Electron Spin Resonance Measurements Research Articles

Humic acids as complexing agents to drive photo-Fenton at mild pH in saline matrices: Process performance and mechanistic studies

The role of iron complexation on (photo)-Fenton process at mild pH has been investigated; in particular, the effect of humic acids, their interaction with chlorides and the involvement of the target pollutants has been studied. For this purpose, solutions consisting in mixture of 6 pollutants (acetaminophen, acetamiprid, amoxicillin, caffeine, carbamazepine and clofibric acid) in different matrices ( a) distilled water, b) low salinity water (1 g·L−1 of Cl-), c) high salinity water (30 g·L−1 of Cl-), d) tap water and e) real sea water) have been irradiated with simulated sunlight with and without humic acids (10 mg L−1). The ability of humic acids to complex Fe(III) resulted in an enhancement of pollutants removal as prevented iron inactivation, but in highly saline waters were they were not able to displace completely Cl- as ligands for Fe(III) and in sea water where other species could also contribute to inhibit photo-Fenton. Furthermore, pollutants with phenolic and/or carboxylic moieties also contribute to keep iron active at pH = 5, most probably by complexation. This is in line with dissolved iron at the end of the experiment and hydrogen peroxide consumption. Electron spin resonance measurements of ·OH show a very good correlation between the radical formation and pollutants removal, indicating that in the presence of complexing agents, generation of ·OH is favoured. These results indicate that HA could be used as auxiliary to apply photo-Fenton in low salinity environments rather than in real seawater.

Electrometric and Electron Paramagnetic Resonance Measurements of a Difference in the Transmembrane Electrochemical Potential: Photosynthetic Subcellular Structures and Isolated Pigment-Protein Complexes.

A transmembrane difference in the electrochemical potentials of protons (ΔμH+) serves as a free energy intermediate in energy-transducing organelles of the living cell. The contributions of two components of the ΔμH+ (electrical, Δψ, and concentrational, ΔpH) to the overall ΔμH+ value depend on the nature and lipid composition of the energy-coupling membrane. In this review, we briefly consider several of the most common instrumental (electrometric and EPR) methods for numerical estimations of Δψ and ΔpH. In particular, the kinetics of the flash-induced electrometrical measurements of Δψ in bacterial chromatophores, isolated bacterial reaction centers, and Photosystems I and II of the oxygenic photosynthesis, as well as the use of pH-sensitive molecular indicators and kinetic data regarding pH-dependent electron transport in chloroplasts, have been reviewed. Further perspectives on the application of these methods to solve some fundamental and practical problems of membrane bioenergetics are discussed.

Mixed-Valence BN-Doped Corannulene Trimer Radical Cations.

Mixed-valence (MV) dimers have been extensively investigated, however, the structure and properties of purely organic MV trimers based on open-shell polycyclic aromatic hydrocarbons remain elusive. Herein, unprecedented MV BN-doped corannulene radical cations [BN-Cor1]3 ⋅⋅2+ ⋅ 2[BArylF 4 ]- and [BN-Cor2]3 ⋅⋅2+ ⋅ 2[BArylF 4 ]- were synthesized via chemical oxidation, and their structures were unambiguously confirmed by single-crystal X-ray diffraction. These uncommon radical cations consist of three corannulene cores and two [BArylF 4 ]- anions, and three corannulene motifs [BN-Cor1]3 ⋅⋅2+ and [BN-Cor2]3 ⋅⋅2+ in the unit cell exhibit a trimer structure with a slipped π-stacking configuration. Detailed structural analyses further revealed that the corannulene cores exhibit an infinite layered self-assembly configuration, allowing their potential applications as building blocks for molecular conductors. The detection of a forbidden transition (Δms =±2) by electron paramagnetic resonance (EPR) spectroscopy further confirmed the existence of two unpaired electrons in the π-trimers and the MV characteristic of these two species. Variable-temperature EPR and conductivity measurements suggested that the BN-doped π-trimers exhibited antiferromagnetic coupling and conductivity properties.

Mixed‐Valence BN‐Doped Corannulene Trimer Radical Cations

AbstractMixed‐valence (MV) dimers have been extensively investigated, however, the structure and properties of purely organic MV trimers based on open‐shell polycyclic aromatic hydrocarbons remain elusive. Herein, unprecedented MV BN‐doped corannulene radical cations [BN‐Cor1]3⋅⋅2+ ⋅ 2[BArylF4]− and [BN‐Cor2]3⋅⋅2+ ⋅ 2[BArylF4]− were synthesized via chemical oxidation, and their structures were unambiguously confirmed by single‐crystal X‐ray diffraction. These uncommon radical cations consist of three corannulene cores and two [BArylF4]− anions, and three corannulene motifs [BN‐Cor1]3⋅⋅2+ and [BN‐Cor2]3⋅⋅2+ in the unit cell exhibit a trimer structure with a slipped π‐stacking configuration. Detailed structural analyses further revealed that the corannulene cores exhibit an infinite layered self‐assembly configuration, allowing their potential applications as building blocks for molecular conductors. The detection of a forbidden transition (Δms=±2) by electron paramagnetic resonance (EPR) spectroscopy further confirmed the existence of two unpaired electrons in the π‐trimers and the MV characteristic of these two species. Variable‐temperature EPR and conductivity measurements suggested that the BN‐doped π‐trimers exhibited antiferromagnetic coupling and conductivity properties.

Probing chirality of crystals using electron paramagnetic resonance (EPR) spectroscopy

One of the most challenging tasks in analytical chemistry is the determination of the chirality (identification of an enantiomeric composition) in solids mainly because of the strict requirements of the pharmaceutical industry for enantiomerically pure drugs. Although there are a few methods available to accomplish enantio‑differentiation in solids, for example: X-ray diffraction (XRD), Thermogravimetric analysis (TGA), CD spectroscopy, and low-frequency (LF) Raman spectroscopy, this is still very challenging. In this work, we have developed a new method to measure the chirality of crystals, based on electron paramagnetic resonance (EPR) spectroscopy of chiral crystals doped with Cu2+ as the EPR active ion. Here, we demonstrate our approach using a model system of l- and DL-Histidine crystals doped with Cu2+. We show that EPR measurements of the Cu2+-doped Histidine crystals can accurately determine the chirality and enantiomeric composition of the crystals. We present a very preliminary example of this technique, and we hope that in the future it will be possible to refine and develop this method for many other chiral organic crystal systems.

Integrating Electron Paramagnetic Resonance Spectroscopy and Computational Modeling to Measure Protein Structure and Dynamics.

Electron paramagnetic resonance (EPR) has become a powerful probe of conformational heterogeneity and dynamics of biomolecules. In this Review, we discuss different computational modeling techniques that enrich the interpretation of EPR measurements of dynamics or distance restraints. A variety of spin labels are surveyed to provide a background for the discussion of modeling tools. Molecular dynamics (MD) simulations of models containing spin labels provide dynamical properties of biomolecules and their labels. These simulations can be used to predict EPR spectra, sample stable conformations and sample rotameric preferences of label sidechains. For molecular motions longer than milliseconds, enhanced sampling strategies and de novo prediction software incorporating or validated by EPR measurements are able to efficiently refine or predict protein conformations, respectively. To sample large-amplitude conformational transition, a coarse-grained or an atomistic weighted ensemble (WE) strategy can be guided with EPR insights. Looking forward, we anticipate an integrative strategy for efficient sampling of alternate conformations by de novo predictions, followed by validations by systematic EPR measurements and MD simulations. Continuous pathways between alternate states can be further sampled by WE-MD including all intermediate states.

A Heterometallic Porphyrin Dimer as a Potential Quantum Gate: Magneto‐Structural Correlations and Spin Coherence Properties

AbstractIn the development of two‐qubit quantum gates, precise control over the intramolecular spin‐spin interaction between molecular spin units plays a pivotal role. A weak but measurable exchange coupling is especially important for achieving selective spin addressability that allows controlled manipulation of the computational basis states |00⟩ |01⟩ |10⟩ |11⟩ by microwave pulses. Here, we report the synthesis and Electron Paramagnetic Resonance (EPR) study of a heterometallic meso‐meso (m‐m) singly‐linked VIVO−CuII porphyrin dimer. X‐band continuous wave EPR measurements in frozen solutions suggest a ferromagnetic exchange coupling of ca. 8 ⋅ 10−3 cm−1. This estimation is supported by Density Functional Theory calculations, which also allow disentangling the ferro‐ and antiferromagnetic contributions to the exchange. Pulsed EPR experiments show that the dimer maintains relaxation times similar to the monometallic CuII porphyrins. The addressability of the two individual spins is made possible by the different g‐tensors of VIV and CuII‐ions, in contrast to homometallic dimers where tilting of the porphyrin planes plays a key role. Therefore, single‐spin addressability in the heterometallic dimer can be maintained even with small tilting angles, as expected when deposited on surface, unlocking the full potential of molecular quantum gates for practical applications.

A Heterometallic Porphyrin Dimer as a Potential Quantum Gate: Magneto-Structural Correlations and Spin Coherence Properties.

In the development of two-qubit quantum gates, precise control over the intramolecular spin-spin interaction between molecular spin units plays a pivotal role. A weak but measurable exchange coupling is especially important for achieving selective spin addressability that allows controlled manipulation of the computational basis states |00⟩ |01⟩ |10⟩ |11⟩ by microwave pulses. Here, we report the synthesis and Electron Paramagnetic Resonance (EPR) study of a heterometallic meso-meso (m-m) singly-linked VIV O-CuII porphyrin dimer. X-band continuous wave EPR measurements in frozen solutions suggest a ferromagnetic exchange coupling of ca. 8 ⋅ 10-3 cm-1 . This estimation is supported by Density Functional Theory calculations, which also allow disentangling the ferro- and antiferromagnetic contributions to the exchange. Pulsed EPR experiments show that the dimer maintains relaxation times similar to the monometallic CuII porphyrins. The addressability of the two individual spins is made possible by the different g-tensors of VIV and CuII -ions, in contrast to homometallic dimers where tilting of the porphyrin planes plays a key role. Therefore, single-spin addressability in the heterometallic dimer can be maintained even with small tilting angles, as expected when deposited on surface, unlocking the full potential of molecular quantum gates for practical applications.

Experimental study of Cu(en)(H2O)2SO4 embedded into mesoporous silica matrix SBA-15 with the hexagonal arrangement of pores

In this work, we present an experimental study to find the optimal way of encapsulation of the magnetic quasi-two-dimensional system Cu(en)(H2O)2SO4 (en = ethylenediamine = C2H8N2) in mesoporous silica SBA-15 with hexagonal pore morphology with a pore size of 5 nm. Our main goal is to achieve the most significant possible degree of pore filling and to study the effect of encapsulation of complex Cu(en)(H2O)2SO4 in SBA-15 silica on the magnetic properties of the studied complex by means of electron paramagnetic resonance (EPR) and magnetization measurements. It was found that the adsorption equilibrium during the adsorption of the Cu(en)(H2O)2SO4 complex from the solution to SBA-15 was reached after only 24 h, and the samples prepared by adsorption for a longer time (72 h, 14 days) did not show an increased amount of the loaded complex. The degree of pore filling represents around 60 % of the total volume of internal pores. The analysis of temperature dependence of susceptibility, the field dependence of magnetization, and EPR spectra showed that due to the encapsulation of Cu(en)(H2O)2SO4 complex in mesoporous silica, the magnetic correlations between Cu(II) ions are significantly weakened, yielding paramagnetic behavior in the studied system.

Co single-atom C2N3 activates peroxymonosulfate for efficient degradation of sulfamethoxazole at 4 °C: A combined experimental and density functional theory study

The Fenton-like reactions for antibiotic degradation become very slow at low temperatures. To overcome this inadequacy, we prepared a rare CxNy allotrope, C2N3, by pyrolysis of HNO3 pretreated melamine and loaded with ultrahigh-density Co single atom (SA) to activate peroxymonosulfate (PMS) to remove sulfamethoxazole (SMX). Results showed that the removal rate of SMX reached 100 % at 4 °C within 8 min. The Co/C2N3-650 + PMS system achieved excellent degradation efficiency for simulated wastewater experiments and various interference factors. The catalyst could efficiently degrade a variety of antibiotics, and achieved more efficient degradation rate in alkaline wastewater. Electron paramagnetic resonance (EPR) measurements and quenching tests confirmed the primary role of singlet oxygen (1O2) in SMX degradation with PMS. Density functional theory (DFT) calculation verified the binding energy of CoN3 site and activation pathway for the different oxygen sites of PMS. The linear sweep voltammetry (LSV) and chronopotentiometry analysis revealed that the electrons of PMS were transferred to the CoN3 sites to form SO5•- intermediates, and proved the generation of 1O2 via the SO5•- self-reaction. This work reveals a new mechanism for the formation of 1O2 and opens up novel approach for SA heterogeneous catalysts in advanced oxidation processes (AOPs).

The aging of polyethylene mulch films in the presence of cadmium

To determine the fates of the persistent pollutants cadmium (Cd) and micro-plastics in agricultural soils, an in-depth understanding of the interactions between Cd and mulching film is required. In the present work, pot experiments are conducted under natural conditions to study the influence of various Cd concentrations on the aging process of polyethylene mulching film in soil collected from Changzhi, Shanxi Province. The results indicate that during 150 days, the aging degree of the mulch film increases gradually as the increased Cd concentration in the soil. Further, the results of attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectrometry and X-ray photoelectron spectroscopy (XPS) demonstrate that the average vinyl index (VI) of the aging mulch film increases from 1.29 to 1.82, while the oxygen-to-carbon (O/C) ratio of the mulch film decreases significantly from 0.344 to 0.045, as the Cd concentration is increased from 0 to 10 mg kg–1. When the aging time exceeds 90 days, the oxygen-containing functional groups (C–O and CO) generated consumed by the adsorbed Cd. In addition, electron paramagnetic resonance (EPR) measurements indicate that Cd both enhances the formation of hydroxyl radical (·OH) on the surface of the mulch film and prevents the combination of ·OH and electrons, thereby accelerating the aging of the mulch. Hence, the present study indicates that the presence of Cd will hasten the decomposition of mulch, which will inevitably result in the faster release of micro-plastics from the mulch into the soil environment.

Iron-loading N and S heteroatom doped porous carbon derived from chitosan and CdS-Tetrahymena thermophila for peroxymonosulfate activation

Transforming waste into resources is an important strategy to enhance the economic efficiency and reduce the waste entering the environment. In this work, iron-loading N and S co-doped porous carbon materials, as peroxymonosulfate (PMS) activator for pollutants degradation, were prepared by pyrolysis of the mixture of iron loading chitosan and CdS-Tetrahymena thermophila under N2 flow. Chitosan is mainly derived from the shell waste of shrimp and crab, and CdS-Tetrahymena thermophila is produced in the removing process of Cd2+ pollution bioremediation using Tetrahymena thermophila. The synergistic effects of iron related species and heteroatoms (S/N) co-doped porous carbon in the obtained carbon materials improved the performance for activating PMS. The prepared Fe-S-CS-1-900 exhibited high performance for the degradation of Rhodamine B (RhB) by activating PMS. Radical quenching tests and electron paramagnetic resonance measurements suggested that superoxide radical (O2−) and singlet oxygen (1O2) were the primary reactive oxygen species in RhB degradation. These results propose new insights of using biomass waste to derive Fe-loading N and S heteroatom co-doping carbon as PMS activator applied in the removal of organic pollutants.

Thin-film assembly via encapsulation of nano-aluminum oxide-linked-pb(II)-2,4-dinitroaniline complex into a polymeric matrix as efficient radiation shielding materials

Radiation safety and protection is a subject of major concern for all communities because of the biological damage caused by different radiation sources. Therefore, the purpose of this study is aimed to synthesize two different thin films from a newly synthesized N-Al2O3@Pb(II)-2,4-DiNA nanocomposite which was prepared by the direct chemical coupling of nano-aluminum oxide (N-Al2O3) with Pb(II)-2,4-dinitroaniline complex. The synthesized materials were characterized by FT-IR, thermogravimetric analysis (TGA), scanning electron microscope SEM, and elemental composition by energy-dispersive X-ray (EDX). The two thin films were assembled by the encapsulation of N-Al2O3@Pb(II)-2,4-DiNAnanocompositeinto hydrolyzed polyurethane and hydrolyzed polyvinyl chloride. Electron spin resonance (ESR) measurements have been used to investigate the newly prepared nanocomposite and thin films before and after gamma irradiation. Gamma spectroscopy, Phy-X software, and SRIM (stopping and range of ions in matter) Monte Carlo simulation code are aimed to apply and investigate radiation shielding efficiency of films for gamma/x-ray, protons, alpha, and thermal neutrons. The gamma shielding characteristics, mass stopping power (MSP), and range for both proton (H-ions) and alpha (He-ions) were also calculated. In addition, the SRIM code’s subroutine TRIM was used to predict the damage production and atomic displacements per atom (dpa) caused by the interaction of high-energy H-ions (proton) and He-ions (alpha) with the studied samples. The data obtained the good radiation shielding effect of the prepared thin films and their possible use as radiation shielding materials for X-rays and low gamma energy.

Preparation of magneto-electro-optically active polymer using Fe ionic liquid as electro-magnetic dopant

In this research, we report the synthesis of conjugated polymers with magnetism. Electrochemical polymerization in liquid crystal was conducted with 1-butyl-3-methylimidazolium tetrachloroferrate (BMITF), which is a paramagnetic character having a large magnetic susceptibility, as a supporting salt. The polymer films thus obtained had magnetism because BMITF remains in the films as a dopant. Poly(2,2′-bithiophene) and poly(bis-(3,4-ethylenedioxythiophene)) were prepared in nematic or cholesteric liquid crystal with BMITF by electrochemical polymerization. Transcription of the liquid crystal structure was succeeded with a small amount of BMITF. Blush or fingerprint structures were confirmed by polarizing optical microscopy observation. The addition of the excess amount of BMITF broke the structure of the liquid crystal. Poly(2,2′-bithiophene) transcribed the cholesteric liquid crystal structure showed a negative Cotton effect, indicating with left-handed helical structure. Poly(bis-(3,4-ethylenedioxythiophene)) transcribed the cholesteric liquid crystal structure showed a positive Cotton effect, indicating the polymer forms a right-handed helical structure. The X-ray photoelectron spectroscopy measurements, confirming the existence of Fe element in the polymers thus obtained. From the electron spin resonance measurements, the polymers thus obtained showed magnetic activity. This method affords facile synthesis of conjugated polymers with magnetism.

Unraveling Triplet Formation Mechanisms in Acenothiophene Chromophores.

The evolution of molecular platforms for singlet fission (SF) chromophores has fueled the quest for new compounds capable of generating triplets quantitatively at fast time scales. As the exploration of molecular motifs for SF has diversified, a key challenge has emerged in identifying when the criteria for SF have been satisfied. Here, we show how covalently bound molecular dimers uniquely provide a set of characteristic optical markers that can be used to distinguish triplet pair formation from processes that generate an individual triplet. These markers are contained within (i) triplet charge-transfer excited state absorption features, (ii) kinetic signatures of triplet-triplet annihilation processes, and (iii) the modulation of triplet formation rates using bridging moieties between chromophores. Our assignments are verified by time-resolved electron paramagnetic resonance (EPR) measurements, which directly identify triplet pairs by their electron spin and polarization patterns. We apply these diagnostic criteria to dimers of acenothiophene derivatives in solution that were recently reported to undergo efficient intermolecular SF in condensed media. While the electronic structure of these heteroatom-containing chromophores can be broadly tuned, the effect of their enhanced spin-orbit coupling and low-energy nonbonding orbitals on their SF dynamics has not been fully determined. We find that SF is fast and efficient in tetracenothiophene but that anthradithiophene exhibits fast intersystem crossing due to modifications of the singlet and triplet excited state energies upon functionalization of the heterocycle. We conclude that it is not sufficient to assign SF based on comparisons of the triplet formation kinetics between monomer and multichromophore systems.

Synthesis, Spectroscopy, and Structure of [FeRu(μ-dithiolate)(CN)2(CO)4]2.

The salt [K(18-crown-6)]2[Ru(CN)2(CO)3] ([K(18-crown-6)]2[1]) was generated by the reaction of Ru(C2H4)(CO)4 with [K(18-crown-6)]CN. An initial thermal reaction gives [Ru(CN)(CO)4]-, which, upon ultraviolet (UV) irradiation, reacts with a second equiv of CN-. Protonation of [1]2- gave [HRu(CN)2(CO)3]- ([H1]-), which was isolated as a single isomer with mutually trans cyanide ligands. The complex cis,cis,cis-[Ru(pdt)(CN)2(CO)2]2- ([2]2-) was prepared by the UV-induced reaction of [1]2- with propanedithiol (pdtH2). The corresponding iron complex cis,cis,cis-[Fe(pdt)(CN)2(CO)2]2- ([3]2-) was prepared similarly. The pdt complexes [2]2- and [3]2- were treated with Fe(benzylideneacetone)(CO)3 to give, respectively, [RuFe (μ-pdt)(CN)2(CO)4]2- ([5]2-) and [Fe2(μ-pdt)(CN)2(CO)4]2- ([4]2-). The pathway from [3]2- to Fe2 complex [4]2- implicates intermetallic migration of CN-. In contrast, the formation of [5]2- leaves the Ru(CN)2(CO) center intact, as confirmed by X-ray crystallography. The structure of [5]2- features a "rotated" square-pyramidal Fe(CO)2(μ-CO) site. NMR measurements indicate that the octahedral Ru site is stereochemically rigid, whereas the Fe site dynamically undergoes turnstile rotation. 57Fe Mössbauer spectral parameters are very similar for rotated [5]2- and unrotated Fe2 complex [4]2-, indicating the insensitivity of that technique to both the geometry and the oxidation state of the Fe site. According to cyclic voltammetry, [5]2- oxidizes at E1/2 ∼ -0.8 V vs Fc+/0. Electron paramagnetic resonance (EPR) measurements show that 1e- oxidation of [5]2- gives an S = 1/2 rhombic species, consistent with the formulation Ru(II)Fe(I), related to the Hox state of the [FeFe] hydrogenases. Density functional theory (DFT) studies reproduce the structure, 1H NMR shifts, and infrared (IR) spectra observed for [5]2-. Related homometallic complexes with both cyanides on a single metal are predicted to not adopt rotated structures. These data suggest that [5]2- is best described as Ru(II)Fe(0). This conclusion raises the possibility that for some reduced states of the [FeFe]-hydrogenases, the [2Fe]H site may be better described as Fe(II)Fe(0) than Fe(I)Fe(I).

1D/0D heterostructured ZnIn2S4@ZnO S-scheme photocatalysts for improved H2O2 preparation

Solar photocatalysis is a promising, green, and sustainable technique for the synthesis of H2O2. In this study, low-dimensional ZnO/ZnIn2S4 S-scheme heterojunction photocatalysts are fabricated using electrostatic spinning and chemical bath deposition methods for the efficient photocatalytic production of H2O2. ZnO nanofibers loaded with 20 wt% ZnIn2S4 exhibit a superior H2O2 production rate of 928 μmol g−1 h−1, which is more than four times higher than that seen in pristine hexagonal phase ZnO and ZnIn2S4. First-principles calculations and in-situ X-ray photoelectron spectroscopy reveal the charge separation and transfer mechanisms in the S-scheme heterojunction. The construction of the S-scheme heterojunction facilitates the spatial separation of charge carriers, and electrons and holes with higher redox abilities are retained. Photoelectrochemical and photoluminescence tests further show that the formation of an S-scheme heterojunction is beneficial for the separation of photoinduced charge carriers. Electrochemical tests and electron paramagnetic resonance measurements indicate that H2O2 production is primarily via a two-step single-electron O2 reduction path. This study provides a new approach for the construction of S-scheme heterojunction materials that can efficiently produce H2O2 under solar irradiation.

Novel azo metal chelates of 3-aminophthalhydrazide derivative: Structural investigation, evaluation of DNA cleavage, anticancer and molecular docking studies

Transition bivalent metal ion (Mn, Co, Ni, Cu, and Zn) complexes derived from an azo ligand (HLCU) having 1,3-diketone moiety with 3-aminophthalhydrazide were prepared and characterized by using elemental analyses, ultraviolet–visible, Fourier transform infrared, nuclear magnetic resonance (1H, 13C), electron spin resonance, molar conductivity and magnetic measurement studies. Molar conductivity value indicated the non-electrolytic nature of all complexes. The ligand coordinates with the metal ion as a tridentate pattern and the binding sites are carbonyl oxygen, hydrazo nitrogen and hydroxy oxygen of phthalhydrazide moiety. The fluorescence spectra of the compounds were recorded and the results revealed that ligand have higher emission intensity than metal complexes. The X-ray powder diffraction indicated that the ligand (HLCU) and nickel(II) complex have orthorhombic crystal lattices. The ligand and metal complexes were subjected to DNA cleavage activity on pUC18 plasmid DNA using the gel electrophoresis method. The cobalt(II) complex completely cleaved DNA and other compounds showing higher cleaving activity than the control. The antitumor activity of the compounds was screened using sulforhodamine B assay towards the breast cancer and leukaemia cancer cell lines. Manganese(II), cobalt(II) and nickel(II) complexes have more promising activity, and the IC50 value is < 10 μg/mL against the leukaemia carcinoma cell line, which is equally potent as the positive control (adriamycin). The molecular docking study was used to find the binding mode of ligand and complexes of cobalt(II) and nickel(II) towards the molecular target protein receptor. The binding affinity of these compounds is −9.8, −13.6 and −10.5 kcal/mol respectively. The cobalt(II) complex has a more effective binding nature than the ligand and nickel(II) complex. Drug-likeness character indicates moderate activity of HLCU, and [Co(HLCU)(H2O)3], [Ni(HLCU)H2O] complexes, in agreement with invitro results.

Activation of peroxymonosulfate by Cu–Ni–Fe layered double oxides for degradation of butyl 4-hydroxybenzoate: Synergistic effect of oxygen vacancy and Cu(I)

In this study, Cu hybridization coupling oxygen defect engineering was adopted to synthesis of CuNiFe layered double oxides (CuNiFe-LDOs) in peroxymonosulfate (PMS) activation for degradation of methyl 4-hydroxybenzoate. The morphology and crystal structure of CuNiFe-LDOs was characterized in detail, which exhibited regular layered-structure at a Cu:Ni doping ratio of 1:1 and annealing temperature of 400 °C, and presented the crystal of CuxO@Fe3O4–NiO. Besides, the X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR) results demonstrated that abundant oxygen vacancies (OVs) and low oxidation state Cu species were composed in CuNiFe-LDOs400. The Cu1·5Ni1·5Fe1-LDOs400/PMS system showed excellent catalytic performance toward the degradation of butyl 4-hydroxybenzoate (BuP), and resistant to the effect of pH value and background inorganic anions. Based on quenching experiments and EPR measurements, singlet oxygen (1O2) was identified as the dominant active species during the heterogeneous catalytic process, which was generated by the synergistic interaction between OVs-Cu(I) site and PMS. In this process, the electron-drawing property of OVs promoted the adsorption of PMS molecule on Cu(I) site, followed by the accumulation of electron and cleavage of O–O bond to generate intermediate oxygen radical species, which donated one electron to eventually generate singlet oxygen.

Microbial-assisted synthesis of Schwertmannite@g-C3N4 composite for bisphenol AF degradation through visible light-driven peroxymonosulfate activation

Iron-based materials are considered as excellent environmental catalysts due to the characteristics of abundant reserves, low biological toxicities, and rich chemical states for redox reactions. The sea urchin-like microscopic morphology of biosynthesized schwertmannite (Sch) with abundant surface active sites is beneficial to the environmental catalytic process. In this study, flake-type graphitic carbon nitride (g-C3N4) was introduced into the mineralization process of Acidithiobacillus ferrooxidans (A. ferrooxidans) as the additive to regulate the biomineralization process and directly control the morphology and structure of iron-based minerals. Schwertmannite@g-C3N4 composites (Sch-CN) with a desired structure of sea urchin-like well-dispersed biosynthesized Sch loaded on flaky g-C3N4 were successfully prepared by A. ferrooxidans-induced biomineralization process. A Light/Peroxymonosulfate/Sch-CN catalytic system was constructed to degrade the model organic pollutant bisphenol AF (BPAF). The system combined two advanced oxidation systems of photocatalysis and peroxymonosulfate (PMS) activation, showing excellent catalytic degradation ability and wide pH adaptability. In addition, the system was also applicable to the catalytic degradation of other bisphenol pollutants. The mechanism was deduced by the results of quenching experiments and electron paramagnetic resonance (EPR) measurements. Several degradation intermediate products were identified and the probable degradation pathways of BPAF were proposed. The toxicity activities of BPAF solution towards Raphidocelis subcapitata were largely reduced after treatment by the photochemical process. Overall, the Light/PMS/Sch-CN system has great potential in treating bisphenol wastewater.