phytochromes constitute a family of photosensory proteins that are utilized by various organisms to regulate several physiological processes. Phytochromes bind a bilin pigment that switches its isomeric state upon absorption of red or far-red photons, resulting in protein conformational changes that are sensed by the organism. Previously, the ultrafast dynamics in bacterial phytochrome was resolved to atomic resolution by time-resolved serial femtosecond X-ray diffraction (TR-SFX), showing extensive changes in its molecular conformation at 1 picosecond delay time. However, the large excitation fluence of mJ/mm2 used in TR-SFX questions the validity of the observed dynamics. In this work, we present an excitation-dependent ultrafast transient absorption study to test the response of a related bacterial phytochrome to excitation fluence. We observe excitation power-dependent sub-picosecond dynamics, assigned to the population of high-lying excited state Sn through resonantly enhanced two-photon absorption, followed by rapid internal conversion to the low-lying S1 state. Inspection of the long-lived spectrum under high fluence shows that in addition to the primary intermediate Lumi-R, spectroscopic signatures of solvated electrons and ionized chromophore radicals are observed. Supported by numerical modelling, we propose that under excitation fluences of tens of μJ/mm2 and higher, bacterial phytochrome partly undergoes photoionization from the Sn state in competition with internal conversion to the S1 state in 300 fs. We suggest that the extensive structural changes of related, shorter bacterial phytochrome, lacking the PHY domain, resolved from TR-SFX may have been affected by the ionized species. We propose approaches to minimize the two-photon absorption process by tuning the excitation spectrum away from the S1 absorption or using phytochromes exhibiting minimized or shifted S1 absorption.

The photo-induced radiolysis of water is an elementary reaction in biology and chemistry, forming solvated electrons, OH radicals, and hydronium cations on fast time scales. Here, we use an optical-pump terahertz-probe spectroscopy setup to trigger the photoionization of water molecules with optical laser pulses at ~400 nm and then time-resolve the transient solvent response with broadband terahertz (THz) fields with a ~90 fs time resolution. We observe three distinct spectral responses. The first is a positive broadband mode that can be attributed to an initial diffuse, delocalized electron with a radius of (22 ± 1) Å, which is short lived (<200 fs) because the absorption is blue-shifting outside of the THz range. The second emerging spectroscopic signature with a lifetime of about 150 ps is attributed to an intermolecular mode associated with a mass rearrangement of solvent molecules due to charge separation of radicals and hydronium cations. After 0.2 ps, we observe a long-lasting THz signature with depleted intensity at 110 cm-1 that is well reproduced by ab initio molecular dynamics. We interpret this negative band at 110 cm-1 as the solvent cage characterized by a weakening of the hydrogen bond network in the first and second hydration shells of the cavity occupied by the localized electron.

An electron solvated in a polar liquid is an elementary quantum system with properties governed by electric interactions with a fluctuating molecular environment. In the prevailing single particle picture, the quantum ground and excited states are determined by a self-consistent potential, as defined by the particular local configuration of the solvation shell. This description neglects collective many-body excitations, which arise from the coupling of electronic degrees of freedom and nuclear motions of the environment. While recent experiments have demonstrated collective nonequilbrium electronic-nuclear motion, i.e. polaron excitations in liquid water, their relevance in the broader context of polar liquids has remained unexplored. Here, we study the nonequilibrium dielectric response of the, compared to water, less polar alcohols isopropanol, and ethylene glycol, that also display a different hydrogen bond pattern. We demonstrate that ultrafast relaxation of photogenerated electrons impulsively induces coherent charge oscillations, which persist for some 10 ps. They emit electric waves in a frequency range from 0.1 to 2 THz, depending on electron concentration. Oscillation frequencies and line shapes are reproduced by a unified polaron picture for alcohols and water, which is based on a Clausius-Mossotti local field approach for the THz dielectric function. The analysis suggests a longitudinal character of many-body polaron excitations and a weak coupling to transverse excitations, supported by the underdamped character of charge oscillations. Polaron dynamics are governed by the long-range Coulomb interaction between an excess electron and several thousands of polar solvent molecules, while local electron solvation geometries play a minor role.

Catalyst recovery is an integral part of photoredox catalysis. It is often solved by adding another component-a sacrificial agent-whose role is to convert the catalyst back into its original oxidation state. However, an additive may cause a side reaction thus decreasing the selectivity and overall efficiency. Herein, we present a novel approach towards chemoselective photooxidation reactions based on suitable solvent-acetonitrile acting simultaneously as an electron acceptor for catalyst recovery, and on anaerobic conditions. This is allowed by the unique properties of the catalyst, 7,8-dimethoxy-3-methyl-5-phenyl-5-deazaflavinium chloride existing in both strongly oxidizing and reducing forms, whose strength is increased by excitation with visible light. Usefulness of this system is demonstrated in chemoselective dehydrogenations of 4-methoxy- and 4-chlorobenzyl alcohols to aldehydes without over-oxidation to benzoic acids achieving yields up to 70 %. 4-Substituted 1-phenylethanols were oxidized to ketones with yields 80-100 % and, moreover, with yields 31-98 % in the presence of benzylic methyl group, diphenylmethane or thioanisole which are readily oxidized in the presence of oxygen but these were untouched with our system. Mechanistic studies based on UV-Vis spectro-electrochemistry, EPR and time-resolved spectroscopy measurements showed that the process involving an electron release from an excited deazaflavin radical to acetonitrile under formation of solvated electron is crucial for the catalyst recovery.

Electron transfer plays a crucial role in ROS generation in living systems. Molecular oxygen acts as the terminal electron acceptor in the respiratory chains of aerobic organisms. Two main mechanisms of antioxidant defense by exogenous antioxidants are usually considered. The first is the inhibition of ROS generation, and the second is the trapping of free radicals. In the present study, we have elucidated both these mechanisms of antioxidant activity of glycyrrhizin (GL), the main active component of licorice root, using the chemically induced dynamic nuclear polarization (CIDNP) technique. First, it was shown that GL is capable of capturing a solvated electron, thereby preventing its capture by molecular oxygen. Second, we studied the effect of glycyrrhizin on the behavior of free radicals generated by UV irradiation of xenobiotic, NSAID-naproxen in solution. The structure of the glycyrrhizin paramagnetic intermediates formed after the capture of a solvated electron was established from a photo-CIDNP study of the model system-the dianion of 5-sulfosalicylic acid and DFT calculations.

The moving single-bubble sonoluminescence of Ce3+ in water and ethylene glycol solutions of CeCl3 and (NH4)2Ce(NO3)6 was studied. As found, a significant part of intensity of the luminescence (100% with cerium concentration less than 10-4 M) is due to the sonochemiluminescence. A key reaction of sonochemiluminescence is the Ce4+ reduction by a solvated (or hydrated in water) electron: Ce4+ + es (eaq) → *Ce3+. Solvated electrons are formed in a solution via electrons ejection from a low-temperature plasma periodically generated in deformable moving bubble at acoustic vibrations. Reactions of heterolytic dissociation of solvents make up the source of electrons in the plasma. In aqueous CeCl3 solutions, the Ce4+ ion is formed at the oxidation of Ce3+ by OH radical. The latter species originates from homolytic dissociation of water in the plasma of the bubble, also penetrating from the moving bubble into the solution. The sonochemiluminescence in cerium trichloride solutions are quenched by the Br- (acceptor of OH) and H+ ions (acceptor of eaq). In water and ethylene glycol solutions of (NH4)2Ce(NO3)6, the sonochemiluminescence also quenched by the H+ ion. The sonochemiluminescence in CeCl3 solutions is registered at [Ce3+] ≥ 10-5 M. Then the sonochemiluminescence intensity increases with the cerium ion concentration and reaches the saturation plateau at 10-2 M. It was shown that sonophotoluminescence (re-emission of light of bubble plasma emitters by cerium ions) also contributes to the luminescence of Ce3+ in solutions with [Ce3+] ≥ 10-4 M. If the cerium concentration is more than 10-2 M, a third source contributes to luminescence, viz., the collisional excitation of Ce3+ ions penetrating into the moving bubble.