Electron Spin Resonance Studies Research Articles

Electron paramagnetic resonance study of the paramagnetic centers in gamma-irradiated 4-Nitrobenzaldehyde single crystal

4-Nitrobenzaldehyde (C7H5NO3) (4NB) single crystals were obtained by slow evaporation technique. Single crystals were made paramagnetic by irradiation with a 60Co-gamma rays. Electron Paramagnetic Resonance (EPR) Spectroscopy method was used to detect the radiation damage center formed in the single crystals. As a result of temperature scanning of EPR spectra at different temperatures between 120 and 470 K, it was found to be independent of temperature. That's why the EPR study was done only at 300 K. The radiation effect caused the formation of the 4NB anion radical in the 4NB single crystal. All the protons in the structure created hyperfine structure splittings. The principal values of the hyperfine structure constants resulting from the interaction of the unpaired electron with protons, the principal values of the g-tensor and their direction cosines were calculated.

Calcination temperature dependence of tri-magnetic nanoferrite Ni0.33Cu0.33Zn0.33Fe2O4: Structural, morphological, and magnetic properties

The calcination temperature plays a pivotal role in determining the physical and magnetic properties of ferrite nanoparticles, influencing their performance and applicability in various applications. In this study, Ni0.33Cu0.33Zn0.33Fe2O4 nano ferrites were produced using the coprecipitation method and subsequently calcined at different temperatures, specifically 500 °C, 550 °C, 600 °C, 650 °C, and 700 °C. The X-ray diffraction analysis confirmed the presence of cubic spinel ferrite phase (Fd-3m) and revealed an increase in crystallite size from 12.84 to 20.19 nm as the calcination temperature increased from 500 °C to 700 °C. X-ray photoelectron spectroscopy analysis provided insights into chemical oxidation states. Scanning electron microscopy and transmission electron microscopy images revealed that at higher calcination temperatures, nanoparticles tend to aggregate. This aggregation is associated with an observable rise in particle size, increasing from 18.16 to 29.11 nm for nanoparticles calcined at 500 °C and 700 °C, respectively. Energy-dispersive X-ray confirmed pure elemental compositions. Fourier transform infrared spectroscopy identified red and blue shifts in wavenumbers corresponding to tetrahedral and octahedral group complexes, respectively. Nanoparticles calcined at 700 °C exhibited the highest saturation magnetization (62.642 emu/g) and coercivity (75.27 G), as revealed from the vibrating sample magnetometry analysis. Upon increasing the calcination temperature from 500 °C to 700 °C, the ferromagnetic contribution was improved from 24.26% to 98.64% along with a reduction in superparamagnetic contribution from 75.74% to 1.34%, respectively. The electron paramagnetic resonance (EPR) study showed an increase in the values of g and ΔHpp with the rise in calcination temperature. This observation suggests an enhancement in dipole–dipole interactions. Furthermore, a linear relationship was discovered between the g factor and crystallite size, inducting the formation of single domain. Finally, altering the calcination temperature adjusted the physical and magnetic properties of Ni0.33Cu0.33Zn0.33Fe2O4 nanoparticles. This adjustment indicates their potential for versatile applications, particularly in hyperthermia treatment and as T2 contrast agents in magnetic resonance imaging.

ZnAl2O4:Er3+ Upconversion Nanophosphor for SPECT Imaging and Luminescence Modulation via Defect Engineering.

This work reports an "all-in-one" theranostic upconversion luminescence (UCL) system having potential for both diagnostic and therapeutic applications. Despite considerable efforts in designing upconversion nanoparticles (UCNPs) for multimodal imaging and tumor therapy, there are few reports investigating dual modality SPECT/optical imaging for theranostics. Especially, research focusing on in vivo biodistribution studies of intrinsically radiolabeled UCNPs after intravenous injection is of utmost importance for the potential clinical translation of such formulations. Here, we utilized the gamma emission from 169Er and 171Er radionuclides for the demonstration of radiolabeled ZnAl2O4:171/169Er3+ as a potent agent for dual-modality SPECT/optical imaging. No uptake of radio nanoformulation was detected in the skeleton after 4 h of administration, which evidenced the robust integrity of ZnAl2O4:169/171Er3+. Combining the therapeutics using the emission of β- particulates from 169Er and 171Er will be promising for the radio-theranostic application of the synthesized ZnAl2O4:169/171Er3+ nanoformulation. Cell toxicity studies of ZnAl2O4:1%Er3+ nanoparticles were examined by an MTT assay in B16F10 mouse melanoma cell lines, which demonstrated good biocompatibility. In addition, we explored the mechanism of UCL modulation via defect engineering by Bi3+ codoping in the ZnAl2O4:Er3+ upconversion nanophosphor. The UCL color tuning was successfully achieved from the red to the green region as a function of Bi3+ codoping concentrations. Further, we tried to establish a correlation of UCL tuning with the intrinsic oxygen and cation vacancy defects as a function of Bi3+ codoping concentrations with the help of electron paramagnetic resonance (EPR) and positron annihilation lifetime spectroscopy (PALS) studies. This study contributes to building a bridge between nature of defects and UC luminescence that is crucial for the design of advanced UCNPs for theranostics.

Carbon Dioxide Electroreduction and Formic Acid Oxidation by Formal Nickel(I) Complexes of Di-isopropylphenyl Bis-iminoacenaphthene.

Processing CO2 into value-added chemicals and fuels stands as one of the most crucial tasks in addressing the global challenge of the greenhouse effect. In this study, we focused on the complex (dpp-bian)NiBr2 (where dpp-bian is di-isopropylphenyl bis-iminoacenaphthene) as a precatalyst for the electrochemical reduction of CO2 into CH4 as the sole product. Cyclic voltammetry results indicate that the realization of a catalytically effective pattern requires the three-electron reduction of (dpp-bian)NiBr2. The chemically reduced complexes [K(THF)6]+[(dpp-bian)Ni(COD)]- and [K(THF)6]+[(dpp-bian)2Ni]- were synthesized and structurally characterized. Analyzing the data from the electron paramagnetic resonance study of the complexes in solutions, along with quantum-chemical calculations, reveals that the spin density is predominantly localized at their metal centers. The superposition of trajectory maps of the electron density gradient vector field and the electrostatic force density field per electron, as well as the atomic charges, discloses that, within the first coordination sphere, the interatomic charge transfer occurs from the metal atom to the ligand atoms and that the complex anions can thus be formally described by the general formulae (dpp-bian)2-Ni+(COD) and (dpp-bian)2 -Ni+. It was also shown that the reduced nickel complexes can be oxidized by formic acid; resulting from this reaction, the two-electron and two-proton addition product dpp-bian-2H is formed.

EPR studies of ferredoxin in spinach and cyanobacterial thylakoids related to photosystem I-driven NADP+ reduction.

Photosynthetic light-dependent reactions occur in thylakoid membranes where embedded proteins capture light energy and convert it to chemical energy in the form of ATP and NADPH for use in carbon fixation. One of these integral membrane proteins is Photosystem I (PSI). PSI catalyzes light-driven transmembrane electron transfer from plastocyanin (Pc) to oxidized ferredoxin (Fd). Electrons from reduced Fd are used by the enzyme ferredoxin-NADP+ reductase (FNR) for the reduction of NADP+ to NADPH. Fd and Pc are both small soluble proteins whereas the larger FNR enzyme is associated with the membrane. To investigate electron shuttling between these diffusible and embedded proteins, thylakoid photoreduction of NADP+ was studied. As isolated, both spinach and cyanobacterial thylakoids generate NADPH upon illumination without extraneous addition of Fd. These findings indicate that isolated thylakoids either (i) retain a "pool" of Fd which diffuses between PSI and membrane bound FNR or (ii) that a fraction of PSI is associated with Fd, with the membrane environment facilitating PSI-Fd-FNR interactions which enable multiple turnovers of the complex with a single Fd. To explore the functional association of Fd with PSI in thylakoids, electron paramagnetic resonance (EPR) spectroscopic methodologies were developed to distinguish the signals for the reduced Fe-S clusters of PSI and Fd. Temperature-dependent EPR studies show that the EPR signals of the terminal [4Fe-4S] cluster of PSI can be distinguished from the [2Fe-2S] cluster of Fd at > 30K. At 50K, the cw X-band EPR spectra of cyanobacterial and spinach thylakoids reduced with dithionite exhibit EPR signals of a [2Fe-2S] cluster with g-values gx = 2.05, gy = 1.96, and gz = 1.89, confirming that Fd is present in thylakoid preparations capable of NADP+ photoreduction. Quantitation of the EPR signals of P700+ and dithionite reduced Fd reveal that Fd is present at a ratio of ~ 1 Fd per PSI monomer in both spinach and cyanobacterial thylakoids. Light-driven electron transfer from PSI to Fd in thylakoids confirms Fd is functionally associated (< 0.4 Fd/PSI) with the acceptor end of PSI in isolated cyanobacterial thylakoids. These EPR experiments provide a benchmark for future spectroscopic characterization of Fd interactions involved in multistep relay of electrons following PSI charge separation in the context of photosynthetic thylakoid microenvironments.

Li3V2(PO4)3 Cathode Material: Synthesis Method, High Lithium Diffusion Coefficient and Magnetic Inhomogeneity.

Li3V2(PO4)3 cathodes for Li-ion batteries (LIBs) were synthesized using a hydrothermal method with the subsequent annealing in an argon atmosphere to achieve optimal properties. The X-ray diffraction analysis confirmed the material's single-phase nature, while the scanning electron microscopy revealed a granular structure, indicating a uniform particle size distribution, beneficial for electrochemical performance. Magnetometry and electron spin resonance studies were conducted to investigate the magnetic properties, confirming the presence of the relatively low concentration and highly uniform distribution of tetravalent vanadium ions (V4+), which indicated low lithium deficiency values in the original structure and a high degree of magnetic homogeneity in the sample, an essential factor for consistent electrochemical behavior. For this pure phase Li3V2(PO4)3 sample, devoid of any impurities such as carbon or salts, extensive electrochemical property testing was performed. These tests resulted in the experimental discovery of a remarkably high lithium diffusion coefficient D = 1.07 × 10-10 cm2/s, indicating excellent ionic conductivity, and demonstrated impressive stability of the material with sustained performance over 1000 charge-discharge cycles. Additionally, relithiated Li3V2(PO4)3 (after multiple electrochemical cycling) samples were investigated using scanning electron microscopy, magnetometry and electron spin resonance methods to determine the extent of degradation. The combination of high lithium diffusion coefficients, a low degradation rate and remarkable cycling stability positions this Li3V2(PO4)3 material as a promising candidate for advanced energy storage applications.

Comparative EPR Studies on the Influence of Genistein on Free Radicals in Non-Irradiated and UV-Irradiated MCF7, T47D and MDA-MB-231 Breast Cancer Cells.

The antioxidant activity and the association of genistein with carcinogenesis are widely documented. Few studies directly measure the number of free radicals generated in cells, either during the action of factors stimulating their formation, e.g., ultraviolet (UV), or after exposure to antioxidants. The most suitable method for analysing free radicals is electron paramagnetic resonance (EPR) spectroscopy. The EPR method detects a paramagnetic centre with a single electron. Antioxidants neutralize free radicals, therefore, EPR analysis of antioxidant efficacy is as valuable and important as studying the paramagnetic centres of radicals. The aim of the study was to determine the influence of genistein on free radicals basal level and after UV exposure in breast cancer cell lines MCF7, T47D and MDA-MB-231 cell lines. The impact of genistein on cell viability was investigated at concentrations of 0.37 μM, 3.7 μM, 37 μM and 370 μM. Genistein at a concentration of 370 μM revealed a cytotoxic effect on the cells of all three tested breast cancer lines. Genistein at a concentration of 0.37 μM showed no significant effect on the cell viability of all tested breast cancer lines. Therefore, cell proliferation and antioxidant properties were examined using genistein at a concentration of 0.37 μM and 37 μM. X-band (9.3 GHz) EPR spectra of three different types of breast cancer cells (ER-positive, PR-positive and HER-2 negative: MCF7 and T47D and triple-negative MDA-MB-231) were compared. UV irradiation was used as a factor to generate free radicals in cells. The effect of free radical interactions with the antioxidant genistein was tested for non-UV-irradiated (corresponding to the basal level of free radicals in cells) and UV-irradiated cells. The levels of free radicals in the non-irradiated cells studied increased in the following order in breast cancer cells: T47D < MDA-MB-231 < MCF7 and UV-irradiated breast cancer cells: MDA-MB-231 < MCF7 < T47D. UV-irradiation altered free radical levels in all control and genistein-cultured cells tested. UV irradiation caused a slight decrease in the amount of free radicals in MCF7 cells. A strong decrease in the amount of free radicals was observed in UV-irradiated MDA-MB-231 breast cancer cells. The amount of free radicals in T47D cancer cells increased after UV irradiation. Genistein decreased the amount of free radicals in non-irradiated and UV-irradiated MCF7 cells, and only a weak effect of genistein concentrations was reported. Genistein greatly decreased the amount of free radicals in UV-irradiated T47D cancer cells cultured with genistein at a concentration of 3.7 μM. The effect of genistein was negligible in the other samples. Genistein at a concentration of 3.7 μM decreased the amount of free radicals in non-irradiated MDA-MB-231 cancer cells, but genistein at a concentration of 37 μM did not change the amount of free radicals in these cells. An increase in the amount of free radicals in UV-irradiated MDA-MB-231 cancer cells was observed with increasing genistein concentration. The antioxidant efficacy of genistein as a potential plant-derived agent supporting the treatment of various cancers may be determined by differences in signalling pathways that are characteristic of breast cancer cell line subtypes and differences in activation of oxidative stress response pathways.

Effect of grain boundary segregation and oxygen vacancy annihilation on aging resistance of cobalt oxide-doped 3Y-TZP ceramics for biomedical applications

Abstract This study aims to investigate the diffusion stabilization process of nano-Co2O3 during the non-precursor transformation of 3Y-TZP. 3Y-TZP was set as the control group, and the experimental groups were 0.1–0.3 mol% nano-Co2O3-doped 3Y-TZP. The samples were prepared by the ball milling process, isostatic cool pressing, and sintering. All samples were hydrothermally treated at 134°C and 2 bar for different time periods. The resistance to low-temperature degradation of nano-Co2O3-doped 3Y-TZP was analyzed by X-ray diffraction. The microstructure of zirconia ceramic samples was determined by scanning electron microscopy, transmission electron microscopy, atomic force microscopy, and electron paramagnetic resonance studies. The addition of nano-Co2O3 into 3Y-TZP resulted in higher hydrothermal aging resistance than 3Y-TZP. The addition of 0.2 mol% nano-Co2O3 dopants resulted in the highest hydrothermal aging resistance among nano-Co2O3-doped 3Y-TZP ceramics. The grain sizes of 3Y-0.2Co are smaller than those in the control group. With the increase of cobaltous oxide doping contents, the segregation of Co3+ ions at the crystal boundary increased. The content of oxygen vacancies on the surface of the sample increased with the increase of the Co2O3 doping content. The oxygen vacancy concentrations of 3Y-0.2Co increased obviously after aging. 3Y-0.1Co, 3Y-0.3Co, and the control showed decreased oxygen vacancy concentrations after aging. Trivalent element doping of 3Y-TZP effectively improved the aging resistance of 3Y-TZP. The addition of 0.2 mol% nano-Co2O3 resulted in the highest hydrothermal aging resistance. Improved aging resistance is attributed to the nano-Co2O3 doping resulting in the 3Y-TZP grain size inhibition, grain boundary segregation of cobalt ions, and oxygen vacancy maintenance. This work is expected to provide an effective reference for the development and application of budget dental materials by regulating grain boundary engineering.

Measuring conformational equilibria in allosteric proteins with time-resolved tmFRET

Proteins are the workhorses of biology, orchestrating a myriad of cellular functions through intricate conformational changes. Protein allostery, the phenomenon where binding of ligands or environmental changes induce conformational rearrangements in the protein, is fundamental to these processes. We have previously shown that transition metal Förster resonance energy transfer (tmFRET) can be used to interrogate the conformational rearrangements associated with protein allostery and have recently introduced novel FRET acceptors utilizing metal-bipyridyl derivatives to measure long (>20Å) intramolecular distances in proteins. Here, we combine our tmFRET system with fluorescence lifetime measurements to measure the distances, conformational heterogeneity, and energetics of maltose-binding protein, a model allosteric protein. Time-resolved tmFRET captures near-instantaneous snapshots of distance distributions, offering insights into protein dynamics. We show that time-resolved tmFRET can accurately determine distance distributions and conformational heterogeneity of proteins. Our results demonstrate the sensitivity of time-resolved tmFRET in detecting subtle conformational or energetic changes in protein conformations, which are crucial for understanding allostery. In addition, we extend the use of metal-bipyridyl compounds, showing that Cu(phen)2+ can serve as a spin label for pulse dipolar electron paramagnetic resonance (EPR) spectroscopy, a method that also reveals distance distributions and conformational heterogeneity. The EPR studies both establish Cu(phen)2+ as a useful spin label for pulse dipolar EPR and validate our time-resolved tmFRET measurements. Our approach offers a versatile tool for deciphering conformational landscapes and understanding the regulatory mechanisms governing biological processes.

Effects of intramolecular hydrogen bonding on nuclear magnetic resonance, electron paramagnetic resonance and molecular docking studies: Mexiletine molecule.

In this study, the molecular structure of the mexiletine molecule was investigated. Since the Mexiletine molecule is a drug active ingredient, its molecular structure and spectroscopic properties are important. The effects of intramolecular hydrogen bonding on Nuclear Magnetic Resonance Parameters (NMR), Electron Paramagnetic Resonance (EPR) parameters and molecular docking studies were examined in the mexiletine molecule. The effects of intramolecular hydrogen bonding on EPR parameters and molecular docking studies are the most important steps for this study. Conformational space scanning required for molecular structure calculations was carried out with the Molecular Mechanic Force Field method. DFT method with 6-311 + + G(d,p) basis set level was used to obtain the most stable structure among the conformations. NMR parameters (1H and 13C chemical shift values) were also performed using the same basis set as the DFT method. The radicals created to calculate the Electron Paramagnetic Resonance parameters were modeled using the DFT/B3LYP/6-311 + + G(d,p) method basis set level. Molecular Docking studies were carried out with the Autodock vina program.

Structure and Function of Canine SP-C Mimic Proteins in Synthetic Surfactant Lipid Dispersions.

Lung surfactant is a mixture of lipids and proteins and is essential for air breathing in mammals. The hydrophobic surfactant proteins B and C (SP-B and SP-C) assist in reducing surface tension in the lung alveoli by organizing the surfactant lipids. SP-B deficiency is life-threatening, and a lack of SP-C can lead to progressive interstitial lung disease. B-YL (41 amino acids) is a highly surface-active, sulfur-free peptide mimic of SP-B (79 amino acids) in which the four cysteine residues are replaced by tyrosine. Mammalian SP-C (35 amino acids) contains two cysteine-linked palmitoyl groups at positions 5 and 6 in the N-terminal region that override the β-sheet propensities of the native sequence. Canine SP-C (34 amino acids) is exceptional because it has only one palmitoylated cysteine residue at position 4 and a phenylalanine at position 5. We developed canine SP-C constructs in which the palmitoylated cysteine residue at position 4 is replaced by phenylalanine (SP-Cff) or serine (SP-Csf) and a glutamic acid-lysine ion-lock was placed at sequence positions 20-24 of the hydrophobic helical domain to enhance its alpha helical propensity. AI modeling, molecular dynamics, circular dichroism spectroscopy, Fourier Transform InfraRed spectroscopy, and electron spin resonance studies showed that the secondary structure of canine SP-Cff ion-lock peptide was like that of native SP-C, suggesting that substitution of phenylalanine for cysteine has no apparent effect on the secondary structure of the peptide. Captive bubble surfactometry demonstrated higher surface activity for canine SP-Cff ion-lock peptide in combination with B-YL in surfactant lipids than with canine SP-Csf ion-lock peptide. These studies demonstrate the potential of canine SP-Cff ion-lock peptide to enhance the functionality of the SP-B peptide mimic B-YL in synthetic surfactant lipids.

Tridentate NacNac Tames T-Shaped Nickel(I) Radical.

The reaction of a nickel(II) chloride complex containing a tridentate β-diketiminato ligand with a picolyl group [2,6-iPr2 -C6 H3 NC(Me)CHC(Me)NH(CH2 py)]Ni(II)Cl (1)] with KSi(SiMe3 )3 conveniently afforded a nickel(I) radical with a T-shaped geometry (2). The compound's metalloradical nature was confirmed through electron paramagnetic resonance (EPR) studies and its reaction with TEMPO, resulting in the formation of a highly unusual three-membered nickeloxaziridine complex (3). When reacted with disulfide and diselenide, the S-S and Se-Se bonds were cleaved, and a coupled product was formed through carbon atom of the pyridine-imine group. The nickel(I) radical activates dihydrogen at room temperature and atmospheric pressure to give the monomeric nickel hydride.

Photophysics and photochemistry of thermally activated delayed fluorescence emitters based on multiple resonance effect: transient optical and electron paramagnetic resonance studies

The photochemistry of two representative thermally activated delayed fluorescence (TADF) emitters based on multiple resonance (MRE) effect (DABNA-1 and DtBuCzB) was studied. No significant TADF was observed in fluid solution,...

A coronene diimide based radical anion for detection of picomolar H2O2: a biochemical assay for detection of picomolar glucose in aqueous medium.

Coronene diimide functionalized with 4-(2-nitrovinyl)phenyl (CDI 2) serves as a precursor for generating a stable radical anion (CDI 2˙-) using H2S as a reductant in 40% H2O-THF solution in the NIR region with stability up to >50 min. The optical, cyclic voltammetry (CV), current-voltage (I-V) and electron paramagnetic resonance (EPR) studies revealed the formation of the radical anion (CDI 2˙-). The addition of a strong oxidant NOBF4 quenches the radical anion (CDI 2˙-). The aggregation studies revealed that CDI 2 exists in the aggregated state in 40% H2O-THF solution, which points to the possibility of stabilization of the radical anion in the aggregates. The radical anion (CDI 2˙-) was explored for the detection of 58.27 pM H2O2 in aqueous medium with the naked eye colour change from green to light yellow. The biochemical assay involving the radical anion (CDI 2˙-) and glucose oxidase (GOx) enzyme can be used for the detection of 16 pM (UV-vis method) and 82.4 pM (fluorescence method) glucose. The naked eye colour change from green to light yellow (daylight) and a colorless non-fluorescent solution to a green fluorescent solution (365 nm) allow the detection of 1 nM glucose.

Spiers Memorial Lecture: Lithium air batteries - tracking function and failure.

The lithium-air battery (LAB) is arguably the battery with the highest energy density, but also a battery with significant challenges to be overcome before it can be used commercially in practical devices. Here, we discuss experimental approaches developed by some of the authors to understand the function and failure of lithium-oxygen batteries. For example, experiments in which nuclear magnetic resonance (NMR) spectroscopy was used to quantify dissolved oxygen concentrations and diffusivity are described. 17O magic angle spinning (MAS) NMR spectra of electrodes extracted from batteries at different states of charge (SOC) allowed the electrolyte decomposition products at each stage to be determined. For instance, the formation of Li2CO3 and LiOH in a dimethoxyethane (DME) solvent and their subsequent removal on charging was followed. Redox mediators have been used to chemically reduce oxygen or to chemically oxidise Li2O2 in order to prevent electrode clogging by insulating compounds, which leads to lower capacities and rapid degradation; the studies of these mediators represent an area where NMR and electron paramagnetic resonance (EPR) studies could play a role in unravelling reaction mechanisms. Finally, recently developed coupled in situ NMR and electrochemical impedance spectroscopy (EIS) are used to characterise the charge transport mechanism in lithium symmetric cells and to distinguish between electronic and ionic transport, demonstrating the formation of transient (soft) shorts in common lithium-oxygen electrolytes. More stable solid electrolyte interphases are formed under an oxygen atmosphere, which helps stabilise the lithium anode on cycling.

Effect of cationic surfactant on the physicochemical and antibacterial properties of colloidal systems (emulsions and microemulsions).

Colloidal systems have been used to encapsulate, protect and release essential oils in mouthwashes. In this study, we investigated the effect of cetylpyridinium chloride (CPC) on the physicochemical properties and antimicrobial activity of oil-in-water colloidal systems containing tea tree oil (TTO) and the nonionic surfactant polysorbate 80. Our main aim was to evaluate whether CPC could improve the antimicrobial activity of TTO, since this activity is impaired when this essential oil is encapsulated with polysorbate 80. These systems were prepared with different amounts of TTO (0-0.5% w/w) and CPC (0-0.5% w/w), at a final concentration of 2% (w/w) polysorbate 80. Dynamic light scattering (DLS) results revealed the formation of oil-swollen micelles and oil droplets as a function of TTO concentration. Increases in CPC concentrations led to a reduction of around 88% in the mean diameter of oil-swollen micelles. Although this variation was of only 20% for the oil droplets, the samples appearance changed from turbid to transparent. The surface charge of colloidal structures was also markedly affected by the CPC as demonstrated by the transition in zeta potential from slightly negative to highly positive values. Electron paramagnetic resonance (EPR) studies showed that this transition is followed by significant increases in the fluidity of surfactant monolayer of both colloidal structures. The antimicrobial activity of colloidal systems was tested against a Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureaus) bacteria. Our results revealed that the inhibition of bacterial growth is observed for the same CPC concentration (0.05% w/w for E. coli and 0.3% w/w for S. aureus) regardless of TTO content. These findings suggest that TTO may not act as an active ingredient in polysorbate 80 containing mouthwashes.

Efficient removal of endocrine disruptors using nano zero-valent iron loaded organo-attapulgite: Mechanism and factors

Endocrine-disrupting pollutants have become a major problem in aquatic environments. Advanced oxidation processes are recognized as promising technologies for treating endocrine disruptor-contaminated water. Herein, a novel nanoscale zero-valent iron loaded organo-attapulgite (NZVI@OATP) was employed as a catalyst to activate persulfate (PDS) for phenanthrene (PHE) and dibutyl phthalate (DBP) degradation. NZVI@OATP with a NZVI:OATP mole ratio of 1:1 (CTAB:ATP = 1:200) exhibited 100 % PHE and 84 % DBP degradation within 30 min, and chloride was found to have a positive effect on their degradation. Radical scavenger and electron paramagnetic resonance studies revealed that the contribution of the active species follows the order of O2- ≈ 1O2>SO4- ≫ OH. The optimal degradation pathways were proposed based on the liquid chromatography-mass spectrometry and density functional theory and the possible degradation paths of PHE and DBP, including the 9,10-phenanthraquinone and phthalic acid pathways, respectively, were proposed. The toxicity estimation software tool showed that the toxicities of PHE and DBP were reduced after degradation. Moreover, 50 % PHE degradation could be achieved after five cycles, demonstrating that NZVI@OATP is a promising catalyst for endocrine disruptor treatment with PDS.

Role of Gd3+ ions in alumino borosilicate glasses studied through structural, optical and thermoluminescence characteristics for gamma dosimetry applications

This paper reports the structural, optical and thermoluminescence properties of Gd3+ ions incorporated alumino-borosilicate glasses, prepared through the melt-quench technique. The amorphous nature of the glasses is confirmed through XRD study. Network vibrations of borate and silicate groups, vibrations of hydrogen bonding and hydroxyl groups are realized via FTIR study. The Gd3+ transition peaks are absent in the near ultraviolet, visible and NIR regions, and the indirect bandgap values were determined through UV–Visible–NIR study. Photoluminescence measurements showed a concentration quenching in the glasses beyond 1.5 mol % of Gd3+ ions. Based on the thermoluminescence (TL) data, the 2 mol % of Gd2O3 doped glass (BSGD5) was chosen as optimum sample because of the presence of maximum TL intensity. The BSGD5 glass displayed TL response linearity in 0.25–1 kGy dose region giving a high signal sensitivity of 220,068 counts. g−1 kGy−1 in this region. With nearer tissue equivalence and a minimum detectable dose of 0.02 Gy, the suitability of BSGD5 glass for gamma dosimetry application was deducted. Electron spin resonance (ESR) study validated the presence of intrinsic defects in Gd3+ glasses which are responsible for changes in the intensity and shape of TL glow curves. Hence, from the obtained results Gd3+ doped alumino borosilicate glasses can be considered as potential candidates for gamma dosimetry application.

Open-Circuit-Voltage Improvement Mechanism of Perovskite Solar Cells Revealed by Operando Spin Observation.

Organic-inorganic hybrid perovskite solar cells have attracted much attention as important next-generation solar cells. Their solar cell performance is known to change during operation, but the root cause of the instability remains unclear. This report describes an investigation using electron spin resonance (ESR) to evaluate an improvement mechanism for the open-circuit voltage, VOC, of inverted perovskite solar cells at the initial stage of device operation. The ESR study revealed electron transfer at the interface from the perovskite layer to the hole-transport layer not only under dark conditions but also under light irradiation, where electrons are subsequently trapped in the hole-transport layer. An electron barrier is enhanced at the perovskite/hole-transport-layer interface, improving field-effect passivation at the interface. Thereby, the interface recombination velocity is reduced, and thus the VOC improves. These findings are crucially important for elucidating the mechanisms of device performance changes under operation. They reveal a relation between charge transfer and performance improvement, which is valuable for the further development of efficient perovskite solar cells.

Two-Dimensional Porphyrinic Metal-Organic Framework Composites as a Photocatalytic Platform for Chemoselective Hydrogenation.

Chemoselective hydrogenation with high efficiency under ambient conditions remains a great challenge. Herein, an efficient photocatalyst, the 2D porphyrin metal-organic framework composite AmPy/Pd-PPF-1(Cu), featuring AmPy (1-aminopyrene) sitting axially on a paddle-wheel unit, has been rationally fabricated. The 2D AmPy/Pd-PPF-1(Cu) composite acts as a photocatalytic platform, promoting the selective hydrogenation of quinolines to tetrahydroquinolines with a yield up to 99%, in which ammonia borane serves as the hydrogen donor. The AmPy molecules coordinated on a 2D MOF not only enhance the light absorption capacity but also adjust the layer spacing without affecting the network structure of 2D Pd-PPF-1(Cu) nanosheets. Through deuterium-labeling experiments, in situ X-ray photoelectron spectroscopy, electron paramagnetic resonance studies, and density functional theory calculations, it is disclosed that Cu paddle-wheel units in 2D AmPy/Pd-PPF-1(Cu) nanosheets behave as the active site for transfer hydrogenation, and metalloporphyrin ligand and axial aminopyrene molecules can enhance the light absorption capacity and excite photogenerated electrons to Cu paddle-wheel units, assisting in photocatalysis.