Electron Spin Resonance Studies Research Articles

Tuning the Electronic And Transport Properties of CaMoO4 Nanofibers with High-Spin Ni for Efficient and Stable Supercapacitors.

Calcium molybdate (CaMoO4) has recently garnered considerable attention for supercapacitors due to its stable crystal structure and cost-effective preparation. However, CaMoO4 prepared by traditional processes still suffered from insufficient electrochemical active sites and poor electrical conductivity so far, thus leading to the performance of CaMoO4-based supercapacitors being inferior to the state-of-the-art ones. CaMoO4 nanofibers with a high specific surface area exhibit great potential for supercapacitors due to their ability to offer increased charge storage. Herein, mesoporous CaMoO4 nanofibers anchored with Ni nanoparticles were fabricated via electrospinning combined with subsequent thermal treatment. Density functional theory calculation and UV-vis spectrophotometer results show that high-spin state Ni nanoparticles can tune the electronic structure of CaMoO4 nanofibers, decreasing the band gap by about 0.67 eV. Electron paramagnetic resonance (EPR) studies imply that Ni doping influences the electronic structure by reducing the oxygen vacancy concentration and introducing hyperfine structures associated with Ni spins. These can result in higher power and energy density in supercapacitors. As a result, a specific capacitance of 1253.7 F·g-1 at a current density of 0.5 A·g-1 and an 86% retention rate after 2000 cycles at a higher current density of 5 A·g-1 have been achieved for Ni0.25Ca0.75MoO4-based supercapacitor. Furthermore, an asymmetric supercapacitor (ASC) device with the optimized CaMoO4/Ni//AC structure has been demonstrated with the energy density of 49.43 Wh·kg-1 and power density of 2700 W·kg-1, thus enabling lightening a red light-emitting diode. The current strategy might pave the way for CaMoO4 for practical applications for high-power supercapacitors.

Biophysical contrast sources for magnetic susceptibility and R2* mapping: A combined 7 Tesla, mass spectrometry and electron paramagnetic resonance study

Iron is the most abundant trace metal in the human brain and consistently shown elevated in prevalent neurological disorders. Because of its paramagnetism, brain iron can be assessed in vivo by quantitative MRI techniques such as R2* mapping and Quantitative Susceptibility Mapping (QSM). While Inductively Coupled Plasma Mass Spectrometry (ICP-MS) has demonstrated good correlations of the total iron content to MRI parameters in gray matter, the relationship to ferritin levels as assessed by Electron Paramagnetic Resonance (EPR) has not been systematically analyzed. Therefore, we included 15 postmortem subjects (age: 26–91 years) which underwent quantitative in-situ MRI at 7 Tesla within a post-mortem interval of 24 h after death. ICP-MS and EPR were used to measure the total iron and ferritin content in 8 selected gray matter (GM) structures and the correlations to R2* and QSM were calculated. We found that R2* and QSM in the iron rich basal ganglia and the red nucleus were highly correlated with iron (R² > 0.7) and ferritin (R² > 0.6), whereas those correlations were lost in cortical regions and the hippocampus. The neuromelanin-rich substantia nigra showed a different behavior with a correlation with total iron only (R² > 0.5) but not with ferritin. Although qualitative results were similar for both qMRI techniques the observed correlation was always stronger for QSM than R2*. This study demonstrated the quantitative correlations between R2*, QSM, total iron and ferritin levels in an in-situ MRI setup and therefore aids to understand how molecular forms of iron are responsible for MRI contrast generation.

Electron paramagnetic resonance study of the paramagnetic centers in gamma-irradiated 2-nitrobenzoic acid single crystal

2-nitrobenzoic acid (C7H5NO4) (2NBA) single crystals were made paramagnetic using 60Co-gamma rays. An attempt was made to detect the resonance form formed in 2-nitrobenzoic acid single crystal with Electron Paramagnetic Resonance (EPR) Spectroscopy. EPR spectra were taken at 125 K in three different axes of the crystal. As a result of EPR analysis of gamma irradiated 2NBA single crystal, it was understood that 2NBA anion radical was formed. The principal values of the hyperfine structure constants, the principal values of the g-tensor and their direction cosines were calculated.

Investigation of electrochemical performance of gadolinium trichloride in asymmetric supercapacitor applications

The commercial Gadolinium tri chloride (GdCl3) electrode material exhibits high specific capacitance of 207.52Fg−1 in three electrode system at 1A/g with potential window 1.0 V. The GdCl3//Activated carbon (AC) asymmetric supercapacitor device in two electrode system achieves 188.14Fg−1 specific capacitance at 1 A/g with high potential window 1.7V. It possess high energy density 75.51Wh/kg, power density 850W/kg. and electrochemical stability of 92% of its initial capacitance after 5000 cycles. These demonstrate GdCl3 as an useful material for electrochemical energy storage devices. Further, electron paramagnetic resonance study on GdCl3 reveals g-factor 1.98 and line width ΔH = 221.8mT.

X-ray diffraction, luminescence, and electron paramagnetic resonance study of LaLuO3:Yb3+ nanopowders

The primary objective of materials science is the study of the properties of the existing materials and the development of new ones. In the present day, the use of solid-state lasers abroad has prompted material scientists globally to develop novel or enhance the properties of the existing active gain media. Materials comprising rare earth elements have historically proven effective in scintillation applications. The synthesis of LaLu1-xYbxO3 monodisperse nanopowders with a particle size of 50–62 nm via the Pechini complexing citrate method has been the subject of investigation using electron paramagnetic resonance (EPR) spectroscopy and photoluminescence (PL) measurements. The EPR data indicate that the Yb³⁺ ions predominantly create a single type of center, whereby the Yb³⁺ ion substitutes for the Lu³⁺ ion. The calculated EPR g-factors are estimated to be g1 = 3.85, g2 = 2.15, g3 = 1.55 and the 171Yb isotope hyperfine interaction constants are A1 = 600 × 10−4 cm−1, A2 = 700 × 10−4 cm−1, A3 ≈ 1800 × 10−4 cm−1. The principal values of the g factors and the hyperfine tensors indicate that the Yb site in LaLu1-xYbxO3 nanopowders exhibits orthorhombic symmetry. The PL measurements in the wavelength range of 350–1800 nm, with excitation provided by either a xenon lamp or a diode laser, indicate the presence of a broad emission band, centered at 404 nm, in addition to the well-known emission spectrum in the IR region (920–1100 nm) arising from Yb3+ ions.

Selective Photocatalytic Oxidation of 5‐Hydroxymethylfurfural using Ce doped TiO2: A Crucial Role of Defective Sites

AbstractTransforming platform compounds with conventional catalysts, such as homogeneous and heterogeneous, into valuable chemicals encounters challenges associated with entailing high temperature/pressure and reusability during the reaction. To address these challenges, photocatalysis is one of the promising approaches, especially with visible‐light‐driven photocatalysts for selective transformation. A series of cerium‐doped TiO2 (CexTiO2; x=0.5, 1, 3 and 5 wt %) are prepared via a simple coprecipitation method for the cocatalyst‐free selective oxidation of 5‐hydroxymethylfurfural (HMF) to 2,5‐diformylfuran (DFF) under visible light illumination. Introducing Ce into the network to TiO2 generates impurity energy levels, reduces the band gap, and extends the spectral response range. This also causes slight distortion to the surface structure, thereby originating defective sites and various surface oxygen species, confirmed by X‐ray photoelectron spectroscopy and electron paramagnetic resonance studies. The HMF adsorption studies infer that HMF forms a surface complex with CeTiO2, facilitating the formation of ligand‐to‐metal charge transfer complex (LMCT) under visible light (~420 nm), which efficiently catalyzes the conversion of HMF (54.4 %) to DFF with a selectivity of >99 %. In‐situ DRIFTS and surface passivation studies provide insight into the interaction between HMF and surface acidic/basic sites along with hydroxyl groups of CeTiO2, which subsequently convert selectively to DFF.

Submicroscopic magnetite may be ubiquitous in the lunar regolith of the high-Ti region

Magnetite is rare on the Moon. The ubiquitous presence of magnetite in lunar soil has been hypothesized in previous Apollo Mössbauer spectroscopy and electron spin resonance studies, but there is currently no mineralogical evidence to prove it. Here, we report a large number of submicroscopic magnetite particles embedded within iron-sulfide on the surface of Chang’e-5 glass, with a close positive correlation between magnetite content and the TiO 2 content of the surrounding glass. The morphology and mineralogy of the iron-sulfide grains suggest that these magnetite particles formed via an impact process between iron-sulfide droplets and silicate glass melt, and ilmenite is necessary for magnetite formation. Magnetite in lunar glass is a potential candidate for the “magnetite-like” phase detected in the Apollo era and suggests that impact-induced submicroscopic magnetite may be ubiquitous in high-Ti regions of the Moon. Moreover, these impact-induced magnetite particles may be crucial for understanding the lunar magnetic anomalies and mineral components of the deep Moon.

An efficient novel NiCu@INA/rGO MOF hollow microsphere Z-scheme heterojunction catalyst for the photocatalytic degradation of tetracycline and simultaneous degradation of cationic and anionic Dyes

Bimetallic metal-organic framework materials have captivated considerable attention in photocatalysis because of their colossal properties like semiconducting, large surface area, and potent visible light harnessing ability. Self-aggregation and rapid recombination rates have greatly hindered their applications in photocatalysis. A novel reduced graphene oxide-incorporated bimetallic nickel copper metal-organic framework (NiCu@INA/rGO MOF) is fabricated using isonicotinic acid as an organic linker. A synergistic effect between the two metals increased the photocatalytic performance. Introducing reduced graphene oxide to nickel-copper MOF increased charge carrier retention transfer and enhanced the catalyst’s water dispersibility. The efficiency of the photocatalyst for the removal of tetracycline (TCn) and a mixture of Rhodamine B (RhB) and Orange G (OrG) dyes was investigated under visible light. A degradation efficiency of up to 89 % for TCn and close to ∼97.8 % and 93.5 % degradation in the case of RhB and OrG dyes was observed. The studies on the photocatalytic degradation mechanism were explored by conducting radical scavenger experiments, Electron spin resonance (ESR) studies, and Mott-Schottky analysis. TCn and RhB degradation pathways were explored by mass spectral analysis of the intermediates during the photocatalytic degradation of TCn and RhB. This work provides new paradigms for the functional modification of MOF for designing efficient photocatalysis.

Defect tuning and its effect on conductivity, dielectric properties of combustion derived nano CeO2: A fuel dependent approach

Oxalyldihydrazide (ODH) and coffee extracted fuel (CEF) were used to synthesize Ceria (CeO2) nanoparticles by solution combustion synthesis route. The cubic fluorite structure, crystalline nature, crystallite size and particle size of ceria nanoparticles were confirmed using the powder X-ray diffraction (PXRD) and High-Resolution Transmission Electron Microscope patterns respectively. Field Emission Scanning Electron Microscope (FESEM) images were used to understand the Surface morphology of the synthesized samples. Based on XRD results the volume of coffee husk extract for the optimum phase formation is found to be 40 mL. The fluorite structure of the samples and the presence of oxygen vacancies in the samples were confirmed from the Raman spectral analysis. ESR (Electron Spin Resonance) studies confirmed formation of relatively more intrinsic defects in CEF-ceria nanoparticles compared to ODH-ceria nanoparticles. The semiconducting nature of the synthesized samples was confirmed by analysing UV–visible absorbance spectra. The functional group confirmation was obtained by analysing Fourier Transform Infrared (FTIR) spectra of both the samples. AC conductivity and dielectric relaxation studies of the samples in pellet form were carried out over a wide frequency (20Hz–10 MHz) and temperature (200–640 °C) range using a precision impedance analyser. A higher value of dielectric constant was observed for CEF-ceria nanoparticles.

Intramolecular Charge Transfer and Spin-Orbit Coupled Intersystem Crossing in Hypervalent Phosphorus(V) and Antimony(V) Porphyrin Black Dyes.

Porphyrin dyes with strong push-pull type intramolecular charge transfer (ICT) character and broad absorption across the visible spectrum are reported. This combination of properties has been achieved by functionalizing the periphery of hypervalent and highly electron-deficient phosphorus(V) and antimony(V) centered porphyrins with electron-rich triphenylamine (TPA) groups. As a result of the large difference in electronegativity between the porphyrin ring and the peripheral groups, their absorption profiles show several strong charge transfer transitions, which in addition to the porphyrin-centered π → π* transitions, make them panchromatic black dyes with high absorption coefficients between 200 and 800 nm. Time-resolved optical and electron paramagnetic resonance (EPR) studies show that the lowest triplet state also has ICT character and is populated by spin-orbit coupled intersystem crossing.

ZnO nanostructures grown from spent batteries: Ambient catalytic aspects and novel mechanistic insights

The present work includes a facile and economic microwave assisted hydrothermal synthesis of Zinc Oxide (ZnO), Diethylene Triamine Pentaacetic Acid (DTPA) stabilized Zinc Oxide (ZD) and DTPA stabilized Silver doped Zinc Oxide (ZAD) nanostructures using Zn from spent alkaline batteries. The synthesised nanostructures were well characterised using electronic, vibrational and X-Ray spectroscopic techniques as well as thermal and microscopic techniques revealing the successful stabilisation of DTPA in ZD and doping of Ag in ZAD. The Fourier Transform Infrared Spectroscopy (FTIR) spectra showed peaks characteristic to the presence of ZnO in the fingerprint region and those to the presence of DTPA. The X-Ray Diffraction Spectroscopy (XRD) pattern of ZnO, ZD and ZAD indicated the hexagonal wurtzite structure of ZnO and face centred cubic metallic Ag in ZAD. The Transmission Electron Microscopy (TEM) images revealed rod shaped morphology for ZnO and spherical morphologies for ZD and ZAD. The nanostructures proved to be efficient catalysts to achieve 100 % degradation of Malachite Green, Crystal Violet and Reactive Blue-21 and their binary mixtures under ambient conditions in presence of Hydrogen peroxide (H2O2). ZAD exhibited relatively rapid degradation with rate constants 0.754 min−1, 0.187 min−1 and 0.0150 min−1 for MG, CV, and RB-21 respectively as well as 99 % reduction in Chemical Oxygen Demand (COD) value of the dye solutions. Scavenging studies and Electron Paramagnetic Resonance (EPR) studies using different spin trapping agents revealed the involvement of singlet oxygen species, hydroxyl radicals (OH.) and superoxide radicals (O2.-) in the degradation process. This work aligns with Sustainable Development Goals 6, 12 and 13.

Weak Exchange Interactions in Multispin Systems: EPR Studies of Metalloporphyrins Decorated with {Cr7Ni} Rings.

Both metalloporphyrins and heterometallic {Cr7Ni} rings are of significant research interest due to their proposed roles in quantum information processing devices. In this study, we present a series of complexes in which [Cr7NiF3(Etglu)(O2CtBu)15] (N-EtgluH5 = N-ethyl-d-glucamine) heterometallic rings are coordinated to metalloporphyrin linkers: the symmetric [M(TPyP)] for M = Cu2+, VO2+, and H2TPyP = 5,10,15,20-tetra(4-pyridyl)porphyrin; and the asymmetric [{VO}(TrPPyP)] for H2(TrPPyP) = 5,10,15-(triphenyl)-20-(4-pyridyl)porphyrin. The magnetic interactions present in these complexes are unraveled using the continuous wave (CW) electron paramagnetic resonance (EPR) technique. The nature of the coupling between the {Cr7Ni} rings and the central metalloporphyrin is assessed by numerical simulations of CW EPR spectra and determined to be on the order of 0.01 cm-1, larger than the dipolar ones and suitable for individual spin addressability in multiqubit architectures.

In Situ Generation and High Bioresistance of Trityl-based Semiquinone Methide Radicals Under Anaerobic Conditions in Cellular Systems.

Bioreduction of spin labels and polarizing agents (generally stable radicals) has been an obstacle limiting the in-cell applications of pulsed electron paramagnetic resonance (EPR) spectroscopy and dynamic nuclear polarization (DNP). In this work, we have demonstrated that two semiquinone methide radicals (OXQM⋅ and CTQM⋅) can be easily produced from the trityl-based quinone methides (OXQM and CTQM) via reduction by various reducing agents including biothiols and ascorbate under anaerobic conditions. Both radicals have relatively low pKa's and exhibit EPR single line signals at physiological pH. Moreover, the bioreduction of OXQM in three cell lysates enables quantitative generation of OXQM⋅ which was most likely mediated by flavoenzymes. Importantly, the resulting OXQM⋅ exhibited extremely high stability in the E.coli lysate under anaerobic conditions with 76- and 14.3-fold slower decay kinetics as compared to the trityl OX063 and a gem-diethyl pyrrolidine nitroxide, respectively. Intracellular delivery of OXQM into HeLa cells was also achieved by covalent conjugation with a cell-permeable peptide as evidenced by the stable intracellular EPR signal from the OXQM⋅ moiety. Owing to extremely high resistance of OXQM⋅ towards bioreduction, OXQM and its derivatives show great application potential in in-cell EPR and in-cell DNP studies for various cells which can endure short-term anoxic treatments.

Photocatalytic Methane Oxidation and Removal Mediated by Free Radicals

Activation and selective oxidation of C-H bond in methane under mild conditions constitutes long-standing challenges which are of fundamental and technological importance, from biological to industrial and environmental. Earth relies on free radicals to remove the climate-damaging methane and other organic pollutants from the air. In recent decades, intensive efforts have been focused on leveraging free radicals for selective methane oxidation. Free radicals are one of key mediators underpinning many active sites in thermal catalysis and these enhancement effects induced by the light and electric fields. However, it remains unclear how free radicals as active species mediate the C-H bond activation in methane and dictate the products distribution.In this talk, we will discuss our recent advances in understanding and promoting the photocatalytic oxidation of methane to methanol by combining the rational design of photocatalysts, photochemical experiments, as well as the in-situ electron paramagnetic resonance studies of free radicals. Our results unravel interactions between these free radicals and the solid co-catalysts, ions, and gases molecules in water, as well as their impact on methane removal and its selective oxidation. Our studies highlight the neglected while important interplay between photogenerated radicals and co-catalysts, ion impurities, and gas molecules in promoting methane removal and controlling the products distribution. Furthermore, we report an inherent trade-off in the photochemical methane to methanol conversion. A new design principle featuring isolating different reaction steps is developed to circumvent this trade-off.Such molecular-level insights into photocatalysts and their interactions with free radicals are expected to promote the methane removal and its selective functionalization and offer informative design principles for chemical bonds activations that are driven by light, heat, and electric fields.

Abstract Tu123: Redox Biology of the Mitochondrial Protein mitoNEET and Ascorbate

Background: It has been proposed that mitoNEET is an Fe-S transfer/repair enzyme, playing a role under conditions of oxidative stress. mitoNEET protects mitochondria against oxidative stress in cardiomyocytes. Loss of mitoNEET is linked with age-related heart failure. Oxidized mitoNEET, [2Fe-2S] 2+ , exports Fe-S cluster from mitochondria to cytosol. Redox control of mitochondrion is essential for the proper functioning of the organelle/mitochondria. However, the molecular mechanisms involved in the redox biology of mitoNEET is not fully studied. Hypothesis: Ascorbate regulates redox reactions and Fe-S cluster transport function of mitoNEET in the mitochondria. Aims: The objective of this work is to evaluate the redox reactions between mitoNEET and ascorbate. Methods: Room temperature and low temperature (77 K) electron paramagnetic resonance (EPR) spectroscopy techniques were used to measure the oxidation of ascorbate and reduced mitoNEET, respectively. Results: EPR spectroscopic study shows that mitoNEET oxidizes ascorbate to ascorbate radical. The formation of ascorbate radical increases with increasing concentration of ascorbate. The formation of ascorbate radical is decreased in the presence of menadione. Low temperature EPR study shows that one electron reduction of mitoNEET by ascorbate. Conclusion: This study suggest that ascorbate is a substrate/cofactor for mitoNEET. Ascorbate regulates the Fe-S cluster transport function of mitoNEET. Ascorbate plays an important role in the redox biology of mitoNEET under physiological and pathophysiological conditions.

The practical utility of nitrogen doped TiO2 as a photocatalyst for the oxidative removal of gaseous formaldehyde

This study reports the development of nitrogen-doped TiO2 (N–TiO2: N/Ti molar ratio = 1) photocatalyst with the enhanced photoelectronic properties for the phtocatalytic oxidation (PCO) of formaldehyde (FA). The N–TiO2 photocatalyst is coated with ceramic beads and placed in a packed-bed tube reactor to examine the PCO-based mineralization of FA vapor (100 - 500 ppm) under ultraviolet (UV)-A illumination (32 W light source) with the control of flow rate (100–500 mL min−1), O2 (0–21%), and relative humidity (RH: 0–100%). Accordingly, the N-TiO2 in dry conditions showcases 100% degradation of 100 ppm FA with high stability over 5 reuse cycles (compared to the P25 (75.9%) and bare TiO2 (69.2%)) at a flow rate of 100 mL min−1 and a 21 % O2 level (quantum yield = 1.72.E−02 molecules photon−1 and space-time yield = 3.44.E−03 molecules photon−1 mg−1). The superior performance of N–TiO2 may reflect the combination of N/O atoms in the crystal structure to enhance the photo-redox reactivities with the heightened valence band enegry and prolonged lifespan of charge carrier (1.34 ns) relative to 1.04 ns of P25 and 1 ns of pure (anatase) TiO2. The PCO efficiency of N–TiO2 increases by around 1.6 times in slightly humid conditions (74.6%: RH 20%) compared to dry conditions (47%: RH 0%) while the absence of oxygen (at 0% O2) reduces it significantly down to 13.6%. In situ diffuse reflectance infrared Fourier transform spectroscopy and electron paramagnetic resonance studies confirm the critical role of O2 and H2O vapor on the enhanced FA mineralization rate (CO2 yield = 91 %) through the generation of •O2-/•OH oxidative radicals. This study offers deep insights into the practical utility of N–TiO2 for the photocatalytic mineralization of aldehyde VOCs.

Encapsulated Atomic Hydrogen in Octamethyl-POSS Cages: A Pulsed EPR Study.

Encapsulated atomic hydrogen in polyhedral oligomeric silsesquioxane (POSS) cages is a promising candidate for spin-based quantum technologies. Key parameters such as spin relaxation times and magnetic interactions with surrounding electron and nuclear spins can be typically probed with advanced electron paramagnetic resonance (EPR) methods. Here we present a detailed pulsed EPR study of the species H@Si8O12R8 with R=CH3, namely encapsulated atomic hydrogen in the octamethyl POSS derivative. The temperature dependence of the spin-lattice relaxation rate 1/ is analyzed in terms of a Raman process with a Debye temperature of K and a thermally activated process with (552 cm-1), whereas, the phase memory time shows the typical shortening behaviour at K observed for all methyl-containing derivatives. The hyperfine coupling of the cage Si nuclei is measured by hyperfine sublevel correlation (HYSCORE) spectroscopy and is found to fulfil the so-called "matching condition" at the low-field EPR transition. The potential of this paramagnetic molecule to perform one-qubit quantum operations is probed by room-temperature Rabi oscillations.

Removal of cyanide by peroxydisulfate activated by copper ions inherently present in the electroplating wastewater

Cyanide is widely used in electroplating processes to ensure the quality of metal plating. Alkaline chlorination process is commonly employed to remove cyanide from electroplating wastewater. However, several drawbacks exist, including the formation of toxic intermediates, high consumption of chemical reagents, and low removal efficiency of metal-cyanide complexes. In this study, persulfate advanced oxidation process was explored for the removal of cyanide from electroplating wastewater. The metal ions typically present in the electroplating wastewater, including Cu2+, Zn2+, Fe2+, Ag+ and Ni2+, may activate peroxydisulfate (PDS) to oxidize cyanide. Among these metal ions, cyanide can be most effectively removed in the presence of Cu2+ and PDS, likely due to the activation of PDS by Cu2+ and Cu(II)-cyanide complex. The results of lab studies indicated that 99 % removal of cyanide (4 mM) could be achieved in the presence of 10 mM PDS and 1 mM Cu2+ within 20 min. The results of radical scavenging experiments, radical probe tests and electron paramagnetic resonance (EPR) studies showed that sulfate radical (SO4•−) and hydroxyl radical (OH•) were primarily responsible for cyanide removal and the complexation of cyanide and Cu2+ significantly enhanced the formation of SO4•−. Cyanate and nitrite were the main by-products detected. For real electroplating wastewater, the addition of 40 mM PDS could almost completely remove cyanide (19.5 mM) in 20 min.

Azido derivatives of sesquiterpene lactones: Synthesis, anticancer proliferation, and chemistry of nitrogen-centered radicals

Sesquiterpene lactones (SLs) such as parthenolide (PTL) and dehydroleucodine (DhL) selectively kill cancer cells without exerting normal tissue toxicity, potentially due to presence of α-methylene-γ-lactone (αMγL) fragment. We hypothesize that the addition of an azido group to the αMγL fragment of PTL or DhL further augments their anticancer properties as well as radiation sensitivity of cancer cells. Azido-SLs containing the azido group at the C14 methyl position of PTL (i.e., azido-melampomagnolide B, AzMMB) while preserving the mechanistically crucial exomethylene unit of αMγL fragment were also prepared. Sham-irradiated (i.e., unirradiated control) or irradiated human breast cancer cells (MCF7) were treated with different concentrations of azido-PTL (AzPTL) or azido-DhL (AzDhL) along with parental SLs. Proliferation rate of MCF7 cells were measured by MTT-assay, and their colony forming ability was determined by colony formation assay. Both AzPTL and AzDhL significantly suppress proliferation rate and colony forming ability of MCF-7 cells. AzPTL suppressed colony forming ability, not cellular proliferation, following irradiation to a greater extent than PTL at lower concentrations (5 and 10 μM). Electron spin resonance (ESR) studies were performed employing gamma-irradiated homogeneous supercooled aqueous solutions to investigate radical formation through addition of radiation-mediated prehydrated electrons to the azide group of AzPTL and AzDhL and to follow subsequent reactions of these radicals. In AzPTL, formation of a tertiary carbon-centered radical plausibly via a metastable aminyl radical was observed, whereas AzDhL produced both π-aminyl and α-azidoalkyl radicals. These radicals may contribute to the antitumor activities of AzPTL and AzDhL.

An EPR study of point defects in zinc oxide thin films

We studied ZnO thin films deposited on glass slides by thermal evaporation in vacuum followed by heat treatment in open air or Ar flow. The samples were characterized using x-ray diffraction, Raman scattering, photoluminescence (PL), and electron paramagnetic resonance (EPR) spectroscopy. We observed a broad PL band in the visible region at spectral positions of 504 and 560 nm and a low-intensity band in the UV region at 390 nm. The EPR spectra display a clear first derivative structure at g=1.96 at temperatures below 200 K. The PL spectrum shows red-shifted valence to conduction band emission due to electron hole recombination through shallow surface states. We found an activation energy of E a = 4.2 meV using the Arrhenius plot and estimated concentrations of paramagnetic defects and spin–spin relaxation time constants of 1016 m−3 and 10–14 s, respectively.