One-step fabrication of a self-driven point-of-care chip by femtosecond laser direct writing and its application in cancer cell H2O2 detection via semiconductor-based SERS.

Self-driven microfluidic systems have attracted significant attention and demonstrated great potential in the field of point-of-care (POC) testing due to their device simplicity, low power consumption, increased portability, and reduced sample consumption. To develop POC detection chips with diverse characteristics that meet different requirements, there is a strong demand for feasible strategies that enable easy operation and reduce processing time. Here, a one-step processing approach using femtosecond laser direct writing technology was proposed to fabricate a capillary-actuated POC microfluidic chip. The driving force of the chip is highly dependent on its surface wettability, which can be easily adjusted by changing the laser processing parameters. This POC microfluidic chip allowed for the detection of intracellular H2O2 through a catalytic reaction system that incorporated 5-aminosalicylic acid -sensitized colloidal TiO2 nanoparticles and horse radish peroxidase, with integrating semiconductor-based surface-enhanced Raman scattering (SERS) quantitative technique. The concentration of H2O2 was determined by the SERS signal of the catalytic products in the microfluidic chip, resulting in rapid detection with minimal sample consumption. Our method provides a simple, feasible, and alternative strategy for POC testing of H2O2, with a linear range of 10-2∼10-6 M and a limit of detection of 0.55 µM. This approach was successfully applied to rapid detection of intracellular H2O2 in MCF-7 breast cancer cells with high sensitivity and minimal sample consumption. Additionally, this study not only demonstrates the exceptional advantages of femtosecond laser processing technology in fabricating diverse microfluidic chips for various applications, but also presents an efficient POC testing strategy for detecting cell signaling molecules.

New Insights into Photo-Fenton Chemistry: The Overlooked Role of Excited IronIII Species.

Direct photoreduction of FeIII is a widely recognized route for accelerating FeIII/FeII cycle in photo-Fenton chemistry. However, most of the wavelengths covering the full spectral range are insufficient to supply enough photon energy for the direct reduction process. Herein, the hitherto neglected mechanism of FeIII reduction that the FeIII indirect reduction pathway initiated by light energy-dependent reactivity variation and reactive excited state (ES) was explored. Evolution of excited-state FeIII species (*FeIII) resulting from metal-centered charge excitation (MCCE) of FeIII is experimentally verified using pulsed laser femtosecond transient absorption spectroscopy with UV-vis detection and theoretically verified by quantum chemical calculation. Intense photoinduced intravalence charge transition was observed at λ = 380 and 466 nm, revealing quartet 4MCCE and doublet 2MCCE and their exponential processes. Light energy-dependent variation of *FeIII reactivity was kinetically certified by fitting the apparent rate constant of the radical-chain sequence of photo-Fenton reactions. Covalency is found to compensate for the intravalence charge separation following photoexcitation of the metal center in the MCCE state of Fenton photosensitizer. The *FeIII is established as a model, demonstrating the intravalence hole delocalization in the ES can be leveraged for photo-Fenton reaction or other photocatalytic schemes based on electron transfer chemistry.

Intensive Treatment of Organic Wastewater by Three-Dimensional Electrode System within Mn-Loaded Steel Slag as Catalytic Particle Electrodes.

Developing a green, low-carbon, and circular economic system is the key to achieving carbon neutrality. This study investigated the organics removal efficiency in a three-dimensional electrode reactor (3DER) constructed from repurposed industrial solid waste, i.e., Mn-loaded steel slag, as the catalytic particle electrodes (CPE). The CPE, a micron-grade material consisting primarily of transition metals, including Fe and Mn, exhibited excellent electric conductivity, catalytic ability, and recyclability. High rhodamine B (RhB) removal efficiency in the 3DER was observed through a physical modelling experiment. The optimal operating condition was determined through a single-factor experiment in which 5.0 g·L-1 CPE and 3 mM peroxymonosulfate (PMS) were added to a 200 mL solution of 10 mM RhB under a current intensity of 0.5 A and a 1.5 to 2.0 cm distance between the 2D electrodes. When the initial pH value of the simulated solution was 3 to 9, the RhB removal rate exceeded 96% after 20 min reaction. In addition, the main reactive oxidation species in the 3DER were determined. The results illustrated that HO• and SO4•- both existed, but that the contribution of SO4•- to RhB removal was much lower than that of HO• in the 3DER. In summary, this research provides information on the potential of the 3DER for removing refractory organics from water.

Ultrasmall Bi/Cu Coordination Polymer Combined with Glucose Oxidase for Tumor Enhanced Chemodynamic Therapy by Starvation and Photothermal Treatment.

Multi-modal combination therapy for tumor is expected to have superior therapeutic effect compared with monotherapy. In this study, a super-small bismuth/copper-gallic acid coordination polymer nanoparticle (BCN) protected by polyvinylpyrrolidone is designed, which is co-encapsulated with glucose oxidase (GOX) by phospholipid to obtain nanoprobe BCGN@L. It shows that BCN has an average size of 1.8 ± 0.7 nm, and photothermal conversion of BCGN@L is 31.35% for photothermal imaging and photothermal therapy (PTT). During the treatment process of 4T1 tumor-bearing nude mice, GOX catalyzes glucose in the tumor to generate gluconic acid and hydrogen peroxide (H2 O2 ), which reacts with copper ions (Cu2+ ) to produce toxic hydroxyl radicals (•OH) for chemodynamic therapy (CDT) and new fresh oxygen (O2 ) to supply to GOX for further catalysis, preventing tumor hypoxia. These reactions increase glucose depletion for starvation therapy , decrease heat shock protein expression, and enhance tumor sensitivity to low-temperature PTT. The in vitro and in vivo results demonstrate that the combination of CDT with other treatments produces excellent tumor growth inhibition. Blood biochemistry and histology analysis suggests that the nanoprobe has negligible toxicity. All the positive results reveal that the nanoprobe can be a promising approach for incorporation into multi-modal anticancer therapy.

Coupled Surface-Confinement Effect and Pore Engineering in a Single-Fe-Atom Catalyst for Ultrafast Fenton-like Reaction with High-Valent Iron-Oxo Complex Oxidation.

The nanoconfinement effect in Fenton-like reactions shows great potential in environmental remediation, but the construction of confinement structure and the corresponding mechanism are rarely elucidated systematically. Herein, we proposed a novel peroxymonosulfate (PMS) activation system employing the single Fe atom supported on mesoporous N-doped carbon (FeSA-MNC, specific surface area = 1520.9 m2/g), which could accelerate the catalytic oxidation process via the surface-confinement effect. The degradation activity of the confined system was remarkably increased by 34.6 times compared to its analogue unconfined system. The generation of almost 100% high-valent iron-oxo species was identified via 18O isotope-labeled experiments, quenching tests, and probe methods. The density functional theory illustrated that the surface-confinement effect narrows the gap between the d-band center and Fermi level of the single Fe atom, which strengthens the charge transfer rate at the reaction interface and reduces the free energy barrier for PMS activation. The surface-confinement system exhibited excellent pollutant degradation efficiency, robust resistance to coexisting matter, and adaptation of a wide pH range (3.0-11.0) and various temperature environments (5-40 °C). Finally, the FeSA-MNC/PMS system could achieve 100% sulfamethoxazole removal without significant performance decline after 10,000-bed volumes. This work provides novel and significant insights into the surface-confinement effect in Fenton-like chemistry and guides the design of superior oxidation systems for environmental remediation.

Shielding analysis of the proton therapy facility at China Medical University Hospital: comparison of a simplified approach with Monte Carlo simulations.

This study comprehensively compared two approaches for analyzing the shielding design of the proton therapy facility at China Medical University Hospital. The first approach essentially involved two approximate models: one for estimating the transmitted radiation through thick shields, and one for estimating radiation streaming at locations near a maze entrance. The second approach relied on Monte Carlo simulations for predicting the radiation field in a complex environment. A total of 22 beam loss scenarios were considered, and dose rates at 32 locations around the facility were estimated using the two approaches. The comparison results demonstrated that the simplified approach proposed in this study can yield fairly accurate or conservative estimates for quickly performing shielding design or dose assessment in a real-world proton therapy facility.

Facilely Tuning the First-Shell Coordination Microenvironment in Iron Single-Atom for Fenton-like Chemistry toward Highly Efficient Wastewater Purification.

Precisely identifying the atomic structures in single-atom sites and establishing authentic structure-activity relationships for single-atom catalyst (SAC) coordination are significant challenges. Here, theoretical calculations first predicted the underlying catalytic activity of Fe-NxC4-x sites with diverse first-shell coordination environments. Substituting N with C to coordinate with the central Fe atom induces an inferior Fenton-like catalytic efficiency. Then, Fe-SACs carrying three configurations (Fe-N2C2, Fe-N3C1, and Fe-N4) fabricate facilely and demonstrate that optimized coordination environments of Fe-NxC4-x significantly promote the Fenton-like catalytic activity. Specifically, the reaction rate constant increases from 0.064 to 0.318 min-1 as the coordination number of Fe-N increases from 2 to 4, slightly influencing the nonradical reaction mechanism dominated by 1O2. In-depth theoretical calculations unveil that the modulated coordination environments of Fe-SACs from Fe-N2C2 to Fe-N4 optimize the d-band electronic structures and regulate the binding strength of peroxymonosulfate on Fe-NxC4-x sites, resulting in a reduced energy barrier and enhanced Fenton-like catalytic activity. The catalytic stability and the actual hospital sewage treatment capacity also showed strong coordination dependency. This strategy of local coordination engineering offers a vivid example of modulating SACs with well-regulated coordination environments, ultimately maximizing their catalytic efficiency.

Sulfasalazine inhibits esophageal cancer cell proliferation by mediating ferroptosis.

This study aimed to explore the potential mechanism by which sulfasalazine (SAS) inhibits esophageal cancer cell proliferation. A cell counting kit-8 (CCK-8) assay was used to detect the effect of SAS (0, 1, 2, and 4 mM) on the proliferation of TE-1 cells. Subsequently, TE-1 cells were divided into control group, SAS group, SAS + ferrostatin-1 (ferroptosis inhibitor) group, and SAS + Z-VAD (OH)-FMK (apoptosis inhibitor) group, and cell proliferation was measured using a CCK-8 assay. Real-time quantitative polymerase chain reaction and western blotting were used to determine the expression of solute carrier family member 7 11 (SLC7A11, also called xCT), glutathione peroxidase 4 (GPX4), and acyl-CoA synthase long-chain family member 4 (ACSL4) in TE-1 cells. Measurement of ferroptosis in TE-1 cells was achieved by flow cytometry. Compared with the control group (0 mM SAS), the proliferation of TE-1 cells was significantly inhibited by different concentrations of SAS for different time lengths, and 4 mM SAS treatment for 48 h could obtain the maximum inhibition rate (53.9%). In addition, SAS treatment caused a significant decrease in the mRNA and protein expression of xCT and GPX4, and a significant increase in ACSL4 expression in TE-1 cells treated with SAS. Flow cytometry results showed that the ferroptosis level was significantly increased after SAS treatment. However, the activation of ferroptosis by SAS was partially eliminated by treatment with ferrostatin-1 or Z-VAD (OH)-FMK. In conclusion, SAS inhibits the proliferation of esophageal carcinoma cells by activating the ferroptosis pathway.

Activation of periodate by N-doped iron-based porous carbon for degradation of sulfisoxazole: Significance of catalyst-mediated electron transfer mechanism.

Periodate (PI) has recently been studied as an excellent oxidant in advanced oxidation processes, and its reported mechanism is mainly the formation of reactive oxygen species (ROS). This work presents an efficient approach using N-doped iron-based porous carbon (Fe@N-C) to activate periodate for the degradation of sulfisoxazole (SIZ). Characterization results indicated the catalyst has high catalytic activity, stable structure, and high electron transfer activity. In terms of degradation mechanism, it is pointed out that the non-radical pathway is the dominant mechanism. In order to prove this mechanism, we have carried out scavenging experiments, electron paramagnetic resonance (EPR) analysis, salt bridge experiments and electrochemical experiments, which demonstrate the occurrence of mediated electron transfer mechanism. Fe@N-C could mediate the electron transfer from organic contaminant molecules to PI, thus improving the efficiency of PI utilization, rather than simply inducing the activation of PI through Fe@N-C. The overall results of this study provided a new understanding into the application of Fe@N-C activated PI in wastewater treatment.

The Comparison of Functional Outcomes in Patients With Unilateral or Bilateral Intracapsular Mandibular Condylar Fractures After Closed or Open Treatment: A 10-Year Retrospective Study.

BACKGROUND: The treatment strategies for mandibular condylar head fractures, also known as intracapsular condylar fractures (ICFs), have not been concluded. We humbly present our treatment outcomes and share our experience in our department. AIMS AND OBJECTIVES: The aim of this study was to compare the functional outcomes between closed reduction (CR) and open reduction and internal fixation (ORIF) for management of unilateral or bilateral ICFs. MATERIALS AND METHODS: This 10-year retrospective cohort study included 71 patients with 102 ICFs who were treated in our department from May 2007 to August 2017. Nine patients mixed with extracapsular fractures were excluded; thus, 62 patients with 93 ICFs were included. All patients received treatment by the senior surgeon in Chang Gung Memorial Hospital, Linkou Branch, Taiwan. The patient's basic data, fracture morphologies, associated injuries, managements, complications, and maximal mouth opening (MMO) measurement at 1, 3, 6, and 12 months postoperative were reviewed for analysis. RESULTS: Among the 93 fractures, 31 (50%) were bilateral and 31 were unilateral (50%). Based on He's classification, 45 (48%) had type A fracture, 13 (14%) had type B, 5 (5%) had type C, 20 (22%) had type M, and 10 (11%) had no displacement. Maximal mouth opening of 37 mm in unilateral cases after 6 months was significantly higher than the 33-mm MMO in bilateral cases. In addition, the MMO in the ORIF group was significantly higher than that of the CR group in 3 months postoperative. Univariate (odds ratio, 4.92; P = 0.01) and multivariate (odds ratio, 4.76; P = 0.027) analyses revealed CR as an independent risk factor for trismus development compared with ORIF. Malocclusion was observed in 5 patients in both CR and ORIF groups. In addition, 1 patient developed temporomandibular joint osteoarthritis in the CR group. No surgical-related temporary or permanent facial nerve palsy was observed. CONCLUSIONS: Open reduction and internal fixation for condylar head fracture provided better recovery in MMO than CR, and the MMO recovery was less in bilateral condylar head fracture than unilateral condylar head fracture. Open reduction and internal fixation in ICFs have a lower risk for trismus development and should be the treatment of choice in selected cases.

Enhancing zerovalent iron-based Fenton-like chemistry by copper sulfide: Insight into the active sites for sustainable Fe(II) supply.

Zerovalent iron (ZVI)-based Fenton-like processes have been widely applied in degrading organic contaminants. However, the surface oxyhydroxide passivation layer produced during the preparation and oxidation of ZVI hinders its dissolution and Fe(III)/Fe(II) cycling, and restricts the generation of reactive oxygen species (ROS). In this study, copper sulfide (CuS) was found to effectively enhance the degradation of diverse organic pollutants in the ZVI/H2O2 system. Moreover, the degradation performance for the actual industrial wastewater (i.e., dinitrodiazophenol wastewater) in the ZVI/H2O2 system was impressively improved by 41% with CuS addition, and the COD removal efficiency could reach 97% after 2 h of treatment. Mechanism investigation revealed that the introduction of CuS accelerated the sustainable supply of Fe(II) in the ZVI/H2O2 system. Specifically, Cu(I) and reductive sulfur species (i.e., S2-, S22-, Sn2- and H2S (aq)) from CuS directly induced efficient Fe(III)/Fe(II) cycling. The iron-copper synergistic effect between Cu(II) from CuS and ZVI expedited Fe(II) generation from ZVI dissolution and Fe(III) reduction by formed Cu(I). This study not only elucidates the promotion effects of CuS on ZVI dissolution and Fe(III)/Fe(II) cycling in ZVI-based Fenton-like processes, but also provides a sustainable and high-efficiency iron-based oxidation system for removal of organic contaminants.

Iron boride boosted Fenton oxidation: Boron species induced sustainable FeIII/FeII redox couple.

The regeneration of Fe(II) is the rate-limiting step in the Fenton/Fenton-like chain reactions that seriously hinder their scientific progress towards practical application. In this study, we proposed iron boride (FeB) for the first time as a new material to sustainably decompose H2O2 to generate hydroxyl radicals, which can non-selectively degrade a wide array of refractory organic pollutants. Fe(II) can be steadily released by the stepwise oxidation of FeB to stimulate Fenton reaction, meanwhile, B-B bonds as electron donors on the surface of FeB effectively promote the regeneration of Fe(II) from Fe(III) species and significantly accelerate the production of hydroxyl radicals. The low generation of toxic by-products and the high utilization rate of iron species validly avoid the secondary organic/metal pollution in the FeB/H2O2 system. Therefore, FeB mediated Fenton oxidation provides a novel strategy to realize a green and long-lasting environmental remediation.

Removal of Bisphenol A via peroxymonosulfate activation over graphite carbon nitride supported NiCx nanoclusters catalyst: Synergistic oxidation of high-valent nickel-oxo species and singlet oxygen.

In this work, a g-C3N4 supported NiCx nanoclusters catalyst (NiCx-CN) was developed, and its performance in activating peroxymonosulfate (PMS) was evaluated. Mechanism investigation stated that although singlet oxygen (1O2) was formed in the catalytic process, its contribution to BPA elimination was weeny. Interestingly, through the experiment with dimethyl sulfoxide as the probe, it was considered that the high-valent nickel-oxo species (Ni&+=O), generated after the interaction of NiCx-CN and PMS, was the dominating reactive oxygen species (ROS). Theoretical calculations (DFT) implied that NiCx-CN might lose electrons to generate high-valent Ni, which was consistent with the detection of Ni3+ on the surface of the used NiCx-CN. Besides, the prepared NiCx-CN showed advantages in resisting the interference of inorganic anions. Meanwhile, three BPA degradation routes had been proposed based on the transformation intermediates. This study will establish a new protocol for PMS activation using heterogeneous Ni-based catalysts to efficiently degrade organic pollutants via a nonradical mechanism.

Peracetic acid activation by mechanochemically sulfidated zero valent iron for micropollutants degradation: Enhancement mechanism and strategy for extending applicability.

In this study, mechanically sulfidated microscale zero valent iron (S-ZVI) was found to effectively activate the peracetic acid (PAA) with a result of almost complete degradation of six micropollutants within 10 min under neutral conditions, and > 95% sulfamethoxazole (SMX) removal after six cycles. Reactive oxidized species (ROS) including HO•, carbon-centered radicals, and Fe(IV) were generated in the S-ZVI/PAA system, while HO• was the main contributor towards micropollutants degradation. This study clearly revealed that enhancement of the electron donating ability of ZVI by the formed conductive iron sulfides was crucial for promoted Fe(II) generation and subsequent PAA activation over several cycles, rather than the ability of sulfides to reduce Fe(III) for Fe(II) regeneration as reported previously. Interestingly, it's discovered that co-existence of Fe(III) would dramatically improve the contaminants removal efficiency of the S-ZVI/PAA system; transform the surfaced Fe(II) dominated ROS generation process to aqueous Fe(II) one; enhance the tolerance of the proposed system to water matrix. The promoting effect of predosed Fe(III) on PAA activation by S-ZVI should be mainly associated with: the greater ability of Fe(III) than H2O to accept electron from Fe0 for obtaining more active sites; slower Fe0 consumption and solid sulfur species release for elevated electron utilization efficiency and PAA activation. Considering the convenient and cost-effective access of Fe(III), the decrease of acute toxicity of treated SMX, excellent stability and good removal of various micropollutants fully demonstrate the superiority of S-ZVI/PAA system for practical application.

Preliminary outcomes of the surgical navigation system combined with intraoperative three-dimensional C-arm computed tomography for zygomatico-orbital fracture reconstruction.

This study analyzed the outcomes of zygomatico-orbital fracture reconstruction using the real-time navigation system with intraoperative three-dimensional (3D) C-arm computed tomography (CT). Fifteen patients with zygomatico-orbital or isolated orbital/zygoma fractures were enrolled in this prospective cohort. For zygoma reduction, the displacement at five key sutures and the differences between preoperative and intraoperative CT images were compared. For orbital reconstruction, the bilateral orbital volume differences in the anterior, middle, and posterior angles over the medial transitional buttress were measured. Two patients required implant adjustment once after the intraoperative 3D C-arm assessment. On comparing the preoperative and postoperative findings for the zygoma, the average sum of displacement was 19.48 (range, 5.1-34.65) vs. 1.96 (0-3.95) mm (P < 0.001) and the deviation index was 13.56 (10-24.35) vs. 2.44 (0.6-4.85) (P < 0.001). For the orbit, the mean preoperative to postoperative bilateral orbital volume difference was 3.93 (0.35-10.95) vs. 1.05 (0.12-3.61) mm3 (P < 0.001). The mean difference in the bilateral angles at the transition buttress was significantly decreased postoperatively at the middle and posterior one-third. There was no significant difference in orbital volume, angle of the transition zone, and the sum of five zygoma distances between post operative results and preoperative virtual planning. The surgical navigation system with the intraoperative 3D C-arm can effectively improve the accuracy of zygomatico-orbital fracture reconstruction and decrease implant adjustment times.

The Effect of Arch Cartilage Graft and Tajima Reverse U Approach in the Secondary Reconstruction of Unilateral Cleft Lip Nasal Deformity.

ABSTRACT: Secondary cleft lip nasal deformity is complicated with wide spectrum of defect and varied reconstructive procedures. There has been no unanimous solution for a given problem. In case of a localized alar depression in unilateral cleft lip nasal deformity, the conchal cartilage applied as arch graft was proposed. Patients were recruited from database of craniofacial center who received Tajima method and arch cartilage graft. Inclusion criteria were patients with unilateral cleft lip nasal deformity after skeletal maturity. Through a reverse U incision, the lower lateral cartilage was dissected and released from the skin and the contralateral cartilage. The harvested conchal cartilage graft was trimmed to 25 to 30 by 8mm in size, and inserted as arch shape overlying the cleft side lower lateral cartilage. Transdomal fixation sutures were made. Outcome assessment was performed, and the nostril and alar dimensions were measured. Thirty-nine patients were eligible for evaluation of the surgical outcome. Majority of patients underwent simultaneous lip revision (97%). No surgery-related complications were noted in this series. Satisfaction to the nasal reconstruction was reported in 85% of patients. Further minor nasal revisions were performed in 6 patients (15%). Quantitative measurement showed statistically significant improvement in nostril height, alar height and alar width after the surgery. It is concluded that the Tajima reverse U approach plus arch cartilage graft is an effective method for secondary reconstruction of the unilateral cleft lip nasal deformity in selected patients presenting with cleft side alar depression.5.

Novel sodalite stabilized zero-valent iron for super stable and outstanding efficiency in activating persulfate for organic pollutants fast removal.

In this study, novel porous sodalite (SOD) was synthesized through Reactive Oxidation Species (ROS) route from industrial waste lithium silicon fume (LSF) to stabilize nZVI (SOD@nZVI), and used as an outstanding persulfate (PS) activator for efficient organic degradation. Characterization results revealed nZVI evenly distributed on SOD via ion-exchange, and the fabricated SOD@nZVI exhibited high stability and superior reactivity over a wide pH range of 2-12 during oxidation reaction. The mechanism responsible for fast organic degradation in the SOD@nZVI+PS system was carefully investigated, and weak magnetic field (WMF) and friction were found to contribute to improved SOD@nZVI performance. The fast redox cycle of Fe2+/Fe3+ on SOD@nZVI can be stimulated by changing the mixing condition and altering the friction layer to harvest mechanical energy during the reaction, which can maximum persulfate activation to generate more reactive radicals for organic fast degradation. This study is of great significance, as it offers a practical route turning waste into excellent PS activator for in-situ organic pollution remediation, as well as proposing a new idea to maximum PS activation performance by manipulating the inner lining of reactor.

Sumoylation participates in the regulation of YB-1-mediated mismatch repair deficiency and alkylator tolerance.

Numerous reports indicate that enhanced expression of Y-box binding protein-1 (YB-1) in tumor cells is strongly associated with tumorigenesis, aggressiveness, drug resistance, as well as poor prognosis in several types of cancers, and YB-1 is considered to be an oncogene. The molecular mechanism contributing to the regulation of the biological activities of YB-1 remains obscure. Sumoylation, a post-translational modification involving the covalent conjugation of small ubiquitin-like modifier (SUMO) proteins to a target protein, plays key roles in the modulation of protein functions. In this study, our results revealed that YB-1 is sumoylated and that Lys26 is a critical residue for YB-1 sumoylation. Moreover, YB-1 was found to directly interact with SUMO proteins, and disruption of the SUMO-interacting motif (SIM) of YB-1 not only interfered with this interaction but also diminished YB-1 sumoylation. The subcellular localization, protein stability, and transcriptional regulatory activity of YB-1 were not significantly affected by sumoylation. However, decreased sumoylation disrupted the interaction between YB-1 and PCNA as well as YB-1-mediated inhibition of the MutSα/PCNA interaction and MutSα mismatch binding activity, indicating a functional role of YB-1 sumoylation in inducing DNA mismatch repair (MMR) deficiency and spontaneous mutations. The MMR machinery also recognizes alkylator-modified DNA adducts to signal for cell death. We further demonstrated that YB-1 sumoylation is crucial for the inhibition of SN1-type alkylator MNNG-induced cytotoxicity, G2/M-phase arrest, apoptosis, and the MMR-dependent DNA damage response. Collectively, these results provide molecular explanations for the impact of YB-1 sumoylation on MMR deficiency and alkylator tolerance, which may provide insight for designing therapeutic strategies for malignancies and alkylator-resistant cancers associated with YB-1 overexpression.

Nitrogen-doped carbon nanotubes enhanced Fenton chemistry: Role of near-free iron(III) for sustainable iron(III)/iron(II) cycles.

The sluggish kinetics of Fe(II) recovery strongly impedes the scientific progress of Fenton reaction (Fe(II)/H2O2) towards practical application. Here, we propose a novel mechanism that metal-free nitrogen-doped carbon nanotubes (NCNT) can enhance Fenton chemistry with H2O2 as electron donors by elevating the oxidation potential of Fe(III). NCNT remarkably promotes the circulation of Fe(III)/Fe(II) to produce hydroxyl radical (•OH) with excellent stability for multiple usages (more than 10 cycles) in the NCNT/Fe(III)/H2O2 system. Although carbonyl on NCNT can act as the electron supplier for Fe(III) reduction, the behavior of NCNT is distinct from common reductants such as hydroxylamine and boron. Electrochemical analysis and density functional theory calculation unveil that nitrogen sites of NCNT can weakly bind with Fe(III) to elevate the oxidation potential of Fe(III) (named near-free Fe(III), primarily FeOH2+) at pH ranging from 2.0 to 4.0. Without inputs of external stimulations or electron sacrificers, near-free Fe(III) can promote H2O2 induced reduction of Fe(III) to initiate Fenton chain reactions for long-lasting generation of •OH. To our delight, it is a common property of N-doped carbon materials (e.g., graphene, carbon nanofibers, and acetylene black), our research thus provides a novel, sustainable, and green strategy for promoting Fenton chemistry.

Iron molydate catalyzed activation of peroxymonosulfate for bisphenol AF degradation via synergetic non-radical and radical pathways.

Though molybdate oxides have been demonstrated as desirable catalysts for environmental remediation, the mechanism of catalytic activation of peroxymonosulfate (PMS) by iron (II) molybdate (FeMoO4) remains unclear. In this study, FeMoO4 was synthesized and applied for the activation of PMS to degrade bisphenol-AF (BPAF). FeMoO4 showed excellent catalytic activity, high stability, and superior mineralization. The influence of operation parameters (i.e., FeMoO4 dosage, PMS concentration, initial pH, co-existing anions, and temperature) on the removal of BPAF were also investigated in detail. Furthermore, the possible oxidation mechanism was proposed via the chemical quenching tests and electron spin resonance (ESR) analysis, which certified that both free radical (SO4-• and •OH) and non-radical (1O2) were the main reactive oxygen species for degrading BPAF. X-ray photoelectron spectroscopy (XPS) analysis indicated that the radicals were mainly generated via the continuous circulation of Fe3+/Fe2+ and Mo6+/Mo4+ redox cycles to enhance PMS activation. Finally, the degradation pathways of BPAF was proposed based on LC/MS results. This work showed the notable potential of the FeMoO4/PMS system for degrading organic contaminants in the environment remediation and would promote the understanding of the mechanism of Fe-based molybdate in advanced oxidation.