Fluorescence-Based Proteoliposome Methods to Monitor Redox-Active Transition Metal Transmembrane Translocation by Metal Transporters.

Transmembrane transition metal transporter proteins are central gatekeepers in selectively controlling vectorial metal cargo uptake and extrusion across cellular membranes in all living organisms, thus playing key roles in essential and toxic metal homeostasis. Biochemical characterization of transporter-mediated translocation events and transport kinetics of redox-active metals, such as iron and copper, is challenged by the complexity in generating reconstituted systems in which vectorial metal transport can be studied in real time. We present fluorescence-based proteoliposome methods to monitor redox-active metal transmembrane translocation upon reconstitution of purified metal transporters in artificial lipid bilayers. By encapsulating turn-on/-off iron or copper-dependent sensors in the proteoliposome lumen and conducting real-time transport assays using small unilamellar vesicles (SUVs), in which selected purified Fe(II) and Cu(I) transmembrane importer and exporter proteins have been reconstituted, we provide a platform to monitor metal translocation events across lipid bilayers in real time. The strategy is modular and expandable toward the study of different transporter families featuring diverse metal substrate selectivity and promiscuity.

Reverse Thiol Trapping Approach to Assess the Thiol Status of Metal-Binding Mitochondrial Proteins.

Thiol-disulfide interconversions are pivotal in the intricate chemistry of biological systems. They play a vital role in governing cellular redox potential and shielding against oxidative harm. These interconversions can also act as molecular switches within an expanding array of redox-regulated proteins, facilitating dynamic and responsive processes. Furthermore, metal-binding proteins often use thiols for coordination. Reverse thiol trapping is a valuable analytical tool to study the redox state of cysteines in biological systems. By selectively capturing and stabilizing free thiol species with an alkylating agent, reverse thiol trapping allows for their subsequent identification and quantification. Various methods can be employed to analyze the trapped thiol adducts, including electrophoresis-based methods, mass spectrometry, nuclear magnetic resonance spectroscopy, and chromatographic techniques. In this chapter, we will focus on describing a simple and sensitive method to sequentially block thiols in their cellular state with a cell-permeant agent (iodoacetamide), and following reduction and denaturation of the samples, trap the native disulfides with a second blocker that shifts the apparent molecular weight of the protein. The oxidation status of proteins for which suitable antibodies are available can then be analyzed by immunoblotting. We present examples of mitochondrial proteins that use cysteine thiols to coordinate metal factors such as iron-sulfur clusters, zinc, and copper.

The influence of chlorination additives on metal separation during the pyrometallurgical recovery of spent lithium-ion batteries.

The difficulty of separating Li during pyrometallurgical smelting of spent lithium-ion batteries (LIBs) has limited the development of pyrometallurgical processes. Chlorination enables the conversion of Li from spent LIBs to the gas phase during the smelting process. In this paper, the effects of four solid chlorinating agents (KCl, NaCl, CaCl2 and MgCl2) on Li volatilization and metal (Co, Cu, Ni and Fe) recovery were investigated. The four solid chlorinating agents were systematically compared in terms of the direct chlorination capacities, indirect chlorination capacities, alloy physical losses and chemical losses in the slag. CaCl2 was better suited for use as a solid chlorinating agent to promote Li volatilization due to its excellent results in these indexes. The temperature required for the release of HCl from MgCl2, facilitated by CO2 and SiO2, was lower than 500 °C. The prematurely released HCl failed to participate in the chlorination reaction. This resulted in approximately 12 % less Li volatilization when MgCl2 was used as a chlorinating agent compared to when CaCl2 was used. In addition, the use of KCl as a chlorinating agent decreased the chemical dissolution loss of alloys in the slag. The performance of NaCl was mediocre. Finally, based on evaluations of the four indexes, recommendations for the selection and optimization of solid chlorinating agents were provided.

The mechanistic insights into different aspects of promiscuity in metalloenzymes.

Enzymes are nature's ultimate machinery to catalyze complex reactions. Though enzymes are evolved to catalyze specific reactions, they also show significant promiscuity in reactions and substrate selection. Metalloenzymes contain a metal ion or metal cofactor in their active site, which is crucial in their catalytic activity. Depending on the metal and its coordination environment, the metal ion or cofactor may function as a Lewis acid or base and a redox center and thus can catalyze a plethora of natural reactions. In fact, the versatility in the oxidation state of the metal ions provides metalloenzymes with a high level of catalytic adaptability and promiscuity. In this chapter, we discuss different aspects of promiscuity in metalloenzymes by using several recent experimental and theoretical works as case studies. We start our discussion by introducing the concept of promiscuity and then we delve into the mechanistic insight into promiscuity at the molecular level.

The Combined ICP-MS, ESEM-EDX, and HAADF-STEM-EDX Approach for the Assessment of Metal Sub-Micro- and Nanoparticles in Wheat Grain.

Metal sub-microparticles (SMPs) and nanoparticles (NPs) presence in food is attributable to increasing pollution from the environment in raw materials and finished products. In the present study, a multifaceted analytical strategy based on Environmental Scanning Electron Microscopy and High-Angle Annular Dark-Field-Scanning Transmission Electron Microscopy coupled with Energy-Dispersive X-ray Spectroscopy (ESEM-EDX, HAADF-STEM-EDX) and Inductively Coupled Plasma Mass Spectrometry (ICP-MS) was proposed for the detection and characterization of metal and metal-containing SMPs and NPs in durum wheat samples, covering a size measurement range from 1 nm to multiple µm. ESEM-EDX and ICP-MS techniques were applied for the assessment of SMP and NP contamination on the surface of wheat grains collected from seven geographical areas characterized by different natural and anthropic conditions, namely Italy, the USA, Australia, Slovakia, Mexico, Austria, and Russia. ICP-MS showed significant differences among the mean concentration levels of metals, with the USA and Italy having the highest level. ESEM-EDX analysis confirmed ICP-MS concentration measurements and measured the highest presence of particles < 0.8 µm in size in samples from Italy, followed by the USA. Less marked differences were observed when particles < 0.15 µm were considered. HAADF-STEM-EDX was applied to a selected number of samples for a preliminary assessment of internal contamination by metal SMPs and NPs, and to expand the measurable particle size range. The multifaceted approach provided similar results for Fe-containing SMPs and NPs. ICP-MS and ESEM-EDX also highlighted the presence of a significant abundance of Ti- and Al-containing particles, while for STEM-EDX, sample preparation artifacts complicated the interpretation. Finally, HAADF-STEM-EDX results provided relevant information about particles in the low nm range, since, by applying this technique, no particles smaller than 50 nm were observed in accordance with ESEM-EDX.

Examining the Oxidation States of Metals in Aerosols Emitted by Electronic Cigarettes.

Electronic cigarettes (ECs) emit many toxic substances, including metals, that can pose a threat to users and the environment. The toxicity of the emitted metals depends on their oxidation states. Hence, this study examines the oxidation states of metals observed in EC aerosols. X-ray photoelectron spectroscopy analysis of the filters that collected EC aerosols identified the oxidation states of five primary metals (based on surface sample analysis), including chromium(III) (close to 100%) under low power setting while a noticeable amount of chromium(VI) (15%) at higher power settings of the EC, and copper(II) (100%), zinc(II) (100%), nickel(II) (100%), lead(II) (65%), and lead(IV) (35%) regardless of power settings. This observation indicates that the increased temperature due to higher power settings could alter the oxidation states of certain metals. We noted that many metals were in their lesser toxic states; however, inhaling these metals may still pose health risks.

Exploring the effect of disease causing mutations in metal binding sites of human ARSA in metachromatic leukodystrophy.

The arylsulfatase A (ARSA) gene is observed to be deficient in patients with metachromatic leukodystrophy (MLD), a type of lysosomal storage disease. MLD is a severe neurodegenerative disorder characterized by an autosomal recessive inheritance pattern. This study aimed to map the most deleterious mutations at the metal binding sites of ARSA and the amino acids in proximity to the mutated positions. We utilized an array of computational tools, including PredictSNP, MAPP, PhD-SNP, PolyPhen-1, PolyPhen-2, SIFT, SNAP, and ConSurf, to identify the most detrimental mutations potentially implicated in MLD collected from UniProt, ClinVar, and HGMD. Two mutations, D29N and D30H, as being extremely deleterious based on assessments of pathogenicity, conservation, biophysical characteristics, and stability analysis. The D29 and D30 are located at the metal-interacting regions of ARSA and found to undergo post-translational modification, specifically phosphorylation. Henceforth, the in-depth effect of metal binding upon mutation was examined using molecular dynamics simulations (MDS) before and after phosphorylation. The MDS results exhibited high deviation for the D29N and D30H mutations in comparison to the native, and the same was confirmed by significant residue fluctuation and reduced compactness. These structural alterations suggest that such mutations may influence protein functionality, offering potential avenues for personalized therapeutic and providing a basis for potential mutation-specific treatments for severe MLD patients.

The Programmable Catalytic Core of 8-17 DNAzymes.

8-17 DNAzymes (8-17, 17E, Mg5, and 17EV1) are in vitro-selected catalytic DNA molecules that are capable of cleaving complementary RNAs. The conserved residues in their similar catalytic cores, together with the metal ions, were suggested to contribute to the catalytic reaction. Based on the contribution of the less conserved residues in the bulge loop residues (W12, A15, A15.0) and the internal stem, new catalytic cores of 8-17 DNAzymes were programmed. The internal stem CTC-GAG seems to be more favorable for the DNAzymes than CCG-GGC, while an extra W12.0 led to a significant loss of activity of DNAzymes, which is contrary to the positive effect of A15.0, by which a new active DNAzyme 17EM was derived. It conducts a faster reaction than 17E. It is most active in the presence of Pb2+, with the metal ion preference of Pb2+ >> Zn2+ > Mn2+ > Ca2+ ≈ Mg2+. In the Pb2+ and Zn2+-mediated reactions of 17EM and 17E, the same Na+- and pH dependence were also observed as what was observed for 17E and other 8-17 DNAzymes. Therefore, 17EM is another member of the 8-17 DNAzymes, and it could be applied as a potential biosensor for RNA and metal ions.

Targeting Biometals in Alzheimer's Disease with Metal Chelating Agents Including Coumarin Derivatives.

Numerous physiological processes happening in the human body, including cerebral development and function, require the participation of biometal ions such as iron, copper, and zinc. Their dyshomeostasis may, however, contribute to the onset of Alzheimer's disease (AD) and potentially other neurodegenerative diseases. Chelation of biometal ions is therefore a therapeutic strategy against AD. This review provides a survey of natural and synthetic chelating agents that are or could potentially be used to target the metal hypothesis of AD. Since metal dyshomeostasis is not the only pathological aspect of AD, and the nature of this disorder is very complex and multifactiorial, the most efficient therapeutics should target as many neurotoxic factors as possible. Various coumarin derivatives match this description and apart from being able to chelate metal ions, they exhibit the capacity to inhibit cholinesterases (ChEs) and monoamine oxidase B (MAO-B) while also possessing antioxidant, anti-inflammatory, and numerous other beneficial effects. Compounds based on the coumarin scaffold therefore represent a desirable class of anti-AD therapeutics.

Efficient extraction of metals (Fe, Zn, Pb) from hazardous jarosite using ionic liquid and waste-derived solvents.

The present study evaluated a solvo-metallurgical technique for metal extraction from industrial solid waste (jarosite) using ionic liquids (ILs) and waste-derived solvents. The jarosite contains a considerable amount of metal ions, namely iron, zinc, and lead. The jarosite was characterized by XRF, XRD, SEM, and FTIR techniques. The parameters affecting metal extraction, such as stirring time, acid molarity, and temperature, have been examined. Aliquat 336 was used to extract metals from fresh and roasted jarosite after equilibration with HCl. The response surface methodology (RSM) was used to optimize the parameters for the maximum metal extraction using [A336] [Cl]. Maximum extraction of iron (86.75%), zinc (51.96%), and lead (94.38%) from roasted jarosite was achieved at optimum conditions (125-min stirring time, 5 M acid molarity, and 20 ml/g liquid-to-solid ratio). Furthermore, the metal extraction was investigated using waste-derived solvents. The results show that waste-derived solvents, such as biomass and plastic pyrolysis oil, can effectively extract metals from fresh and roasted jarosite. Biomass pyrolysis oil achieved the highest extraction at 50 °C for 90 min, while plastic pyrolysis oil achieved the highest extraction at 50 °C for 60 min from roasted jarosite. These solvents are also cost-effective because they are made from waste plastic and biomass.

Bacterial adhesion and corrosion behavior of different pure metals induced by sulfate reducing bacteria.

The corrosion behaviors of four pure metals (Fe, Ni, Mo and Cr) in the presence of sulfate reducing bacteria (SRB) were investigated in enriched artificial seawater (EASW) after 14-day incubation. Metal Fe and metal Ni experienced weight losses of 1.96 mg cm-2 and 1.26 mg cm-2, respectively. In contrast, metal Mo and metal Cr exhibited minimal weight losses, with values of only 0.05 mg cm-2 and 0.03 mg cm-2, respectively. In comparison to Mo (2.2 × 106 cells cm-2) or Cr (1.4 × 106 cells cm-2) surface, the sessile cell counts on Fe (4.0 × 107 cells cm-2) or Ni (3.1 × 107 cells cm-2) surface was higher.

MOC1 cleaves Holliday junctions through a cooperative nick and counter-nick mechanism mediated by metal ions.

Holliday junction resolution is a crucial process in homologous recombination and DNA double-strand break repair. Complete Holliday junction resolution requires two stepwise incisions across the center of the junction, but the precise mechanism of metal ion-catalyzed Holliday junction cleavage remains elusive. Here, we perform a metal ion-triggered catalysis in crystals to investigate the mechanism of Holliday junction cleavage by MOC1. We capture the structures of MOC1 in complex with a nicked Holliday junction at various catalytic states, including the ground state, the one-metal ion binding state, and the two-metal ion binding state. Moreover, we also identify a third metal ion that may aid in the nucleophilic attack on the scissile phosphate. Further structural and biochemical analyses reveal a metal ion-mediated allosteric regulation between the two active sites, contributing to the enhancement of the second strand cleavage following the first strand cleavage, as well as the precise symmetric cleavage across the Holliday junction. Our work provides insights into the mechanism of metal ion-catalyzed Holliday junction resolution by MOC1, with implications for understanding how cells preserve genome integrity during the Holliday junction resolution phase.

Prosthetic Metals: Release, Metabolism and Toxicity.

The development of metallic joint prostheses has been ongoing for more than a century alongside advancements in hip and knee arthroplasty. Among the materials utilized, the Cobalt-Chromium-Molybdenum (Co-Cr-Mo) and Titanium-Aluminum-Vanadium (Ti-Al-V) alloys are predominant in joint prosthesis construction, predominantly due to their commendable biocompatibility, mechanical strength, and corrosion resistance. Nonetheless, over time, the physical wear, electrochemical corrosion, and inflammation induced by these alloys that occur post-implantation can cause the release of various metallic components. The released metals can then flow and metabolize in vivo, subsequently causing potential local or systemic harm. This review first details joint prosthesis development and acknowledges the release of prosthetic metals. Second, we outline the metallic concentration, biodistribution, and elimination pathways of the released prosthetic metals. Lastly, we discuss the possible organ, cellular, critical biomolecules, and significant signaling pathway toxicities and adverse effects that arise from exposure to these metals.

Carbon and metal based magnetic porous materials - Role in drug removal: A Comprehensive review.

Development of effective adsorbents for the removal of contaminants from wastewater is indispensable due to increasing water scarcity and a lack of pure drinking water, which are prevailing as a result of rapid industrialization and population growth. Recently, the development of new adsorbents and their effective use without generating secondary waste is receiving huge consideration. In order to protect the environment from primary and secondary pollution, the development of adsorbents from wastes and their recycling have become conventional practices aimed at waste management. As a result, significant progress has been made in the synthesis of new porous carbon and metal-organic frameworks as adsorbents, with the objective of using them for the removal of pollutants. While many different kinds of pollutants are produced in the environment, drug pollutants are the most vicious because of their tendency to undergo significant structural changes, producing metabolites and residues with entirely different properties compared to their parent compounds. Chemical reactions involving oxidation, hydrolysis, and photolysis transform drugs. The resulting compounds can have detrimental effects on living beings that are present in soil and water. This review stresses the development of adsorbents with adjustable porosities for the broad removal of primary drug pollutants and their metabolites, which are formed as a result of drug transformations in environmental matrices. This keeps adsorbents from building up in the environment and prevents them from becoming significant pollutants in the future. Additionally, it stops secondary pollution caused by the deterioration of the used adsorbents. Focus on the development of effective adsorbents with flexible porosities allows for the complete removal of coexisting contaminants and makes a substantial contribution to wastewater management. In order to concentrate more on the development of flexible pore adsorbents, it is crucial to comprehend the milestones reached in the research and applications of porous magnetic adsorbents based on metal and carbon, which are discussed here.

Characterizing the Stoichiometry of Individual Metal Sulfide and Phosphate Colloids in Soils, Sediments, and Industrial Processes by Inductively Coupled Plasma Time-of-Flight Mass Spectrometry.

Size and purity of metal phosphate and metal sulfide colloids can control the solubility, persistence, and bioavailability of metals in environmental systems. Despite their importance, methods for detecting and characterizing the diversity in the elemental composition of these colloids in complex matrices are missing. Here, we develop a single-particle inductively coupled plasma time-of-flight mass spectrometry (sp-icpTOF-MS) approach to characterize the elemental compositions of individual metal phosphate and sulfide colloids extracted from complex matrices. The stoichiometry was accurately determined for particles of known composition with an equivalent spherical diameter of ≥∼200 nm. Assisted by machine learning (ML), the new method could distinguish particles of the copper sulfides covellite (CuS), chalcocite (Cu2S), and chalcopyrite particles (CuFeS2) with 75% (for Cu2S) to 99% (for CuFeS2) accuracy. Application of the sp-icpTOF-MS method to particles recovered from natural samples revealed that iron sulfide (FeS) particles in lake sediment contained ∼4% copper and zinc impurities, whereas pure pyrite (FeS2) was identified in hydraulic fracturing wastewater and confirmed by selected area electron diffraction. Colloidal mercury in an offshore marine sediment was present as pure mercury sulfide (HgS), whereas geogenic HgS recovered from an industrial process contained ∼0.08 wt % silver per Hg, enabling source apportionment of these colloids using ML. X-ray absorption spectroscopy confirmed that Hg was predominantly present as metacinnabar (ß-HgS) in the industrial process sample. The determination of impurities in individual colloids, such as zinc and copper in FeS, and silver in HgS may enable improved assessment of their origin, reactivity, and bioavailability potential.

Metal Strip Implanted Tunneling Field-Effect Transistor Biosensor as a Label-Free Biosensor.

In this study, we design and simulate a metal implanted dielectrically modulated tunneling field-effect transistor (MI-DMTFET). In the ambipolar conduction state, the proposed structure works as an efficient sensor for the detection of a wide range of biomolecules. A metal strip (MS) is implanted above the drain-channel junction in the gate dielectric to improve the alignment of band gaps. Therefore, with the help of implanted metal work function engineering, the tunneling barrier gets lowered, which in turn increases the ambipolar current. An optimum metal-strip implant work function of 4.85 eV and a length of 1.5 nm have resulted in significantly improved performance of the proposed device. It has been observed that when the biomolecules with varying dielectric constants and charge densities are captured in the nanogap cavity, the ambipolar current of the biosensor changes, resulting in the detection of the biomolecules. Quantitative and comprehensive analyses of device parameters such as surface potential, electric field, band-to-band tunneling, subthreshold slope, and ION/IOFF ratio analysis have been performed. Rigorous comparative analyses of key performance-measuring parameters have been performed with a conventional sensor device. It has been found that the proposed device offers maximum sensitivity of 1220 under an ambipolar state at k = 12.

Fabrication of lignocellulose/liquid metal-based conductive eutectic hydrogel composite for strain sensors.

High conductive and freeze-resistant hydrogels with adhesion function are ideal candidates for soft electronic devices. However, it remains a challenge to design appropriate conductive nanofillers to endow hydrogels with all these characteristics. Liquid metal (LM) exhibits exceptional electrical conductivity and convenient processability, rendering it a highly promising contender. Cellulose nanofibrils (CNFs) were employed as the interfacial stabilizer in synthesizing stable CNFs encapsulated LM solutions. Then the lignin was further coated on the surface of CNFs-LM (LCL) to prepare lignin-coated hybrid hydrogels. The obtained LCL displayed outstanding water-dispersible stability and were promising conductive nanofillers for hydrogels. During the fabrication of poly N-(hydroxymethyl) acrylamide (PHA) hydrogels, the LM was dispersed into LM particles with smaller sizes, leading to highly conductive LCL-PHA hydrogels (0.38 S·m-1). The prepared LCL-PHA hydrogels exhibited exceptional mechanical properties, including a strain at a break of 134.6 %, stress at a break of 22.7 Kpa, and a toughness of 16.3 KJ·m-3. Additionally, the LCL-PHA hydrogels demonstrated favorable electrical conductivity and adhesion. Notably, even after being subjected to freezing at -20 °C for 24 h, they remained suitable for effective real-time monitoring of all types of human activities, demonstrating superior environmental stability.

A review on the recent advances of interaction studies of anticancer metal-based drugs with therapeutic targets, DNA and RNAs.

Metal-based drugs hold promise as potent anticancer agents owing to their unique interactions with cellular targets. This review discusses recent advances in our understanding of the intricate molecular interactions of metal-based anticancer compounds with specific therapeutic targets in cancer cells. Advanced computational and experimental methodologies delineate the binding mechanisms, structural dynamics and functional outcomes of these interactions. In addition, the review sheds light on the precise modes of action of these drugs, their efficacy and the potential avenues for further optimization in cancer-treatment strategies and the development of targeted and effective metal-based therapies for combating various forms of cancer.

Asymmetric ionic bond shielding encountering with carboxylate capturing metal ions for enhancing the flame retardant durability of regenerated cellulose fibers.

Enhancing the flame retardancy and durability of cellulose fibers, particularly environmentally friendly regenerated cellulose fibers types like Lyocell fibers, is essential for advancing their broader application. This study introduced a novel approach to address this challenge. Cationic-modified Lyocell fibers (Lyocell@CAT) were prepared by introducing quaternary ammonium structures into the molecular chain of Lyocell fibers. Simultaneously, a flame retardant, APA, containing -COO-NH4+ and -P=O(O-NH4+)2 groups was synthesized. APA was then covalently bonded to Lyocell@CAT to prepare Lyocell@CAT@APA. Even after undergoing 30 laundering cycles (LCs), Lyocell@CAT@APA maintained a LOI value of 37.2 %, exhibiting outstanding flame retardant durability. The quaternary ammonium structure within Lyocell@CAT@APA formed asymmetric ionic bonds with the phosphate and carboxylate groups in APA, effectively shielding the binding of Na+ ions with phosphate groups during laundering, thereby enhancing the durability. Additionally, the consumption of Na+ ions by carboxylate groups further prevented their binding to phosphate groups, which contributed to enhance the durability properties. Flame retardant mechanism analysis revealed that both gas and condensed phase synergistically endowed excellent flame retardancy to Lyocell fibers. Overall, this innovative strategy presented a promising prospect for developing bio-safe, durable, and flame retardant cellulose textiles.

Unlocking Mixed-Metal Oxides Active Centers via Acidity Regulation for K&SO2 Poisoning Resistance: Self-Detoxification Mechanism of Zeolite-Confined deNOx Catalysts.

Selective catalytic reduction of nitrogen oxides (NOx) with ammonia (NH3-SCR) is an efficient NOx reduction strategy, while the denitrification (deNOx) catalysts suffer from serious deactivation due to the coexistence of multiple poisoning substances, such as alkali metal (e.g., K), SO2, etc., in industrial flue gases. It is essential to understand the interaction among various poisons and their effects on the deNOx process. Herein, the ZSM-5 zeolite-confined MnSmOx mixed (MnSmOx@ZSM-5) catalyst exhibited better deNOx performance after the poisoning of K, SO2, and/or K&SO2 than the MnSmOx and MnSmOx/ZSM-5 catalysts, the deNOx activity of which at high temperature (H-T) increased significantly (>90% NOx conversion in the range of 220-480 °C). It has been demonstrated that K would occupy both redox and acidic sites, which severely reduced the reactivity of MnSmOx/ZSM-5 catalysts. The most important, K element is preferentially deposited at -OH on the surface of ZSM-5 carrier due to the electrostatic attraction (-O-K). As for the K&SO2 poisoning catalyst, SO2 preferred to be combined with the surface-deposited K (-O-K-SO2ads) according to XPS and density functional theory (DFT) results, the poisoned active sites by K would be released. The K migration behavior was induced by SO2 over K-poisoned MnSmOx@ZSM-5 catalysts, and the balance of surface redox and acidic site was regulated, like a synergistic promoter, which led to K-poisoning buffering and activity recovery. This work contributes to the understanding of the self-detoxification interaction between alkali metals (e.g., K) and SO2 on deNOx catalysts and provides a novel strategy for the adaptive use of one poisoning substance to counter another for practical NOx reduction.