Neutral Phenolic Contaminants Are Not Necessarily More Resistant to Permanganate Oxidation Than Their Dissociated Counterparts: Importance of Proton-Coupled Electron Transfer.

Despite decades of research on phenols oxidation by permanganate, there are still considerable uncertainties regarding the mechanisms accounting for the unexpected parabolic pH-dependent oxidation rate. Herein, the pH effect on phenols oxidation was reinvestigated experimentally and theoretically by highlighting the previously unappreciated proton transfer. The results revealed that the oxidation of protonated phenols occurred via proton-coupled electron transfer (PCET) pathways, which can switch from ETPT (electron transfer followed by proton transfer) to CEPT (concerted electron-proton transfer) or PTET (proton transfer followed by electron transfer) with an increase in pH. A PCET-based model was thus established, and it could fit the kinetic data of phenols oxidation by permanganate well. In contrast with what was previously thought, both the simulating results and the density functional theory calculation indicated the rate of CEPT reaction of protonated phenols with OH- as the proton acceptor was much higher than that of deprotonated phenols, which could account for the pH-rate profiles for phenols oxidation. Analysis of the quantitative structure-activity relationships among the modeled rate constants, Hammett constants, and pKa values of phenols further supports the idea that the oxidation of protonated phenols is dominated by PCET. This study improves our understanding of permanganate oxidation and suggests a new pattern of reactivity that may be applicable to other systems.

Understanding the Importance of Periodate Species in the pH-Dependent Degradation of Organic Contaminants in the H2O2/Periodate Process.

Although periodate-based advanced oxidation processes have been proven to be efficient in abating organic contaminants, the activation properties of different periodate species remain largely unclear. Herein, by highlighting the role of H4IO6-, we reinvestigated the pH effect on the decontamination performance of the H2O2/periodate process. Results revealed that elevating pH from 2.0 to 10.0 could markedly accelerate the rates of organic contaminant decay but decrease the amounts of organic contaminant removal. This pH-dependent trend of organic contaminant degradation corresponded well with the HO· yield and the variation of periodate species. Specifically, although 1O2 could be detected at pH 9.0, HO· was determined to be the major reactive oxidizing species in the H2O2/periodate process under all the tested pH levels. Furthermore, it was suggested that only H4IO6- and H2I2O104- could serve as the precursors of HO·. The second-order rate constant for the reaction of H2I2O104- species with H2O2 was determined to be ∼1199.5 M-1 s-1 at pH 9.0, which was two orders of magnitude greater than that of H4IO6- (∼2.2 M-1 s-1 at pH 3.0). Taken together, the reaction pathways of H2O2 with different periodate species were proposed. These fundamental findings could improve our understanding of the periodate-based advanced oxidation processes.

Oxidation of Microcystin-LR via Activation of Peroxymonosulfate Using Ascorbic Acid: Kinetic Modeling and Toxicity Assessment.

Advanced oxidation processes (AOPs) have been widely used for the destruction of organic contaminants in the aqueous phase. In this study, we introduce an AOP on activated peroxymonosulfate (PMS) by using ascorbic acid (H2A) to generate sulfate radicals (SO4•-). Sulfate radicals, hydroxyl radicals (HO•), and ascorbyl radicals (A•-) were found using electron spin resonance (ESR). But we found A•- is negligible in the degradation of microcystin-LR (MCLR) due to its low reactivity. We developed a first-principles kinetic model to simulate the MCLR degradation and predict the radical concentrations. The MCLR degradation rate decreased with increasing pH. The scavenging effect of natural organic matter (NOM) on SO4•- was relatively small compared to that for HO•. Considering both energy consumption and MCLR removal, the optimal H2A and PMS doses for H2A/PMS process were determined at 1.0 × 10-6 M and 1.6 × 10-5 M, respectively. In addition, we determined the toxicity using the protein phosphatase 2A (PP2A) test and the results showed that MCLR was readily detoxified and its oxidation byproducts were not hepatotoxic. Overall, our work provides a new type of AOP and a promising, efficient, and environmental-friendly method for removing microcystins in algae-laden water.

Metal ions-mediated concerted electron-proton transfer enables catalytic oxidation of phenolic contaminants by permanganate.

Permanganate has been extensively applied in water treatment due to its ease of handling and high stability. However, the impact of common water constituents, especially metal ions, on permanganate oxidation is poorly understood. Here, we report that many redox-inactive metal ions, such as Ca2+, Mg2+, Zn2+, Cu2+, and Al3+, can enhance the reactivity of permanganate with phenolic compounds. Moreover, the enhancing effects of metal ions are highly pH-dependent with the largest promotion effect obtained at the pH close to phenols' pKa. Experimental and computational analysis revealed that the oxidation of protonated phenols by permanganate underwent proton-coupled electron transfer (PCET) pathways, regardless of the presence of metal ions. Nonetheless, metal ions could catalyze the concerted electron-proton transfer (CEPT) but exhibited negligible effect on ETPT (electron transfer followed by proton transfer) and PTET (proton transfer followed by electron transfer) reactions, accounting for the pH-dependent effects of metal ions. Correlation between CEPT rate constants and the complexing capability of metal ions with phenols suggested that the co-existing metal ions may coordinate to phenolic O-H group and thus facilitate the CEPT reaction of phenols. This study could shed light on the application of permanganate in real practice and the modulation of CEPT reactions.

Facile solution synthesis of α-FeF3·3H2O nanowires and their conversion to α-Fe2O3 nanowires for photoelectrochemical application.

We report for the first time the facile solution growth of α-FeF(3)·3H(2)O nanowires (NWs) in large quantity at a low supersaturation level and their scalable conversion to porous semiconducting α-Fe(2)O(3) (hematite) NWs of high aspect ratio via a simple thermal treatment in air. The structural characterization by transmission electron microscopy shows that thin α-FeF(3)·3H(2)O NWs (typically <100 nm in diameter) are converted to single-crystal α-Fe(2)O(3) NWs with internal pores, while thick ones (typically >100 nm in diameter) become polycrystalline porous α-Fe(2)O(3) NWs. We further demonstrated the photoelectrochemical (PEC) application of the nanostructured photoelectrodes prepared from these converted hematite NWs. The optimized photoelectrode with a ~400 nm thick hematite NW film yielded a photocurrent density of 0.54 mA/cm(2) at 1.23 V vs reversible hydrogen electrode potential after modification with cobalt catalyst under standard conditions (AM 1.5 G, 100 mW/cm(2), pH = 13.6, 1 M NaOH). The low cost, large quantity, and high aspect ratio of the converted hematite NWs, together with the resulting simpler photoelectrode preparation, can be of great benefit for hematite-based PEC water splitting. Furthermore, the ease and scalability of the conversion from hydrated fluoride NWs to oxide NWs suggest a potentially versatile and low-cost strategy to make NWs of other useful iron-based compounds that may enable their large-scale renewable energy applications.

Green polyaspartic acid as a novel permanganate activator for enhanced degradation of organic contaminants: Role of reactive Mn(III) species.

Attention has been long focused on enhancing permanganate (Mn(VII)) oxidation capacity for eliminating organic contaminants via generating active manganese intermediates (AMnIs). Nevertheless, limited consideration has been given to the unnecessary consumption of Mn(VII) due to the spontaneous disproportionation of AMnIs during their formation. In this work, we innovatively introduced green polyaspartic acid (PASP) as both reducing and chelating agents to activate Mn(VII) to enhance the oxidation capacity and utilization efficiency of Mn(VII). Multiple lines of evidence suggest that Mn(III), existing as Mn(III)-PASP complex, was generated and dominated the degradation of bisphenol A (BPA) in the Mn(VII)/PASP system. The stabilized Mn(III) species enabled Mn(VII) utilization efficiency in the Mn(VII)/PASP system to be higher than that in Mn(VII) alone. Moreover, the electrophilic Mn(III) species was verified to mainly attack the inclusive benzene ring and isopropyl group to realize BPA oxidation and its toxicity reduction in the Mn(VII)/PASP system. In addition, the Mn(VII)/PASP system showed the potential for selectively oxidizing organic contaminants bearing phenol and aniline moieties in real waters without interference from most of coexisting water matrices. This work brightens an overlooked route to both high oxidation capacity and efficient Mn(VII) utilization in the Mn(VII)-based oxidation processes.

Unraveling the intrinsic mechanism behind the selective oxidation of sulfonamide antibiotics in the Mn(II)/periodate process: The overlooked surface-mediated electron transfer process.

Mn(II) exhibits a superb ability in activating periodate (PI) for the efficient degradation of aqueous organic contaminants. Nevertheless, ambiguous conclusions regarding the involved reactive species contributing to the removal of organic contaminants remain unresolved. In this work, we found that the Mn(II)/PI process showed outstanding and selective reactivity for oxidizing sulfonamides with the removal ranging from 57.1% to 100% at pH 6.5. Many lines of evidence suggest that the in-situ formed colloidal MnO2 (cMnO2) served as a catalyst to mediate electron transfer from sulfonamides to PI on its surface via forming cMnO2-PI complex (cMnO2-PI*) for the efficient oxidation of sulfonamides in the Mn(II)/PI process. Experimental results and density functional theory (DFT) calculations verify that the inclusive aniline moiety was the key site determining the electron transfer-dominated oxidation of sulfonamides. Furthermore, DFT calculation results reveal that the discrepancies in the removal of sulfonamides in the Mn(II)/PI process were attributed to different kinetic stability and chemical reactivity of sulfonamides caused by their heterocyclic substituents. In addition, a high utilization efficiency of PI was achieved in the Mn(II)/PI process owing to the surface-mediated electron transfer mechanism. This work provides deep insights into the surface-promoted mechanism in the cMnO2-involved oxidation processes.

Enhanced dewaterability of waste activated sludge by a combined use of permanganate and peroxymonosulfate.

Ever-increasing efforts have been made to develop rapid and practical conditioning methods of sludge dewatering. This study demonstrated an innovative combination of potassium permanganate (KMnO4) and peroxymonosulfate (PMS) for sludge dewatering. The combined use of KMnO4 and PMS (KMnO4/PMS) showed its superiority in improving sludge dewaterability over the separate use of KMnO4 or PMS. By dosing 4 mmol g-1 VSS KMnO4 and 3 mmol g-1 VSS PMS, the dewaterability of waste activated sludge (WAS) significantly enhanced as capillary suction time (CST) decreased from 73.65 s to 24.65 s while the water content of dewatered sludge cake (W C) decreased from 78.96% to 70.47%. Apart from CST and W C, the KMnO4/PMS process could also affect negative zeta potential, sludge flocs size and the concentrations of protein and polysaccharide in extracellular polymeric substances (EPS). The enhanced sludge dewaterability and changes of the physicochemical characteristics of the WAS samples during the KMnO4/PMS process were actually ascribed to sulfate radicals (SO4˙-) and hydroxyl radicals (HO˙) in situ generated via PMS activation by manganese oxides (MnO x ) in the states of MnO2 and Mn3O4 transferred from KMnO4 oxidation, which was verified by transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX) techniques and radical scavenging experiments. Moreover, the Fourier transform infrared spectroscopy (FTIR) analysis further confirmed that the in situ generated SO4˙- and HO˙ could improve sludge dewaterability. Thus, the KMnO4/PMS process could be considered as a promising conditioning method of sludge dewatering.

Direct visualization of colloidal gelation under confinement.

The physical mechanism of colloidal gelation remains inadequately understood, particularly for intermediate to high volume fractions. Experiments to directly probe the complex evolution of structural and viscoelastic properties of gels have been few despite their fundamental importance in elucidating the physical mechanisms responsible for gelation. In this study, we use a home-built micron-gap rheometer combined with confocal microscopy to directly investigate the coupled structural and dynamic properties of colloidal gelation transition by spatial confinement. We observe that confinement-induced gelation proceeds by a spinodal decomposition route where strongly confined colloidal suspensions evolve into "colloid-rich" and "colloid-poor" regions; the propagation of the "colloid-rich" region in three dimensions is responsible for structural arrest and strong viscoelastic enhancement when a critical film thickness approaches 16-25 particle layers.

A comparative study of microcystin-LR degradation by electrogenerated oxidants at BDD and MMO anodes.

This study investigated the electrochemical degradation of microcystin-LR (MC-LR) using boron-doped diamond (BDD) anode and mixed metal oxides (MMO, IrO2Ta2O5/Ti) anode in different medium. In-situ electrogenerated oxidants including hydroxyl radical, active chlorine, and persulfate were confirmed in phosphate, chloride, and sulfate medium, respectively. Different from MMO anode, hydroxyl radical was observed to play a significant role in chlorine generation at BDD anode in chloride medium. Besides, BDD anode could activate sulfate electrochemically due to its high oxygen evolution potential, and MC-LR degradation rate increased with the decrease of solution pH. The effects of natural organic matters (NOM) and algal organic matters (AOM) on MC-LR degradation were evaluated and NOM presented stronger inhibition ability than AOM. Furthermore, the intermediates generated in MC-LR degradation in chloride and sulfate medium were identified by LC/MS/MS and possible degradation pathways were proposed based on the experiments results. Benzene ring and conjugated diene bonds of Adda group and double bonds of Mhda group were found to be the reactive sites of MC-LR. Overall, this study broadens the knowledge of electrochemical oxidation in removing microcystins in algae-laden water.

Low temperature solution-phase growth of ZnSe and ZnSe/CdSe core/shell nanowires.

High quality ZnSe nanowires (NWs) and complementary ZnSe/CdSe core/shell species have been synthesized using a recently developed solution-liquid-solid (SLS) growth technique. In particular, bismuth salts as opposed to pre-synthesized Bi or Au/Bi nanoparticles have been used to grow NWs at low temperatures in solution. Resulting wires are characterized using transmission electron microscopy and possess mean ensemble diameters between 15 and 28 nm with accompanying lengths ranging from 4-10 µm. Subsequent solution-based overcoating chemistry results in ZnSe wires covered with CdSe nanocrystals. By varying the shell's growth time, different thicknesses can be obtained and range from 8 to 21 nm. More interestingly, the mean constituent CdSe nanocrystal diameter can be varied and results in size-dependent shell emission spectra.

Photocurrent polarization anisotropy of randomly oriented nanowire networks.

While the polarization sensitivity of single or aligned NW ensembles is well-known, this article reports on the existence of residual photocurrent polarization sensitivities in random NW networks. In these studies, CdSe and CdTe NWs were deposited onto glass substrates and contacted with Au electrodes separated by 30-110 microm gaps. SEM and AFM images of resulting devices show isotropically distributed NWs between the electrodes. Complementary high resolution TEM micrographs reveal component NWs to be highly crystalline with diameters between 10 and 20 nm and with lengths ranging from 1 to 10 microm. When illuminated with visible (linearly polarized) light, such random NW networks exhibit significant photocurrent anisotropies rho = 0.25 (sigma = 0.04) [rho = 0.22 (sigma = 0.04)] for CdSe (CdTe) NWs. Corresponding bandwidth measurements yield device polarization sensitivities up to 100 Hz. Additional studies have investigated the effects of varying the electrode potential, gap width, and spatial excitation profile. These experiments suggest electrode orientation as the determining factor behind the polarization sensitivity of NW devices. A simple geometric model has been developed to qualitatively explain the phenomenon. The main conclusion from these studies, however, is that polarization sensitive devices can be made from random NW networks without the need to align component wires.

A study on relationship of nitric oxide, oxidation, peroxidation, lipoperoxidation with chronic chole-cystitis.

AIM:To study relationship of injury induced by nitric oxide, oxidation, peroxidation,lipoperoxidation with chronic cholecystitis.METHODS:The values of plasma nitric oxide (P-NO), plasma vitamin C (P-VC), plasma vitamin E (P-VE), plasma beta-carotene (P-beta-CAR), plasma lipoperoxides (P-LPO), erythrocyte superoxide dismutase (E-SOD), erythrocyte catalase (E-CAT), erythrocyte glutathione peroxidase (E-GSH-Px) activities and erythrocyte lipoperoxides (E-LPO) level in 77 patients with chronic cholecystitis and 80 healthy control subjects were determined, differences of the above average values between the patient group and the control group and differences of the average values between preoperative and postoperative patients were analyzed and compared, linear regression and correlation of the disease course with the above determination values as well as the stepwise regression and correlation of the course with the values were analyzed.RESULTS:Compared with the control group, the average values of P-NO, P-LPO, E-LPO were significantly increased (P<0.01), and of P-VC, P-VE, P-beta-CAR, E-SOD, E-CAT and E-GSH-Px decreased (P <0.01) in the patient group. The analysis of the linear regression and correlation showed that with prolonging of the course, the values of P-NO, P-LPO and E-LPO in the patients were gradually ascended and the values of P-VC,P-VE, P-beta-CAR, E-SOD, E-CAT and E-GSH-Px descended (P<0.01). The analysis of the stepwise regression and correlation indicated that the correlation of the course with P-NO, P-VE and P-beta-CAR values was the closest. Compared with the preoperative patients, the average values of P-NO, P-LPO and E-LPO were significantly decreased (P <0.01) and the average values of P-VC, E-SOD, E-CAT and E-GSH-Px in postoperative patients increased (P <0.01) in postoperative patients. But there was no significant difference in the average values of P-VE, P-beta-CAR preoperative and postoperative patients.CONCLUSION:Chronic cholecystitis could induce the increase of nitric oxide, oxidation, peroxidation and lipoperoxidation.