Low Molecular Weight Products Research Articles

Electrochemical oxidation of bisphenol A with a Fe-N-C/persulfate three-dimensional electrochemical system

In this study, an effective three-dimensional (3D) electrochemical system based on persulfate was developed, utilizing Fe-N-C compostie as the particle electrodes, and its electrocatalytic performance for the oxidation of bisphenol A was evaluated. With the synergetic effect of Fe-N-C catalyst and electric current, peroxydisulfate is activated to generate highly oxidative sulfate radicals (SO4•−) and hydroxyl radicals (•OH), and the •OH playing a leading role in the oxidation of BPA. In this process, the redox cycle of Fe2+/Fe3+ acts as the main catalytic active center to produce SO4•−, •OH and O2•−, while pyridine N and graphite carbon cooperate to catalyze the formation of 1O2 and promote direct electron transfer, with their reduction by 37.19 % and 3.34 %, respectively, highlighting their crucial role in these processes. During the degradation of bisphenol A, coupling polymerization occurred at the same time, which may be due to the stabilization and instantaneous resonance of the intermediate on the surface of the catalyst caused by direct electron transfer, which induced the polymerization of oxide intermediate. 1O2 not only oxidizes BPA into low molecular weight products, but also extracts hydrogen atoms to form phenoxy free radicals. The coupling of these free radicals promotes the formation of macromolecular polymers and separation from water. This parallel treatment mechanism of degradation and polymerization effectively reduces the emission of CO2 and the mineralization of organic matter. Based on the above findings, the E/PDS/Fe-N-C system has broad potential in the treatment of environmental pollutants.

Effect of chemical structures and environmental factors on the thermal degradation mechanism of polyimide: Experiments and molecular dynamics simulations

The impact of chemical structure and environment on the thermal stability of polyimide (PI) was examined, and the degradation mechanism was determined using a combination of experiments and molecular simulations. Changes in mechanical properties and thermogravimetric analysis (TGA) were used to characterize the thermal stability of PI. Pyrolysis gas chromatography mass spectrometry (Py-GCMS) and thermogravimetric-infrared spectroscopy (TG-IR) were used to analyze the degradation products both qualitatively and quantitatively. Molecular simulation was employed to analyze the primary bond breakage and thermal degradation pathways of PI, as well as to investigate the effects of the chemical structure, atmosphere, and temperature on degradation properties. The findings indicated that p-benzene-structured 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA)/p-phenylenediamine (PDA) has the best thermal stability, whereas weak bonds like C–O–C in 4,4′-oxydianiline (ODA) and C–N in the 2-(4-aminophenyl)-1H-benzimidazol-5-amine (BIA) imidazole group decrease thermal stability. The formation path of low molecular weight products (CO2, CO, HCN, and NH3) and the potential degradation mechanism of PI were proposed. The process of PI thermal degradation accelerated by oxygen and high temperature was observed at the atomic level. Taken together, this work offers the possibility of monitoring the structural evolution of PI degradation process in real-time.

N-doped carbon dots/g-C3N4 photoexcitation simultaneously enhanced the microbial degradation of nitrate and oxytetracycline in a low C/N ratio aquaculture wastewater

The low carbon-to-nitrogen (C/N) ratio in aquaculture wastewater presents challenges for biological treatments, particularly regarding combined pollution, such as nitrate and oxytetracycline. Herein, this study introduces a synergistic system that integrates photocatalysts (N-doped carbon dots/g-C3N4) with a domesticated microbial community. In artificial wastewater at a C/N ratio of 2, the synergistic system removed completely nitrate and degraded 91.2 % of oxytetracycline simultaneously at 24 h. Moreover, within this system, the accumulation of nitrite was effectively eliminated and the nitrogen production ratio was increased to 82.6 %. Noticeably, oxytetracycline was transformed efficiently into low molecular weight products. In the synergistic treatment process, photocatalysis serves a role in enhancing biodegradation. The generated photoelectrons are efficiently transported through the biofilms, boosting microbial metabolic activity. This increase in microbial activity leads to improved removal of both nitrate and oxytetracycline. The synergistic system was also operated in actual aquaculture wastewater environment to evaluate its practical application potential. The Synergistic system exhibited removal efficiencies for nitrate and oxytetracycline that were 2.1 and 1.8 times higher, respectively, compared to biodegradation treatments. The proposed synergistic system offers a promising strategy to simultaneously tackle nitrate-oxytetracycline pollution, particularly in wastewater characterized by a low C/N ratio, without limiting its applicability to aquaculture wastewater.

Interactions of ferrate(VI) and aquatic humic substances in water treatment

Aquatic humic substances, encompassing humic acid (HA) and fulvic acid (FA), can influence the treatment of ferrate(VI), an emerging water treatment agent, by scavenging Fe(VI) to accelerate its decomposition and hinder the elimination of target micro-pollutants. Meanwhile, HA and FA degrade the water quality through the transformation to disinfection byproducts over disinfection, contribution to water color, and enhanced mobility of toxic metals. However, the interplay with ferrate(VI) and humic substances is not well understood. This study aims to elucidate the interactions of ferrate(VI) with HA and FA for harnessing ferrate(VI) in water treatment. Laboratory investigations revealed distinctive biphasic kinetic profiles of ferrate(VI) decomposition in the presence of HA or FA, involving a 2nd order kinetic reaction followed by a 1st-order kinetic reaction. Both self-decay and reactions with the humic substances governed the ferrate(VI) decomposition in the initial phase. With increasing dissolved organic carbon (DOC), the contribution of self-decomposition to ferrate(VI) decay declined, while humic substance-induced ferrate(VI) consumption increased. To assess relative contributions of the two factors, DOC50% was first introduced to represent the level at which the two factors equally contribute to the ferrate(VI) loss. Notably, DOC50% (11.90 mg/L for HA and 13.10 mg/L for FA) exceeded typical DOC in raw water, implying that self-decay predominantly governs ferrate(VI) consumption. Meanwhile, ferrate(VI) could degrade and remove HA and FA across different molecular weight (MW) ranges, exhibiting treatment capabilities that are either better or, at least, equivalent to ozone. The ferrate(VI) treatment attacked high MW, hydrophobic organic molecules, accompanied by the production of low MW, more hydrophilic compounds. Particularly, FA was more effectively removed due to its smaller molecular sizes, higher solubility, and lower carbon contents. This study provides valuable insights into the effective utilization of ferrate(VI) in water treatment in presence of humic substances.

Synthesis of degradable polymers via 1,5-shift radical isomerization polymerization of vinyl ether derivatives with a cleavable bond

AbstractWe report a novel method for synthesizing degradable polymers based on 1,5-shift radical isomerization polymerizations of vinyl ethers with transferable atoms or groups and in-between acid-cleavable ether linkages in the side chains. In particular, vinyl ethers with side chains composed of thiocyano and p-methoxybenzyl ether groups underwent radical isomerization polymerizations via 1,5-shifts, in which a vinyl ether radical abstracted the cyano group intramolecularly to generate a thiyl radical and result in a polymer with a p-methoxybenzyl ether linkage in the main chain. The obtained polymer was easily degraded into low molecular-weight products with HCl solution. Furthermore, the copolymerization with vinyl acetate proceeded via 1,5-shift isomerization to introduce cleavable linkages in the main chains of the copolymers, which were similarly degraded.

Investigation of the kinetics of heat treatment of epoxy polymers

The study examines the effect of the concentration of modifiers (BDI) on the annihilation characteristics of cured epoxy polymers using the positron annihilation method. The results show that both the concentration and size of microcavity defects decrease, which can be explained by the formation of densely sewn areas due to the production of additional bridges. The supramolecular structure of the formed epoxy polymer is discussed, with the identification of several distinct areas, including polymer globules formed by stacking chains of simple polyester macromolecules around polymerization centers, and the interglobular space consisting of the ends of macro chains and low molecular weight products. The end groups of polymerization-cured epoxy polymers, such as double bonds of the vinylidene type, hydroxyl and unreacted epoxy groups, create conditions for the splitting of BDI in the interglobular space. The study also demonstrates that at optimal concentrations of modifiers, there is a decrease in the radius and concentration of micropore defects, as well as a general decrease in the proportion of free volume. The curing processes of epoxy polymers and their heat treatment in the presence of modifiers are investigated, with BDI having a significant effect on the formation of the epoxy polymer structure.

Metabolites and degradation pathways of microbial detoxification of aflatoxins: a review.

The degradation of aflatoxins using nonpathogenic microbes and their enzymes is emerging as a safe and economical alternative to chemical and physical methods for the detoxification of aflatoxins in food and feeds. Many bacteria and fungi have been identified as aflatoxin degraders. This review is focused on the chemical identification of microbial degradation products and their degradation pathways. The microbial degradations of aflatoxins are initiated by oxidation, hydroxylation, reduction, or elimination reactions mostly catalyzed by various enzymes belonging to the classes of laccase, reductases, and peroxidases. The resulting products with lesser chemical stability further undergo various reactions to form low molecular weight products. Studies on the chemical and biological nature of degraded products of aflatoxins are necessary to ensure the safety of the decontamination process. This review indicated the need for an integrated approach including decontamination studies using culture media and food matrices, proper identification and toxicity profiling of degraded products of aflatoxins, and interactions of microbes and the degradation products with food matrices for developing practical and effective microbial detoxification process.

α‐Amylase Inhibitors Based on Thiazolidinone Skeleton: A Promising Approach in Diabetes Management

AbstractThiazolidinone scaffold has become a promising scaffold when it comes to therapeutic importance, and researchers are quite interested in it because of its wide range of applications in the different fields of chemistry. The capacity of this nucleus to interact with a variety of biological targets, including the peroxisome proliferator‐activated receptor (PPAR), protein tyrosine phosphatase 1B, aldose reductase, α‐glucosidase, and α‐amylase, has led to the observation of its antidiabetic effect. α‐Amylase (α‐1,4‐glucan‐4‐glucanohydrolase, EC 3.2.1.1) is one of the most important industrial endoamylases capable of hydrolyzing the internal α‐1,4‐glycosidic bonds in polysaccharides with net retention of α‐anomeric configuration in low molecular weight products, such as glucose, maltose, and maltotriose units. The inhibitors of α‐amylase have the ability to lower endogenous activity, which is crucial for the management of agricultural pests as well as the treatment and prevention of human disorders. In the present review, we attempted to compile the most recent studies on thiazolidinone‐based α‐amylase inhibitors, investigate their therapeutic potential in treating diabetes, comprehend the relationships between structure and activity, offer suggestions for future research and translation of these findings into clinical applications. This comprehensive review strives to be a valuable resource for researchers, medicinal chemists, and healthcare professionals involved in developing and applying novel therapeutics for treating metabolic disorders.

Polylactide Degradation in the Presence of Members of the Genus <i>Bacillus</i>

Abstract—Microorganisms of the genus Bacillus were shown to have different effects on the degradation of polylactide packaging material. The degradation experiment was carried out on an agar medium at a temperature of 55°C and pH 5.9 for 14 days. This is the first report on the abiotic hydrolysis significantly slowing down during incubation with B. licheniformis S8 and occurring in parallel with the main process, enzymatic hydrolysis. The latter involved sequential cleavage of monomer units from the end of the macromolecule and the formation of low molecular weight products used by microorganisms as a substrate; it contributed to a decrease in the mass of polylactide by 5.1%, while maintaining its molecular weight and decreasing the dispersion of molecular weights. In the presence of bacteria B. amyloliquefaciens, B. subtilis subsp. spizizenii, and B. subtilis subsp. inaquosorum, the polymer weight did not decrease, but the molecular weight decreased significantly, similar to abiotic hydrolysis.

Vanadium Complexes Derived from O,N,O-tridentate 6-bis(o-hydroxyalkyl/aryl)pyridines: Structural Studies and Use in the Ring-Opening Polymerization of ε-Caprolactone and Ethylene Polymerization

Interaction of [VO(OiPr)3] with 6-bis(o-hydroxyaryl)pyridine, 2,6-{HOC(Ph)2CH2}2(NC5H3), LH2, afforded [VO(OiPr)L] (1) in good yield. The reaction of LNa2, generated in-situ from LH2 and NaH, with [VCl3(THF)3] led to the isolation of [VL2] (2) in which the pyridyl nitrogen atoms are cis; a regioisomer 3∙2THF, in which the pyridyl nitrogen atoms are trans, was isolated when using [VCl2(TMEDA)2]. The reaction of the 2,6-bis(o-hydroxyalkyl)pyridine {HOC(iPr)2CH2}2(NC5H3), L1H2, with [VO(OR)3] (R = nPr, iPr) led, following work-up, to [VO(OR)L1] (R = nPr (4), iPr (5)). Use of the bis(methylpyridine)-substituted alcohol (tBu)C(OH)[CH2(C5H3Me-5)]2, L2H, with [VO(OR)3] (R = Et, iPr) led to the isolation of [VO(μ-O)(L2)]2 (6). Complexes 1 to 6 have been screened for their ability to act as pre-catalysts for the ring opening polymerization (ROP) of ε-caprolactone (ε-CL), δ-valerolactone (δ-VL), and rac-lactide (r-LA) and compared against the known catalyst [Ti(OiPr)2L] (I). Complexes 1, 4–6 were also screened as catalysts for the polymerization of ethylene (in the presence of dimethylaluminium chloride/ethyltrichloroacetate). For the ROP of ε-CL, in toluene solution, conversions were low to moderate, affording low molecular weight products, whilst as melts, the systems were more active and afforded higher molecular weight polymers. For δ-VL, the systems run as melts afforded good conversions, but in the case of r-LA, all systems as melts exhibited low conversions (<10%) except for 6 (<54%) and I (<39%). In the case of ethylene polymerization, the highest activity (8600 Kg·mol·V−1bar−1h−1) was exhibited by 1 in dichloromethane, affording high molecular weight, linear polyethylene at 70 °C. In the case of 4 and 5, which contain the propyl-bearing chelates, the activities were somewhat lower (≤1500 Kg·mol·V−1bar−1h−1), whilst 6 was found to be inactive.

Preparation of high‐performance polyurethane elastomers via direct use of alcoholyzed waste PET by high molecular weight polyester diols

AbstractProducts obtained by alcoholysis of waste PET are promising raw materials for the synthesis of polyurethane elastomers (PUEs). Alcoholysis of PET by low molecular weight diols such as ethylene glycol yields low molecular weight products. The latter need to be polymerized to high molecular weight polyols which are subsequently used as soft segments for the synthesis of PUEs. This work aims to look for suitable high molecular weight diols for the alcoholysis of waste PET to yield high molecular weight products which can be directly used as soft segments for the synthesis of PUEs. This approach allows to save the polymerization step for the formation of high molecular weight polyols. Specifically, polyester diols such as polycaprolactone diol (Mn = 2000) were used for the alcoholysis of waste PET. The resulting PUEs exhibited very good mechanical properties: a tensile strength of up to 40.95 MPa, an elongation at break of up to 1219%, and a toughness of up to 237 MJ·m−3, along with good transparency and thermal stability.

Chitooligosaccharide accelerated wound healing in potato tubers by promoting the deposition of suberin polyphenols and lignin at wounds

Chitooligosaccharide (COS) is a low molecular weight product of chitosan degradation. Although COS induces plant resistance by activating phenylpropanoid metabolism, there are few reports on whether COS accelerates wound healing in potato tubers by promoting the deposition of phenolic acids and lignin monomers at wounds. The results showed that COS activated phenylalanine ammonialyase and cinnamate 4-hydroxylase and promoted the synthesis of cinnamic, caffeic, p-coumaric, ferulic acids, total phenolics and flavonoids. COS activated 4-coumaric acid coenzyme A ligase and cinnamyl alcohol dehydrogenase and promoted the synthesis of sinapyl, coniferyl and cinnamyl alcohols. COS also increased H2O2 levels and peroxidase activity and accelerated the deposition of suberin polyphenols and lignin on wounds. In addition, COS reduced weight loss and inhibited lesion expansion in tubers inoculated with Fusarium sulfureum. Taken together, COS accelerated wound healing in potato tubers by inducing phenylpropanoid metabolism and accelerating the deposition of suberin polyphenols and lignin at wounds.

Effect of water on the accelerated sulfur vulcanization of natural rubber

Water present in natural rubber was found to play a role in forming carbon-carbon crosslinking junctions before forming carbon-sulfur crosslinking junctions when its effect on the accelerated sulfur vulcanization was investigated by analyzing low–molecular weight products through various instrumental analytical techniques. Samples were prepared by mixing deproteinized natural rubber (DPNR) with various moisture contents with stearic acid, ZnO, sulfur, and N-tert-butylbenzothiazole-2-sulfenamide, and they were vulcanized at 150 °C for various cure times. Low–molecular weight products such as 2,2′-dibenzothiazole disulfide (MBTS), 2-mercaptobenzothiazole (MBT), ZnMBT, Zn2+ and sulfur linked to the rubber were extracted from the vulcanized natural rubbers using benzene and dioxane, and subsequently measured by high-performance liquid chromatography, UV–visible spectroscopy, inductively coupled plasma atomic emission spectroscopy, and combustion analysis. The water present in natural rubber was found to strongly affect the production and formation rate of the low–molecular weight products in the accelerated sulfur vulcanization of natural rubber. As the result it suggests that the water promotes the formation of the C-C linkages, and then it sequentially promotes the formation of the C-S linkages.

Influence of oxygen, UV light and reactive dissolved organic matter on the photodemethylation and photoreduction of monomethylmercury in model freshwater

The key factors which affect the abiotic photodemethylation process of monomethylmercury (MMHg) in the freshwaters has remained unclear. Hence, this work aimed to better elucidate the abiotic photodemethylation pathway in a model freshwater. Anoxic and oxic conditions were implemented to investigate the simultaneous photodemethylation to Hg(II) and photoreduction to Hg(0). MMHg freshwater solution was irradiated through exposure to three wavelength ranges of full light (280–800 nm), without short UVB (305–800 nm), and visible light (400–800 nm). The kinetic experiments were performed following dissolved and gaseous Hg species concentrations (i.e., MMHg, iHg(II), Hg(0)). A comparison between two methods of post-irradiation purging and continuous-irradiation purging confirmed MMHg photodecomposition to Hg(0) is mainly induced by a first photodemethylation step to iHg(II) followed by a photoreduction step to Hg(0). Photodemethylation under full light extent normalized to absorbed radiation energy showed a higher rate constant in anoxic conditions at 18.0 ± 2.2 kJ−1 compared to oxic conditions at 4.5 ± 0.4 kJ−1. Moreover, photoreduction also increased up to four-fold under anoxic conditions. Normalized and wavelength-specific photodemethylation (Kpd) and photoreduction (Kpr) rate constants were also calculated for natural sunlight conditions to evaluate the role of each wavelength range. The relative ratio in wavelength-specific KPAR: Klong UVB+ UVA: K short UVB showed higher dependence on UV light for photoreduction at least ten-fold compared to photodemethylation, regardless of redox conditions. Both results using Reactive Oxygen Species (ROS) scavenging methods and Volatile Organic Compounds (VOC) measurements revealed the occurrence and production of low molecular weight (LMW) organic compounds that are as photoreactive intermediates responsible for MMHg photodemethylation and iHg(II) photoreduction in the dominant pathway. This study also supports the role of dissolved oxygen as an inhibitor for the photodemethylation pathways driven by LMW photosensitizers.

Evaluation of Selected Cellulose Macromolecular Properties after Its Chemical Treatment Using Size Exclusion Chromatography.

This work evaluates the effect of using selected inorganic chemicals as the main components of waterborne wood preservative systems on the degradation of the cellulose constituent in wood from model samples. The polymeric properties of cellulose and the homogeneity of the degradation process primarily reflect very well the degree of cellulose deterioration. Whatman papers, as pure cellulose model samples, were impregnated with 10 different 5 wt% solutions of inorganic salts and distilled water and consequently subjected to wet-thermal accelerated aging (T = 85 °C, RH = 65%, for 30 days). The samples were then derivatized to cellulose tricarbanilates (CTCs) through two different procedures (by precipitation in a methanol-water mixture/by evaporation of pyridine from the reaction mixture) and finally analyzed using size exclusion chromatography (SEC). Chemically treated and aged cellulose samples showed different changes in the degree of polymerization (DP) and polydispersity (PD) in terms of untreated non-aged standard caused by different ongoing degradation reactions, such as dehydration, hydrolysis, oxidation, and crosslinking. In general, the lowest degradation rate after treatment by chemicals and after accelerated aging was observed in samples treated by borates, NaCl, and ZnSO4·7H2O. The greatest depolymerization after treatment and after accelerated aging was caused by sulphates containing NH4+, Cu2+, and Fe3+ cations, with aging by NH4Cl and (NH4)2HPO4-treated samples also leading to significant depolymerization. The higher DP values are linked to the precipitated method of CTC preparation, though not for chlorides and phosphates. PD is also generally higher in precipitated and aged samples and is heavily influenced by the presence of low molecular weight products. This paper brings new insights regarding the complex evaluation of the polymeric properties of degraded cellulose by considering all important factors affecting the sample and the analysis itself through the use of statistics. From the statistical point of view, the influences of all factors (solution, aging, method) and their interactions (except aging*method) on DP are statistically significant. The influence of the sample processing method used for analysis of the desired results becomes important mainly in practice. This work recommends the evaporation method for more accurate description of more degraded cellulose.

Optimization of the ultrasonic treatment for Tara gum using response surface methodology

High-intensity ultrasound irradiation proved to be an effective method for modifying tara gum by generating low molecular weight products and better water solubility. The objectives of this research were to optimize the parameters for the high-intensity ultrasonic treatment with response surface methodology and improve the tara gum solubility. The results demonstrated that after the ultrasound treatment, the solubility of the tara gum had increased (17.7%) as a result of the reduced intrinsic viscosity (70%). The molecular weight of the untreated tara gum was 1.89 x 106 Da, and after ultrasound treatment, it was reduced to 0.47 x 106 Da. Rheological analyses confirmed the reduction in molecular weight for the modified and optimized tara gum and the resulting increase in solubility. This knowledge provides a better understanding of ultrasound treatment technology and increases the scope for use of tara gum in the food industry.

Експериментальне дослідження залежності питомого електричного опору коксу від кінцевої температури

The dependence of the resistivity on the final coking temperature was studied on cokes obtained from the charge of one of the leading coke plants in Ukraine in a laboratory furnace designed by SE "UKHIN" with electric heating. The increase in the final temperature naturally contributes to an increase in coke readiness and the degree of orderliness of its structure. This is manifested in an increase in coke strength (increased resistance to grinding forces and post-reaction strength, reduced abrasion), increased coke density and porosity, reduced reactivity, volatile substance yield and specific electrical resistance. The increase in the final temperature contributes to the deepening of thermochemical polycondensation processes of coke formation, which causes the loss of additional low-molecular weight products, resulting in a slight decrease in the yield of gross coke and its sulphur content with a simultaneous increase in ash content. The previously theoretically substantiated hypothesis about the exponential nature of the dependence of the decrease in the specific electric coke with an increase in the final coking temperature was experimentally confirmed. Processing of the obtained experimental data made it possible to determine the numerical characteristics of this dependence, which makes it possible to determine the rational level of final coking temperatures when producing coke for various applications. In particular, to produce coke with a resistivity not exceeding 0.1 ohm∙cm, the final coking temperature should not be less than 957 oC. This is in line with the practice of coke production. To produce blast furnace coke with a lower resistivity, a higher temperature is required, while to produce ferroalloy coke with a higher resistivity, on the contrary, a lower temperature level is sufficient. Keywords: coal coke, electrical resistivity, final coking temperature, coke readiness, blast furnace coke, ferroalloy coke. Corresponding author I.V. Shulga, e-mail: ko@ukhin.org.ua

Selective photocatalytic removal of sulfonamide antibiotics: The performance differences in molecularly imprinted TiO2 synthesized using four template molecules

Four types of molecularly imprinted TiO2 photocatalysts named MIP-TiO2/sulfadiazine (SD), MIP-TiO2/sulfamethoxazole (SMX), MIP-TiO2/sulfonamide (SN) and MIP-TiO2/aniline (AN), were synthesized. The five catalysts exhibited different degrees of selectivity for two types of sulfonamide antibiotics (SAs), SD and SMX. In the systems of NIP–TiO2, MIP-TiO2/SD, MIP-TiO2/SMX, MIP-TiO2/SN and MIP-TiO2/AN, the degradation rate constants of SD were 0.0789, 0.1031, 0.0859, 0.1034 and 0.1051 min−1, respectively. Moreover, the removal rate constants of SMX on the mentioned catalysts were 0.1076, 0.3250, 0.4260, 0.3885 and 0.5848 min−1, correspondingly. The single bond cleavage (C–S, C–N, and S–N bonds), hydroxylation, ring-opening, oxidation, and deamination were the major transformation pathways of SAs. With the presence of MIP-TiO2/SN and MIP-TiO2/AN, more low molecular weight products were generated, and the intermediates preferred to go through further hydroxylation and oxidation reactions. Therefore, besides MIP-TiO2/SD and MIP-TiO2/SMX, the novel MIP-TiO2/SN and MIP-TiO2/AN, which were prepared by using substances with the similar main functional groups as SAs as template molecules, had excellent catalytic abilities and less byproducts formed in the situation. The results may provide an effective idea to level up the SAs degradation rates, control the generation of intermediates, and reduce environmental risks.

Isoprene Epoxydiol-Derived Sulfated and Nonsulfated Oligomers Suppress Particulate Mass Loss during Oxidative Aging of Secondary Organic Aerosol.

Acid-driven multiphase chemistry of isoprene epoxydiols (IEPOX) with inorganic sulfate aerosols contributes substantially to secondary organic aerosol (SOA) formation, which constitutes a large mass fraction of atmospheric fine particulate matter (PM2.5). However, the atmospheric chemical sinks of freshly generated IEPOX-SOA particles remain unclear. We examined the role of heterogeneous oxidation of freshly generated IEPOX-SOA particles by gas-phase hydroxyl radical (•OH) under dark conditions as one potential atmospheric sink. After 4 h of gas-phase •OH exposure (∼3 × 108 molecules cm-3), chemical changes in smog chamber-generated IEPOX-SOA particles were assessed by hydrophilic interaction liquid chromatography coupled with electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (HILIC/ESI-HR-QTOFMS). A comparison of the molecular-level compositional changes in IEPOX-SOA particles during aging with or without •OH revealed that decomposition of oligomers by heterogeneous •OH oxidation acts as a sink for •OH and maintains a reservoir of low-volatility compounds, including monomeric sulfate esters and oligomer fragments. We propose tentative structures and formation mechanisms for previously uncharacterized SOA constituents in PM2.5. Our results suggest that this •OH-driven renewal of low-volatility products may extend the atmospheric lifetimes of particle-phase IEPOX-SOA by slowing the production of low-molecular weight, high-volatility organic fragments and likely contributes to the large quantities of 2-methyltetrols and methyltetrol sulfates reported in PM2.5.

Occurrence of Iodophenols in Aquatic Environments and the Deiodination of Organic Iodine with Ferrate(VI).

Toxic and odorous iodophenols are commonly identified as disinfection by-products (DBPs) in drinking water. Herein, ng/L levels of iodophenols were identified in river water, wastewater treatment plant effluent, and medical wastewater, with the simultaneous identification of μg/L to mg/L levels of iodide (I-) and total organic iodine (TOI). Oxidation experiment suggested that the I-, TOI, and iodophenols could be oxidized by ferrate [Fe(VI)], and more than 97% of TOI had been transformed into stable and nontoxic IO3-. Fe(VI) initially cleaved the C-I bond of iodophenols and led to the deiodination of iodophenols. The resulted I- was swiftly oxidized into HOI and IO3-, with the intermediate phenolic products be further oxidized into lower molecular weight products. The Gibbs free energy change (ΔG) of the overall reaction was negative, indicating that the deiodination of iodophenols by Fe(VI) was spontaneous. In the disinfection of iodine-containing river water, ng/L levels of iodophenols and chloro-iodophenols formed in the reaction with NaClO/NH2Cl, while Fe(VI) preoxidation was effective for inhibiting the formation of iodinated DBPs. Fe(VI) exhibited multiple functions for oxidizing organic iodine, abating their acute toxicity/cytotoxicity and controlling the formation of iodinated DBPs for the treatment of iodide/organic iodine-containing waters.