Electron Paramagnetic Resonance Research Articles

Honey induces changes in the molecular structure and microstructure of gluten in wheat-rye sourdoughs.

Chemical oxidizers and redox enzymes have traditionally been used to enhance the quality of baked goods. However, consumers now seek natural and clean-label ingredients, avoiding those with chemical-sounding names. Honey, a natural source of glucose oxidase (GOX), represents a promising alternative to purified enzymes for baking purposes. This study aimed to evaluate the effect of honey on the molecular structure and microstructure of gluten proteins in sourdough fermented by different lactic acid bacteria (LAB) strains. Four wheat-rye (1:1) sourdoughs were prepared, each supplemented with honey and inoculated with a different LAB strain. Additionally, two uninoculated doughs, one with honey (honey dough) and the other without (control dough), were prepared under identical conditions. Electronic paramagnetic resonance spectroscopy revealed the presence of hydrogen peroxide in honey solutions, indicating its role as an active source of GOX. Raman spectroscopy showed that honey addition altered the molecular structure of gluten by increasing the proportion of random coils at the expense of α-helix structures. This change is likely attributed to the competition between honey sugars and gluten proteins for water molecules in this system. Moreover, honey led to a decrease in the free sulfhydryl content of gluten compared to the control dough, suggesting an increase in disulfide crosslinking points. These enhanced protein-protein interactions were observed in scanning electron microscopy micrographs as a coarse gluten network composed of interconnected strands and fibrils. All LAB strains exhibited optimal acidification (pH < 4.3) in honey-supplemented sourdoughs, promoting the hydrolysis of gluten proteins into smaller fragments. Overall, honey-supplemented sourdoughs showed a gradual increase in the β-sheet content while decreasing the proportion of random coils over time. This trend suggests that the polypeptide fragments interacted through interchain hydrogen bonds, leading to a more ordered structure, which likely contributes to providing dough with good baking aptitude.

S‐Scheme g‐C3N4/CdS Heterostructures Grafting Single Pd Atoms for Ultrafast Charge Transport and Efficient Visible‐Light‐Driven H2 Evolution

AbstractEmerging step‐scheme (S‐scheme) heterostructures hold unique superiority in steering directional charge transport and reinforcing redox capacity, yet rational modification of S‐scheme heterostructures by single atoms (SAs) for efficient photocatalytic H2 evolution is rarely reported. In this work, Pd SAs‐modulated organic–inorganic g‐C3N4/CdS S‐scheme heterostructures are designed and prepared by a one‐pot mechanochemical approach allowing for g‐C3N4 nanosheets/CdS nanoparticles to confine atomically dispersed Pd co‐catalysts. The g‐C3N4/CdS S‐scheme charge‐transfer pathway is corroborated by a combination of in situ irradiated X‐ray photoelectron spectroscopy, electron paramagnetic resonance, and Kelvin probe force microscopy. Density functional theory (DFT) calculations, high‐angle annular dark‐field scanning transmission electron microscopy, and X‐ray absorption fine structure identify Pd‐S3 and Pd‐N2 atomic moieties underpinned by the electronic interaction between Pd SAs and g‐C3N4/CdS heterostructures, in which the d‐band center of Pd SAs is optimized for proton adsorption thermodynamically. Further, the g‐C3N4/CdS S‐scheme heterostructures alongside Pd SAs in concert boost the rapid migration of photogenerated electrons (1.05 ps) via Pd─S and Pd─N bond‐derived channels. A maximal H2 evolution rate of 85.66 mmol h−1 g−1 is achieved by 1 wt% Pd‐20 wt% g‐C3N4/CdS hierarchical composites. This work may guide the design of high‐efficiency S‐scheme‐based photocatalysts for solar‐to‐H2 conversion and beyond.

The Influence of Blood and Serum Microenvironment on Spin-Labeled Magnetic Nanoparticles

The investigation and clarification of the properties of surface-functionalized superparamagnetic nanoparticles in a biological environment are key challenges prior to their medical applications. In the present work, electron paramagnetic resonance spectroscopy (EPR) combined with the spin labeling technique was utilized to better understand the behavior of nitroxides attached to magnetite nanoparticles dispersed in body fluid. EPR spectra of spin-labeled, silane-coated Fe3O4 nanoparticles in human serum and whole blood were recorded and analyzed for both room- and low-temperature values. In all cases, the obtained EPR signal consisted of a broad line from magnetite cores and a characteristic signal from the attached 4-Amino-2,2,6,6-tetramethylpiperidine-1-oxyl (4-amino-TEMPO). Even for liquid samples, the anisotropic components of magnetic tensors did not fully average out, which was reflected in the differences in the intensity of three narrow hyperfine lines from nitroxide. At 230 K the irregular slow-motion signal from the attached radical was also simulated using the EasySpin toolbox, which allowed to determine the parameters related to magnetic tensors and the dynamics of the spin label. The study showed that the anisotropy of the motion of the spin label 4-amino-TEMPO reflects its interactions with the surrounding medium and the manner of the attachment of the nitroxide to the surface of nanoparticles.

Directional TV algorithm for image reconstruction from sparse-view projections in EPR imaging.

Electron paramagnetic resonance (EPR) imaging is an advanced in vivo oxygen imaging modality. The main drawback of EPR imaging is the long scanning time. Sparse-view projections collection is an effective fast scanning pattern. However, the commonly-used filtered backprojection (FBP) algorithm is not competent to accurately reconstruct images from sparse-view projections because of the severe streak artifacts. The aim of this work is to develop an advanced algorithm for sparse reconstruction of 3D EPR imaging. The optimization based algorithms including the total variation (TV) algorithm have proven to be effective in sparse reconstruction in EPR imaging. To further improve the reconstruction accuracy, we propose the directional TV (DTV) model and derive its Chambolle-Pock (CP) solving algorithm. After the algorithm correctness validation on simulation data, we explore the sparse reconstruction capability of the DTV algorithm via a simulated six-sphere phantom and two real bottle phantoms filled with OX063 trityl solution and scanned by an EPR imager with a magnetic field strength of 250G. Both the simulated and real data experiments show that the DTV algorithm is superior to the existing FBP and TV-type algorithms and a deep learning based method according to visual inspection and quantitative evaluations in sparse reconstruction of EPR imaging. These insights gained in this work may be used in the development of fast EPR imaging workflow of practical significance.

Field-Induced Slow Magnetization Relaxation of a Tetrahedral S=2 FeIIS4-Containing Complex.

In the work described herein, the spin relaxation properties of the mononuclear tetrahedral S = 2 [Fe{(SPiPr2)2N}2] complex (1) were studied by employing static and dynamic magnetic measurements al liquid helium temperatures. In the absence of an external direct current (DC) magnetic field, 1 exhibits fast magnetization relaxation. However, in the presence of external magnetic fields of a few kOe, slow relaxation is induced as monitored by alternating current (AC) magnetic susceptibility measurements up to 10 kHz, in the temperature range 2-5 K. Analysis of the temperature dependence of the corresponding relaxation time reveals contributions by Quantum Tunnelling of Magnetization, and the Direct and Orbach processes in the magnetization relaxation mechanism of 1. The energy barrier, Ueff, of the Orbach process, as determined by this analysis, is compared with that related to the zero field splitting parameters of 1 which were previously determined by high- frequency and -field electron paramagnetic resonance and Mössbauer spectroscopies.

The Use of Spectroscopic Methods to Study Organic Matter in Virgin and Arable Soils: A Scoping Review

The use of modern spectroscopic methods of analysis, which provide extensive information on the chemical nature of substances, significantly expands our understanding of the molecular composition and properties of soil organic matter (SOM) and its transformation and stabilization processes in various ecosystems and geochemical conditions. The aim of this review is to identify and analyze studies related to the application of nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) spectroscopy techniques to study the molecular composition and transformation of organic matter in virgin and arable soils. This article is mainly based on three research questions: (1) Which NMR spectroscopy techniques are used to study SOM, and what are their disadvantages and advantages? (2) How is the NMR spectroscopy technique used to study the molecular structure of different pools of SOM? (3) How is ESR spectroscopy used in SOM chemistry, and what are its advantages and limitations? Relevant studies published between 1996 and 2024 were searched in four databases: eLIBRARY, MDPI, ScienceDirect and Springer. We excluded non-English-language articles, review articles, non-peer-reviewed articles and other non-article publications, as well as publications that were not available according to the search protocols. Exclusion criteria for articles were studies that used NMR and EPR techniques to study non-SOM and where these techniques were not the primary methods. Our scoping review found that both solid-state and solution-state NMR spectroscopy are commonly used to study the structure of soil organic matter (SOM). Solution-phase NMR is particularly useful for studying soluble SOM components of a low molecular weight, whereas solid-phase NMR offers advantages such as higher 13C atom concentration for stronger signals and faster analysis time. However, solution-phase NMR has limitations including sample insolubility, potential signal aggregation and reduced sensitivity and resolution. Solid-state NMR is better at detecting non-protonated carbon atoms and identifying heterogeneous regions within structures. EPR spectroscopy, on the other hand, offers significant advantages in experimental biochemistry due to its high sensitivity and ability to provide detailed information about substances containing free radicals (FRs), aiding in the assessment of their reactivity and transformations. Understanding the FR structure in biopolymers can help to study the formation and transformation of SOM. The integration of two- and three-dimensional NMR spectroscopy with other analytical methods, such as chromatography, mass spectrometry, etc., provides a more comprehensive approach to deciphering the complex composition of SOM than one-dimensional techniques alone.

Copper(II) coordination to the intrinsically disordered region of SARS-CoV-2 Nsp1

The intrinsically disordered C-terminal peptide region of severe acute respiratory syndrome coronavirus 2 nonstructural protein-1 (Nsp1-CT) inhibits host protein synthesis by blocking messenger RNA (mRNA) access to the 40S ribosome entrance tunnel. Aqueous copper(II) ions bind to the disordered peptide with micromolar affinity, creating a possible strategy to restore protein synthesis during host infection. Electron paramagnetic resonance (EPR) and tryptophan fluorescence measurements on a 10-residue model of the disordered protein region (Nsp1-CT 10 ), combined with advanced quantum mechanics calculations, suggest that the peptide binds to copper(II) as a multidentate ligand. Two optimized computational models of the copper(II)-peptide complexes were derived: One corresponding to pH 6.5 and the other describing the complex at pH 7.5 to 8.5. Simulated EPR spectra based on the calculated model structures are in good agreement with experimental spectra.

Ultrasound enhances the removal of V5+ in wastewater by ball-milled zero-valent iron: Effects and mechanisms

Vanadium is considered to be a harmful industrial pollutant that poses a serious threat to health. In this study, the effect of ultrasonic-enhanced ball milling zero-valent iron removal of vanadium in wastewater was investigated and the basic mechanism of this process was elucidated. The results of the study confirmed that the ultrasonic intervention significantly accelerated the vanadium removal rate and greatly shortened the time required to achieve equilibrium. Under certain experimental conditions, the removal efficiency of vanadium under ultrasonic conditions is 99.1 %, which is 1.4 times higher than that of the traditional constant-temperature water bath device (70.86 %). Analytical techniques such as electron paramagnetic resonance (EPR) and ultraviolet (UV) spectroscopy have confirmed that ultrasonic-induced cavitation and microjet phenomena actively stimulate the formation of more H radicals and Fe2+. The key role of Fe2+ in the removal reaction was further explored and confirmed by a quenching experiment. Through fitting the experimental data of different isothermal adsorption models and reaction kinetics, it is concluded that the adsorption process conforms to the pseudo-second-order kinetics and the Langmuir isothermal model. The adsorption process is dominated by chemisorption, and the maximum adsorption capacity is 153.033 mg·g−1. X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and other analyses show that under the action of ultrasonic waves, V5+ is rapidly reduced to its lower oxidation state through reduction within the first 10 min of the reaction. Secondly, as the reaction progresses and the pH value increases, electrostatic adsorption and coprecipitation are involved in the removal reaction.

Spectroscopic, electrochemical, and kinetic trends in Fe(III)-thiolate disproportionation near physiologic pH.

In addition to its primary oxygen-atom-transfer function, cysteamine dioxygenase (ADO) exhibits a relatively understudied anaerobic disproportionation reaction (ADO-Fe(III)-SR → ADO-Fe(II) + ½ RSSR) with its native substrates. Inspired by ADO disproportionation reactivity, we employ [Fe(tacn)Cl3] (tacn = 1,4,7-triazacyclononane) as a precursor for generating Fe(III)-thiolate model complexes in buffered aqueous media. A series of Fe(III)-thiolate model complexes are generated in situ using aqueous [Fe(tacn)Cl3] and thiol-containing ligands cysteamine, penicillamine, mercaptopropionate, cysteine, cysteine methyl ester, N-acetylcysteine, and N-acetylcysteine methyl ester. We observe trends in UV-Vis and electron paramagnetic resonance (EPR) spectra, disproportionation rate constants, and cathodic peak potentials as a function of thiol ligand. These trends will be useful in rationalizing substrate-dependent Fe(III)-thiolate disproportionation reactions in metalloenzymes.

Synthesis, Spectral Characteristics, Sensing Properties and Microbiological Activity of New Water-Soluble 4-Sulfo-1,8-naphthalimides

A new water-soluble polyamidoamine (PAMAM) dendrimer modified with 4-sulfo-1,8-naphthalimide (DSNI) and its monomeric structural analogue (MSDI) were synthesized. Their photophysical properties were investigated in organic solvents of different polarities and aqueous solutions. The effect of pH on fluorescence intensity was determined. It was found that the dendrimer emits blue fluorescence in an acidic medium, which is quenched in an alkaline environment. This phenomenon is due to the possibility of suppression of nonradiative photoinduced electron transfer in acidic media. The influence of different metal ions (Cu2+, Pb2+, Sn2+, Sr2+, Mg2+, Ba2+, Co2+, Hg2+, Zn2+, Ni2+, Fe3+, Al3+) and anions (CN−, S2−, S2O52−, HPO42−, H2PO4−, F−, CH3COO−, NO2−, CO32−, SO42−) on the intensity of the emitted fluorescence was studied. Quenching was only found in the presence of Cu2+. This makes the dendrimer suitable for determining copper ions in water solutions in the presence of other metal ions and anions. Additionally, DSNI was used as a ligand to obtain a stable copper complex, the structure of which was investigated by electron paramagnetic resonance (EPR), infrared spectrum, and elemental analysis. Two copper ions were found to form a complex with one dendrimer. The in vitro microbiological activity of the new compounds against bacteria Pseudomonas aeruginosa and two viruses HRSV-2 and HAdV-5 was investigated. With a view to obtaining antibacterial and anti-viral textiles, cotton fabrics were treated with the three compounds, and then their activity against the same microbial strains was investigated. It was found that the microbiological activity was preserved after the application of the new compounds to the cotton fabrics.

Bovine Serum Albumin Effect on Collapsing PNIPAM Chains in Aqueous Solutions: Spin Label and Spin Probe Study

The influence of bovine serum albumin (BSA) on collapsing poly(N-isopropylacrylamide) (PNIPAM) chains was studied with turbidimetry and spin probe and spin label electron paramagnetic resonance spectroscopy. An increased ratio of collapsed chains in aqueous solutions in the narrow temperature region near the LCST appeared in the presence of 2.5–10 wt% BSA. The spin probe EPR data indicate that the inner cavities of the BSA dimers are probably responsive to the capture of small hydrophobic or amphiphilic molecules, such as TEMPO nitroxyl radical. The observed features of the structure and dynamics of inhomogeneities of aqueous PNIPAM-BSA solutions, including their mutual influence on the behavior of the polymer and protein below the LCST, should be considered when developing and investigating PNIPAM-based drug delivery systems.

Revealing the Singlet Fission Mechanism for a Silane-Bridged Thienotetracene Dimer.

Tetraceno[2,3-b]thiophene is regarded as a strong candidate for singlet fission-based solar cell applications due to its mixed characteristics of tetracene and pentacene that balance exothermicity and triplet energy. An electronically weakly coupled tetraceno[2,3-b]thiophene dimer (Et2Si(TIPSTT)2) with a single silicon atom bridge has been synthesized, providing a new platform to investigate the singlet fission mechanism involving the two acene chromophores. We study the excited state dynamics of Et2Si(TIPSTT)2 by monitoring the evolution of multiexciton coupled triplet states, 1TT to 5TT to 3TT to T1 + S0, upon photoexcitation with transient absorption, temperature-dependent transient absorption, and transient/pulsed electron paramagnetic resonance spectroscopies. We find that the photoexcited singlet lifetime is 107 ps, with 90% evolving to form the TT state, and the complicated evolution between the multiexciton states is unraveled, which can be an important reference for future efforts toward tetraceno[2,3-b]thiophene-based singlet fission solar cells.

Enhancement of microplastics degradation with MIL-101 modified BiOI photocatalyst under light and dark alternated system

The composite material combining BiOI with metal-organic frameworks, was developed as catalyst for microplastics degradation. The preparation was modified to achieve the optimal composite catalyst BiOI/MIL-101–40%. The composites exhibited a larger surface area, superior photo-activity, and a distinct heterojunction structure, which accelerated the separation of electrons and holes. Besides, the inclusion of Fe(II) within MIL-101 could construct a photo-Fenton reaction upon the addition of H2O2 in the solution. The carbonyl index of treated polyethylene microplastics increased by 0.127 after 6 h reaction, which was 5.3 and 3.7 times higher than monomer BiOI and MIL-101, respectively. Efficient electron-hole separation and Fe(III)/Fe(II) conversion improved the rate-limiting step of the Fenton process, leading to a synergistic effect between photocatalysis and Fenton reaction, significantly enhancing PE degradation efficiency. Electron spin resonance spectroscopy and selective radical quenching experiments were performed to detect the active components, and the main active species proved to be the hydroxyl radical and the hole. The band structure of the photocatalyst and intermediate products in the reaction solution were subsequently analyzed, leading to the inference of potential reaction mechanisms and pathways. The catalyst-built Fenton system demonstrated outstanding proficiency even under alternating light and dark conditions. The extracted microplastic samples also confirmed the feasibility of this system for complex samples. In conclusion, this study highlighted a green and efficient approach that may be used in future industrial applications to combat microplastic pollution.

α-Cleavage of 2,2-Diazido-2,3-dihydroinden-1-one in Solution and Cryogenic Matrices.

The Norrish type I (α-cleavage) reaction is an excellent photochemical method for radical-pair formation in solution. However, in cryogenic matrices, the starting material typically re-forms before the radical pair diffuses apart. This study focused on N2 extrusion from an azido alkyl radical to prevent radical-pair recombination. Irradiation of 2,2-diazido-2,3-dihydroinden-1-one (1) in methanol mainly yielded methyl 2-cyanomethylbenzoate (2) and 2-cyanomethylbenzoic acid (3) via α-cleavage. Laser flash photolysis of 1 in argon-saturated acetonitrile resulted in α-cleavage to form triplet biradical 31Br1 (λmax ∼ 410 nm, τ ∼ 400 ns). In contrast, upon irradiation in glassy 2-methyltetrahydrofuran matrices, triplet alkylnitrene 31N was directly detected using electron spin resonance (D/hc = 1.5646 cm-1, E/hc = 0.00161 cm-1) and absorption spectroscopy (λmax = 276 and 341 nm). Irradiation of 1 in argon matrices generated 31N, benzoyl azide 4, singlet benzoylnitrene 14N, and isocyanide 5, as revealed by IR spectroscopy. The experimental results supported by density functional theory calculations [B3PW91/6-311++G(d,p)] suggest that irradiation of 1 in matrices results in α-cleavage to form biradical 31Br1, which extrudes N2 to yield 31Br2. Rearrangement of 31Br2 into 31N competes with cleavage of a N3 radical to form radical 1Ra3. The N3/1Ra3 radical pair combines to form 4, which upon irradiation yields 14N and 5.

Non-radical activation of peroxymonosulfate by modified activated carbon for efficient degradation of oxytetracycline: Mechanisms and applications

The application of heterogeneous metal-free catalysis for non-radical peroxymonosulfate (PMS) oxidation is of great significance because of its low environmental effects and mild oxidant dosage. The purpose of this study was to investigate the activation mechanism of PMS using acid-modified activated carbon and oxytetracycline (OTC) as a representative pollutant. Modified activated carbon (MAC)/PMS system was capable of achieving 100 % degradation efficiency of OTC within 60 min, with an observed rate constant (kobs) of 0.0414 min−1. The degradation of OTC is dominated by non-radical oxidation pathways involved in mediated singlet oxygen (1O2) and electron-transfer process through electron paramagnetic resonance (EPR) and radicals quenching studies. The activation of PMS is attributed to the structural defects of MAC, persistent free radicals, and oxygen functional groups such as C-OOH. Moreover, the MAC/PMS system consistently demonstrates high and reliable contaminant removal in various water matrices. A continuous-flow device utilizing MAC shows excellent performance in purifying micro-polluted water. Additionally, the degradation pathways of pollutants and changes in toxicity during the degradation process were identified through density functional theory (DFT) calculations, liquid chromatography-mass spectrometry (LC-MS), and toxicological analysis. Finally, the cultivation of green beans, peas, and wheat was found to significantly decrease the toxicity of contaminated water through degradation. This study proposes a low-cost method to enhance the activation pathway of non-radical PMS by utilizing modified activated carbon materials for pollutant remediation.

Ruthenium decorated nickel-iron layered double hydroxides (NiFe-LDH) for promoting peroxymonosulfate activation and atrazine degradation

With the extensive use of atrazine (ATZ), its potential hazards to ecological environment and human health have raised public concerns. This study reports the effective degradation of ATZ via advanced oxidation processes (AOPs) using peroxymonosulfate (PMS) activated by heterogeneous catalysts of Ru loaded NiFe-LDH blossom nanosheets (Ru/NiFe-LDH). During AOPs, the highly dispersed Ru sites as the main catalytic centers and the NiFe-LDH substrate synergistically stimulated PMS to efficiently produce reactive oxygen species to oxidize ATZ. Under optimal conditions, the degradation activity of ATZ by 5.8Ru/NiFe-LDH/PMS system reached 100% within 90 min. Additionally, it also exhibited good environmental applicability. Besides, electron paramagnetic resonance along with quenching experiments illustrated the production of 1O2, O2• −, •OH, SO4• − and surface-bond radicals during the degradation, where 1O2, •OH and surface-bond radicals were further identified as the dominant oxygen species for the oxidation. The ATZ degradation pathway was determined using the liquid chromatography-mass spectrometry to discern the intermediate products, e.g., dealkylation, alkylic-hydroxylation and dechlororination-hydroxylation processes. This work holds a potential application value for the removal of atrazine and other pollutants.

Identification, Characterization, and Electronic Structures of Interconvertible Cobalt-Oxygen TAML Intermediates.

The reaction of Li[(TAML)CoIII]·3H2O (TAML = tetraamido macrocyclic tetraanionic ligand) with iodosylbenzene at 253 K in acetone in the presence of redox-innocent metal ions (Sc(OTf)3 and Y(OTf)3) or triflic acid affords a blue species 1, which is converted reversibly to a green species 2 upon cooling to 193 K. The electronic structures of 1 and 2 have been determined by combining advanced spectroscopic techniques (X-band electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR), X-ray absorption spectroscopy/extended X-ray absorption fine structure (XAS/EXAFS), and magnetic circular dichroism (MCD)) with ab initio theoretical studies. Complex 1 is best represented as an S = 1/2 [(Sol)(TAML•+)CoIII---OH(LA)]- species (LA = Lewis/Brønsted acid and Sol = solvent), where an S = 1 Co(III) center is antiferromagnetically coupled to S = 1/2 TAML•+, which represents a one-electron oxidized TAML ligand. In contrast, complex 2, also with an S = 1/2 ground state, is found to be multiconfigurational with contributions of both the resonance forms [(H-TAML)CoIV═O(LA)]- and [(H-TAML•+)CoIII═O(LA)]-; H-TAML and H-TAML•+ represent the protonated forms of TAML and TAML•+ ligands, respectively. Thus, the interconversion of 1 and 2 is associated with a LA-associated tautomerization event, whereby H+ shifts from the terminal -OH group to TAML•+ with the concomitant formation of a terminal cobalt-oxo species possessing both singlet (SCo = 0) Co(III) and doublet (SCo = 1/2) Co(IV) characters. The reactivities of 1 and 2 at different temperatures have been investigated in oxygen atom transfer (OAT) and hydrogen atom transfer (HAT) reactions to compare the activation enthalpies and entropies of 1 and 2.

Encapsulating stable perovskite catalysts in hollow nanoreactors for enhanced pollutants degradation

Creating a microenvironment for enhanced peroxymonosulfate (PMS) activation is vital in advanced oxidation processes. The objective of this study was to fabricate nanoshells composed of titanium dioxide embedded with cobalt titanate nanoparticles of perovskite to act as nanoreactors for effectively initiating PMS and degrading contaminants. The unique porous structure and confined space of the nanoreactor facilitated reactant absorption and mass transfer to the active sites, resulting in exceptional catalytic performance for pollutant elimination. Experimental findings revealed close to 100% decomposition efficiency of 4-chlorophenol (4-CP) within an hour utilizing the nanoreactors over a wide pH range. The TiO2/CoTiO3 hollow nanoshells catalysts also displayed adaptability in disintegrating organic dyes and antibiotics. The radicals SO4•-, •OH, and non-radicals 1O2 were determined to be accountable for eliminating pollutants, as supported by trapping experiments and electron paramagnetic resonance spectra. The catalyst was confirmed as an electron donor and PMS as an electron acceptor through electrochemical tests and density functional theory calculations. This study underscores the potential of incorporating stable perovskite catalysts in hollow nanoreactors to enhance wastewater treatment.

Radiation-induced graft copolymerization of a phosphonate monomer onto short flax fibers and Miscanthus x giganteus stem fragments: Influence of substrate composition

The functionalization of Miscanthus x giganteus stems fragments (R-MSF) by dimethyl(methacryloyloxy)methyl phosphonate (MAPC1) using pre-irradiation was studied. The influence of the composition and the structure of the substrate on the grafting efficiency was investigated by comparing the results with short flax fibers (SFF) and bleached Miscanthus x giganteus stems fragments (B-MSF). The lignocellulosic substrates were irradiated at several target doses ranging from 11 to 108.1 kGy using e-Beam. Electron Paramagnetic Resonance spectroscopy (EPR) highlighted major differences in terms of radical nature between R-MSF, SFF, and B-MSF samples. Following the polymerization reactions, washing, and drying steps, the phosphorus contents were measured by X-ray fluorescence spectrometry (XRF). Unlike Flax, pre-irradiation grafting was not efficient on R-MSF. The role of lignin content on grafting reactions was then evaluated by comparing R-MSF with SFFand B-MSF), showing only a minor impact. Using a reducing agent, it was possible to reach a phosphorus content of about 1.4 wt% for R-MSF and up to 4.0 wt% for B-MSF for a 100 kGy dose. Furthermore, phosphorus mapping using scanning electron microscopy coupled with energy-dispersive X-ray spectrometry (SEM-EDX) highlighted a homogeneous dispersion of the grafted macromolecules. This demonstrates the possibility of conducting pre-irradiation grafting on lignin-rich substrates without bleaching. Efforts were then made to optimize the operating conditions in terms of storage temperature, reaction temperature and Fe2+ concentration. Finally, the fire behavior of treated Miscanthus x giganteus stem fragments was evaluated by pyrolysis-combustion flow calorimetry (PCFC).

Mechanistic Basis of the Cu(OAc)2 Catalyzed Azide-Ynamine (3 + 2) Cycloaddition Reaction.

The Cu-catalyzed azide-alkyne cycloaddition (CuAAC) reaction is used as a ligation tool throughout chemical and biological sciences. Despite the pervasiveness of CuAAC, there is a need to develop more efficient methods to form 1,4-triazole ligated products with low loadings of Cu. In this paper, we disclose a mechanistic model for the ynamine-azide (3 + 2) cycloadditions catalyzed by copper(II) acetate. Using multinuclear nuclear magnetic resonance spectroscopy, electron paramagnetic resonance spectroscopy, and high-performance liquid chromatography analyses, a dual catalytic cycle is identified. First, the formation of a diyne species via Glaser-Hay coupling of a terminal ynamine forms a Cu(I) species competent to catalyze an ynamine-azide (3 + 2) cycloaddition. Second, the benzimidazole unit of the ynamine structure has multiple roles: assisting C-H activation, Cu coordination, and the formation of a postreaction resting state Cu complex after completion of the (3 + 2) cycloaddition. Finally, reactivation of the Cu resting state complex is shown by the addition of isotopically labeled ynamine and azide substrates to form a labeled 1,4-triazole product. This work provides a mechanistic basis for the use of mixed valency binuclear catalytic Cu species in conjunction with Cu-coordinating alkynes to afford superior reactivity in CuAAC reactions. Additionally, these data show how the CuAAC reaction kinetics can be modulated by changes to the alkyne substrate, which then has a predictable effect on the reaction mechanism.