CC-90009, a novel cereblon E3 ligase modulator, targets acute myeloid leukemia blasts and leukemia stem cells.

A number of clinically validated drugs have been developed by repurposing the CUL4-DDB1-CRBN-RBX1 (CRL4CRBN) E3 ubiquitin ligase complex with molecular glue degraders to eliminate disease-driving proteins. Here, we present the identification of a first-in-class GSPT1-selective cereblon E3 ligase modulator, CC-90009. Biochemical, structural, and molecular characterization demonstrates that CC-90009 coopts the CRL4CRBN to selectively target GSPT1 for ubiquitination and proteasomal degradation. Depletion of GSPT1 by CC-90009 rapidly induces acute myeloid leukemia (AML) apoptosis, reducing leukemia engraftment and leukemia stem cells (LSCs) in large-scale primary patient xenografting of 35 independent AML samples, including those with adverse risk features. Using a genome-wide CRISPR-Cas9 screen for effectors of CC-90009 response, we uncovered the ILF2 and ILF3 heterodimeric complex as a novel regulator of cereblon expression. Knockout of ILF2/ILF3 decreases the production of full-length cereblon protein via modulating CRBN messenger RNA alternative splicing, leading to diminished response to CC-90009. The screen also revealed that the mTOR signaling and the integrated stress response specifically regulate the response to CC-90009 in contrast to other cereblon modulators. Hyperactivation of the mTOR pathway by inactivation of TSC1 and TSC2 protected against the growth inhibitory effect of CC-90009 by reducing CC-90009-induced binding of GSPT1 to cereblon and subsequent GSPT1 degradation. On the other hand, GSPT1 degradation promoted the activation of the GCN1/GCN2/ATF4 pathway and subsequent apoptosis in AML cells. Collectively, CC-90009 activity is mediated by multiple layers of signaling networks and pathways within AML blasts and LSCs, whose elucidation gives insight into further assessment of CC-90009s clinical utility. These trials were registered at www.clinicaltrials.gov as #NCT02848001 and #NCT04336982).

New insights into FeS/persulfate system for tetracycline elimination: Iron valence, homogeneous-heterogeneous reactions and degradation pathways.

In this study, complete tetracycline (TTC) and above 50% of total organic carbon (TOC) were removed by FeS/PS after 30 min under optimized conditions. Although free radicals and high-valent iron ions were identified to generate in the process, the apparent similarity between intermediate products of FeS/PS, Fe/PS, and UV/PS systems demonstrated that the degradation of TTC was due to sulfate radicals (SO4⋅-) and hydroxyl radicals (⋅OH). Based on the reaction between free radicals and organic matter, we speculated that TTC in the FeS/PS system was decomposed and mineralized by dehydration, dehydrogenation, hydroxyl addition, demethylation, substitution, E-transfer, and ring-opening. Furthermore, a new understanding of FeS-mediated PS activation based on stoichiometry and kinetic analysis showed that there were both homogeneous and heterogeneous reactions that occurred in the entire progress. However, due to the effect of pH on the dissolution of iron ions, the homogeneous reaction became the principal process with iron ions concentration exceeding 1.35 mg/L. This work provides a theoretical basis for the study of the degradation of TTC-containing wastewater by the iron-based advanced oxidation process.

Formation and transformation of schwertmannite in the classic Fenton process.

The massive amount of sludge generated by the classic Fenton process, which has often been hypothesized to consist of ferric hydroxide, remains a major obstacle to its large-scale application. Therefore, reutilization of Fenton sludge has recently gained more attention. Understanding the formation, transformation, and properties of Fenton sludge combined with the stages of the Fenton reaction is pivotal, but not well illustrated yet. In this study, SEM-EDS, FT-IR, XRD, and XPS were applied to study the morphology, crystallinity, elemental composition, and valence state of Fenton sludge. The authors report that schwertmannite and 2-line ferrihydrite were generated and transformed in the oxidation phase and the neutralization phase of the Fenton process. SO42- in the solution decreased by 8.7%-26.0% at different molar ratios of Fe(II) to H2O2; meanwhile, iron ion precipitated completely at pH 3.70 with the formation of schwertmannite containing sulfate groups in the Fenton sludge. The structural sulfate (Fe-SO4) in schwertmannite was released from the precipitate with the addition of OH-, and the production of Fenton sludge decreased with increasing pH when pH > 3.70. Goethite was found to form when the final pH was adjusted to 12 or at a reaction temperature of 80°C. Moreover, the possible thermal transformation to goethite and hematite indicated that Fenton sludge can be reused as a raw material for synthesizing more stable iron (hydro)oxides. The results provide useful insights into the formation and transformation of Fenton sludge, with implications for regulating the crystal type of Fenton sludge for further reuse.

Ilexgenin A exerts anti-inflammation and anti-angiogenesis effects through inhibition of STAT3 and PI3K pathways and exhibits synergistic effects with Sorafenib on hepatoma growth.

Recently, we reported that Ilexgenin A exhibits anti-cancer activities and induces cell arrest. Here, we investigated the effect of Ilexgenin A on the inflammation, angiogenesis and tumor growth of hepatocellular carcinoma (HCC). Our current study revealed that Ilexgenin A significantly inhibited the inflammatory cytokines TNF-α and IL-6 levels and downregulated pro-angiogenic factor VEGF production and transcription in HepG2 cells. The underlying mechanism for Ilexgenin A effects appears to be through inhibiting STAT3 and PI3K pathways. Furthermore, we found that not only Ilexgenin A inhibited STAT3 and PI3K pathways in HepG2 cells but also blocked these signaling pathways in HUVECs. Most importantly, by employing two HCC xenografts models - HepG2 and H22, we showed that Ilexgenin A reduced tumor growth and exhibited synergy effect with Sorafenib. ELISA assay, histological analysis and immunohistochemistry examination revealed that the expression of VEGF and MVD was significantly decreased after the treatment with Ilexgenin A and the combination. Moreover, Ilexgenin A could enhance caspase-3/7 activity in vitro and transmission electron microscope indicated that the combination induced evident apoptosis of tumor cells and caused the structural changes of mitochondria in vivo. Although no apparent adverse effects occurred during the treatment period, Sorafenib monotherapy elicited hepatotoxicity for specific expression in the increased level of AST and the ratio of AST/ALT. However, the combination could remedy this adverse effect. In conclusion, the results described in the present study identifies Ilexgenin A as a promising therapeutic candidate that modulates inflammation, angiogenesis, and HCC growth.

New insight into the effects of Ca(II) on cake layer structure in submerged membrane bioreactors.

The effects of Ca(II) on the structure of the cake layer in submerged membrane bioreactors (SMBRs) were investigated in this study. Three parallel laboratory-scale SMBRs were operated with synthetic municipal wastewater with three Ca(II) levels (82, 208 and 410 mg l(-1)). As the Ca(II) concentration increased, the sludge floc size increased and the molecular weight of the soluble microbial products (SMP) in the bulk liquid decreased. These observations were attributed to the neutralization and bridging function of Ca(II). Furthermore, Ca(II) addition did not change the thickness of the cake layer, but inhibited the deposition of other elements, such as Al, Si, Mg, and Fe. As a result of Ca(II) addition, the cake layer became less compact and more porous. The interspaces among the flocs in the cake layer helped to reduce the membrane fouling potential.

Effects of low-concentration Cr(VI) on the performance and the membrane fouling of a submerged membrane bioreactor in the treatment of municipal wastewater.

The effects of low-concentration Cr(VI) (0.4 mg l(-1)) on the performance of a submerged membrane bioreactor (SMBR) in the treatment of municipal wastewater, as well as membrane fouling were investigated. Compared with the SMBR for control municipal wastewater, the SMBR for Cr(VI)-containing municipal wastewater had a higher concentration of soluble microbial products (SMP) with lower molecular weights, and smaller sludge particle sizes. Furthermore, low-concentration Cr(VI) induced membrane fouling, especially irreversible membrane pore blocking, which markedly shortened the service life of the membrane.

The key role of unique crystalline property in the hydrolytic degradation process of microcrystalline cellulose-reinforced stereo-complexed poly(lactic acid) composites.

Stereo-complexed poly(lactic acid) (SC-PLA) has unique stereo-complexed crystallites (SC) and homogeneous crystallites (HC), but the effect of this special crystalline property on the hydrolytic degradation of SC-PLA has not been researched. In this study, the hygrothermal aging behaviour of injection-molded SC-PLA and SC-PLA/microcrystalline cellulose (MCC) composites at different temperatures (25 °C and 60 °C) was investigated from micro- and macroscopic perspectives. The results demonstrated that the hydrolysis of SC-PLA was sequentially dominated by the amorphous region, the homogeneous crystalline region, the stereo-complexed crystalline region (three stages). The hydrolytic degradation of SC-PLA only completed the first stage after 4 weeks aging at 25 °C, while it was in the third stage after 4 weeks aging at 60 °C. On this basis, the accelerating effect of 10 wt% MCC on the hydrolysis process of SC-PLA at different stages was investigated. It was found that MCC shortened the hydrolysis time in the stereo-complexed crystalline region by reducing the rearrangement of amorphous structure to form SC and causing cracks and interfacial deterioration by water absorption-swelling-degradation. In addition, the thermal properties and impact strength of SC-PLA and SC-PLA/MCC composites decreased dramatically due to rapid hydrolytic degradation at 60 °C. Overall, the results of this study can provide theoretical basis for the application of SC-PLA and SC-PLA/MCC composites in hygrothermal environment.

New insight into the mechanism of ferric hydroxide-based heterogeneous Fenton-like reaction.

The heterogeneous Fenton-like reaction (HeFR) has always been a research focus for environmental applications. However, it has long been difficult to reach a consensus on the reaction mechanism because the process of metal ions dissolution and its role were not well understood. In this paper, we propose the courses of organics-mediated coordination or/and reduction dissolution of ferric hydroxide to initiate the autocatalytic kinetics of phenol degradation and illustrate it through density functional theory (DFT) and experiments. With the increase of hydrogen peroxide concentration, the degradation of phenol changes from autocatalytic kinetics to first-order kinetics. Furthermore, a novel "limit segmentation method" initiated by us indicates that homogeneous reaction plays a decisive role in the phenol degradation process. The dominant roles of the reactive organics in both iron dissolution and the iron cycle and of the homogeneous reaction in the whole degradation process in the ferric hydroxide-based HeFR system are brand-new insights that pave the pathway for future research.

Tensile Fatigue Properties of Ordinary Plain Concrete and Reinforced Concrete under Flexural Loading.

Many bridge structural components are subjected to repetitive vehicle load and temperature gradient action. The resulting cyclic tensile stresses within the structures could cause premature fatigue failure of concrete, dramatically impairing structural components' durability and sustainability. Although substantial knowledge of fatigue properties on low-strength pavement concrete and high-strength structural concrete has been obtained, research on the most widely used normal-grade ordinary concrete in bridge engineering is still ongoing. Therefore, a four-point bending fatigue test of 97 C50 concrete specimens under a constant amplitude sinusoidal wave was conducted in the laboratory, the flexural fatigue behavior of plain and reinforced concrete specimens was studied, and the cyclic deformation evolution of concrete under fatigue loading was obtained. The empirical fatigue S-N equations of concrete with a failure probability p of 0.1~0.5 were derived through statistical analysis of the test results. The fatigue life of the tested specimens exhibited a two-parameter Weibull distribution. In addition to the maximum stress level Smax, the stress ratio R is also a key factor affecting the flexural fatigue life of concrete N. The semi-logarithmic and logarithmic equations were almost identical at the tested stress levels, the latter predicting longer fatigue life for Smax < 0.70. The restraining effect from steel reinforcement slightly lengthened the concrete's fatigue cracking initiation life. The insight into concrete flexural fatigue properties from this study not only contributes to a better understanding of structural concrete, but also provides a basis for the practical evaluation of concrete or composite bridge decks.

Pilot-scale study on an advanced Fe-Cu process for refractory wastewater pretreatment.

The extreme pH, high color, and poor biodegradability of refractory wastewater have severe impacts on its biological treatment. To address this issue, an advanced Fe-Cu process with redox reaction and spontaneous coagulation was investigated and applied for pilot-scale (wastewater flow rate of 2000 m3·day-1) pretreatment of separately discharged acidic chemicals and alkaline dyeing wastewater. The advanced Fe-Cu process had five functions: (1) increasing the pH of chemical wastewater to 5.0 and above, with an influent pH of approximately 2.0; (2) transforming refractory organics of chemical wastewater with 10.0% chemical oxygen demand (COD) and 30.8% color removal, thereby enhancing the ratio of biological oxygen demand after five days (BOD5) to COD (B/C) from 0.21 to 0.38; (3) neutralizing the pH of the pretreated chemical wastewater for coagulation application with alkaline dyeing wastewater to avoid adding alkaline chemical; (4) achieving average nascent Fe(II) concentrations of 925.6 mg∙L-1 using Fe-Cu internal electrolysis for mixed wastewater coagulation, resulting in an average of 70.3% color removal and 49.5% COD removal; (5) providing more efficient COD removal and B/C enhancement than FeSO4∙7 H2O coagulation while avoiding secondary pollution. The green process offers an effective, easy-implemented solution for the pretreatment of separately discharged acidic and alkaline refractory wastewater.

Synergistic Antibacterial Effect of Phage pB3074 in Combination with Antibiotics Targeting Cell Wall against Multidrug-Resistant Acinetobacter baumannii In Vitro and Ex Vivo.

Synergistic effects of phages in combination with antibiotics have received increasing attention. In this present study, we isolated a new phage pB3074 against clinically isolated multidrug-resistant Acinetobacter baumannii. Phage pB3074 combined with cell wall-targeting antibiotics could produce synergistic antibacterial effect in vitro bactericidal activities. Further research indicates that the bacteriophage dose is critical to synergistic antimicrobial effect of phage and antibiotic combination. Cefotaxime and meropenem were selected as the representative cell wall-targeting antibiotics for further synergistic antibacterial study. Results illustrated that phage pB3074 and cefotaxime or meropenem combination was very effective for the removal of mature biofilm and inhibition of biofilm formation. In a pig skin explant model, results also showed that phage pB3074 and cefotaxime or meropenem combination was very effective for the treatment of wound infection ex vivo. Subsequent studies showed that some extent recovery of drug sensitivity to cell wall-targeting antibiotics might be vital mechanism of synergistic antibacterial effect between bacteriophage pB3074 and these antibiotics. The existence of antibiotics could promote phage adsorption and proliferation, which might also be potential mechanism for synergistic antibacterial activities and have been observed in cefotaxime and meropenem application. In summary, results in the current study demonstrated that phage pB3074 has the potential to be developed as an antibacterial agent and combined application of phages and antibiotics might be a new choice for the treatment of current multidrug-resistant bacterial infections. IMPORTANCE Combined application of phages and antibiotics cannot only effectively inhibit the appearance of phage-resistant bacteria, but also reduce the effective use concentration of antibiotics, and even make some bacteria regain sensitivity to some resistant antibiotics. Therefore, phage-antibiotic combination (PAC) could improve the antibacterial activity of individual drug, providing a new choice for clinical treatment of multidrug-resistant bacterial infections.

Enhanced degradation of tetracycline over FeS-based Fenton-like process: Autocatalytic decomposition of H2O2 and reduction of Fe(III).

This study constructed a FeS-based Fenton-like process to explore the degradation of TTC in the presence of copper ions. The acidic condition of pH 3 was more favorable to the H2O2 decomposition and TTC degradation, and it was slightly enhanced by Cu(II). The production of •OH from H2O2 was revealed through radical scavenging and benzoic acid probe experiments, and the ratio of H2O2 decomposition to •OH production was about 1-1.5, which is comparatively consistent with the theoretical ratio. FeS-based Fenton process was proved to be a homogenous system, the slow release of Fe(II) source and the autocatalytic cycle of Fe(III) to Fe(II) resulting from the reductive species of TTC and dissolved S(-II) improved the production of •OH and the degradation of TTC, which was proved by comparing TTC degradation, TOC removal, H2O2 decomposition and Fe(II) concentration with different iron sources (FeS, Fe(II) and Fe(III)) and external addition of dissolved S(-II). The possible degradation pathways of TTC were subsequently inferred according to the detected products by LC-MS. Understanding these autocatalytic processes is essential to reveal the transformation of redox-active substances in environments and may have potential significance in applying FeS-based Fenton-like process for the treatment of wastewater containing reductive organic matters.

Enhanced degradation of tetracycline by Cu(II) complexation in the FeS/sulfite system.

This study applied a mineral material of FeS to activate sulfite for efficient degradation of TTC in the presence of Cu(II) based on the identified complexation mechanism through UV-Vis spectra, FTIR spectroscopy and DFT calculation. pH plays an important role in TTC degradation and the initial pH of 6 and 7 were the divide in the contributions of FeS/sulfite oxidation and complex-precipitation. TTC-Cu(II) exhibits a superior promoting effect on the TTC degradation in FeS/sulfite system due to the improvement of TTC electron transfer reactivity and Fe(II) dissolution from FeS. Moreover, the formation of Cu(I) improved the recycling of Fe(II) from Fe(III). Dissolved oxygen-dependent free radicals' generation was confirmed, and TTC degradation was mainly attributed to SO4·- and ·OH. The characterization of FeS surface through XPS, XRD, SEM-EDS, Fe(II) deactivation tests, together with the comparison of pseudo-first-order rate constants for TTC degradation by FeS and ferrous ion supported the important role of surface and dissolved Fe(II) in sulfite activation. Furthermore, reasonable degradation pathways of TTC have been proposed according to the detected products by LC-MS. This work highlights the important role of pH, DO and Cu(II) complexation in sulfite activation and TTC degradation, furnishing theoretical support for further relevant studies.

Mn3O4-g-C3N4 composite to activate peroxymonosulfate for organic pollutants degradation: Electron transfer and structure-dependence.

A novel heterogeneous manganese/graphitic carbon nitride (Mn3O4-CN) catalyst for activating peroxymonosulfate (PMS) was successfully assembled using alkali precipitation. The g-C3N4 improved the composite's surface morphology, micro-porous structure, surface area, and particle size distribution, and an electron-rich center with Mn site was created. The Mn3O4-CN/PMS system exhibited high efficiency and stability when the solution pH varied from 3.0 to 9.0, with more than 90% of p-acetaminophen (ACT) removal in 30 min under experimental conditions. A possible reaction mechanism was proposed, primarily involving electron transfer from Mn (II) and Mn (III) to PMS along with the generation of·O2- and 1O2, and the degradation of ACT was attributed to the 1O2. Specifically, the degradation rate of phenolic compounds varied with their molecular structure in the following order: ACT > bisphenol A (BPA) > p-cresol (MP) > p-chlorophenol (CP) > phenol (Ph) > p-nitrophenol (NP). Further, the density functional theory (DFT) calculations indicated that the phenols' degradation efficiency was related to their adsorption energy and Bader charge value. These results improved our understanding of the manganese-based PMS non-radical dominated process and provided a method for predicting the degradation performance of phenols for the first time.

Dynamic changes and prevalence of SARS-CoV-2 IgG/IgM antibodies: Analysis of multiple factors.

OBJECTIVE: To investigate the dynamic characteristics of serological antibodies against the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), which is of much current significance. METHODS: The dynamic changes and prevalence of immunoglobulin M (IgM) and immunoglobulin G (IgG) antibodies against SARS-CoV-2 were assessed from the time of symptom onset up to 210 days. Antibodies were detected using a chemiluminescence immunoassay. RESULTS: The average titers and IgG/IgM positivity rates reached a peak within 30 days of symptom onset and then began to decline continuously. Between 180 and 210 days following symptom onset, the titers of IgG and IgM were 43.1 ± 27.0 AU/mL and 4.4 ± 5.2 AU/mL, respectively, while the respective positivity rates were 84.3% and 12.0%. Further statistical analyses revealed that the dynamic changes and prevalence of the SARS-CoV-2 IgG/IgM antibodies were related to age and disease severity, but not to sex. The dynamic changes and the prevalence were similar for both the IgM and the IgG antibodies. Even so, there was a more rapid rate of decline for the IgM antibodies. It was found that an IgG level of 16.33 ± 3.15 AU/mL may represent a threshold value that should act as an alert, as it may indicate that the IgG level will become undetectable within the next 30-60 days. CONCLUSION: The results provide important information concerning COVID-19 and may be of relevance for diagnosis, treatment, and vaccine development.

Degradation of 4-chlorophenol by BM Fe/Cu-O2 system: The symbiosis of · O 2 - and ·OH radicals.

In this study, Fe/Cu bimetal composite was prepared by high-energy ball milling (BM) method for the removal of refractory organics. The BM Fe/Cu bimetal was characterized by SEM-EDS, XRD, and XPS. Evenly distributed Fe and Cu was observed in the EDS mapping. In contrasting experiments, the removal rate of 4-chlorophenol (4-CP) by BM Fe/Cu materials was about 10-fold faster than that by chemical substitution deposition (CSD) of Fe/Cu material. Complete 4-CP removal and 66.7% of total organic carbon (TOC) mineralization in the BM Fe/Cu-O2 system were achieved. Dissolved oxygen plays a crucial role for 4-CP degradation through the in situ generation of reactive oxygen species (ROS) such as H2 O2 , ·OH, and · O 2 - via oxygen activation reactions. The predominant reactive radicals were identified to be · O 2 - and ·OH through ESR technique and inhibition experiments. The coexistence of oxidation and reduction of 4-CP in the BM Fe/Cu-O2 system was proposed. PRACTITIONER POINTS: 4-CP removal rate by BM Fe/Cu is 10-fold faster than that by CSD Fe/Cu at the same conditions. Complete 4-CP removal and 66.7% of TOC reduction were achieved. All three ROS including ·OH, · O 2 - , and H2 O2 coexisted in the BM Fe/Cu-O2 system. A harmonious coexistence of oxidation and reduction mechanism was proposed.

Reduction of nitrobenzene by the catalyzed Fe/Cu process.

The polarization behavior of the couple Fe/Cu in 100 mg/L nitrobenzene aqueous solution was studied using Evans coupling diagrams. The results indicated that the iron corrosion was limited by both anodic and cathodic half-cell reactions under the neutral conditions, and cathodically controlled under the alkaline conditions. Batch experiments were performed to study the effect of solution pH, reaction duration, concentration, type of electrolyte, and dissolved oxygen (DO) on the reduction of nitrobenzene by the catalyzed Fe/Cu process. This process proved effective in the pH range of 3 to 11. The conversion efficiency of nitrobenzene at pH around 10.1 was almost the same as that under highly acid conditions (pH around 3). The degradation of nitrobenzene fell into two phases: adsorption and surface reduction, and the influence of adsorption and mass transfer became more extensive with solution concentration. The reduction rate decreased in the presence of DO in the solution, indicating that a need for aeration was eliminated in the catalyzed Fe/Cu process. Accordingly, spending on energy consumption would be reduced. Economic analysis indicated that merely 0.05 kg was required for the treatment of a ton of nitrobenzene-containing water with pH from 3 to 11. The catalyzed Fe/Cu process is cost-effective and of practical value.

Industrial wastewater advanced treatment via catalytic ozonation with an Fe-based catalyst.

An Fe-based catalyst was used as a heterogeneous catalyst for the ozonation of industrial wastewater, and key operational parameters (pH and catalyst dosage) were studied. The results indicated that the Fe-based catalyst significantly improved the mineralization of organic pollutants in wastewater. TOC (total organic carbon) removal was high, at 78.7%, with a catalyst concentration of 200 g/L, but only 31.6% with ozonation alone. The Fe-based catalyst significantly promoted ozone decomposition by 70% in aqueous solution. Hydroxyl radicals (·OH) were confirmed to be existed directly via EPR (electron paramagnetic resonance) experiments, and ·OH were verified to account for about 34.4% of TOC removal with NaHCO3 as a radical scavenger. Through characterization by SEM-EDS (field emission scanning electron microscope with energy-dispersive spectrometer), XRD (X-ray powder diffraction) and XPS (X-ray photoelectron spectroscopy), it was deduced that FeOOH on the surface of the catalyst was the dominant contributor to the catalytic efficiency. The catalyst was certified as having good stability and excellent reusability based on 50 successive operations and could be used as a filler simultaneously. Thereby, it is a promising catalyst for practical industrial wastewater advanced treatment.

Copper-catalyzed activation of molecular oxygen for oxidative destruction of acetaminophen: The mechanism and superoxide-mediated cycling of copper species.

In this study, the commercial zero-valent copper (ZVC) was investigated to activate the molecular oxygen (O2) for the degradation of acetaminophen (ACT). 50 mg/L ACT could be completely decomposed within 4 h in the ZVC/air system at initial pH 3.0. The H2O2, hydroxyl radical (OH) and superoxide anion radical (O2-) were identified as the main reactive oxygen species (ROSs) generated in the above reaction; however, only OH caused the decomposition and mineralization of ACT in the copper-catalyzed O2 activation process. In addition, the in-situ generated Cu+ from ZVC dissolution not only activated O2 to produce H2O2, but also initiated the decomposition of H2O2 to generate OH. Meanwhile, the H2O2 could also be partly decomposed into O2-, which served as a mediator for copper cycling by reduction of Cu2+ to Cu+ in the ZVC/air system. Therefore, OH could be continuously generated; and then ACT was effectively degraded. Additionally, the effect of solution pH and the dosage of ZVC were also investigated. As a result, this study indicated the key behavior of the O2- during Cu-catalyzed activation of O2, which further improved the understanding of O2 activation mechanism by zero-valent metals.

Oxalate-assisted oxidative degradation of 4-chlorophenol in a bimetallic, zero-valent iron-aluminum/air/water system.

The reaction of zero-valent iron and aluminum with oxygen produced reactive oxidants that can oxidize 4-chlorophenol (4-CP). However, oxidant yield without metal surface cleaning to dissolve the native oxide layer or in the absence of ligands was too low for practical applications. The addition of oxalate (ox) to dissolved oxygen-saturated solution of Fe(0)-Al(0) significantly increased oxidant yield because of the dissolution, pH buffer, and complexing characteristics of ox. Ox-enhanced reactive oxidant generation was affected by ox concentration and solution pH. The critical effect of ox dosing was confirmed with the reactive species of [Fe(II)(ox)0] and [Fe(II)(ox)2 (2-)]. Systematic studies on the effect of the initial and in situ solution pH revealed that 4-CP oxidation was controlled by the continuous release of dissolved Fe(2+) and Al(3+), their fate, and the activation mechanisms of O2 reduction. The degradation pathway of 4-CP in ox-enhanced Fe(0)-Al(0)/O2 may follow the 4-chlorocatechol pathway. The robustness of the ox-enhanced Al(0)-Fe(0)-O2 process was determined with one-time dosing of ox. Therefore, ox is an ideal additive to enhancing the Fe(0)-Al(0)/O2 system for the oxidative degradation of aqueous organic pollutants.