Disinfection experiments were carried out in which a slurry of titanium dioxide/Escherichia coli was mixed intensively with a magnetic stirrer to allow a complete mixing, and then five sets of ...photocatalytic disinfection experiments were conducted involving varying parameters: DO or hydroxyl radical scavenger, TiO sub(2) concentration, light intensity, temperature, and pH. The aim was to examine how OH radical, acting either independently or in collaboration with other reactive oxygen species, was related to the inactivation of E. coli. p-Chlorobenzoic acid was used as an OH radical formation probe. A linear correlation was found between the amount of OH radical formed and the extent of E. coli inactivation in TiO sub(2) photocatalytic disinfection at a constant reaction temperature. More rapid inactivation occurred at higher light intensity, but the relationship was not proportional, which was also found in terms of the concentration of TiO sub(2). No significant pH effect was noted. Overall, the OH radical was determined to be 1000 10,000 times as effective for E. coli inactivation as other chemical disinfectants.
Photocatalytic Water Oxidation
The art representing article number 2203102 by Nathan I. Hammer, Jared H. Delcamp, and co‐workers depicts the organic molecular photosensitizer QL11‐OEG being ...irradiated with visible light under water. The strong photooxidant QL11‐OEG is in a 16 microsecond long‐lived excited state near a ruthenium‐based water oxidation catalyst. QL11‐OEG is oxidizing the ruthenium‐based catalyst to drive the conversion of water molecules to molecular oxygen which is shown as bubbles rising to the surface.
The atmospheric aqueous-phase is a rich medium for chemical transformations of organic compounds, in part via photooxidants generated within the drops. Here we measure light absorption, ...photoformation rates and steady-state concentrations of two photooxidants – hydroxyl radical (•OH) and singlet molecular oxygen (1O2*) – in 8 illuminated fog waters from Davis, California and Baton Rouge, Louisiana. Mass absorption coefficients for dissolved organic compounds (MACDOC) in the samples are large, with typical values of 10,000–15,000 cm2 g-C−1 at 300 nm, and absorption extends to wavelengths as long as 450–600 nm. While nitrite and nitrate together account for an average of only 1% of light absorption, they account for an average of 70% of •OH photoproduction. Mean •OH photoproduction rates in fogs at the two locations are very similar, with an overall mean of 1.2 (±0.7) μM h−1 under Davis winter sunlight. The mean (±1σ) lifetime of •OH is 1.6 (±0.6) μs, likely controlled by dissolved organic compounds. Including calculated gas-to-drop partitioning of •OH, the average aqueous concentration of •OH is approximately 2 × 10−15 M (midday during Davis winter), with aqueous reactions providing approximately one-third of the hydroxyl radical source. At this concentration, calculated lifetimes of aqueous organics are on the order of 10 h for compounds with •OH rate constants of 1 × 1010 M−1 s−1 or higher (e.g., substituted phenols such as syringol (6.4 h) and guaiacol (8.4 h)), and on the order of 100 h for compounds with rate constants near 1 × 109 M−1 s−1 (e.g., isoprene oxidation products such as glyoxal (152 h), glyoxylic acid (58 h), and pyruvic acid (239 h)). Steady-state concentrations of 1O2* are approximately 100 times higher than those of •OH, in the range of (0.1–3.0) × 10−13 M. Since 1O2* is a more selective oxidant than •OH, it will only react appreciably with electron-rich species such as dimethyl furan (lifetime of 2.0 h) and substituted polycyclic aromatic hydrocarbons (e.g., 9,10-dimethylbenzaanthracene with a lifetime of 0.7 h). Comparing our current Davis samples with Davis fogs collected in the late 1990s shows a decrease in dissolved organic carbon content, similar mass absorption coefficients, lower •OH concentrations, but very similar 1O2* concentrations.
•Dissolved organic carbon (DOC) and light absorption are well correlated.•DOC mass absorption coefficients (MAC) are large and extend into visible region.•NO2− and NO3− photolysis are main sources of •OH; organics are main sinks.•Compared to •OH, 1O2* levels are 100 times higher but reactivity is lower.•Compared to past fog, current samples have less DOC and •OH but similar MAC, 1O2*.
•Electron-poor phenoxyl radicals (R-PhOep•) were tested as oxidants.•R-PhOep• were used as surrogates of aquatic long-lived photooxidants.•Various R-PhOep• oxidized electron-rich phenols and ...anilines.•Increasing R-PhOep• reduction potential correlated with increasing reactivity.
Reactive intermediates formed upon irradiation of chromophoric dissolved organic matter (CDOM) contribute to the degradation of various organic contaminants in surface waters. Besides well-studied “short-lived” photooxidants, such as triplet state CDOM (3CDOM*) or singlet oxygen, CDOM-derived “long-lived” photooxidants (LLPO) have been suggested as key players in the transformation of electron-rich contaminants. LLPO were hypothesized to mainly consist of phenoxyl radicals derived from phenolic moieties in the CDOM. To test this hypothesis and to better characterize LLPO, the transformation kinetics of selected target compounds (phenols and anilines) induced by a suite of electron-poor model phenoxyl radicals was studied in aerated aqueous solution at pH 8. The phenoxyl radicals were generated by photosensitized oxidation of the parent phenols using aromatic ketones as photosensitizers. Under steady-state irradiation, the presence of any of the electron-poor phenols lead to an enhanced abatement of the phenolic target compounds (at an initial concentration of 1.0 × 10−7 M) compared to solutions containing the photosensitizer but no electron-poor phenol. A trend of increasing reactivity with increasing one-electron reduction potential of the electron-poor phenoxyl radical (range: 0.85‒1.12 V vs. standard hydrogen electrode) was observed. Using the excited triplet state of 2-acetonaphthone as a selective oxidant for phenols, it was observed that the reactivity correlated with the concentration of electron-poor phenoxide present in solution. The rates of transformation of anilines induced by the 4-cyanophenoxyl radical were an order of magnitude smaller than for the phenolic target compounds. This was interpreted as a reduction of the radical intermediates back to the parent compound by the superoxide radical anion. Laser flash photolysis measurements confirmed the formation of the 4-cyanophenoxyl radical in solutions containing 2-acetonaphthone and 4-cyanophenol, and yielded values of (2.6 − 5.3) × 108 M−1 s−1 for the second-order rate constant for the reaction of this radical with 2,4,6-trimethylphenol. These and further results indicate that electron-poor model phenoxyl radicals generated through photosensitized oxidation are useful models to understand the photoreactivity of LLPO as part of the CDOM.
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•Photochemistry of pre-oxidized SRFA was tested with DMOP, DMOP0 = 0.1, 5.0 μM.•With increasing oxidant dose, strong transformation decline for DMOP0 = 0.1 μM.•Transformation decline is correlated ...with decrease of phenolic moieties in SRFA.•LLPO likely consist of phenoxyl radicals in SRFA.
Recent studies suggested that long-lived photooxidants (LLPO), which are reactive intermediates formed during irradiation of dissolved organic matter (DOM), may consist of phenoxyl radicals derived from phenolic moieties of the DOM. Besides the well-studied excited triplet states of chromophoric DOM (3CDOM*), LLPO presumably are important photooxidants for the transformation of electron-rich contaminants in surface waters. The main objective of this study was to further test the potential role of phenoxyl radical as LLPO. Suwannee River fulvic acid (SRFA) as a model DOM was pre-oxidised using the phenol-reactive oxidants chlorine and ozone, followed by its characterization by the specific UV absorption at 254 nm (SUVA254), the ratio of absorbance at λ = 254 nm and λ = 365 nm (E2:E3), and the electron donating capacity (EDC). Subsequently, the photoreactivity of pre-oxidized SRFA was tested using 3,4-dimethoxyphenol (DMOP) as a LLPO probe compound at two initial concentrations (DMOP0 = 0.1 and 5.0 μM). Linear inter-correlations were observed for the relative changes in SUVA254, E2:E3, and EDC for increasing oxidant doses. Pseudo-first-order transformation rate constants normalized to the changing SRFA absorption rate (i.e., k0.1obs/rCDOMabsand k5.0obs/rCDOMabs, for 0.1 and 5.0 µM, respectively) exhibited the following distinct trends: The LLPO-dominated k0.1obs/rCDOMabsratio decreased with increasing oxidant dose and with decreasing SUVA254 and EDC, while the 3CDOM*-dominated k5.0obs/rCDOMabsratio positively correlated with E2:E3. Finally, it was concluded that precursors of 3CDOM* and LLPO are chemically modified differently by pre-oxidation of DOM, and LLPO precursors likely consist of phenolic moieties of DOM, suggesting phenoxyl radicals as LLPO.
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Oxidizing triplet excited states of organic matter (3C*) drive numerous reactions in fog/cloud drops and aerosol liquid water (ALW). Quantifying oxidizing triplet concentrations in ALW is difficult ...because 3C* probe loss can be inhibited by the high levels of dissolved organic matter (DOM) and copper in particle water, leading to an underestimate of triplet concentrations. In addition, illuminated ALW contains high concentrations of singlet molecular oxygen (1O2*), which can interfere with 3C* probes. Our overarching goal is to find a triplet probe that has low inhibition by DOM and Cu(II) and low sensitivity to 1O2*. To this end, we tested 12 potential probes from a variety of compound classes. Some probes are strongly inhibited by DOM, while others react rapidly with 1O2*. One of the probe candidates, (phenylthiol)acetic acid (PTA), seems well suited for ALW conditions, with mild inhibition and fast rate constants with triplets, but it also has weaknesses, including a pH-dependent reactivity. We evaluated the performance of both PTA and syringol (SYR) as triplet probes in aqueous extracts of particulate matter. While PTA is less sensitive to inhibition than SYR, it results in lower triplet concentrations, possibly because it is less reactive with weakly oxidizing triplets.
Phenols emitted from biomass burning contribute significantly to secondary organic aerosol (SOA) formation through the partitioning of semivolatile products formed from gas-phase chemistry and ...multiphase chemistry in aerosol liquid water and clouds. The aqueous-phase SOA (aqSOA) formed via hydroxyl radical (•OH), singlet molecular oxygen (1O2*), and triplet excited states of organic compounds (3C*), which oxidize dissolved phenols in the aqueous phase, might play a significant role in the evolution of organic aerosol (OA). However, a quantitative and predictive understanding of aqSOA has been challenging. Here, we develop a stand-alone box model to investigate the formation of SOA from gas-phase •OH chemistry and aqSOA formed by the dissolution of phenols followed by their aqueous-phase reactions with •OH, 1O2*, and 3C* in cloud droplets and aerosol liquid water. We investigate four phenolic compounds, i.e., phenol, guaiacol, syringol, and guaiacyl acetone (GA), which represent some of the key potential sources of aqSOA from biomass burning in clouds. For the same initial precursor organic gas that dissolves in aerosol/cloud liquid water and subsequently reacts with aqueous phase oxidants, we predict that the aqSOA formation potential (defined as aqSOA formed per unit dissolved organic gas concentration) of these phenols is higher than that of isoprene-epoxydiol (IEPOX), a well-known aqSOA precursor. Cloud droplets can dissolve a broader range of soluble phenols compared to aqueous aerosols, since the liquid water contents of aerosols are orders of magnitude smaller than cloud droplets. Our simulations suggest that highly soluble and reactive multifunctional phenols like GA would predominantly undergo cloud chemistry within cloud layers, while gas-phase chemistry is likely to be more important for less soluble phenols. But in the absence of clouds, the condensation of low-volatility products from gas-phase oxidation followed by their reversible partitioning to organic aerosols dominates SOA formation, while the SOA formed through aqueous aerosol chemistry increases with relative humidity (RH), approaching 40% of the sum of gas and aqueous aerosol chemistry at 95% RH for GA. Our model developments of biomass-burning phenols and their aqueous chemistry can be readily implemented in regional and global atmospheric chemistry models to investigate the aqueous aerosol and cloud chemistry of biomass-burning organic gases in the atmosphere.
Strong photoinduced oxidants are important to organic synthesis and solar energy conversion, to chemical fuels or electric. For these applications, visible light absorption is important to solar ...energy conversion and long‐lived excited states are needed to drive catalysis. With respect to these desirable qualities, a series of five 5,6‐dicyano2,1,3benzothiadiazole (DCBT) dyes are examined as organic chromophores that can serve as strong photooxidants in catalytic systems. The series utilizes a DCBT core with aryl groups on the periphery with varying electron donation strengths relative to the core. The dyes are studied via both steady‐state and transient absorption and emission studies. Additionally, computational analysis, voltammetry, crystallography, and absorption spectroelectrochemistry are also used to better understand the behavior of these dyes. Ultimately, a strong photooxidant is arrived at with an exceptionally long excited state lifetime for an organic chromophore of 16 µs. The long‐lived excited state photosensitizer is well‐suited for use in catalysis, and visible light driven photosensitized water oxidation is demonstrated using a water‐soluble photosensitizer.
A strong photooxidant organic dye that absorbs visible light is designed with a long‐lived excited state at 16 microseconds. This dye can power photocatalytic water oxidation and is a more potent photooxidant than acridinium based photosensitizers with an excited state potential of 2.5 V versus normal hydrogen electrode.
Coronavirus disease 2019 (COVID-19) caused by SARS-CoV-2 virus was first recognized in late 2019 and remains a significant threat. We therefore assessed the use of local methylene blue photodynamic ...viral inactivation (MB-PDI) in the oral and nasal cavities, in combination with the systemic anti-viral, anti-inflammatory and antioxidant actions of orally ingested methylene blue (MB) and photobiomodulation (PBM) for COVID-19 disease. The proposed protocol leverages the separate and combined effects of MB and 660nm red light emitted diode (LED) to comprehensively address the pathophysiological sequelae of COVID-19. A total of eight pilot subjects with COVID-19 disease were treated in the Bahamas over the period June 2021–August 2021, using a remote care program that was developed for this purpose. Although not a pre-requisite for inclusion, none of the subjects had received any COVID-19 vaccination prior to commencing the study. Clinical outcome assessment tools included serial cycle threshold measurements as a surrogate estimate of viral load; serial online questionnaires to document symptom response and adverse effects; and a one-year follow-up survey to assess long-term outcomes. All subjects received MB-PDI to target the main sites of viral entry in the nose and mouth. This was the central component of the treatment protocol with the addition of orally ingested MB and/or PBM based on clinical requirements. The mucosal surfaces were irradiated with 660 nm LED in a continuous emission mode at energy density of 49 J/cm2 for PDI and 4.9 J/cm2 for PBM. Although our pilot subjects had significant co-morbidities, extremely high viral loads and moderately severe symptoms during the Delta phase of the pandemic, the response to treatment was highly encouraging. Rapid reductions in viral loads were observed and negative PCR tests were documented within a median of 4 days. These laboratory findings occurred in parallel with significant clinical improvement, mostly within 12–24 h of commencing the treatment protocol. There were no significant adverse effects and none of the subjects who completed the protocol required in-patient hospitalization. The outcomes were similarly encouraging at one-year follow-up with virtual absence of “long COVID” symptoms or of COVID-19 re-infection. Our results indicate that the protocols may be a safe and promising approach to challenging COVID-19 disease. Moreover, due its broad spectrum of activity, this approach has the potential to address the prevailing and future COVID-19 variants and other infections transmitted via the upper respiratory tract. Extensive studies with a large cohort are warranted to validate our results.
Our undergraduate research group has long focused on the preparation and investigation of electron-deficient analogs of the perimidinespirohexadienone (PSHD) family of photochromic molecular switches ...for potential application as "photochromic photooxidants" for gating sensitivity to photoinduced charge transfer. We previously reported the photochemistry of two closely related and more reducible quinazolinespirohexadienones (QSHDs), wherein the naphthalene of the PSHD is replaced with a quinoline. In the present work, we report our investigation of the electrochemistry of these asymmetric QSHDs. In addition to the short wavelength and photochromic long-wavelength isomers, we have found that a second, distinct long-wavelength isomer is produced electrochemically. This different long-wavelength isomer arises from a difference in the regiochemistry of spirocyclic ring-opening. The structures of both long-wavelength isomers were ascertained by cyclic voltammetry and
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H NMR analyses, in concert with computational modeling. These results are compared to those for the symmetric parent PSHD, which due to symmetry possesses only a single possible regioisomer upon either electrochemical or photochemical ring-opening. Density functional theory calculations of bond lengths, bond orders, and molecular orbitals allow the rationalization of this differential photochromic vs electrochromic behavior of the QSHDs.
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