Syrosingopine and UK5099 synergistically suppress non-small cell lung cancer by activating the integrated stress response.

Non-small cell lung cancer (NSCLC) presents a global health challenge due to its low five-year survival rates, underscoring the need for novel therapeutic strategies. Our research explored the synergistic mechanisms of syrosingopine and UK-5099 in treating NSCLC. In vitro experiments showed that the combination of syrosingopine and UK-5099 significantly synergized to suppress NSCLC proliferation. Further experiments revealed that this combination induced cell cycle arrest and promoted apoptosis in NSCLC cells. In vivo experiments demonstrated that the combination of syrosingopine and UK-5099 markedly inhibited tumor growth. Mechanistic studies revealed that this drug combination promoted mitochondrial damage by inducing lactate accumulation and oxidative stress. Additionally, the combination triggered an integrated stress response (ISR) through the activation of heme-regulated inhibitor kinase (HRI). Importantly, our findings suggested that the synergistic suppression of NSCLC by syrosingopine and UK-5099 was dependent on ISR activation. In summary, our study proposed a promising therapeutic approach that involved the combination of Syrosingopine and UK-5099 to activate ISR, significantly hindering NSCLC growth and proliferation.

Flexible electronics for heavy metal ion detection in water: a comprehensive review.

Flexible electronics offer a versatile, rapid, cost-effective and portable solution to monitor water contamination, which poses serious threat to the environment and human health. This review paper presents a comprehensive exploration of the versatile platforms of flexible electronics in the context of heavy metal ion detection in water systems. The review overviews of the fundamental principles of heavy metal ion detection, surveys the state-of-the-art materials and fabrication techniques for flexible sensors, analyses key performance metrics and limitations, and discusses future opportunities and challenges. By highlighting recent advances in nanomaterials, polymers, wireless integration, and sustainability, this review aims to serve as an essential resource for researchers, engineers, and policy makers seeking to address the critical challenge of heavy metal contamination in water resources. The versatile promise of flexible electronics is thoroughly elucidated to inspire continued innovation in this emerging technology arena.

Deep dewatering of sludge and resource recovery of hydroxyapatite: A recyclable approach via ionic liquid biphasic system and hydrogen bonds reformation.

Deep dewatering of Waste Activated Sludge (WAS) through mechanical processes remains inefficient, primarily due to the formation of a stable hydrogen bonding network between the biopolymers and water, which consequently leads to significant water trapped by Extracellular Polymeric Substances (EPS). In this study, a novel and recyclable treatment for WAS based on Ionic Liquids (ILs) was established, named IL-biphasic aqueous system (IL-ABS) treatment. Specifically, the IL-ABS formed in WAS facilitated rapid and efficient in-situ deep dewatering while concurrently recovering hydroxyapatite. The water content decreased from an initial 98.27 % to 65.35 % with IL-ABS, formed by 1-Butyl-3-methylimidazolium bromide (BmimBr) and K3PO4 synthesized from waste H3PO4. Moreover, the recycled BmimBr maintaining the water content of the dewatered sludge consistently between 65.61 % and 67.25 % across five cycles, exhibited remarkable reproducibility. Through three-dimensional excitation-emission matrix, lactate dehydrogenase analyses and confocal laser scanning microscopy, the high concentration of BmimBr in the upper phase effectively disrupted the cells and EPS, which exposed protein and polysaccharide on the EPS surface. Subsequently, the K3PO4 in the lower phase led to an enhanced salting-out effect in WAS. Furthermore, FT-IR analysis revealed that K3PO4 disrupted the original hydrogen bonds between EPS and water. Then, BmimBr formed numerous hydrogen bonds with the sludge flocs, leading to deep dewatering and agglomeration of the sludge flocs during the unique phase separation process of IL-ABS. Notably, sludge-derived hydroxyapatite product exhibited remarkable adsorption capacity for prevalent heavy metal contaminants such as Pb2+, Cd2+ and Cu2+, with efficiencies comparable to those of commercial hydroxyapatite, thereby achieving the resource utilization of waste H3PO4. Moreover, economic calculations demonstrated the suitability of this novel treatment. This innovative treatment exhibits potential for practical applications in the non-mechanical deep dewatering of WAS.

Formation mechanism of persistent free radicals during pyrolysis of Fenton-conditioned sewage sludge: Influence of NOM and iron.

The present study provided an innovative insight into the formation mechanism of persistent free radicals (PFRs) during the pyrolysis of Fenton-conditioned sludge. Fenton conditioners simultaneously improve the dewatering performance of sewage sludge and catalyze the pyrolysis of sewage sludge for the formation of PFRs. In this process, PFRs with a total number of spins of 9.533×1019 spins/g DS could be generated by pyrolysis of Fenton-conditioned sludge at 400°C. The direct thermal decomposition of natural organic matter (NOM) fractions contributed to the formation of carbon-centered radicals, while the Maillard reaction produced phenols precursors. Additionally, the reaction between aromatic proteins and iron played a crucial role in the formation of phenoxyl or semiquinone-type radicals. Kinetics analysis using discrete distributed activation energy model (DAEM) demonstrated that the average activation energy for pyrolysis was reduced from 178.28 kJ/mol for raw sludge to 164.53 KJ/mol for Fenton conditioned sludge. The reaction factor (fi) indicated that the primary reaction in Fenton-conditioned sludge comprised of 27 parallel first-order reactions, resulting from pyrolysis cleavage of the NOM fractions, the Maillard reaction, and iron catalysis. These findings are significant for understanding the formation process of PFRs from NOM in Fenton-conditioned sludge and provide valuable insight for controlling PFRs formation in practical applications.

Peroxymonosulfate activation by trace iron(III) porphyrin for facile degradation of organic pollutants via nonradical oxidation.

Nonradical species with great resistance to interference have shown great advantages in complex wastewater treatment. Herein, a novel system constructed by biodegradable tetrakis-(4-carboxyphenyl)-porphyrinatoiron(III) (FeIII-TCPP) and peroxymonosulfate (PMS) was proposed for facile decontamination. Nonradical pathway is observed in FeIII-TCPP/PMS, where 1O2 and high-valent iron-oxo species play dominant roles. The genres and valence of high-valent iron-oxo species, including iron(IV)-oxo porphyrin radical-cationic species [OFeIV-TCPP•+] and iron(IV)-hydroxide species [FeIV-TCPP(OH)], are ascertained, along with their generation mechanism. The axial ligand on the iron axial site affects the ground spin state of FeIII-TCPP, further influencing the thermodynamic reaction pathway of active species. With trace catalyst in micromoles, FeIII-TCPP exhibits high efficiency by degrading bisphenol S (BPS) completely within 5 min, while Co2+/PMS can only achieve a maximum of 26.2% under identical condition. Beneficial from nonradical pathways, FeIII-TCPP/PMS demonstrates a wide pH range of 3-10 and exhibits minimal sensitivity to interference of concomitant materials. BPS is primarily eliminated through ß-scission and hydroxylation. Specifically, 1O2 electrophilically attacks the C-S bond of BPS, while high-valent iron-oxo species interacts with BPS through an oxygen-bound mechanism. This study provides novel insights into efficient activation of PMS by iron porphyrin, enabling the removal of refractory pollutants through nonradical pathway.

Revealing the roles of chemical communication in restoring the formation and electroactivity of electrogenic biofilm under electrical signaling disruption.

Electrogenic biofilms in microbial electrochemical systems have played significant roles in simultaneous wastewater treatment and energy recovery owing to their unique extracellular electron transfer. Their formation has been shown to be regulated by electrical and chemical communication, but the interaction between these signal communication pathways has not been studied. This research investigated the coordination between intracellular c-di-GMP signaling and reinforced quorum sensing with or without exogenous HSL (a common quorum sensing molecule), on the formation of mixed-cultured electrogenic biofilm under electrical signaling disruption by tetraethylammonium (TEA, a broad-range potassium channel blocker). Intracellular c-di-GMP was spontaneously reinforced in response to TEA stress, and metagenomic analysis revealed that the dominant DGC (the genes for producing c-di-GMP) induced the eventual biofilm formation by mediating exopolysaccharide synthesis. Meanwhile, reinforced quorum sensing by exogenous HSL could also benefit the biofilm restoration, however, it alleviated the TEA-induced communication stress, resulting in the weakening of c-di-GMP dominance. Interestingly, suppressing electrical communication with or without HSL addition both induced selective enrichment of Geobacter of 85.5% or 30.1% respectively. Functional contribution analysis revealed the significant roles of Geobacter and Thauera in c-di-GMP signaling, especially Thauera in resistance to TEA stress. This study proposed a potential strategy for electrogenic biofilm regulation from the perspectives of cell-to-cell communication.

Peroxymonosulfate activated by natural porphyrin derivatives for rapid degradation of organic pollutants via singlet oxygen and high-valent iron-oxo species.

The activation of peroxymonosulfate (PMS) by sodium ferric chlorophyllin (SFC), a natural porphyrin derivative extracted from chlorophyll-rich substances, was systematically investigated for facile degradation of bisphenol A (BPA). SFC/PMS is capable of degrading 97.5% of BPA in the first 10 min with the initial BPA concentration of 20 mg/L and pH = 3, whereas conventional Fe2+/PMS could only remove 22.6% of BPA under identical conditions. It demonstrates a prominent flexibility to a broad pH range of 3-11 with complete pollutant degradation. A remarkable tolerance toward concomitant high concentration of inorganic anions (100 mM) was also observed, among which (bi)carbonates can even accelerate the degradation. The nonradical oxidation species, including high-valent iron-oxo porphyrin species and 1O2, are identified as dominant species. Particularly, the generation and participation of 1O2 in the reaction is evidenced by experimental and theoretical methods, which is vastly different from the previous study. The specific activation mechanism is unveiled by density functional theory (DFT) calculations and ab initio molecular dynamics (AIMD) simulations. The results shed light on effective PMS activation by iron (III) porphyrin and the proposed natural porphyrin derivative would be a promising candidate for efficient abatement of recalcitrant pollutants toward complicated aqueous media in wastewater treatment.

Novel PbO@C composite material directly derived from spent lead-acid batteries by one-step spray pyrolysis process.

A one-step spray pyrolysis process is investigated for the first time in the field of spent lead-acid batteries (LABs) recycling. The spent lead paste that derived from spent LAB is desulfurized and then leached to generate the lead acetate (Pb(Ac)2) solution, which is then sprayed directly into a tube furnace to prepare the lead oxide (PbO) product by pyrolysis. The low-impurity lead oxide product (9 mg/kg Fe and 1 mg/kg Ba) is obtained under the optimized conditions (the temperature of 700 °C, the pumping rate of 50 L/h, and the spray rate of 0.5 mL/min). The major crystalline phases of the synthesized products are identified to be α-PbO and ß-PbO. In the spray pyrolysis process, Pb(Ac)2 droplets are sequentially transformed into various intermediate products: H2O(g)@Pb(Ac)2 solution, Pb(Ac)2 crystals@PbO, and the final PbO@C product. Owning its carbon skeleton structure, the recovered PbO@C product (carbon content of 0.14%) shows better performance than the commercial ball-milled lead oxide powder in battery tests, with higher initial capacity and better cycling stability. This study could provide a strategy for the short-route recovery of spent LABs.

Enhanced bromine fixation and tar lightweighting in co-pyrolysis of non-metallic fractions of waste printed circuit boards with Bayer red mud.

A co-pyrolysis process for non-metallic fractions (NMFs) from WPCBs with Bayer red mud (RM) is proposed to upgrade pyrolysis products in this study. High bromine fixation efficiency was realized, and higher content of lightweight pyrolysis tar was obtained. The mechanism of catalytic pyrolysis and simultaneous bromine fixation of NMFs by RM was investigated by experiments and theoretical calculations. The three inorganic components of Fe2O3, CaCO3 and Al2O3 in RM played key roles in the catalytic pyrolysis of NMFs, and their order of catalytic debromination effect was CaCO3 > Fe2O3 > Al2O3. By adding 15 wt% RM, the pyrolysis solid residue could fix 89.55 wt% bromine, compared with 35.42 wt% of NMFs without adding RM, due to the formation of FeBr2 and CaBr2 from Fe2O3 and CaCO3 in RM, respectively. Tar lightweighting was realized by reducing the energy barrier of the direct decomposition of tetrabromobisphenol A (TBBPA) in NMFs. The order of effect of the three key components on the tar lightweighting was Fe2O3 > Al2O3 > CaCO3. The content of lightweight tar in the tar obtained by catalytic pyrolysis of NMFs with 15 wt% RM was 44.29% higher than that in the tar obtained by direct pyrolysis of NMFs. This work provides a theoretical guidance for the low-cost and eco-friendly recycling of e-wastes by co-pyrolysis with RM.

Insights into Nitrogen-doped Carbon for Oxygen Reduction: The Role of Graphitic and Pyridinic Nitrogen Species.

Nitrogen-doped carbons (N/Cs) manifest good catalytic performance for oxygen reduction reaction (ORR) for fuel cell systems. However, to date, controversies remain on the role of active sites in N/Cs. In the present study, ORR test was conducted on three N/Cs in O2 -saturated 0.1 M KOH aqueous solution, where apparent linear correlation between graphitic N contents and ORR activity was observed. Theoretical calculations demonstrated that graphitic N doping is energetically more favorable than that of pyridinic N doping for ORR and the pyridinic N leads to more preferential with 2 e- ORR pathway. These results reveal that graphitic N plays a key role in N/Cs mediated ORR activity. This work lays a solid foundation on identifying the active sites in heteroatom-doped carbons and can be exploited for rational design and engineering of effective carbon-based ORR catalysts.

A sustainable strategy for recovery of phosphorus as vivianite from sewage sludge via alkali-activated pyrolysis, water leaching and crystallization.

A sustainable strategy for P recovery from sewage sludge via alkali-activated pyrolysis, water leaching and crystallization was proposed, and a high value-added product of vivianite was recovered. Effects of the type and dose of alkali activator on P transformation during sludge pyrolysis were investigated. 50 wt% dose of KHCO3 was determined as the alkali-activated pyrolysis condition. The content of water-soluble P (referred to as Water-P) in biochar derived from raw sludge (referred to as RS) and ferric sludge (Fenton's reagent conditioned sludge, referred to as FS) by KHCO3-activated pyrolysis at different temperatures was compared. The Fe element in the Fenton's reagent enhanced the content of Fe-bound P in the dewatered sludge, which was readily transformed into potassium phosphate during KHCO3-activated pyrolysis, thus increasing the Water-P content in the biochar derived from FS. The proportions of Water-P to total P in the biochar samples obtained by KHCO3-activated pyrolysis of RS and FS at 600 °C were 72.5% and 96.2%, respectively, which were notably higher than those in the biochar samples obtained by direct pyrolysis of RS and FS (3.5% and 0.5%), respectively. The water leaching solution of biochar obtained by KHCO3-activated pyrolysis of FS at 600 °C was purified to remove impurity elements, and vivianite with high purity was finally recovered by crystallization. A total P recovery efficiency of 88.08% was achieved throughout the process from sewage sludge to the final vivianite product. This study proposes a promising and sustainable approach for realizing the recovery of high value-added product vivianite from sewage sludge.

Recycled biochar adsorption combined with CaCl2 washing to increase rice yields and decrease Cd levels in grains and paddy soils: A field study.

Field-scale trials were conducted to remove cadmium (Cd) from paddy soil by using recycled hydroxyapatite modified biochar (HBC) plus low-level CaCl2 washing. Synergistic reduction efficiencies of total and available Cd in soil (45.6 % and 36.8 %) were achieved by the combined amendments compared with only HBC or CaCl2. The release of Cd from soil particulates was facilitated by CaCl2 washing and the increased soluble Cd in soil water (hardly removed by drainage) could be removed efficiently by recycled HBC adsorption. Significantly decreases in Cd translocation and accumulation in rice plants benefited from the decrease of Cd level and availability in soil and the increase of available silicon (Si). As a result, Cd contents in early/late rice grains decreased by ~85 % and met the Chinese national food standard. SOM, CEC, and soil nutrients after remediation were increased due to 10 %-15 % of HBC residual. Grain yields of the early and late rice increased by 34.1 % and 9.91 %, respectively. The collected HBC (>85 % of the total used HBC) was in-situ regenerated and could be used in the next field trials. The generated wastewater together with drainage from field treatment could be reused as irrigation water after the treatment with a small-scale reclamation ecosystem. The work provides a novelty remediation strategy for Cd-contaminated paddy soil. The noticeable remediation efficiency for Cd reduction in soil and grains, and improved productivity-relevant soil properties have important implications for paddy soil with poor fertility, severe desilicification, and Cd contamination in South China whereas the application of biochar or chemical washing alone did not.

Generation of high-valent iron-oxo porphyrin cation radicals on hemin loaded carbon nanotubes for efficient degradation of sulfathiazole.

Hemin has attracted considerable interest as an efficient catalyst recently, however, its direct application is inefficient due to severe molecular aggregation. Immobilizing hemin on various supports is a feasible approach to address this issue. In this work, a CNTs-hemin catalyst was prepared by loading hemin onto multiwalled carbon nanotubes (CNTs) through ball milling. Compared with hemin, CNTs-hemin demonstrates remarkably enhanced performance in the peroxymonosulfate system, with a 650-fold improvement of apparent rate constant, reaching 97.8% degradation of sulfathiazole in 5 min. High-valent iron-oxo porphyrin cation ((Porp)+•FeIV=O) radicals are proposed as the dominant reactive species in the CNTs-hemin/peroxymonosulfate system instead of sulfate radicals (SO4•-), hydroxyl radicals (•OH), superoxide radicals (O2•-) and singlet oxygen (1O2). More in-depth mechanisms reveal that the strong electron transfer between CNTs and hemin promotes the generation of (Porp)+•FeIV=O radicals through a heterolysis pathway. This research enriches the understanding of the catalytic mechanism of supported biomimetic catalysts for PMS activation and provides a perspective on the role of support materials for catalytic activity.

Iron-calcium reinforced solidification of arsenic alkali residue in geopolymer composite: Wide pH stabilization and its mechanism.

Arsenic-alkali residue (AAR) from antimony production can pose significant health and environmental hazards due to the risk of arsenic (As) leaching. In this study, geopolymer composite synthesized from fly ash (FA) was investigated for efficient stabilization of high-arsenic-containing AAR (As2O3 of 22.74 wt%). Two industrial wastes, e.g., granulated blast furnace slag (GBFS) with active calcium composition and water-quenched slag (WQS) from lead-zinc smelting with active iron composition, were investigated for the reinforcement of AAR geopolymer solidification. A wide pH stabilization (from pH = 3-pH = 12) of AAR with the geopolymer composite was successfully achieved, and As leaching concentration of geopolymer with the addition of 5 wt% AAR was significantly reduced from 2343.73 mg/L (AAR) to that below 0.18 mg/L, which successfully meet the regulatory limit of Chinese domestic waste landfill (GB, 18598-2019, 1.2 mg/L) and hazardous waste landfill (GB16889-2008, 0.3 mg/L). Johnbaumite (Ca5(AsO4)3(OH)) was formed in geopolymer composite and leached samples with initial pH from 2.6 to 6 (final pH from 5.54 to 13.15). Magnetite and iron hydroxide phases with strong adsorption and/or As co-precipitation capability were also observed. As stabilization was also achieved with iron oxidation from As(III) to As(V). This study solves the problem of unstable As leaching at different pH for the solidification of arsenic-bearing solid waste, and provides a promising and practical strategy for efficient solidification/stabilization of AAR as well as other similar arsenic-bearing solid wastes with geopolymer composite.

Potassium channel blocker selectively enriched Geobacter from mixed-cultured electroactive biofilm: Insights from microbial community, functional prediction and gene expressions.

This study investigated the effects of electrical signaling disruption induced by adding tetraethylammonium (TEA, a potassium channel blocker) on the formation of mixed-cultured electroactive biofilms, especially the relative abundance of Geobacter over time. Results showed that TEA addition decelerated the biofilm formation, but selectively enriched Geobacter over time (45.8% on Day 32, 67.7% on Day 60 and 78.1% on Day 90), thus resulting in higher final extracellular electron transfer (EET) efficiency. Redundancy analysis (RDA) confirmed that TEA and operation time were significant factors for the selective enrichment of Geobacter. Moreover, increase in cellular processes and signal processing by PICRUSt analysis indicated adaptive responses of electrogenic biofilms to electrical signaling disruption. Furthermore, qRT-PCR indicated the compensatory roles of key cytochromes and pilA in electrochemical communication, which induced Geobacter enrichment. This work provided a broader understanding of electroactive biofilm regulation and potential applications for electricity generation and biosensor in the future.

Iron porphyrin-TiO2 modulated peroxymonosulfate activation for efficient degradation of 2,4,6-trichlorophenol with high-valent iron-oxo species.

Developing efficient catalysts with low cost and environmental friendliness for peroxymonosulfate (PMS) activation attracts broad interest. In this study, TiO2-hemin was prepared by immobilizing hemin on TiO2 using a ball milling method, demonstrating 126.9-fold enhanced catalytic degradation efficiency compared with unsupported hemin in the PMS activation system, with 92.9% of 2,4,6-trichlorophenol (2,4,6-TCP) removed in 10 min. The superior performance is attributed to the strong interaction between TiO2 and hemin, which induces the redistribution of the electron density of hemin molecules. In the TiO2-hemin/PMS system, sulfate radicals (SO4•-), hydroxyl radicals (•OH), singlet oxygen (1O2), and superoxide radicals (O2•-) were identified, which only played a minor role in the elimination of 2,4,6-TCP. Instead, high-valent iron-oxo species were proposed and identified as the primary active species. This study provides a facile strategy to enhance the activity of the biomimetic catalyst and offers insight into the catalytic mechanism of iron porphyrin with PMS activation.

Ca and Cu doped LaFeO3 to promote coupling of photon carriers and redox cycling for facile photo-Fenton degradation of bisphenol A.

Enhancements in the light response and hydrogen peroxide utilization are critical to the catalytic performance of heterogeneous Fenton-like perovskites. Here, in this research, oxygen vacancy-enriched La0.9Ca0.1Cu0.5Fe0.5O3-δ was prepared by a co-precipitation method with Cu substitution and Ca doping and demonstrated excellent performance for the degradation of bisphenol A. Both total organic carbon (TOC) removal and hydrogen peroxide utilization were close to 90% within 120 min at pH 3-7, where the TOC removal and hydrogen peroxide utilization were 2.5 times and 5.5 times of LaFeO3 in the absence of Ca and Cu doping. It demonstrated excellent stability to light irradiation and oxidation with respect to cycling and metal ion leaching. This revealed that oxygen vacancies were enriched in the catalyst with the substitution of Ca and Cu and contributed to the recombination of photogenerated electrons, thereby increasing the reduction efficiency of copper ions and accelerating the redox cycling of iron ions.