Adjacent Bonds Research Articles

Assembling phthalaldehyde and o-aminochalcones by Pd(II) catalyzed tandem reaction for synthesizing isoindoloindonole fluorophores

One-pot synthesis of isoindoloindonoles having various auxochrome, from easily available starting materials phthalaldehyde and o-aminochalcone, involving palladium(II) acetate catalysis in acetic acid is reported. A mechanism based on the formation of 2-aryl-2H-isoindol-1-ol (22) intermediate is proposed for the formation of the tetracyclic core of isoindoloindonoles. The possible intramolecular cyclization via the direct participation of the carbonyl vs the adjacent αβ-conjugated double bond was evaluated. Thus, a detailed study on how the presence of electronically different groups at the β position of chalcones affects the outcome of the cyclization reaction and the photophysical properties of the resulting isoindoloindolones is presented here. Furthermore, the core structure was determined using NMR, mass and single-crystal X-ray diffraction analysis.

Chromophore Optimization in Organometallic Au(III) Cys Arylation of Peptides and Proteins for 266 nm Photoactivation.

Cysteine is the most reactive naturally occurring amino acid due to the presence of a free thiol, presenting a tantalizing handle for covalent modification of peptides/proteins. Although many mass spectrometry experiments could benefit from site-specific modification of Cys, the utility of direct arylation has not been thoroughly explored. Recently, Spokoyny and co-workers reported a Au(III) organometallic reagent that robustly arylates Cys and tolerates a wide variety of solvents and conditions. Given the chromophoric nature of aryl groups and the known susceptibility of carbon-sulfur bonds to photodissociation, we set out to identify an aryl group that could efficiently cleave Cys carbon-sulfur bonds at 266 nm. A streamlined workflow was developed to facilitate rapid examination of a large number of aryls with minimal sample using a simple test peptide, RAAACGVLK. We were able to identify several aryl groups that yield abundant homolytic photodissociation of the adjacent Cys carbon-sulfur bonds with short activation times (<10 ms). In addition, we characterized the radical products created by photodissociation by subjecting the product ions to further collisional activation. Finally, we tested Cys arylation with human hemoglobin, identified reaction conditions that facilitate efficient modification of intact proteins, and evaluated the photochemistry and activation of these large radical ions.

Theoretical study on the cascaded double proton transfer mechanism involving two adjacent hydrogen bonds in conjugated organic molecules

The cascaded double proton transfer reaction has attracted the interest of many researchers due to its effective six-level system cycle. Herein, the double proton transfer mechanism of naphthalene-based analog NDH and anthracene-based analog ADH in different solvents is investigated using density functional theory (DFT) and time-dependent density functional theory (TDDFT). The results indicate that the first occurrence of excited-state intramolecular proton transfer (ESIPT) in NDH and ADH is an ultrafast, barrierless process. Additionally, ADH undergoes a second ESIPT reaction, radiating a wider range of fluorescence spectrum. Theoretical studies reveal that this is due to the significantly increased hydrogen bond strength of ADH compared to NDH in the first excited (S1) state, creating favorable conditions for the second ESIPT. Analysis of electronic properties indicates that ADH exhibits enhanced chemical and kinetic activity, with a more pronounced intramolecular charge transfer (ICT), leading to increased stability of the keto structure (KB2*) after the second ESIPT. Finally, we identify the factors influencing the cascaded double proton transfer reaction. The second ESIPT process is promoted by extending the π-conjugated skeleton of the core molecule horizontally and leveraging the driving force provided by the H3 atom near the proton donor O3–H2. It is expected that these studies will provide theoretical guidance and new insights for the design and synthesis of near infrared (NIR) organic materials.

Bond pairs and the term structure

AbstractIn the US Treasury bond market, the existence of a bond pair (two bonds with the same maturity but different coupons) is shown to allow the computation of the zero‐coupon interest rate for that maturity directly from the bond prices, as well as the zero‐coupon interest rates for adjacent maturity bonds with the same number of coupon payments. Since the 2008–2009 financial crisis, the number of bond pairs has increased, allowing for the direct estimation from bond prices of the zero‐coupon interest rates for an average of 180 individual maturities for bond maturities between 6 months and 30 years. The bond pairs approach outperforms popular yield‐curve‐fitting models in accurately reproducing original bond prices.

Mitochondria-Targeted Prodrug Nanoassemblies for Efficient Ferroptosis-Based Therapy via Devastating Ferroptosis Defense Systems.

Ferroptosis is a form of regulated cell death accompanied by lipid reactive oxygen species (ROS) accumulation in an iron-dependent manner. However, the efficiency of tumorous ferroptosis was seriously restricted by intracellular ferroptosis defense systems, the glutathione peroxidase 4 (GPX4) system, and the ubiquinol (CoQH2) system. Inspired by the crucial role of mitochondria in the ferroptosis process, we reported a prodrug nanoassembly capable of unleashing potent mitochondrial lipid peroxidation and ferroptotic cell death. Dihydroorotate dehydrogenase (DHODH) inhibitor (QA) was combined with triphenylphosphonium moiety through a disulfide-containing linker to engineer well-defined nanoassemblies (QSSP) within a single-molecular framework. After being trapped in cancer cells, the acidic condition provoked the structural disassembly of QSSP to liberate free prodrug molecules. The mitochondrial membrane-potential-driven accumulation of the lipophilic cation prodrug was delivered explicitly into the mitochondria. Afterward, the thiol-disulfide exchange would occur accompanied by downregulation of reduced glutathione levels, thus resulting in mitochondria-localized GPX4 inactivation for ferroptosis. Simultaneously, the released QA from the hydrolysis reaction of the adjacent ester bond could further devastate mitochondrial defense and evoke robust ferroptosis via the DHODH-CoQH2 system. This subcellular targeted nanoassembly provides a reference for designing ferroptosis-based strategy for efficient cancer therapy through interfering antiferroptosis systems.

Hydrogen-triggered metal filament rupture in Cu-based Resistance Switches

Cation based resistance switches have been considered as promising candidates for memory cells and other novel devices. So far, the most accepted switching processes of such devices are based on the formation/rupture of metallic filaments between two electrodes. Although many recent studies have identified the existence of H2O (and resulting -OH groups) in such devices, their effects on the switching process are still unclear. In the present work, by taking Cu/Ta2O5/Pt device as an example, we have theoretically revealed that H ions may dissociate from -OH groups and accumulate onto the Cu filament in amorphous Ta2O5. After that, the adsorbed H ions will induce a series of changes, such as the elongation of the adjacent Cu-Cu bonds, the weakening of the Cu-Cu bonds, the increase of charge on Cu cations, and the enhancement of diffusivities of Cu cations, all of which eventually lead to the rupture of the Cu filament. Interestingly, our proposed “H-triggered metal filament rupture” model is similar to the widely studied “hydrogen embrittlement phenomenon”. The crucial point of this model is the high catalytic activity of Cu towards the splitting of -OH group. Consequently, it is expected that this model could be applicable to other Cu-cation based resistance switches.

Melt polycondensation of poly (butylene oxalate-co-succinate) with great potential in curbing marine plastic pollution

Marine plastic pollution, with annual emissions into the marine over 53 million metric tons, has been a major worldwide concern. Many of so-called “biodegradable” polymers degrade very slowly in seawater. Oxalate have attracted attention because the electron-withdrawing effect of adjacent ester bonds promotes their natural hydrolysis, particularly in the ocean. However, the low boiling point and poor thermal stability of oxalic acids severely limits their applications. The successful synthesis of light-colored poly(butylene oxalate-co-succinate) (PBOS), with weight average molecular weight higher than 1 × 105 g/mol, displays the breakthroughs in the melt polycondensation of oxalic acid-based copolyesters. The copolymerization of oxalic acid retains the crystallization rate of PBS, with minimum half-crystallization times from 16 s (PBO10S) to 48 s (PBO30S). PBO10S-PBO40S exhibit good mechanical properties with elastic modulus of 218–454 MPa, and tensile strength between 12 and 29 MPa, better than packaging materials such as biodegradable PBAT and non-degradable LLDPE. PBOS achieve rapid degradation in the marine environment, with a mass loss 8%− 45% after 35 days. The characterization of structural changes demonstrate that the introduced oxalic acid plays a key role in the process of seawater degradation. This new class of polymers therefore provide highly promising materials for sustainable packaging with unique seawater degradation properties.

Structural organization and properties of surface layers of WC–Co hard alloys after pulsed laser processing

The article presents the metal-physical studies results of the structure formation effects in surface layers in the hard alloys of the WC–Co system under extreme thermal and deformation effects of pulsed laser radiation. It is shown that the structural organization and properties of hard alloys VK6, VK8, VK10 upon radiation treatment with a power density of 175 MW/m2 are determined by state of the zones which are formed around carbide inclusions due to the various kinds of stresses appearance at the “carbide-bond” composition boundaries, including thermostrictive and phase stresses. The result is dissolution of the carbides boundary zones due to contact melting, which is accompanied by mutual mass transfer of atoms at the boundaries in the “carbide-bond” system with the possible formation of a thin amorphous-like super hard shell. These processes make it possible to create compositions in hard alloys with a set of differentiated properties specified by varying the laser treatment process parameters and composition of the starting materials. After laser alloying with a radiation power density of 200 MW/m2, temperature gradients and thermal stresses appearing in the surface layers of hard alloys with coatings (cobalt, nickel) contribute to convective mixing of the molten coating components and their penetration into the hard alloy to a depth of more than 20 μm. Simultaneously, despite the extremely short laser pulse time (10–3 s), mass transfer of tungsten, carbon and titanium atoms from the melted boundary zones of carbides to the adjacent bond zones with their hardening is possible in the irradiated zones. It was established that after high-temperature laser heating, carbides, in contrast to the initial ones, achieve a globular shape of grains. They are dispersed, and stoichiometric characteristics change in the local zones bordering the bond (the complex type carbide CoxWyCz is formed). As a result, due to these processes, the surface layers’ viscosity of hard alloys and the irradiated products performance increase. Compared to non-irradiated samples of hard alloy, the ultimate strength increases by 15 %, strength and durability – by 30 – 40 %.

MD-Based Assessment of Covalent Inhibitors in Noncovalent Association Complexes: Learning from Cathepsin K as a Test Case.

A sufficiently stable noncovalent association complex between a covalent inhibitor and its protein target is regarded as a prerequisite for the formation of a covalent complex. As this transient form can hardly be assessed experimentally, computational modeling is required to probe the suitability of a given ligand at this particular stage. To investigate which criteria should be fulfilled by suitable candidates in a molecular dynamics (MD) assessment, a systematic study was conducted with 20 complexes of cathepsin K, a papain-like cysteine protease of pharmaceutical relevance. The covalent inhibitors in these complexes were converted to their pre-reaction states, and the resulting noncovalent complexes were subjected to MD simulations. The critical distance between the electrophilic and nucleophilic reaction partners was monitored as a potential parameter to assess the suitability for covalent bond formation. Across various warhead types, a distance between 3.6 and 4.0 Å, comparable to the sum of the generalized Born radii of carbon and sulfur, was found to be stably maintained under appropriate conditions. The protonation state of the catalytic dyad and the resulting solvation pattern dramatically affected the noncovalent binding mode and the distance of the warhead to the active site. For several complexes, fluctuations in the orientation of the warhead were observed due to torsional rotations in adjacent bonds. This observation helped to explain the gradual transitions from noncovalent to covalent complexes observed in the crystal structures of three closely related nitrile-based inhibitors. According to comparative simulations conducted for a set of 13 cathepsin S complexes, the overall findings of the study appear to be transferable to related cysteine proteases as targets of covalent inhibitors.

Macro peroxide initiators based on autoxidized unsaturated plant oils: Block/graft copolymer conjugates for nanotechnology and biomedical applications

AbstractThe autoxidation of unsaturated fatty acids and their esters is one of the most important reactions in food and biological systems. Autoxidation is a type of reaction between air oxygen and unsaturated plant oils. This reaction starts with a hydrogen abstraction on the methylene group adjacent double bond, leaving a radical onto the carbon atom. Molecular oxygen attacks this radical leading to produce peroxide and hydroperoxide derivatives of the oligomerized unsaturated plant oils. Because peroxide groups thermally cleave to produce free radicals, hydroperoxide derivatives of unsaturated plant oil oligomers can be used in the free radical polymerization of vinyl monomers leading to the related block/graft copolymers. The obtained copolymers combined with the biodegradable natural plant oil gain superior properties such as biodegradability and softness. In this review article, the in vitro autoxidation of well‐known unsaturated plant oils‐soybean oil, linseed oil, and castor oil and some related unsaturated fatty acids‐oleic acid, linoleic acid, and ricinoleic acid was carried out under atmospheric conditions with or without exposing white light. Because the autoxidized unsaturated oil/fatty acids contain peroxide/hydroperoxide groups (they are referred to as macro peroxide initiators) that they are used in the free radical polymerization of vinyl monomers to obtain block/graft copolymers. The improved polymerization conditions, characterization, and applications of the obtained products will be discussed.

Controlled Growing of Graphdiyne Film for Friction Reduction and Antiwear

Like the multilayered graphene which is the most widely used solid lubricant, graphdiyne (GDY) as a 2D material holds potential similar prospects but has been rarely researched so far. One reason is that growing a GDY film in a controllable manner on diverse material surfaces remains a great challenge. To address the issue, a catalytic pregrowth and solution polymerization method is developed to synthesize a GDY film on various substrates. It allows fine control over film structure and thickness. A macroscopic ultralow friction coefficient of 0.08 is obtained, and a relatively long life of more than 5 h under a high load of 1378 MPa is achieved. Molecular dynamics simulations together with the surface analysis demonstrate that the increased deformation degree and weakened relative motion between GDY layers contribute to the low friction. Especially, different from graphene, the friction of GDY exhibits a double increase and decrease in one period of λ ≈ 8-9 Å, and it is roughly equal to the distance between two adjacent alkyne bonds in the x direction, indicating GDY's structure and lattice play an important role in reducing friction.

Critical roles of linker length in determining the chemical and self-assembly stability of SN38 homodimeric nanoprodrugs.

Homodimeric prodrug nanoassemblies (HDPNs) have been widely studied for efficient cancer therapy by virtue of their ultra-high drug loading and distinct nanostructure. However, the development of SN38 HDPNs is still a great challenge due to the rigid planar aromatic ring structure. Improving the structural flexibility of homodimeric prodrugs by increasing the linker length may be a potential strategy for constructing SN38 HDPNs. Herein, three SN38 homodimeric prodrugs with different linker lengths were synthesized. The number of carbon atoms from the disulfide bond to the adjacent ester bond is 1 (denoted as α-SN38-SS-SN38), 2 (β-SN38-SS-SN38), and 3 (γ-SN38-SS-SN38), respectively. Interestingly, we found that α-SN38-SS-SN38 exhibited extremely low yield and poor chemical stability. Additionally, β-SN38-SS-SN38 demonstrated suitable chemical stability but poor self-assembly stability. In comparison, γ-SN38-SS-SN38 possessed good chemical and self-assembly stability, thereby improving the tumor accumulation and antitumor efficacy of SN38. We developed the SN38 HDPNs for the first time and illustrated the underlying molecular mechanism of increasing the linker length to enhance the chemical and self-assembly stability of homodimeric prodrugs. These findings would provide new insights for the rational design of HDPNs with superior performance.

Secondary Structure in Amyloids in Relation to Their Wild Type Forms.

The amyloid structures and their wild type forms, available in the PDB database, provide the basis for comparative analyses. Globular proteins are characterised by a 3D spatial structure, while a chain in any amyloid fibril has a 2D structure. Another difference lies in the structuring of the hydrogen bond network. Amyloid forms theoretically engage all the NH and C=O groups of the peptide bonds in a chain with two hydrogen bonds each. In addition, the hydrogen bond network is highly ordered-as perpendicular to the plane of the chain. The β-structure segments provide the hydrogen bond system with an anti-parallel system. The folds appearing in the rectilinear propagation of the segment with the β-structure are caused by just by one of the residues in the sequence-residues with a Rα-helical or Lα-helical conformation. The antiparallel system of the hydrogen bonds in the β-structure sections at the site of the amino acid with a Rα- or Lα-helical conformation changes into a parallel system locally. This system also ensures that the involvement of the C=O and H-N groups in the construction of the interchain hydrogen bond, while maintaining a perpendicular orientation towards the plane of the chain. Conformational analysis at the level of the Phi and Psi angles indicates the presence of the conditions for the structures observed in the amyloids. The specificity of amyloid structures with the dominant conformation expressed as |Psi| = |Phi| reveals the system of organisation present in amyloid fibrils. The Phi, Psi angles, as present in this particular structure, transformed to form |Psi| = |Phi| appear to be ordered co-linearly. Therefore, the calculation of the correlation coefficient may express the distribution around this idealised localisation on the Ramachandran map. Additionally, when the outstanding points are eliminated, the part of amyloid chain can be classified as fulfilling the defined conditions. In addition, the presentation of the chain structure using geometric parameters, V-angle-the angle between the planes of the adjacent peptide bonds (angle versus the virtual axis Cα-Cα) and the radius of the curvature R, depending on the size of the angle V, allows for a quantitative assessment of changes during amyloid transformation.

Identification and structural basis of C-terminal cyclic imides as natural degrons for cereblon

Cereblon (CRBN) is a ubiquitously expressed E3 ligase substrate receptor and a key player in pharmaceutical targeted protein degradation. Despite substantial insight gained into its chemical ligand space that is exploited in small-molecule protein degraders, its cellular role and native mechanism of substrate recognition remained elusive so far. In this communication, we report the discovery of C-terminal aspartimide and aminoglutarimide residues as natural degron motifs that are recognized by CRBN with high specificity. These C-terminal cyclic imides are known to form in ageing proteins as a result of spontaneous chain breaks after an attack of an asparagine or glutamine side chain amide on the adjacent peptide bond, and thereby mark potentially malfunctional protein fragments. In crystal structures, we uncover that these C-terminal cyclic imides are bound in the same fashion as small-molecule CRBN modulators, and that the residues preceding the cyclic terminus contribute to the interaction with a sequence-unspecific backbone hydrogen bonding pattern with strictly conserved residues in CRBN. We postulate that C-terminal aspartimide and aminoglutarimide residues resulting from chain breaks are largely underappreciated protein damages and represent the native degrons of CRBN.

Exploring of catalytic oxygen reduction reaction activity of lattice carbons of vanadium and niobium doped nitrogen codoped carbon nanotubes by density functional theory

AbstractThe oxygen electroreduction mechanism on the V‐ and Nb‐doped nitrogen‐codoped (6,6)armchair carbon nanotube with incorporated MN4 fragment has been studied using the ωB97XD and PBE density functional theory approaches. The metal center in MN4 fragment and the adjacent NCCN double bond (C2 site) of the support have been revealed as active centers. The metal active centers turned out to be irreversibly oxidized at the first step of ORR affording stable O*, 2O*, or O*HO* adsorbates depending on the applied electrode potential U, that makes them no longer active in ORR. Therefore, the C2 site comes at the forefront in ORR catalysis. Among the metal oxidized forms M(O)N4, M(O)(O)N4, and M(O)(OH)N4CNT, the C2 site of the latter turned out to be most active for 4e dissociative ORR. For both metals the last protonation/electron transfer step, HO* + H* → H2O, is the rate‐limiting step. The alternative hydrogen peroxide formation is not only thermodynamically less favorable but also kinetically slower than the 4e dissociative ORR route on the C2 site of model M(O)(OH)N4CNT catalyst.

Finding Fluorine: Photoproduct Formation during the Photolysis of Fluorinated Pesticides.

The photolysis of pesticides with different fluorine motifs was evaluated to quantify the formation of fluorinated products in buffered aqueous systems, advanced oxidation (AOP) and reduction processes (ARP), and river water. Simulated sunlight quantum yields at pH 7 were 0.0033, 0.0025, 0.0015, and 0.00012 for penoxsulam, florasulam, sulfoxaflor, and fluroxypyr, respectively. The bimolecular rate constants with hydroxyl radicals were 2 to 5.7 × 1010 M-1 s-1 and, with sulfate radicals, 1.6 to 2.6 × 108 M-1 s-1 for penoxsulam, florasulam, and fluroxypyr, respectively. The rate constants of sulfoxaflor were 100-fold lower. Using quantitative 19F-NMR, complete fluorine mass balances were obtained. The maximum fluoride formation was 53.4 and 87.4% for penoxsulam and florasulam under ARP conditions, and 6.1 and 100% for sulfoxaflor and fluroxypyr under AOP conditions. Heteroaromatic CF3 and aliphatic CF2 groups were retained in multiple fluorinated photoproducts. Aryl F and heteroaromatic F groups were readily defluorinated to fluoride. CF3 and CF2 groups formed trifluoroacetate and difluoroacetate, and yields increased under oxidizing conditions. 19F-NMR chemical shifts and coupling analysis provided information on hydrogen loss on adjacent bonds or changes in chirality. Mass spectrometry results were consistent with the observed 19F-NMR products. These results will assist in selecting treatment processes for specific fluorine motifs and in the design of agrochemicals to reduce byproduct formation.

Intermolecular interactions in the crystalline structure of some polyhalogenated Di– And triamino Pyridines: Spectroscopical perspectives

Supramolecular synthon is identified as a unit and provides important structural and energetic information in the study of organic crystals. However, the direct estimation of the supramolecular interaction remains challenging. In the present work six polyhalogenated di– or triamino pyridines were synthesised, their crystalline structure was characterised, and corresponding supramolecular synthons were studied using a combination of quantum mechanical calculations and FT–IR and Raman spectroscopy. Some distinctive features were identified especially for three vibrational normal modes (RNMs) related to the pyridine ring (viz. RNM1, RNM3 and RNM7) in the vibrational spectra (FT–IR and Raman) of the solid samples, which are due to the supramolecular interactions, hydrogen bond (hb) in particular, according to the quantum mechanical calculations. The comparison between the IR and Raman spectra of experimental and simulated results indicates that the adjacent intermolecular hydrogen bonds between two same molecules extensively exist in the solid samples. Moreover, some quantitative correlation was established among the dimerisation energies for hb dimers (hb1 dimers for compounds 1 and 2), the ring structure defined by the distribution of the substituents and quantitative characteristics of the vibrational spectra, for instance, the splitting magnitudes for RNM3(2) in IR spectra and the peak gap between RNM1 and RNM2 in Raman spectra.

Acid Etching-Induced In Situ Growth of λ-MnO2 over CoMn Spinel for Low-Temperature Volatile Organic Compound Oxidation.

Surface lattice oxygen is crucial to the degradation of volatile organic compounds (VOCs) over transition metal oxides according to the Mars-van Krevelen mechanism. Herein, λ-MnO2 in situ grown on the surface of CoMn spinel was prepared by acid etching of corresponding spinel catalysts (CoMn-Hx-Ty) for VOC oxidation. Experimental and relevant theoretical exploration revealed that acid etching on the CoMn spinel surface could decrease the electron cloud density around the O atom and weaken the adjacent Mn-O bond due to the fracture of the surface Co-O bond, facilitating electron transfer and subsequently the activation of surface lattice oxygen. The obtained CoMn-H1-T1 exhibited an excellent catalytic performance with a 90% acetone conversion at 149 °C, which is 42 °C lower than that of CoMn spinel. Furthermore, the partially maintained spinel structure led to better stability than pure λ-MnO2. In situ diffuse reflectance infrared Fourier transform spectroscopy confirmed a possible degradation pathway where adsorptive acetone converted into formate and acetate species and into CO2, in which the consumption of acetate was identified as the rate-limiting step. This strategy can improve the catalytic performance of metal oxides by activating surface lattice oxygen, to broaden their application in VOC oxidation.

Effect of interlayer adherend inclusions on strength of composite bonded joints

Foreign objects such as backing tapes may get embedded between the plies of a laminated polymer composite during its fabrication which can compromise the composite panel or the adjacent bond joint. This paper investigates the effect of such inter-layer inclusion defects in laminated carbon fiber composite adherends, on the strength of an adjacent single lap bonded joints, using both experimental and computational methods. Composite laminates composed of 0° unidirectional lamina were fabricated with Polytetrafluoroethylene (PTFE) strips embedded between the first two plies closest to the bond line. Three different inclusion positions were investigated and the location of the inclusion defect yielding the lowest strength was identified. The inclusion location in the most compromised joint was then used to study the effect of this type of defect in adherends having different ply orientations. Finite Element (FE) stress analysis was performed to understand the variation in the shear and peel stresses due to the presence of the inclusion. FE analysis revealed higher shear and peel stresses in bonded joints adjacent to inclusion defects.

Activation or passivation: Influence of halogen dopant (F, Cl, Br) on photothermal activity of Mn2O3 in degrading toluene

Mn2O3 is an exceptional earth-abundant mineral that has been extensively applied in catalytic oxidation because of the strong redox couples like Mn3+/Mn2+ and Mn4+/Mn3+ exposed on Mn2O3 surface. Herein, the catalytic activity of Mn2O3 in photothermal degradation of toluene was regulated by halogens including F-, Cl-, and Br-. As the electronegativity ordered in F (3.98) > O (3.44) > Cl (3.16) > Br (2.96), F- doped Mn2O3 overperforms Cl- doped and Br- doped Mn2O3 in decomposing toluene. DFT theoretical calculation illustrates that F- attracts the shared electrons from Mn to itself, the deviated charge center stretches the adjacent Mn-O bonds and boosts the generation of abundant oxygen vacancies, helping to strengthen the catalytic activity of Mn2O3. Conversely, Mn-O bonds are shortened by Cl- and Br- that have lower electronegativity than O. The multiple electrons circling Cl- and Br- push Mn towards O and squeeze Mn-O bonds, resulting in the formation of passivated Mn2O3. In conjunction with Mn redox couples and oxygen vacancies, 99% of 400 ppm toluene can be eliminated by F- doped Mn2O3, corresponding mineralization rate is high up to 95.8%.