Electron Paramagnetic Resonance Spectroscopic Studies Research Articles

Streptomycin generates oxidative stress in melanin-producing cells: In vitro study with EPR spectroscopy evidence

Streptomycin (STR) is an aminoglycoside antibiotic with a broad-spectrum of activity and ototoxic potential. The mechanism of STR-induced inner ear damage has not been fully elucidated. It was previously found that STR binds to melanin, which may result in the accumulation of the drug in melanin-containing tissues. Melanin pigment is present in various parts of the inner ear, including the cochlea and vestibular organ.The present study aimed to assess if streptomycin generates oxidative stress and affects melanogenesis in normal human melanocytes. Moreover the variation of free radical concentration in STR-treated melanocytes was examined by electron paramagnetic resonance spectroscopy (EPR). We found that STR decreases cell metabolic activity and reduces melanin content. The observed changes in the activity of antioxidant enzymes activity in HEMn-DPs treated with streptomycin may suggest that the drug affects redox homeostasis in melanocytes. In this work EPR study expanded knowledge about free radicals in interactions of STR and melanin in melanocytes. The results may help elucidate the mechanisms of STR toxicity on pigment cells, including melanin-producing cells in the inner ear. This is important because understanding the mechanism of STR-induced ototoxicity would be helpful in developing new therapeutic strategies to protect patients' hearing.

Evaluation of PEGylation efficacy of curcumin-loaded nanoemulsions using complementary methods to assess protein interactions and physicochemical properties

Nanoemulsions (NEs) are frequently used in the food, cosmetics and pharmaceutical industries to deliver nutraceuticals, pharmaceutical or cosmetic active ingredients. When administering NEs parenterally, various stabilisers are added to prevent rapid plasma clearance and to successfully deliver the active ingredient to the target site. For this purpose, PEGylation is often used to prolong the circulation time of the droplets. However, the problem is to determine the optimal concentration of the PEGylating agent – the PEGylation efficacy – that ensures adequate surface protection. This is a particular challenge when the active ingredient is incorporated into the stabilising layer, where any changes could disrupt the stability of the droplet. For this reason, we aimed to determine the optimal concentration of PEG2000-DSPE for surface protection of curcumin-loaded NEs for parenteral administration using electron paramagnetic resonance (EPR) spectroscopy. NEs were prepared using the high pressure homogenisation technique with 0.1 %, 0.3 % or 0.6 % of the PEGylated phospholipid. A droplet size of approximately 100 nm and polydispersity index below 0.25 indicated suitability for parenteral application. EPR analysis showed that PEG2000-DSPE had a stabilising effect on selected NEs, which was most pronounced in the part of the stabilising layer closest to the aqueous phase. To confirm these results, protein interaction studies were carried out using dynamic light scattering, UV–Vis spectroscopy, atomic force microscopy and release studies from protein-enriched media – bovine serum albumin (BSA) or foetal bovine serum (FBS) in phosphate-buffered saline. These analyses confirmed that the addition of PEG2000-DSPE reduced protein binding to the droplets as a function of concentration, with 0.3 % providing the best protection for the droplets. Our conclusions from the EPR spectroscopy study demonstrate the usefulness of EPR in determining the optimal concentrations of PEGylating agents for surface coverage and its usefulness in the formulation development phase.

Disentangling the Unusual Magnetic Anisotropy of the Near‐Room‐Temperature Ferromagnet Fe4GeTe2

AbstractIn the quest for 2D conducting materials with high ferromagnetic ordering temperature the new family of the layered FenGeTe2 compounds, especially the near‐room‐temperature ferromagnet Fe4GeTe2, receives a significant attention. Fe4GeTe2 features a peculiar spin reorientation transition at TSR ≈ 110 K suggesting a non‐trivial temperature evolution of the magnetic anisotropy (MA)—one of the main contributors to the stabilization of the magnetic order in the low‐dimensional systems. An electron spin resonance (ESR) spectroscopic study reported here provides quantitative insights into the unusual magnetic anisotropy of Fe4GeTe2. At high temperatures the total MA is mostly given by the demagnetization effect with a small contribution of the counteracting intrinsic magnetic anisotropy of an easy‐axis type, whose growth below a characteristic temperature Tshape ≈ 150 K renders the sample seemingly isotropic at TSR. Below one further temperature Td ≈ 50 K the intrinsic MA becomes even more complex. Importantly, all the characteristic temperatures found in the ESR experiment match those observed in transport measurements, suggesting an inherent coupling between magnetic and electronic degrees of freedom in Fe4GeTe2. This finding together with the observed signatures of the intrinsic two‐dimensionality should facilitate optimization routes for the use of Fe4GeTe2 in the magneto‐electronic devices, potentially even in the monolayer limit.

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.

Adsorption and degradation of tetracycline hydrochloride in aqueous solutions using activated carbon with Fe/Ag nanoparticles

In this study, a new adsorbent denoted as nAg/nZVI/AC was developed using activated carbon (AC) loaded with nanosized zero-valent iron (nZVI) and nanosilver (nAg). Then, the adsorption and degradation of tetracycline hydrochloride (TCH) in aqueous solutions using nAg/nZVI/AC was examined. At pH 3.8, the adsorbed amount of TCH on nAg/nZVI/AC was 191.18 mg/g, which is 78.95 mg/g higher than that adsorbed on the pristine AC support. The adsorption process could be explained adequately using the Freundlich (R2 = 0.9641) and pseudo-second-order kinetic models (R2 = 0.9967). Thermodynamic analyses revealed that TCH removal is a spontaneous chemisorption-dominated process. Free-radical-quenching experiments and electron paramagnetic resonance spectroscopic studies revealed that hydroxyl (·OH) and superoxide (·O2−) radicals are the main species involved in the degradation of TCH. Finally, the intermediates generated during the degradation were examined using liquid chromatography-mass spectrometry, and possible deterioration pathways are proposed.

Characterization of ferredoxins involved in electron transfer pathways for nitrogen fixation implicates differences in electronic structure in tuning 2[4Fe[sbnd]4S] Fd activity

Ferredoxins (Fds) are small proteins which shuttle electrons to pathways like biological nitrogen fixation. Physical properties tune the reactivity of Fds with different pathways, but knowledge on how these properties can be manipulated to engineer new electron transfer pathways is lacking. Recently, we showed that an evolved strain of Rhodopseudomonas palustris uses a new electron transfer pathway for nitrogen fixation. This pathway involves a variant of the primary Fd of nitrogen fixation in R. palustris, Fer1, in which threonine at position 11 is substituted for isoleucine (Fer1T11I). To understand why this substitution in Fer1 enables more efficient electron transfer, we used in vivo and in vitro methods to characterize Fer1 and Fer1T11I. Electrochemical characterization revealed both Fer1 and Fer1T11I have similar redox transitions (−480 mV and − 550 mV), indicating the reduction potential was unaffected despite the proximity of T11 to an iron‑sulfur (FeS) cluster of Fer1. Additionally, disruption of hydrogen bonding around an FeS cluster in Fer1 by substituting threonine with alanine (T11A) or valine (T11V) did not increase nitrogenase activity, indicating that disruption of hydrogen bonding does not explain the difference in activity observed for Fer1T11I. Electron paramagnetic resonance spectroscopy studies revealed key differences in the electronic structure of Fer1 and Fer1T11I, which indicate changes to the high spin states and/or spin-spin coupling between the FeS clusters of Fer1. Our data implicates these electronic structure differences in facilitating electron flow and sets a foundation for further investigations to understand the connection between these properties and intermolecular electron transfer.

Designing surface exposed sites on Bacillus subtilis lipase A for spin-labeling and hydration studies

Spin-labeling with electron paramagnetic resonance spectroscopy (EPR) is a facile method for interrogating macromolecular flexibility, conformational changes, accessibility, and hydration. Within we present a computationally based approach for the rational selection of reporter sites in Bacillus subtilis lipase A (BSLA) for substitution to cysteine residues with subsequent modification with a spin-label that are expected to not significantly perturb the wild-type structure, dynamics, or enzymatic function. Experimental circular dichroism spectroscopy, Michaelis-Menten kinetic parameters and EPR spectroscopy data validate the success of this approach to computationally select reporter sites for future magnetic resonance investigations of hydration and hydration changes induced by polymer conjugation, tethering, immobilization, or amino acid substitution in BSLA. Analysis of molecular dynamic simulations of the impact of substitutions on the secondary structure agree well with experimental findings. We propose that this computationally guided approach for choosing spin-labeled EPR reporter sites, which evaluates relative surface accessibility coupled with hydrogen bonding occupancy of amino acids to the catalytic pocket via atomistic simulations, should be readily transferable to other macromolecular systems of interest including selecting sites for paramagnetic relaxation enhancement NMR studies, other spin-labeling EPR studies or any method requiring a tagging method where it is desirable to not alter enzyme stability or activity.

An Isolable Phosphinogermylyne as a Synthon of One‐Coordinate GeI Radical

Comprehensive SummaryReduction of chlorogermylene MsFluindtBu‐GeCl 1 with potassium graphite (KC8) afforded putative germylyne radical MsFluindtBu‐Ge 2 as confirmed by electron paramagnetic resonance (EPR) spectroscopy. However, it slowly decayed via C—H bond activation at the fluorenyl moiety to yield a bis(germylene) 3 at room temperature. By using a Lewis base to stabilize the unoccupied p orbital at the GeI radical center, acyclic two‐coordinate GeI radicals MsFluindtBu‐Ge(IMe4) 4 (IMe4 = 1,3,4,5‐tetramethyl‐imidazolin‐2‐ylidene), MsFluindtBu‐Ge(IiPr) 5 (IiPr = 1,3‐diisopropyl‐4,5‐dimethyl‐imidazolin‐2‐ylidene), MsFluindtBu‐Ge(PMe3) 6 were isolated in crystalline forms. The unpaired electron in 4—6 mainly resides at the Ge 4p orbital as revealed by EPR spectroscopic studies and theoretical calculations. Interestingly, facile ligand exchange of PMe3 in 6 with IMe4 and IiPr was observed to afford 4 and 5, respectively. Moreover, phosphinogermylyne 6 reacted with PhEEPh (E = S, Se), 4‐tetrabutylphenylacetylene (Ar'CCH), [CpMo(CO)3]2 and nBu3SnH to furnish germylenes MsFluindtBu‐GeEPh (E = S 7, Se 8), MsFluindtBu‐GeCH=CHAr’ 9, a germylyne complex MsFluindtBu‐Ge≡Mo(CO)2Cp 10 and a Ge(IV) compound MsFluindtBu‐GeH2SnnBu3 11, respectively. The reactivity studies demonstrate that 6 can act as a synthon of one‐coordinate germylyne radical attributing to labile coordination of trimethylphosphine.

Steering Single-Electron Metal-Metal Bonds and Hyperfine Coupling between a Transition Metal-Lanthanide Heteronuclear Bimetal Confined in Carbon Cages.

Metal complexes bearing single-electron metal-metal bonds (SEMBs) exhibit unusual electronic structures evoking strong magnetic coupling, and such bonds can be stabilized in the form of dimetallofullerenes (di-EMFs) in which two metals are confined in a carbon cage. Up to now, only a few di-EMFs containing SEMBs are reported, which are all based on a high-symmetry icosahedral (Ih) C80 cage embedding homonuclear rare-earth bimetals, and a chemical modification of the Ih-C80 cage is required to stabilize the SEMB. Herein, by introducing 3d-block transition metal titanium (Ti) along with 4f-block lanthanum (La) into the carbon cage, we synthesized the first crystallographically characterized SEMB-containing 3d-4f heteronuclear di-EMFs based on pristine fullerene cages. Four novel La-Ti heteronuclear di-EMFs were isolated, namely, LaTi@D3h(5)-C78, LaTi@Ih(7)-C80, LaTi@D5h(6)-C80, and LaTi@C2v(9)-C82, and their molecular structures were unambiguously determined by single-crystal X-ray diffraction. Upon increasing the cage size from C78 to C82, the La-Ti distance decreases from 4.31 to 3.97 Å, affording fine-tuning of the metal-metal bonding and hyperfine coupling, as evidenced by an electron spin resonance (ESR) spectroscopic study. Density functional theory (DFT) calculations confirm the existence of SEMB in all four LaTi@C2n di-EMFs, and the accumulation of electron density between La and Ti atoms shifts gradually from the proximity of the Ti atom inside C78 to the center of the LaTi bimetal inside C82 due to the decrease of the La-Ti distance. The electronic properties of LaTi@C2n heteronuclear dimetallofullerenes differ apparently from their homonuclear La2@C2n counterparts, revealing the peculiarity of heteronuclear dimetallofullerenes with the involvement of 3d-block transition metal Ti.

N-Sulfenylation of β-Lactams: Radical Reaction of N-Bromo-azetidinones by TEMPO Catalysis.

Azetidinones with a sulfenyl group on the β-lactam nitrogen atom show interesting biological activities as antimicrobial agents and enzyme inhibitors. We report in the present study a versatile synthesis of N-sulfenylated azetidinones starting from the corresponding N-bromo derivatives by means of the (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) radical as the catalyst and disulfides. Preparation of N-halo-azetidinones was studied and optimized. The reactivity of N-bromo-azetidinone 2a as a model compound in the presence of TEMPO radical was investigated by NMR and electron paramagnetic resonance (EPR) spectroscopy studies. Optimization of the reaction conditions allowed the access of N-alkylthio- or N-arylthio-azetidinones from 55 to 92% yields, and the method exhibited a good substrate scope.

Realism-based assessment of the efficacy of potassium peroxymonosulphate on Stenotrophomonas maltophilia biofilm control

The potential of pentapotassium bis(peroxymonosulphate) bis(sulphate) (OXONE) to control biofilms in drinking water distribution systems (DWDS) was evaluated and compared to chlorine disinfection. Mature biofilms of drinking water (DW)-isolated Stenotrophomonas maltophilia were formed using a simulated DWDS with a rotating cylinder reactor (RCR). After 30 min of exposure, OXONE at 10 × minimum bactericidal concentration (MBC) caused a significant 4 log reduction of biofilm culturability in comparison to the unexposed biofilms and a decrease in the number of non-damaged cells below the detection limit (4.8 log cells/cm2). The effects of free chlorine were restricted to approximately 1 log reduction in both biofilm culturability and non-damaged cells. OXONE in synthetic tap water (STW) at 25 ºC was more stable over 40 days than free chlorine in the same conditions. OXONE solution exhibited a disinfectant decrease of about 10% of the initial concentration during the first 9 days, and after this time the values remained stable. Whereas possible reaction of chlorine with inorganic and organic substances in STW contributed to free chlorine depletion of approximately 48% of the initial concentration. Electron paramagnetic resonance (EPR) spectroscopy studies confirmed the presence of singlet oxygen and other free radicals during S. maltophilia disinfection with OXONE. Overall, OXONE constitutes a relevant alternative to conventional DW disinfection for effective biofilm control in DWDS.

A Conserved Second Sphere Residue Tunes Copper Site Reactivity in Lytic Polysaccharide Monooxygenases.

Lytic polysaccharide monooxygenases (LPMOs) are powerful monocopper enzymes that can activate strong C-H bonds through a mechanism that remains largely unknown. Herein, we investigated the role of a conserved glutamine/glutamate in the second coordination sphere. Mutation of the Gln in NcAA9C to Glu, Asp, or Asn showed that the nature and distance of the headgroup to the copper fine-tune LPMO functionality and copper reactivity. The presence of Glu or Asp close to the copper lowered the reduction potential and decreased the ratio between the reduction and reoxidation rates by up to 500-fold. All mutants showed increased enzyme inactivation, likely due to changes in the confinement of radical intermediates, and displayed changes in a protective hole-hopping pathway. Electron paramagnetic resonance (EPR) and X-ray absorption spectroscopic (XAS) studies gave virtually identical results for all NcAA9C variants, showing that the mutations do not directly perturb the Cu(II) ligand field. DFT calculations indicated that the higher experimental reoxidation rate observed for the Glu mutant could be reconciled if this residue is protonated. Further, for the glutamic acid form, we identified a Cu(III)-hydroxide species formed in a single step on the H2O2 splitting path. This is in contrast to the Cu(II)-hydroxide and hydroxyl intermediates, which are predicted for the WT and the unprotonated glutamate variant. These results show that this second sphere residue is a crucial determinant of the catalytic functioning of the copper-binding histidine brace and provide insights that may help in understanding LPMOs and LPMO-inspired synthetic catalysts.

ATCUN-like Copper Site in βB2-Crystallin Plays a Protective Role in Cataract-Associated Aggregation.

Cataract is the leading cause of blindness worldwide, and it is caused by crystallin damage and aggregation. Senile cataractous lenses have relatively high levels of metals, while some metal ions can directly induce the aggregation of human γ-crystallins. Here, we evaluated the impact of divalent metal ions in the aggregation of human βB2-crystallin, one of the most abundant crystallins in the lens. Turbidity assays showed that Pb2+, Hg2+, Cu2+, and Zn2+ ions induce the aggregation of βB2-crystallin. Metal-induced aggregation is partially reverted by a chelating agent, indicating the formation of metal-bridged species. Our study focused on the mechanism of copper-induced aggregation of βB2-crystallin, finding that it involves metal-bridging, disulfide-bridging, and loss of protein stability. Circular dichroism and electron paramagnetic resonance (EPR) revealed the presence of at least three Cu2+ binding sites in βB2-crystallin, one of them with spectroscopic features typical for Cu2+ bound to an amino-terminal copper and nickel (ATCUN) binding motif, which is found in Cu transport proteins. The ATCUN-like Cu binding site is located at the unstructured N-terminus of βB2-crystallin, and it could be modeled by a peptide with the first six residues in the protein sequence (NH2-ASDHQF-). Isothermal titration calorimetry indicates a nanomolar Cu2+ binding affinity for the ATCUN-like site. An N-truncated form of βB2-crystallin is more susceptible to Cu-induced aggregation and is less thermally stable, indicating a protective role for the ATCUN-like site. EPR and X-ray absorption spectroscopy studies reveal the presence of a copper redox active site in βB2-crystallin that is associated with metal-induced aggregation and formation of disulfide-bridged oligomers. Our study demonstrates metal-induced aggregation of βB2-crystallin and the presence of putative copper binding sites in the protein. Whether the copper-transport ATCUN-like site in βB2-crystallin plays a functional/protective role or constitutes a vestige from its evolution as a lens structural protein remains to be elucidated.

Observation of Long-Lived Charge-Separated States in Anthraquinone-Phenothiazine Electron Donor-Acceptor Dyads: Transient Optical and Electron Paramagnetic Resonance Spectroscopic Studies.

We prepared a series of phenothiazine (PTZ)-anthraquinone (AQ) electron donor-acceptor dyads to study the relationship between molecular structures and the possibility of charge transfer (CT) and intersystem crossing (ISC). As compared to the previously reported PTZ-AQ dyad with a direct connection of two units via a C-N single bond, the PTZ and AQ units are connected via a p-phenylene or p-biphenylene linker. Conformation restriction is imposed by attaching ortho-methyl groups on the phenylene linker. UV-vis absorption spectra indicate electronic coupling between the PTZ and AQ units in the dyads without conformation restriction. Different from the previously reported PTZ-AQ, thermally activated delayed fluorescence (TADF) is observed for the dyads containing one phenylene linker (PTZ-Ph-AQ and PTZ-PhMe-AQ). The prompt fluorescence lifetime in cyclohexane is exceptionally long (τPF = 62.0 ns, population ratio: 99.2%) and 245.0 ns (93.5%) for PTZ-Ph-AQ and PTZ-PhMe-AQ, respectively (normally τPF <20 ns); the delayed fluorescence lifetimes for these two dyads were determined as τDF = 2.4 μs (6.5%) and 7.6 μs (0.8%), respectively. For the dyad containing a biphenylene linker (PTZ-Ph2Me-AQ), no TADF was observed. Charge-separated (CS) states were observed for PTZ-Ph-AQ and PTZ-PhMe-AQ, and the lifetimes were determined as 7.0 and 1.3 μs, respectively, indicating the triplet spin multiplicity of the CS state. The 3CS state lifetimes are shortened to 100 ns and 440 ns for the two dyads, respectively, in the polar solvent acetonitrile. For dyads with a longer linker, i.e., PTZ-Ph2Me-AQ, the CS state lifetime is not sensitive to solvent polarity (τCS = 1.8 and 1.3 μs in cyclohexane and acetonitrile, respectively). In reference dyads, where the PTZ unit is oxidized to sulfoxide, no CT absorption band and TADF were observed, which is attributed to the increased CS state energy (>3 eV) becoming higher than that of the AQ triplet (3AQ*) state (ca. 2.7 eV). These experimental evidence show that the presence of 1CS, 3CS, and 3LE (LE: locally excited) states sharing similar energy is essential for the occurrence of TADF. Population of the long-lived 3CS state (with a lifetime of a few μs) does not produce by itself TADF, because the ISC process of 1CS→3CS is nonsufficient. Femtosecond transient absorption spectra show that charge separation (CS) occurs readily (<5 ps) for most dyads, even in nonpolar solvents. Nanosecond pulsed laser-excited time-resolved electron paramagnetic resonance (TREPR) spectra show that either a spin correlated radical pair (SCRP) is formed, with the electron exchange energy 2J = +2.14 mT, or radical pairs with stronger interaction, |2J| > 6.57 mT. These studies are useful for in-depth understanding of the CS and ISC in compact electron donor-acceptor dyads and for design of efficient TADF emitters.

Different Biophysical Properties of Cell Surface α2,3- and α2,6-Sialoglycans Revealed by Electron Paramagnetic Resonance Spectroscopic Studies.

Sialoglycans on HeLa cells were labeled with a nitroxide spin radical through enzymatic glycoengineering (EGE)-mediated installation of azide-modified sialic acid (Neu5Ac9N3) and then click reaction-based attachment of a nitroxide spin radical. α2,6-Sialyltransferase (ST) Pd2,6ST and α2,3-ST CSTII were used for EGE to install α2,6- and α2,3-linked Neu5Ac9N3, respectively. The spin-labeled cells were analyzed by X-band continuous wave (CW) electron paramagnetic resonance (EPR) spectroscopy to gain insights into the dynamics and organizations of cell surface α2,6- and α2,3-sialoglycans. Simulations of the EPR spectra revealed average fast- and intermediate-motion components for the spin radicals in both sialoglycans. However, α2,6- and α2,3-sialoglycans in HeLa cells possess different distributions of the two components, e.g., a higher average population of the intermediate-motion component for α2,6-sialoglycans (78%) than that for α2,3-sialoglycans (53%). Thus, the average mobility of spin radicals in α2,3-sialoglycans was higher than that in α2,6-sialoglycans. Given the fact that a spin-labeled sialic acid residue attached to the 6-O-position of galactose/N-acetyl-galactosamine would experience less steric hindrance and show more flexibility than that attached to the 3-O-position, these results may reflect the differences in local crowding/packing that restrict the spin-label and sialic acid motion for α2,6-linked sialoglycans. The studies further suggest that Pd2,6ST and CSTII may have different preferences for glycan substrates in the complex environment of the extracellular matrix. The discoveries of this work are biologically important as they are useful for interpreting the different functions of α2,6- and α2,3-sialoglycans and indicate the possibility of using Pd2,6ST and CSTII to target different glycoconjugates on cells.

Low-temperature persulfate activation by powdered activated carbon for simultaneous destruction of perfluorinated carboxylic acids and 1,4-dioxane.

Carbonaceous materials have emerged as a method of persulfate activation for remediation. In this study, persulfate activation using powdered activated carbon (PAC) was demonstrated at temperatures relevant to groundwater (5-25°C). At room temperature, increasing doses of PAC (1-20gL-1) led to increased persulfate activation (3.06×10-6s-1 to 2.10×10-4 with 1 and 20gL-1 PAC). Activation slowed at lower temperatures (5 and 11°C); however, substantial (>70 %) persulfate activation was achieved. PAC characterization showed that persulfate is activated at the surface of the PAC, as indicated by an increase in the PAC C:O ratio. Similarly, electron paramagnetic resonance (EPR) spectroscopy studies with a spin trapping agents (5,5-dimethyl-1-pyrroline N-oxide (DMPO)) and 2,2,6,6-tetramethylpiperidine (TEMP) revealed that singlet oxygen was not the main oxidizing species in the reaction. DMPO was oxidized to form 5,5-dimethylpyrrolidone-2(2)-oxyl-(1) (DMPOX), which forms in the presence of strong oxidizers, such as sulfate radicals. The persulfate/PAC system is demonstrated to simultaneously degrade both perfluorooctanoic acid (PFOA) and 1,4-dioxane at room temperature and 11°C. With a 20gL-1 PAC and 75mM persulfate, 80 % and 70 % of the PFOA and 1,4-dioxane, respectively, degraded within 6h at room temperature. At 11°C, the same PAC and persulfate doses led to 57% dioxane degradation and 54 % PFOA degradation within 6h. Coupling PAC with persulfate offers an effective, low-cost treatment for simultaneous destruction of 1,4-dioxane and PFOA.

An isolable germylyne radical with a one-coordinate germanium atom.

Carbynes (R-[Formula: see text]), species that bear a monovalent carbon atom with three non-bonding valence electrons, are important intermediates and potentially useful in organic synthetic chemistry. However, free species of the type R-[Formula: see text] of any group 14 element (E) have eluded isolation in the condensed phase due to their high reactivity. Here we report the isolation, characterization and reactivity of a crystalline germylyne radical by using a sterically hindered hydrindacene ligand. The germylyne radical bears an essentially one-coordinate germanium atom as shown by single-crystal X-ray diffraction analysis. Electron paramagnetic resonance spectroscopic studies and theoretical calculations show that the germylyne radical features a doublet ground state, and the three non-bonding valence electrons at the germanium atom contribute to the lone pair of electrons as the highest occupied molecular orbital-3 and one unpaired electron as the singly occupied molecular orbital.

Dimensional reduction and incommensurate dynamic correlations in the S=frac{1}{2} triangular-lattice antiferromagnet Ca3ReO5Cl2

The observation of spinon excitations in the S=frac{1}{2} triangular antiferromagnet Ca3ReO5Cl2 reveals a quasi-one-dimensional (1D) nature of magnetic correlations, in spite of the nominally 2D magnetic structure. This phenomenon is known as frustration-induced dimensional reduction. Here, we present high-field electron spin resonance spectroscopy and magnetization studies of Ca3ReO5Cl2, allowing us not only to refine spin-Hamiltonian parameters, but also to investigate peculiarities of its low-energy spin dynamics. We argue that the presence of the uniform Dzyaloshinskii-Moriya interaction (DMI) shifts the spinon continuum in momentum space and, as a result, opens a zero-field gap at the Γ point. We observed this gap directly. The shift is found to be consistent with the structural modulation in the ordered state, suggesting this material as a perfect model triangular-lattice system, where a pure DMI-spiral ground state can be realized.

Intrinsic defect-induced magnetism and enhanced photocatalytic activity in Zn1−xZrxO (0.0 ≤ x ≤ 0.07) nanoparticles for spintronic device and photocatalytic application

In this study, ZnO nanoparticles were synthesized by sol-gel auto combustion technique with and without Zr4+ doping. The synthesized nanoparticles were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive X-ray analysis (EDAX), selected area diffraction pattern (SAED), transmission electron microscopy (TEM), photoluminescence spectroscopy (PL), fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance spectroscopy (EPR). A rietveld refinement analysis was performed using fullprof software on the XRD patterns of ZnO and Zr4+ doped ZnO nanoparticles, analysis showed a hexagonal wurtzite structure with an average crystallite size between 19 and 15 nm. SEM were employed to examine the surface morphology. TEM used to determine the particle size and size distribution histogram. SAED pattern confirmed the single-crystalline wurtzite structure. The compositional stoichiometry was verified by energy dispersive spectroscopy (EDAX). The PL spectrum reveals UV emission at the near band edge, as well as defect-related blue and green emission. In the PL spectrum, the green emission of Zr doped ZnO nanoparticles correlates strongly with their magnetic properties.An oxygen vacancy defect was confirmed by EPR studies for Zr doped ZnO nanoparticles. Sample (x = 0.03) exhibited very high coercivity value due to higher oxygen vacancies (Vo). X-ray photoelectron spectroscopy showed the oxidation state of Zn and Zr4+ atoms exist as Zn2+ and Zr4+ in the ZnO structure respectively. A vibrating sample magnetometer (VSM) was used to quantify the magnetic properties. Field-dependent magnetization measurements show diamagnetic behavior for pristine and Zr (x = 0.01 mol) doped ZnO. However, other doped samples (x = 0.03, 0.05, and 0.07 mol) exhibited ferromagnetic behavior at room temperature due to intrinsic defects (Zni and Vo). A UV–visible absorption spectrum was used to determine the energy band gap. Compared with pristine ZnO nanoparticles, doped samples exhibit a redshift in absorption edge. In addition, the photocatalytic activity of synthesized samples was determined by degrading the dye methylene blue (M.B.) in the presence of sunlight. An extensive evaluation of the effect of Zr concentrations on photocatalytic degradation was conducted. Zr4+ doped ZnO nanoparticles exhibit emission peaks detected at 424, 446, and 573 nm. These emission peaks result from electron movement from the deep donor level, zinc interstitial (Zni), and oxygen vacancy(Vo), which ultimately leads to higher photocatalytic efficiency.

EPR study of self-organized magnetic nanoparticles in biomaterials

An innovative approach based on the effect of bio-mineralization as a response reaction of cells to decrease their damage under stress was applied to Juniperus communis (JC) and JC-based biomaterials (Nefrovil and Immunostan drugs with properties increasing the antioxidant activity and improving the immune system of human organism, respectively). Electron paramagnetic resonance spectroscopy (EPR), also called electron spin resonance (ESR), was used as the main experimental tool for detecting paramagnetic species resulted from the existence of antioxidant activity system, represented by superoxide dismutase with manganese, catalase etc., as well as formation of superparamagnetic iron oxide nanoparticles (SPIONs). The influence of temperature and microwave power on the intensity of EPR signals detected in JC, Nefrovil and Immunostan was examined. Obtained g-factor values of EPR signals from JC shell and seeds as well as from Nefrovil and Immunostan were attributed to the paramagnetic species of Mn (g = 2.0), Fe3O4 SPIONs (g = 2.17…2.60), Fe aggregates (g = 3.22…3.94) and Fe3+ ions (g = 4.3). The EPR signals from SPIONs and Fe3+ ions in Immunostan were found to be fully correlated, showing an additional experimental evidence of the bio-mineralization effect (i.e., transformation of Fe3+ ions to Fe3O4 SPIONs). The results of the EPR study of Fe3O4 SPIONs incorporated into polymer matrix were taken into account in comparative analysis. The results reported in the present work support well self-organization of magnetic nanoparticles in the investigated biomaterials.