Six-line Spectrum Research Articles

Optimized Mn4+ doped Sr9Y2W4O24 perovskite for enhanced far-red-emitting luminescent material

In this study, a new perovskite Sr9Y2W4O24:Mn4+ is presented and its photoluminescence properties are examined in conjunction with electron paramagnetic resonance (EPR) analysis for comparison. Sol-gel synthesis resulted in a series of samples, that were characterized in detail using X-ray diffraction (XRD), Fourier Transform Infrared spectroscopy (FT-IR), diffuse reflectance spectrum (DRS), photoluminescence spectra (PL) and EPR. XRD patterns are consistent with standard data, affirming the tetragonal crystal arrangement of the synthesized samples. The band gap estimation based on DRS indicated a value of 5 eV. PL emission analysis identified a far-red emission peak (2Eg→4A2) at 677 nm, confirms the presence of Mn in the 4+ ionic state in the inorganic matrix. Crystal field analysis also demonstrated the presence of Mn4+ in a strong crystal field environment. Additionally, EPR analysis revealed distinct features of the observed broad line with a width of approximately 400 G and a six-line spectrum with g ∼1.98 characteristic of the Mn4+ doped Sr9Y2W4O24 perovskite. The prevailing evidence strongly suggests the likelihood of Mn4+ dopant ions occupying W6+ sites within the perovskite lattice. The EPR experimental data also confirmed the simulation data indicating the presence of Mn4+ ions in a given inorganic matrix. This investigation provides a comprehensive insight into the structural and spectroscopic properties of Mn4+ doped Sr9Y2W4O24 perovskites, confirming their potential as advanced lighting technologies to facilitate enhanced agricultural practices and plant cultivation.

A three-dimensional manganese(II) coordination polymer: synthesis, structure and catecholase activity

A manganese-based coordination polymer, [Mn2L2(µ-MeOH)2]n (H2L = 2-hydroxy-1-naphthaldehyde isonicotinoylhydrazone) was obtained by self-assembly of 2-hydroxy-1-naphthaldehyde isonicotinoylhydrazone and manganese(II) acetate. The coordination polymer was characterized by IR, EPR and UV–Vis spectroscopy. The single-crystal X-ray diffraction study reveals that the dibasic tridentate ligand (L2−) is bound via ONO donor sites to manganese(II). Two such [ML] fragments are connected by µ2-bridged methanol (MeOH) to form a di-manganese species. The sixth site of each of the manganese is occupied by the pyridyl N atom of the isonicotinoyl group. This arrangement gives a polynuclear complex of the formula [Mn2L2(µ-MeOH)2]n. The coordination geometry of manganese is distorted octahedral. The X-band electron paramagnetic resonance (EPR) measurement of the complex at 77 K shows a six-line spectrum and a signal at the half field, with g = 4.88. The half-field signal indicates the dimeric nature of the complex in the solution state. The cyclic voltammetric measurement of the complex shows a reversible MnIII/MnII redox couple. The complex catalyzes the conversion of 3,5-di-tert-butyl catechol to the corresponding o-quinone with a catalytic turnover rate of (kcat) 27.22 h−1.

α-Phenyl-N-cyclohexyl Nitrones: Preparation and Use as Spin-Traps.

Two bifunctional α-phenyl-N-cyclohexyl nitrones were synthesized with the expectation that the cyclohexyl ring will impart lipophilicity to the molecule, high reactivity to the nitronyl group, and stability to the spin adducts formed. The synthesis of the acid nitrone 4 and its corresponding tert-butyl ester 3 was initiated by a Michael reaction to introduce the cyclohexyl ring. A Zn/AcOH-mediated reduction of the nitro functionality followed by condensation onto benzaldehyde generated the nitronyl function. In agreement with their high lipophilicity values, nitrone 3 was insoluble in water, while nitrone 4 exhibited a poor water solubility. It was determined that the presence of the cyclohexyl ring did not affect either the reduction or oxidation potentials of the nitronyl group in comparison to the classical α-phenyl-N-tert-butylnitrone (PBN). The spin trapping ability of 3 and 4 was investigated by EPR for oxygen- and carbon-centered radicals. In most cases, the nitrones gave rise to a standard six-line EPR spectrum whose values were in agreement with the literature, accompanied by a minor second species. In DMSO, the half-lives of nitrone 3 and 4-OOH adducts were double that of PBN, suggesting that the stabilization comes from the cyclohexyl ring and/or the electronic effect of the carboxylic acid.

Mn(II) complexes of different nuclearity: synthesis, characterization and catecholase-like activity.

Two "end-off" compartmental ligands, 2-formyl-4-chloro-6-N-ethylmorpholine-iminomethyl-phenol (HL1) and 2-formyl-4-methyl-6-N-ethylpyrrolidine-iminomethyl-phenol (HL2) have been designed and three complexes of Mn(ii), one mono-, one di- and a polynuclear, namely Mn(L1)(SCN)2(H2O)] (), [Mn2(L1)(OAc)2](BPh4)] (), and [Mn2(L2)(OAc)2(dca)]n () have been synthesized and structurally characterized. Variable temperature magnetic studies of and have been performed and data analyses reveal that Mn centers are antiferromagnetic coupled with J = -9.15 cm(-1) and J = -46.89, respectively. Catecholase activity of all the complexes has been investigated using 3,5-di-tert-butyl catechol (3,5-DTBC). All are highly active and the activity order on the basis of the kcat value is > > . In order to unveil whether the metal centered redox participation or the radical pathway is responsible for the catecholase-like activity of the complexes, detailed EPR and cyclic voltammetric (CV) studies have been performed. In addition to the six-line EPR spectrum characteristic to Mn(ii), an additional peak at g ∼ 2 is observed when the EPR study is done with the mixture of 3,5-DTBC and the catalyst, suggesting the formation of an organic radical, most likely ligand centered. The CV experiment with the mixture of 3,5-DTBC and the catalyst reveals ligand centered reduction rather than reduction of Mn(ii) to Mn(i). It is thus inferred that complexes show catecholase-like activity due to radical generation.

Monohydroxylated Polybrominated Diphenyl Ethers (OH-PBDEs) and Dihydroxylated Polybrominated Biphenyls (Di-OH-PBBs): Novel Photoproducts of 2,6-Dibromophenol

Hydroxylated polybromodiphenyl ethers (OH-PBDEs) are emerging aquatic pollutants, but their origins in the environment are not fully understood. There is evidence that OH-PBDEs are formed from bromophenols, but the underlying transformation processes remain unknown. Here, we investigate if the photoformation of OH-PBDEs from 2,6-dibromophenol in aqueous solution involves 2,6-bromophenoxyl radicals. After the UV irradiation of an aqueous 2,6-dibromophenol solution, HPLC-LTQ-Orbitrap MS and GC-MS analysis revealed the formation of a OH-PBDE and a dihydroxylated polybrominated biphenyl (di-OH-PBB). Both dimeric photoproducts were tentatively identified as 4'-OH-BDE73 and 4,4'-di-OH-PBB80. In addition, three debromination products (4-OH-BDE34, 4'-OH-BDE27, and 4,4'-di-OH-PBBs) were observed. Electron paramagnetic resonance spectroscopy revealed the presence of a 2,6-dibromophenoxyl radical with a six-line spectrum (a(H) (2 meta) = 3.45 G, a(H) (1 para) = 1.04 G, g = 2.0046) during irradiation of a 2,6-dibromophenol solution in water. The 2,6-dibromophenoxyl radical had a relatively long half-life (122 ± 5 μs) according to laser flash photolysis experiments. The para-para C-C and O-para-C couplings of these 2,6-dibromophenoxyl radicals are consistent with the observed formation of both dimeric OH-PBDE and di-OH-PBB photoproducts. These findings show that bromophenoxyl radical-mediated phototransformation of bromophenols is a source of OH-PBDEs and di-OH-PBBs in aqueous environments that requires further attention.

Structure and composition of iron nanoparticles synthesized using a novel anionic-element complex

We use a novel solution-based disassociation synthesis scheme of the ionic complex Fe(LiBH4)2 to form Fe nanoparticles. The complex was formed initially using a gentle mechanochemical process, and the Fe nanoparticles emerged after 4 h of ball milling in an air-free environment. Rietveld refinement of x-ray diffraction measurements in an air-free sample holder identified a Im3¯m α-Fe phase. A room temperature Mössbauer spectrum of the sample presented a six-line spectrum unique to Fe0 metal, and the Fe nanoparticles were extremely well crystallized. Magnetometry results presented a reduced saturation magnetization (e.g., Ms∼ 85 emu/g at 50 K) that had a Bloch-like T2 temperature dependence, consistent with a gap in the magnon fluctuation spectrum due to finite-size effects. The Fe nanoparticles were magnetically soft, with a coercivity ranging from ∼10 to 20 mT with decreasing temperature from 350 K.

Radicals in the reaction between peroxynitrite and uric acid identified by electron spin resonance spectroscopy and liquid chromatography mass spectrometry

Peroxynitrite is a reactive oxidant produced in vivo in response to oxidative and other stress by the diffusion-limited reaction of nitric oxide and superoxide. This article is focused on the identification of free radical intermediates of uric acid formed during its reaction with peroxynitrite. The experimental approach included the ESR spin trapping of the radical generated from the reaction between uric acid and peroxynitrite at pH 7.4 and mass spectrometry studies of the trapped radicals. Using PBN (N-tert-butyl-α-phenylnitrone) as the spin trapping agent, a six-line ESR spectrum was obtained and its hyperfine coupling constants, aN=15.6G and aH=4.4G, revealed the presence of carbon-based radicals. Further structural identification of the PBN–radical adducts was carried out using liquid chromatography–mass spectrometry. After comparison with the control reactions, two species were identified that correspond to the protonated molecules (M+1) at m/z 352 and 223, respectively. The ions of m/z 352 were characterized as the PBN–triuretcarbonyl radical adduct and the m/z 223 ion was identified as the PBN–aminocarbonyl radical adduct. Their mechanism of formation is discussed.

High efficiency of natural lamellar remanent magnetisation in single grains of ilmeno-hematite calculated using Mössbauer spectroscopy

Rocks from large remanent magnetic anomalies on Earth have been found to contain exsolved rhombohedral oxides, which also have been proposed as earth analogues for the rocks creating the observed large remanent anomalies on Mars. Theoretical considerations and previous case studies of natural rocks have shown that the natural magnetisation is carried by lamellar magnetism due to uncompensated moments at the interface between antiferromagnetic hematite and paramagnetic ilmenite. Here, single grains (≈ 250 µm) of titanohematite with ferri-ilmenite exsolution lamellae from Mesoproterozoic metamorphic rock samples in southwest Sweden and the Adirondack Mountains, USA, are studied using room-temperature Mössbauer spectroscopy to identify possible characteristic magnetic signatures of lamellar magnetism. Mössbauer spectra of synthetic samples of titanohematite (Fe 0.95Ti 0.05O 3 and Fe 0.9Ti 0.1O 3) were collected for comparison and showed a dominant six-line magnetic spectrum due to Fe 3+ in titanohematite with a weak sextet due to Fe 2 +–Fe 3+ charge transfer. Mössbauer spectra of the natural ilmeno-hematite grains are similar to those for synthetic titanohematite, but contain additionally two paramagnetic doublets corresponding to Fe 2+ and Fe 3+ in ilmenite. However, several grains also contain an additional weak, broad magnetic component that we assign to iron in contact layers according to the lamellar magnetism model. Similar to the previous Mössbauer results for natural hemo-ilmenite, there is no evidence for superparamagnetic behaviour of the nanoscale titanohematite lamellae contained within coarser ferri-ilmenite lamellae, and no evidence for single-domain or superparamagnetic magnetite. The compositions of titanohematite and ferri-ilmenite in the individual ilmeno-hematite grains calculated from the Mössbauer area ratios show that compositions are closer to end-member values than the compositions inferred from electron microprobe and transmission electron microscopy on the same grains, consistent with observations that lamella thicknesses are as small as a few nm. Bulk compositions of ilmeno-hematite grains calculated from the Mössbauer data confirm that the Swedish samples are significantly more ilmenite-rich than the Adirondack samples, and agree with an estimation of bulk composition through point counting of electron backscatter images. The Mössbauer data allow a quantitative estimation of contact layer abundance, which is used to determine the efficiency of lamellar natural remanent magnetisation acquisition. Because minerals with a high natural remanent magnetisation efficiency are expected to create larger remanent magnetic anomalies, contact layer abundance determination by Mössbauer spectroscopy provides a valuable new tool for mineral-based magnetic anomaly interpretation on Earth and other planetary bodies.

Direct evidence of iNOS-mediated in vivo free radical production and protein oxidation in acetone-induced ketosis

Diabetic patients frequently encounter ketosis that is characterized by the breakdown of lipids with the consequent accumulation of ketone bodies. Several studies have demonstrated that reactive species are likely to induce tissue damage in diabetes, but the role of the ketone bodies in the process has not been fully investigated. In this study, electron paramagnetic resonance (EPR) spectroscopy combined with novel spin-trapping and immunological techniques has been used to investigate in vivo free radical formation in a murine model of acetone-induced ketosis. A six-line EPR spectrum consistent with the alpha-(4-pyridyl-1-oxide)-N-t-butylnitrone radical adduct of a carbon-centered lipid-derived radical was detected in the liver extracts. To investigate the possible enzymatic source of these radicals, inducible nitric oxide synthase (iNOS) and NADPH oxidase knockout mice were used. Free radical production was unchanged in the NADPH oxidase knockout but much decreased in the iNOS knockout mice, suggesting a role for iNOS in free radical production. Longer-term exposure to acetone revealed iNOS overexpression in the liver together with protein radical formation, which was detected by confocal microscopy and a novel immunospin-trapping method. Immunohistochemical analysis revealed enhanced lipid peroxidation and protein oxidation as a consequence of persistent free radical generation after 21 days of acetone treatment in control and NADPH oxidase knockout but not in iNOS knockout mice. Taken together, our data demonstrate that acetone administration, a model of ketosis, can lead to protein oxidation and lipid peroxidation through a free radical-dependent mechanism driven mainly by iNOS overexpression.

Synthesis and spectroscopic characterization of organophosphoryl polyoxotungstates α-[PhP(Y)]2X n +W11

Organophosphoryl polyoxotungstate derivatives α-[PhP(Y)]2X n +W11 (X n + = Ge4+, B3+; Y = O, S) have been obtained by the reaction of the monovacant α-[X n +W11O39](12− n )− (X n + = Ge4+, B3+) anions with PhP(O)Cl2 or PhP(S)Cl2 in acetonitrile. These new organic–inorganic hybrid anions have been characterized by elemental analysis, IR, 31P and 183W NMR spectroscopy. According to the elemental analysis and spectroscopic data, the hybrid anions consist of an α-[XW11O39] framework on which are grafted two equivalent PhP(O) or PhP(S) groups through P–O–W bridges. The six-line 183W NMR spectrum indicates that the hybrid anions possess C s symmetry in acetonitrile.

Characterization of the high-resolution ESR spectra of superoxide radical adducts of 5-(diethoxyphosphoryl)-5-methyl-1-pyrroline N-oxide (DEPMPO) and 5,5-dimethyl-1-pyrroline N-oxide (DMPO). Analysis of conformational exchange

It has been previously reported that the spin trap 5-(diethoxyphosphoryl)-5-methyl-1-pyrroline N-oxide (DEPMPO) can form stable radical adducts with superoxide radical. However, the presence of diastereomers of DEPMPO radical adducts and the appearance of superhyperfine structure complicates the interpretation of the ESR spectra. It has been suggested that the superhyperfine structure in the ESR spectrum of DEPMPO/⋅OOH is a result of conformational exchange between conformers. The analysis of the temperature dependence of the ESR spectrum of DEPMPO/⋅OOH and of its structural analog DMPO/⋅OOH have demonstrated that both ESR spectra contain exchange effects resulting from conversion between two conformers. Computer simulation calculates a conformer lifetime on the order of 0.1 μs for DMPO/⋅OOH at room temperature. However, temperature dependence of the ESR spectrum of DEPMPO/⋅OOH suggests that superhyperfine structure does not depend on the conformational exchange. We have now found that the six-line ESR spectrum with superhyperfine structure should be assigned to a DEPMPO-superoxide-derived decomposition product. Therefore, ESR spectra previously assigned to DEPMPO/⋅OOH contain not only the two diastereomers of DEPMPO/⋅OOH but also the decomposition product, and these spectra should be simulated as a combination of four species: two conformers of the first diastereomer, one conformer of the second diastereomer and the superoxide-derived decomposition product. The presence of four species has been supported by the temperature dependence of the ESR spectra, nucleophilic synthesis of radical adducts, and isotopic substitution experiments. It is clear that to correctly interpret DEPMPO spin trapping of superoxide radicals, one must carefully consider formation of secondary radical adducts.

Electron paramagnetic resonance evidence of hydroxyl radical generation and oxidative damage induced by tetrabromobisphenol A in Carassius auratus

Tetrabromobisphenol A (TBBPA) is one of the most widely used brominated flame retardants (BFRs). To confirm its putative oxidative stress-inducing activity, freshwater fish Carassius auratus were injected intraperitoneally with TBBPA. One experiment lasted 3 h to 28 days after a single injection of 100 mg/kg TBBPA, and the other lasted 24 h after a single injection of 0–300 mg/kg TBBPA. Reactive oxygen species (ROS) were trapped by phenyl- tert-butyl nitrone (PBN) and detected by electron paramagnetic resonance (EPR). Protein carbonyl (PCO) and lipid peroxidation product (LPO) content were also determined. A six-line EPR spectrum was detected in the sample prepared in air, and a multiple one was obtained in nitrogen. The observed spectrum in nitrogen fits the simulation one with PBN/ OCH 3 and PBN/ CH 3 quite well. As compared to the control group, TBBPA significantly induced ROS production marked by the intensity of the prominent spectra in liver and bile. TBBPA (100 mg/kg) also significantly increased PCO content in liver starting 24 h and LPO content 3 days after injection. Either PCO or LPO content showed significant relation with ROS production. Based on the hyperfine constants and shape of the spectrum, ROS induced by TBBPA was determined as OH. The results clearly indicated that TBBPA could induce OH generation and result in oxidative damage in liver of C. auratus.

Temperature-Dependent Coordination in E. coli Manganese Superoxide Dismutase

Two different temperature dependences of the manganese(II) high-field electron paramagnetic resonance spectrum of manganese superoxide dismutase from E. coli were observed. In the 25-200 K range, the zero-field interaction steadily decreased with increasing temperature. This was likely due to the thermal expansion of the protein. From these results, it was possible to deduce an approximately r(-)(2.5) dependence of Mn(II) zero-field interaction on ligand-metal distance. At temperatures above 240 K, a distinct six-line component was detected, the amplitude of which decreased with increasing temperature. On the basis of similarities to the six-line spectrum observed for the azide-complexed E. coli manganese superoxide dismutase, the newly detected six-line spectrum was assigned to a hexacoordinate Mn(II) center resulting from the coordination of a nearby water molecule to the normally five-coordinate center. The changes in enthalpy and entropy characterizing the hexacoordinate-pentacoordinate equilibrium in the 240-268 K range were -5 kcal/mol and -24 cal/mol.K, respectively. The structural implications of the zero-field parameters of the newly found hexacoordinate form in comparison to those of the Mn(II) centers in concanavalin-A and manganese-containing R. spheroides photosynthetic reaction centers and the values predicted by the superposition model are discussed.

An Electron Spin Resonance Investigation of the Radiolysis of Hexamethylbenzene and Hexamethyl(Dewar)Benzene

Exposure of hexamethyl(Dewar)benzene (HMD) to γ-rays in a solid CFC13 matrix at 77K generated the corresponding radical cation (HMD+•) as shown by the observation of hyperfine coupling (A = 9·5 G) to the protons of four equivalent methyl groups: thus the 2B2 state (I) of the ion is established. On annealing to 140 K, ring-opening occurred to give the hexamethylbenzene cation (HMB+•). When CF2ClCFCl2 was used as the matrix material, a completely different spectrum was produced, consisting of seven lines with a common spacing of 14 G. Results obtained using different batches of the freon, and from careful annealing and concentration studies, establish that the low-field line is not part of the remaining six-line spectrum which can be assigned to the allylic radical (III), formed by deprotonation of the parent cation. γ-Irradiation of HMD in 2- methyltetrahydro-furan (MeTHF) followed by annealing gave the ψs* Jahn-Teller distorted form of the (ring-opened) HMB-• radical anion [A(6H) = 9 G] and so the parent anion is unstable, as is the cation. This was confirmed by an identical spectrum being obtained after the irradiation of an authentic sample of HMB in MeTHF. γ-Irradiation of pure HMD gave rise to a spectrum that can be analysed in terms of (III) and the endo H-atom adduct of HMD (IV). Hexamethylbenzene (HMB) on γ-irradiation in solid CFC13 gave the parent radical cation (HMB+•) At 130 K, this has a 6·7 G splitting and correct binomial intensities for 18 equivalent protons; on cooling to 77 K, the cation distorts so that a ψA type SOMO is adopted with four strongly coupled (A = 11·5G) and two weakly coupled (A = −2·8G) methyl groups. γ-Irradiation of pure HMB gave only broad features which we ascribe to a mixture of pentamethylbenzyl (VIII) and hexamethylcyclohexadienyl (IX) radicals, in which proton hyperfine structure is unresolved due to a range of restricted conformations being adopted by various methyl groups because of steric hindrance between them.

Synthesis and characterization of organophosphoryl polyoxotungstates [RP(O)] 2 X n+ W 11 O 39 (8−n)− (X n+ = P 5+ , Si 4+ , Ge 4+ , Ga 3+ )

In the presence of n-Bu4NBr acting as phase-transfer reagent, n-Bu4N+ salts of organophosphoryl polyoxotungstate derivatives [RP(O)]2Xn+W11O39(8−n)− [R = PhCH2CH2P(O), X = P, Si; R = C6H11P(O); X = Ge, Ga] have been prepared and characterized by elemental analysis, i.r., 31P- and 183W-n.m.r. spectroscopy. According to the elemental analysis and spectroscopic data, the hybrid anions consist of an α-[XW11O39] framework on which are grafted two equivalent organophosphoryl groups through P—O—W bridges; these new species still retain the Keggin structure. The six-line 183W spectrum indicates that hybrid anions possess Cs symmetry in MeCN.

Oxygen consumption and electron spin resonance studies of free radical production by alveolar cells exposed to anoxia: inhibiting effects of the antibiotic ceftazidime

By EPR spectroscopy, we investigated free radical production by cultured human alveolar cells subjected to anoxia/re-oxygenation (A/R), and tested the effects of ceftazidime, an antibiotic previously demonstrated to possess antioxidant properties. Two A/R models were performed on type II pneumocytes (A549 cell line), either on cells attached to culture dishes (monolayer A/R model; 3.5 h of anoxia, 30 min of re-oxygenation) or after cell detachment (suspension A/R model; 1 h of anoxia, 10 min of re-oxygenation). Ceftazidime and selective inhibitors (SOD, Tiron, L-NMMA) were added before anoxia. Free radical production was assessed by the EPR spin trapping technique. Oxygen consumption was monitored, in parallel with EPR studies, in the suspension A/R model. The production of free radical species was demonstrated by the generation of PBN-radical adducts: (aN = 15.2 G) in the monolayer A/R model and a six-line EPR spectrum (aN = 15.7 G and aH = 2.7 G) in the suspension A/R model. A kinetic study performed by oximetry, in parallel with EPR spectroscopy, demonstrated marked alterations of the cell respiratory function and that the free radical production started during anoxia and increased during re-oxygenation. In the suspension A/R model, the amplitude of EPR spectra were decreased upon the addition of 200 U/ml SOD (37% inhibition), 0.1 mM Tiron (67% inhibition) and 1 mM L-NMMA (43% inhibition). Addition of 1 mM ceftazidime decreased the amplitude of EPR spectra (37% inhibition) in both A/R models. Complementary in vitro EPR studies demonstrated that CAZ scavenged the hydroxyl radical (produced by the Fenton reaction). The protective effect of ceftazidime in the cell model could thus be linked to its ability to scavenge superoxide anions, nitrogen-derived species and hydroxyl radicals.

Oxidation of tetrahydrobiopterin by peroxynitrite or oxoferryl species occurs by a radical pathway

The molecular mechanisms of tetrahydrobiopterin (BH4) oxidation by peroxynitrite (ONOO-) was studied using ultra-weak chemiluminescence, electron paramagnetic resonance (EPR) and UV-visible diodearray spectrophotometry, and compared to BH4 oxidation by oxoferryl species produced by the myoglobin/hydrogen peroxide (Mb/H2O2) system. The oxidation of BH4 by ONOO- produced a weak chemiluminescence, which was altered by addition of 50 mM of the spin trap α-(4-pyridyl-1-oxide)-N-tert butylnitrone (POBN). EPR spin trapping demonstrated that the reaction occurred at least in part by a radical pathway. A mixture of two spectra composed by an intense six-line spectrum and a fleeting weak nine-line one was observed when using ONOO-. Mb/H2O2 produced a short-living light emission that was suppressed by the addition of BH4. Simultaneous addition of POBN, BH4 and Mb/H2O2 produced the same six-line EPR spectrum, with a signal intensity depending on BH4 concentration. Spectrophotometric studies confirmed the rapid disappearance of the characteristic peak of ONOO- (302 nm) as well as substantial modifications of the initial BH4 spectrum with both oxidant systems. These data demonstrated that BH4 oxidation, either by ONOO- or by Mb/H2O2, occurred with the production of activated species and by radical pathways.

New plenary and lacunary polyoxotungstate structures assembled from nonatungstoarsenate(III) anions and uranyl cations

A new structural family of heteropolytungstate complexes containing trans-dioxo uranium(VI) (uranyl) groups has been isolated in good yield by reaction of UO22+ with [NaAs4W40O140]27− (W40) in aqueous solution. The “lacunary” anion, [(UO2)3(H2O)5As3W29O104]19−1 is formed by the reaction of W40 with UO2(MeCO2)2 at pH 7, and the crystal structure of (NH4)19[(UO2)3(H2O)5As3W29O104]·28H2O [orthorhombic, P212121, a = 17.5626(2), b = 24.4929(2), c = 33.3019(3) Å] is reported. The “plenary” anion, [(UO2)3(H2O)6As3W30O105]15−2 is formed by reaction of W40 with UO2(NO3)2 at pH 4, and the crystal structure of (NH4)15[(UO2)3(H2O)6As3W30O105]·20H2O [monoclinic, P21/c, a = 23.63520(10), b = 18.0646(2), c = 35.32640(10) Å, β = 107.46°] is reported. Both heteropolyanions contain three B-AsW9O339− groups linked by uranyl cations (pentagonal bipyramids) and three (or two) additional corner-sharing WO6 octahedra cap the structure of 2 (1). A six-line 183W NMR spectrum of 2 is consistent with an effective C3v symmetry for the anion in solution. Addition of VO2+ to a solution of 1 yields the V-substituted anion (3) confirmed by a structure determination of (NH4)17[(UO2)3(H2O)6As3W29VIVO105]·44H2O [orthorhombic, Pnma, a = 31.1821(4), b = 24.9672(3) Å, c = 20.3460(3) Å]. The cyclic voltammogram of 3 in 0.5 M sodium acetate buffer (pH 4.7) shows the VIV/V couple at +0.26 V (Epc) and +0.40 V (Epa).

High-Quality Manganese-Doped ZnSe Nanocrystals

We demonstrate high-quality, highly fluorescent, ZnSe colloidal nanocrystals (or quantum dots) that are doped with paramagnetic Mn2+ impurities. We present luminescence, magnetic circular dichroism (MCD), and electron paramagnetic resonance (EPR) measurements to confirm that the Mn impurities are embedded inside the nanocrystal. Optical measurements show that by exciting the nanocrystal, efficient emission from Mn is obtained, with a quantum yield of 22% at 295 K and 75% below 50 K (relative to Stilbene 420). MCD spectra reveal an experimental Zeeman splitting in the first excited state that is large (28 meV at 2.5 T), depends on doping concentration, and saturates at modest fields. In the low field limit, the magnitude of the effective g factor is 430 times larger than in undoped nanocrystals. EPR experiments exhibit a six-line spectrum with a hyperfine splitting of 60.4 × 10-4 cm-1, consistent with Mn substituted at Zn sites in the cubic ZnSe lattice.

Oxidation of Adrenaline by Ferrylmyoglobin

The oxidation of adrenaline by ferrylmyoglobin, the product formed by the oxidation of myoglobin with H 2O 2, was examined by absorption, fluorescence, and EPR spectroscopy in terms of the formation of intermediate free radicals and stable molecular products and the binding of adrenaline oxidation products to the apoprotein. The reaction of adrenaline with ferrylmyoglobin resulted in reduction of the hemoprotein to metmyoglobin and consumption of adrenaline. Quantification of metmyoglobin formed per adrenaline yielded a ratio of 1.66. The reaction was found first order on adrenaline concentration and second order on ferrylmyoglobin concentration. This, together with the above ratio, suggested a mechanism by which two oxoferryl moieties (ferrylmyoglobin) were reduced by adrenaline yielding metmyoglobin and the o-semiquinone state of adrenaline. The decay of the o-semiquinone to adrenochrome was confirmed by an increase in absorbance at 485 nm. The product was nonfluorescent; alkalinization of the reaction mixture resulted in a strong fluorescence at 540 nm ascribed to 3,5,6-trihydroxyindol or adrenolutin. Hence, adrenochrome and its alkali-catalyzed product, adrenolutin, are the major molecular products formed during the oxidation of adrenaline by ferrylmyoglobin. Semiquinones formed during the adrenaline/ferrylmyoglobin interaction were detected by EPR, spin stabilizing these species with Mg 2+. The six-line EPR spectrum observed (a N = 4.5 G, a N(CH 3) = 5.1, and a 2H = 0.91; g = 2.0040) may be assigned to the semiquinone forms of adrenochrome and/or adrenolutin or a composite of these species. The intensity of the EPR signal increased with time and its subsequent decay followed a second-order kinetics as inferred by the proportionality of the square of the EPR line intensity with H 2O 2 concentration. Heme destruction and lysine loss, inherent in the reaction of metmyoglobin with H 2O 2, were prevented 80 and 34% by adrenaline, respectively. The low protection exerted by adrenaline against lysine loss was possibly due to the formation of Schiff bases between the ϵ-NH 2 group of lysine and the o-quinone oxidation product(s) of adrenaline. The yield of Schiff base formation was 20–25%. The autoxidation of adrenaline at physiological pH is extremely slow or nonexistent. These data provide a rationale for the primary oxidation of adrenaline by the pseudoperoxidatic activity of ferrylmyoglobin and suggest implications of the free radicals thereby formed for the oxidative damage in reperfusion injury.