Computational Study of the Gas-Phase Thermal Degradation and the Reaction Rate Coefficients of Perfluoroalkyl Ether Carboxylic Acids.

Perfluoroalkyl ether carboxylic acids (PFECA), which are replacements for legacy per- and polyfluorinated alkyl substances (PFAS), exhibit undesirable properties and often require thermal remediation. Detailed kinetic evaluation of the pyrolysis of PFECA was achieved computationally using density functional ωB97xD/6-311+G (d,p) to establish homolytic bond dissociation energies for the carboxylic acid and carboxylate forms of ∼90-100 kcal/mol and as low as 65 ± 3 kcal/mol, respectively. The negatively charged oxygenated radical products collapse with activation energies () of (β-scission) ∼ 12-42 kcal/mol, (1,2-F-shift) ∼ 24-47 kcal/mol, and (oxygen atom-shift) ∼ 33-35 kcal/mol and enthalpies (Δ) of Δ(F-loss) ∼ 56-71 kcal/mol.

Guarding Drinking Water Safety against Harmful Algal Blooms: Could UV/Cl Treatment Be the Answer?

Frequent and severe occurrences of harmful algal blooms increasingly threaten human health by the release of microcystins (MCs). Urgent attention is directed toward managing MCs, as evidenced by rising HAB-related do not drink/do not boil advisories due to unsafe MC levels in drinking water. UV/chlorine treatment, in which UV light is applied simultaneously with chlorine, showed early promise for effectively degrading MC-LR to values below the World Health Organization's guideline limits.

Molecular insights into the bonding mechanisms between selenium and dissolved organic matter.

Natural organic matter (NOM) plays a critical role in the mobilization and bioavailability of metals and metalloids in the aquatic environment. Selenium (Se), an environmental contaminant of aquatic systems, has drawn increasing attention over the years. While Se is a vital micronutrient to human beings, animals and plants, excess Se intake may pose serious long-term risks.

Impact of chromium (VI) as a co-contaminant on the sorption and co-precipitation of uranium (VI) in sediments under mildly alkaline oxic conditions.

Uranium (U) waste, generated at a variety of mines and nuclear production sites, migrates in the subsurface, posing a serious threat to contaminate groundwater systems. In this study, batch equilibrium and kinetic experiments, geochemical modeling and solid phase characterization were conducted to investigate the impact of Cr(VI), a common co-contaminant, on the adsorption of U(VI) to quartz, plagioclase feldspar, and carbonate-dominated sediment (≤2 mm). Batch experiments were performed under slightly alkaline conditions (7.

Detail study on the interaction between perfluorooctanoic acid (PFOA) with human hemoglobin (Hb).

Perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) are often referred to as legacy perfluoroalkyl substances (PFAS). Human exposure to PFAS leads to severe negative health impacts including cancers, infertility, and dysfunction in the kidneys. Steady-state absorbance, fluorescence, and circular dichroism (CD) methods were used to study the interactions between PFOA and Hb.

Bisindolyl Maleimides and Indolylmaleimide Derivatives-A Review of Their Synthesis and Bioactivity.

The evolution of bisindolyl maleimides and indolyl maleimide derivatives and their unique biological activities have stimulated great interest in medicinal chemistry programs. Bisindolylmaleimide (BIM)-type compounds arise from natural sources such as arcyriarubin and are biosynthetically related to indolocarbazoles. BIMs are commonly the immediate synthetic precursors of indolocarbazoles, lacking a central bond between the two aromatic units and making them more flexible and drug-like.

Ferrate(VI) mediated degradation of the potent cyanotoxin, cylindrospermopsin: Kinetics, products, and toxicity.

The presence of cylindrospermopsin (CYN), a potent cyanotoxin, in drinking water sources poses a tremendous risk to humans and the environment. Detailed kinetic studies herein demonstrate ferrate(VI) (FeO, Fe(VI)) mediated oxidation of CYN and the model compound 6-hydroxymethyl uracil (6-HOMU) lead to their effective degradation under neutral and alkaline solution pH. A transformation product analysis indicated oxidation of the uracil ring, which has functionality critical to the toxicity of CYN.

Computational Study of the Gas-Phase Thermal Degradation of Perfluoroalkyl Carboxylic Acids.

Perfluoroalkyl carboxylic acids (PFCAs) are persistent and ubiquitous pollutants. Environmental remediation is often achieved by absorption on matrices followed by high-temperature thermal treatment to desorb and decompose the PFCAs. Detailed product studies of the thermal degradation of PFCAs have been hampered by the complex nature of product mixtures and associated analytical challenges.

UV/Sodium percarbonate for bisphenol A treatment in water: Impact of water quality parameters on the formation of reactive radicals.

Reported herein is an investigation of the impact of water quality parameters on the formation of carbonate radical anion (CO) and hydroxyl radical (HO) in UV/sodium percarbonate (UV/SPC) system versus in UV/hydrogen peroxide (UV/HO) system for bisphenol A (BPA) degradation in water. Pathways of CO oxidation of BPA were proposed in this study based on the evolution of direct transformation products of BPA. Observed in this study, the degradation of BPA in the UV/SPC system was slower than that in the UV/HO system in the secondary effluents collected from a local wastewater treatment plant due to the significant impact of coexisting constituents in the matrices on the former system.

Making waves: Defining advanced reduction technologies from the perspective of water treatment.

Studies related to advanced reduction technologies (ARTs) have grown exponentially since the term was first coined in 2013. Despite recent interests in ARTs, the conditions and requirements for these processes have yet to be defined and clarifed. In comparision to well defined advanced oxidation technologies/processes (AOTs/AOPs) which involve the generation of hydroxyl radical as the common characteristic, ARTs function by electron donation from a variety of reducing agents and activators.

Elucidation of specific binding sites and extraction of toxic Gen X from HSA employing cyclodextrin.

The presence of per and poly-fluoroalkyl substances (PFAS), commonly referred to as forever chemicals, in aquatic systems is a serious global health problem. While the remediation of PFAS from aqueous media has been extensively investigated, their interactions with and removal from biological systems have received far less attention. We report herein structural alterations to human serum albumin (HSA) upon addition of perfluoro(2-methyl-3-oxahexanoic) acid (Gen X) monitored by changes to the fluorescence and circular dichroism (CD) spectra of HSA.

Application of dimensional analysis in sorption modeling of the styryl pyridinium cationic dyes on reusable iron based humic acid coated magnetic nanoparticles.

Cationic dyes exist in various industrial wastewaters and removal prior to discharge is necessary due to their carcinogenic behavior which poses a serious threat to human health. Iron based humic acid coated magnetic nanoparticles (HA-MNPs) were evaluated for the removal of 2-[4-(dimethylamino) styryl]-1-methylpyridinium iodide (2-ASP) as a model compound for cationic styryl pyridinium dyes from aqueous media. HA-MNPs were prepared by co-precipitation and characterized.

Novel franklinite-like synthetic zinc-ferrite redox nanomaterial: synthesis, and evaluation for degradation of diclofenac in water.

The current study investigates a novel redox technology based on synthetic franklinite-like zinc-ferrite nanomaterial with magnetic properties and redox nature for potential use in water treatment. Physicochemical characterization revealed the nanoscale size and ABO spinel configuration of the zinc-ferrite nanomaterial. The redox activity of nanoparticles was tested for degradation of diclofenac (DCF) pharmaceutical in water, without any added external oxidants and under dark experimental conditions.

Determination and Environmental Implications of Aqueous-Phase Rate Constants in Radical Reactions.

Interests in the kinetics of radical-induced reactions in aqueous solution have grown remarkably due to their water engineering significance (e.g., advanced oxidation processes).

Selective oxidation of H-antihistamines by unactivated peroxymonosulfate (PMS): Influence of inorganic anions and organic compounds.

The rapid and selective peroxymonosulfate (PMS) induced transformation of H-antihistamines cetirizine (CET) and diphenhydramine (DPH) can be influenced by the presence of common organic and inorganic water constituents. Presence of HCO and/or CO, which often exhibit powerful inhibition on the advanced oxidation processes (AOPs), can enhance the PMS mediated transformation of CET/DPH. The observed promotion is demonstrated by the changed solution pH through detailed kinetic studies.

Removal of As(III) from Water Using the Adsorptive and Photocatalytic Properties of Humic Acid-Coated Magnetite Nanoparticles.

The oxidation of highly toxic arsenite (As(III)) was studied using humic acid-coated magnetite nanoparticles (HA-MNP) as a photosensitizer. Detailed characterization of the HA-MNP was carried out before and after the photoinduced treatment of As(III) species. Upon irradiation of HA-MNP with 350 nm light, a portion of the As(III) species was oxidized to arsenate (As(V)) and was nearly quantitatively removed from the aqueous solution.

Rapid transformation of H-antihistamines cetirizine (CET) and diphenhydramine (DPH) by direct peroxymonosulfate (PMS) oxidation.

With growing interest in advanced oxidation processes (AOPs), the number of research studies on peroxymonosulfate (PMS) mediated pollutant degradation has increased significantly due to its high radical generation potential upon activation. However, rare studies have focused on the non-radical based PMS reactions. In this study, degradation of model H-antihistamines cetirizine (CET) and diphenhydramine (DPH) by unactivated PMS was investigated.

Circulating transcripts in maternal blood reflect a molecular signature of early-onset preeclampsia.

Circulating RNA (C-RNA) is continually released into the bloodstream from tissues throughout the body, offering an opportunity to noninvasively monitor all aspects of pregnancy health from conception to birth. We asked whether C-RNA analysis could robustly detect aberrations in patients diagnosed with preeclampsia (PE), a prevalent and potentially fatal pregnancy complication. As an initial examination, we sequenced the circulating transcriptome from 40 pregnancies at the time of severe, early-onset PE diagnosis and 73 gestational age-matched controls.

Comparative toxicometabolomics of perfluorooctanoic acid (PFOA) and next-generation perfluoroalkyl substances.

Owing to environmental health concerns, a number of per- and polyfluoroalkyl substances (PFAS) have been phased-out, and increasingly replaced by various chemical analogs. Most prominent among these replacements are numerous perfluoroether carboxylic acids (PFECA). Toxicity, and environmental health concerns associated with these next-generation PFAS, however, remains largely unstudied.

Fundamental Studies of the Singlet Oxygen Reactions with the Potent Marine Toxin Domoic Acid.

Domoic acid (DA), a potent marine toxin, is readily oxidized upon reaction with singlet oxygen (O). Detailed product studies revealed that the major singlet oxygenation reaction pathways were the [2 + 2] cycloaddition (60.2%) and ene reactions (39.

Degradation and transformation of bisphenol A in UV/Sodium percarbonate: Dual role of carbonate radical anion.

The bicarbonate and carbonate ions (HCO &CO) will consume hydroxyl radical (HO) to generate carbonate radical anion (CO) in hydroxyl radical based advanced oxidation processes (HO-AOPs) resulting in reduced oxidation efficiencies of the systems. However, despite the HO quenching effect of carbonate species, the contribution of CO to the degradation of bisphenol A (BPA) was observed in UV/sodium percarbonate (UV/SPC). In order to study the performance of UV/SPC for BPA degradation and the role of CO in this process, the degradation kinetics and mechanisms of BPA in UV/SPC and in UV/hydrogen peroxide (UV/HO) were compared at equivalent concentration of HO.

UV and Visible Light-Driven Production of Hydroxyl Radicals by Reduced Forms of N, F, and P Codoped Titanium Dioxide.

The photocatalytic activities of reduced titanium dioxide (TiO) materials have been investigated by measuring their ability to produce hydroxyl radicals under UV and visible light irradiation. Degussa P25 TiO was doped with nitrogen (N), fluorine (F), and/or phosphorus (P) and then subjected to surface modification employing a thermo-physicochemical process in the presence of reducing agent sodium borohydride (NaBH). The reduced TiO materials were characterized by a number of X-ray, spectroscopic and imaging methods.

Fundamental study of the ultrasonic induced degradation of the popular antihistamine, diphenhydramine (DPH).

Diphenhydramine (DPH) the active ingredient in Benadryl, has been detected in streams, rivers and other surface water sources. As a bioactive compound, DPH impacts human health even at low concentrations. Ultrasonic irradiation at 640 kHz leads to the rapid degradation of DPH in aqueous solution.

Synthesis and anticancer activity of novel bisindolylhydroxymaleimide derivatives with potent GSK-3 kinase inhibition.

Synthesis and biological evaluation of a series of novel indole derivatives as anticancer agents is described. A bisindolylmaleimide template has been derived as a versatile pharmacophore with which to pursue chemical diversification. Starting from maleimide, the introduction of an oxygen to the headgroup (hydroxymaleimide) was initially investigated and the bioactivity assessed by screening of kinase inhibitory activity, identifying substituent derived selectivity.

β-Cyclodextrin Reverses Binding of Perfluorooctanoic Acid to Human Serum Albumin.

Perfluorooctanoic acid (PFOA), a persistent organic pollutant known to cause adverse health effects, strongly binds to human serum albumin (HSA). β-Cyclodextrin (β-CD), a nontoxic cyclic sugar, strongly complexes PFOA in a host-guest complex and has been proposed for environmental remediation of PFOA. The interactions between HSA, PFOA, and β-CD were investigated in order to determine if β-CD can reverse the binding of PFOA to HSA, with potential therapeutic applications toward exposure to PFOA.