Amperometric determination of ecotoxic N-methyl-p-aminophenol sulfate in photographic solution and river water samples based on graphene oxide/CeNbO4 nanocomposite catalyst.

The electronic conductivity of the metal oxides is generally increased by hybridization of highly conductive carbon supportive materials. In this present work, we have demonstrated a novel one-pot preparation of cerium niobate (CeNbO4) nanoparticles embedded with graphene oxide (GO/CeNbO4) composite, for ultrasensitive detection of the photographic developing agent, metol (MTL). The as-prepared GO/CeNbO4 was analyzed by various characterization techniques. The intensive characterization techniques were used to affirm the detailed structural moiety, size, morphology, and surface area of GO/CeNbO4. The GO/CeNbO4 modified glassy carbon electrode (GCE) affords a superior electrocatalytic activity toward MTL. The obtained amperometric response on the GO/CeNbO4/GCE holding an extremely low level detection of 10 nM and superior sensitivity of 10.97 µA µM-1 cm-2 toward MTL detection. Besides, the GO/CeNbO4/GCE also gives excellent selectivity, stability, repeatability, and reproducibility. We achieved excellent recovery results in real photographic solution and river water samples analysis with great accuracy. This work offers a novel insight into the growth of the carbon-based niobate family with electrochemical sensor applications.

Note: Effective anvil size for transverse delamination test of rare-earth-Ba2Cu3Oy coated conductor tapes.

In coated conductor (CC) tapes used in magnet and coil applications, delamination due to excessive transverse tensile stresses is still one of the major issues that need considerations. Recently, several methods in evaluating the delamination strength of CC tapes are being used. In the case of anvil test, size of the anvils will be an important factor considering its applications (i.e., superconducting coil impregnation). In this study, delamination strength of CC tape was examined using different upper anvil sizes and their effects were discussed. Finally, reasonable sizes of upper anvil to be used were proposed considering the application conditions.

The unexpected mechanism underlying the high-valent mono-oxo-rhenium(V) hydride catalyzed hydrosilylation of C=N functionalities: insights from a DFT study.

In this study, we theoretically investigated the mechanism underlying the high-valent mono-oxo-rhenium(V) hydride Re(O)HCl2(PPh3)2 (1) catalyzed hydrosilylation of C=N functionalities. Our results suggest that an ionic S(N)2-Si outer-sphere pathway involving the heterolytic cleavage of the Si-H bond competes with the hydride pathway involving the C=N bond inserted into the Re-H bond for the rhenium hydride (1) catalyzed hydrosilylation of the less steric C=N functionalities (phenylmethanimine, PhCH=NH, and N-phenylbenzylideneimine, PhCH=NPh). The rate-determining free-energy barriers for the ionic outer-sphere pathway are calculated to be ∼28.1 and 27.6 kcal mol(-1), respectively. These values are slightly more favorable than those obtained for the hydride pathway (by ∼1-3 kcal mol(-1)), whereas for the large steric C=N functionality of N,1,1-tri(phenyl)methanimine (PhCPh=NPh), the ionic outer-sphere pathway (33.1 kcal mol(-1)) is more favorable than the hydride pathway by as much as 11.5 kcal mol(-1). Along the ionic outer-sphere pathway, neither the multiply bonded oxo ligand nor the inherent hydride moiety participate in the activation of the Si-H bond.

Enzymatic epoxidation of soybean oil using ionic liquid as reaction media.

An ionic liquid (IL) system for the enzymatic epoxidation of soybean oil was studied. The effects of active oxygen carriers (different fatty acids) and ILs ([Bmim]PF6 and [Bmim]BF4) on the enzymatic epoxidation were investigated. Response surface methodology (RSM) was used to study and optimize the effects of variables (reaction time, reaction temperature, molar ratio of H2O2/C=C-bonds, and molar ratio of fatty acid/C=C-bonds) on the epoxy oxygen group content (EOC) of epoxidized soybean oil (ESO). Results showed that the enzymatic epoxidation of soybean oil can be enhanced using tetradecanoic acid (C13H27COOH) as active oxygen carrier and [Bmim]PF6 as reaction medium. The optimum EOC of ESO was 5.9 ± 0.3% under the following conditions: reaction temperature 46°C, reaction time 11 h, enzyme load 3% (w/w, relative to the weight of soybean oil), molar ratio of H2O2/C=C-bonds 1.8:1, and molar ratio of C13H27COOH/C=C-bonds 0.5:1.

Paper-based colorimetric immunosensor for visual detection of carcinoembryonic antigen based on the high peroxidase-like catalytic performance of ZnFe2O4-multiwalled carbon nanotubes.

A new paper-based colorimetric immunosensor for the detection of carcinoembryonic antigen (CEA) was developed based on the intrinsic peroxidase activity of ZnFe2O4-multiwalled carbon nanotubes (ZnFe2O4@MWNTs). The immunosensor platform was prepared by depositing chitosan and porous gold onto filter paper and entrapping the primary antibodies (Ab1) onto the layers. Secondary antibodies (Ab2) were assembled on the surface of the functionalized ZnFe2O4@MWNTs. The immunosensor response was quantified as a color change resulting from ZnFe2O4@MWNTs catalyzing the oxidation of 3,3',5,5'-tetramethylbenzidine in the presence of H2O2. The catalytic performance of ZnFe2O4@MWNTs was higher than ZnFe2O4 due to the high electrical conductance of MWNTs, moreover, the electron communications between ZnFe2O4@MWNTs and substrates are electrically "wired". Detection was achieved by measuring the color change when the concentrations of CEA were different. The color change can be quantified with the naked eye but a digitalized picture can also be used to provide more sensitive comparison to a calibrated color scheme. This method was simple for CEA detection with a linear range from 0.005 to 30 ng mL(-1) and a detection limit of 2.6 pg mL(-1). Such an equipment-free immunoassay has great potential in resource-limited environments.

Experimental determinations and quantum-chemical calculations of the vibrational spectra of ß-ZnB4O7 and ß-CaB4O7.

The two oxoborates ß-ZnB4O7 and ß-CaB4O7 were synthesized and investigated by FTIR- and Raman spectroscopy and ab initio quantum chemical calculations. Maximum and mean deviations between experimentally determined bands and calculated modes ranged between 15-36 cm(-1) and 5-7 cm(-1), respectively, allowing band assignments to vibrational modes in most cases. The complex network structures with tetrahedral BO4 and planar OB3 groups are mirrored by the spectra and numerous vibrational modes, not assignable by standard borates classification schemes. It was confirmed that OB3 units, despite similar force constants and geometry, do not absorb in the same range as BO3 units. Bands in the high wavenumber range are rather caused by B-O-(Zn/Ca), O-B-O, B-O-B, and B-O stretching and bending vibrations. The experimental observation of inactive or Raman-active modes in the absorption spectra indicates defects or structural distortions in both compounds.

Structural characterization and unusual reactivity of oxosulfido-Mo(V) compounds: implications for the structure and electronic description of the very rapid form of xanthine oxidase.

The first structural characterization of a mononuclear, EPR-active, oxosulfido-Mo(V) compound related to the very rapid form of xanthine oxidase (VR-XnO) is reported. The compound, [CoCp2][Tp(iPr)Mo(V)OS(2-OC6H4CO2Et)] [Cp = cyclopentadienyl; Tp(iPr) = hydrotris(3-isopropylpyrazol-1-yl)borate], exhibits a distorted octahedral geometry with Mo═O and Mo=/--S distances of 1.761(5) and 2.215(2) Å, respectively, and an O═Mo=/--S angle of 107.33(14)°. Significantly, the Mo(V)=/--S distance is much shorter than the value of 2.36 Å reported for oxosulfido-Mo(V) compounds (Singh, R.; et al. Inorg. Chem. 1989, 28, 8) but close to the range established for VR-XnO by protein crystallography. The methyl and phenyl esters were also prepared but the latter is highly reactive and undergoes an intramolecular, radical-based cyclization/elimination reaction to form [CoCp2][Tp(iPr)Mo(IV)O{2-OC6H4C(O)S-κO,κS}]. This study provides the first definitive measurement of the Mo(V)=/--S bond distance in an unambiguously characterized oxosulfido-Mo(V) compound and supports the presence of a short (ca. 2.22 Å) Mo=/--S bond in VR-XnO. It also demonstrates that the Mo(V)=/--S moiety participates in radical-based reactions that are facilitated by the facile redox interplay of Mo and S and by substrates susceptible to radical eliminations.

Optical properties of cerium doped oxyfluoroborate glass.

Cerium doped oxyfluoroborate glasses have been prepared and its spectroscopic properties have been discussed. It is found that the absorption edge shifts towards the lower energy side for the higher concentration of cerium dopant. Optical band gap for these glasses have been calculated and it is found that the number of non-bridging oxygen increases with cerium content. The emission spectra of these glasses have been recorded using UV laser radiations (266 and 355 nm) and it is observed that these glasses show bright blue emission. On the basis of excitation and emission spectra we have reported the existence of at least two different emission centers of Ce(3+)ions.

Sulfur, oxygen, and nitrogen mustards: stability and reactivity.

Mustard gas, bis(ß-chloroethyl) sulfide (HD), is highly toxic and harmful to humans and the environment. It comprises one class of chemical warfare agents (CWAs) that was used in both World Wars I and II. The three basic analogues or surrogates are: the monochloro derivative, known as the half mustard, 2-chloroethyl ethyl sulfide (CEES); an oxygen analogue, bis(ß-chloroethyl) ether (BCEE); and several nitrogen analogues based on the 2,2'-dichlorodiethylamine framework (e.g., HN1, HN2, and HN3). The origin of their toxicity is considered to be from the formation of three-membered heterocyclic ions, a reaction that is especially accelerated in aqueous solution. The reaction of these cyclic ion intermediates with a number of important biological species such as DNA, RNA and proteins causes cell toxicity and is responsible for the deleterious effects of the mustards. While a number of studies have been performed over the last century to determine the chemistry of these compounds, early studies suffered from a lack of more sophisticated NMR and X-ray techniques. It is now well-established that the sulfur and nitrogen mustards are highly reactive in water, while the oxygen analog is much more stable. In this study, we review and summarize results from previous studies, and add results of our own studies of the reactivity of these mustards toward various nonaqueous solvents and nucleophiles. In this manner a more comprehensive evaluation of the stability and reactivity of these related mustard compounds is achieved.

A binuclear Mn(III) complex of a scorpiand-like ligand displaying a single unsupported Mn(III)-O-Mn(III) bridge.

The crystal structure of a binuclear Mn(III) complex of a scorpiand-like ligand (L) displays an unsupported single oxo bridging ligand with a Mn(III)-O-Mn(III) angle of 174.7°. Magnetic susceptibility measurements indicate strong antiferromagnetic coupling between the two metal centers. DFT calculations have been carried out to understand the magnetic behavior and to analyze the nature of the observed Jahn-Teller distortion. Paramagnetic (1)H NMR has been applied to rationalize the formation and magnetic features of the complexes formed in solution.

Protonation of a peroxodiiron(III) complex and conversion to a diiron(III/IV) intermediate: implications for proton-assisted O-O bond cleavage in nonheme diiron enzymes.

Oxygenation of a diiron(II) complex, [Fe(II)(2)(µ-OH)(2)(BnBQA)(2)(NCMe)(2)](2+) [2, where BnBQA is N-benzyl-N,N-bis(2-quinolinylmethyl)amine], results in the formation of a metastable peroxodiferric intermediate, 3. The treatment of 3 with strong acid affords its conjugate acid, 4, in which the (µ-oxo)(µ-1,2-peroxo)diiron(III) core of 3 is protonated at the oxo bridge. The core structures of 3 and 4 are characterized in detail by UV-vis, Mössbauer, resonance Raman, and X-ray absorption spectroscopies. Complex 4 is shorter-lived than 3 and decays to generate in ~20% yield of a diiron(III/IV) species 5, which can be identified by electron paramagnetic resonance and Mössbauer spectroscopies. This reaction sequence demonstrates for the first time that protonation of the oxo bridge of a (µ-oxo)(µ-1,2-peroxo)diiron(III) complex leads to cleavage of the peroxo O-O bond and formation of a high-valent diiron complex, thereby mimicking the steps involved in the formation of intermediate X in the activation cycle of ribonucleotide reductase.

Electron paramagnetic resonance and Mössbauer spectroscopy and density functional theory analysis of a high-spin Fe(IV)-oxo complex.

High-spin Fe(IV)-oxo species are known to be kinetically competent oxidants in non-heme iron enzymes. The properties of these oxidants are not as well understood as the corresponding intermediate-spin oxidants of heme complexes. The present work gives a detailed characterization of the structurally similar complexes [Fe(IV)H(3)buea(O)](-), [Fe(III)H(3)buea(O)](2-), and [Fe(III)H(3)buea(OH)](-) (H(3)buea = tris[(N'-tert-butylureaylato)-N-ethylene]aminato) using Mössbauer and dual-frequency/dual-mode electron paramagnetic resonance (EPR) spectroscopies. The [Fe(IV)H(3)buea(O)](-) complex has a high-spin (S = 2) configuration imposed by the C(3)-symmetric ligand. The EPR spectra of the [Fe(IV)H(3)buea(O)](-) complex presented here represent the first documented examples of an EPR signal from an Fe(IV)-oxo complex, demonstrating the ability to detect and quantify Fe(IV) species with EPR spectroscopy. Quantitative simulations allowed the determination of the zero-field parameter, D = +4.7 cm(-1), and the species concentration. Density functional theory (DFT) calculations of the zero-field parameter were found to be in agreement with the experimental value and indicated that the major contribution to the D value is from spin-orbit coupling of the ground state with an excited S = 1 electronic configuration at 1.2 eV. (17)O isotope enrichment experiments allowed the determination of the hyperfine constants ((17)O)A(z) = 10 MHz for [Fe(IV)H(3)buea(O)](-) and ((17)O)A(y) = 8 MHz, ((17)O)A(z) = 12 MHz for [Fe(III)H(3)buea(OH)](-). The isotropic hyperfine constant (((17)O)A(iso) = -16.8 MHz) was derived from the experimental value to allow a quantitative determination of the spin polarization (ρ(p) = 0.56) of the oxo p orbitals of the Fe-oxo bond in [Fe(IV)H(3)buea(O)](-). This is the first experimental determination for non-heme complexes and indicates significant covalency in the Fe-oxo bond. High-field Mössbauer spectroscopy gave an (57)Fe A(dip) tensor of (+5.6, +5.3, -10.9) MHz and A(iso) = -25.9 MHz for the [Fe(IV)H(3)buea(O)](-) complex, and the results of DFT calculations were in agreement with the nuclear parameters of the complex.

Oxomanganese complexes for natural and artificial photosynthesis.

The oxygen-evolving complex (OEC) of Photosystem II (PSII) is an oxomanganese complex that catalyzes water-splitting into O2, protons and electrons. Recent breakthroughs in X-ray crystallography have resolved the cuboidal OEC structure at 1.9 Å resolution, stimulating significant interest in studies of structure/function relations. This article summarizes recent advances on studies of the OEC along with studies of synthetic oxomanganese complexes for artificial photosynthesis. Quantum mechanics/molecular mechanics hybrid methods have enabled modeling the S1 state of the OEC, including the ligation proposed by the most recent X-ray data where D170 is bridging Ca and the Mn center outside the CaMn3 core. Molecular dynamics and Monte Carlo simulations have explored the structural/functional roles of chloride, suggesting that it regulates the electrostatic interactions between D61 and K317 that might be critical for proton abstraction. Furthermore, structural studies of synthetic oxomanganese complexes, including the [H2O(terpy)MnIII(µ-O)2MnIV(terpy)OH2]3+ (1, terpy=2,2':6',2″-terpyridine) complex, provided valuable insights on the mechanistic influence of carboxylate moieties in close contact with the Mn catalyst during oxygen evolution. Covalent attachment of 1 to TiO2 has been achieved via direct deposition and by using organic chromophoric linkers. The (III,IV) oxidation state of 1 attached to TiO2 can be advanced to (IV,IV) by visible-light photoexcitation, leading to photoinduced interfacial electron transfer. These studies are particularly relevant to the development of artificial photosynthetic devices based on inexpensive materials.

Quantum chemical investigation of the thermal pyrolysis reactions of the carboxylic group in a brown coal model.

Different reaction pathways of the carboxylic group in a brown coal model were investigated by applying density function quantum chemical theory, examining the possible cross-linking and decomposition reactions between the hydrogen bonded carboxylic group-carboxylic group and the carboxylic group-hydroxyl group during the thermal pyrolysis process. The results show that bimolecular dehydration and decarboxylation of hydrogen bonded carboxylic groups have distinctly lower activation barriers and therefore, proceed preferentially at low temperature. The esterification reaction between the hydrogen bonded carboxylic group and hydroxyl group, together with unimolecular decarboxylation of isolated single carboxylic groups were also possible at moderate temperature. Aryl-aryl coupling is thought to occur via radical pyrolysis and recombination at relatively high temperature.

Concentration and photochemistry of PAHs, NPAHs, and OPAHs and toxicity of PM2.5 during the Beijing Olympic Games.

Atmospheric particulate matter with diameter <2.5 um (PM(2.5)) was collected at Peking University (PKU) in Beijing, China before, during, and after the 2008 Olympics and analyzed for black carbon (BC), organic carbon (OC), lower molecular weight (MW < 300) and MW302 Polycyclic Aromatic Hydrocarbons (PAHs), nitrated PAHs (NPAHs) and oxygenated PAHs (OPAHs). In addition, the direct and indirect acting mutagenicity of the PM(2.5) and the potential for DNA damage to human lung cells were also measured. Significant reductions in BC (45%), OC (31%), MW< 300 PAH (26-73%), MW 302 PAH (22-77%), NPAH (15-68%), and OPAH (25-53%) concentrations were measured during the source control and Olympic periods. However, the mutagenicity of the PM(2.5) was significantly reduced only during the Olympic period. The PAH, NPAH, and OPAH composition of the PM(2.5) was similar throughout the study, suggesting similar sources during the different periods. During the source control period, the parent PAH concentrations were correlated with NO, CO, and SO(2) concentrations, indicating that these PAHs were associated with both local and regional emissions. However, the NPAH and OPAH concentrations were only correlated with the NO concentrations, indicating that the NPAH and OPAH were primarily associated with local emissions. The relatively high 2-nitrofluoranthene/1-nitropyrene ratio (25-46) and 2-nitrofluoranthene/2-nitropyrene ratio (3.4-4.8), suggested a predominance of photochemical formation of NPAHs through OH-radical-initiated reactions in the atmosphere. On average, the ∑NPAH and ∑OPAH concentrations were 8% of the parent PAH concentrations, while the direct-acting mutagenicity (due to the NPAH and OPAH) was 200% higher than the indirect-acting mutagenicity (due to the PAH). This suggests that NPAH and OPAH make up a significant portion of the overall mutagenicity of PM(2.5) in Beijing.

Highly substituted oxabicyclic derivatives from furan: synthesis of (±)-platensimycin.

A stereocontrolled approach to a key platensimycin intermediate was achieved from a commercially available furylcarboxylate. Key to our approach is the highly efficient formal [4 + 3] cyclocondensation of a substituted furan with tetrabromocyclopropene along with an intramolecular γ-alkylation to construct the final ring of the caged intermediate.

1,3-Dioxopyrrolo[3,4-b]porphyrins: synthesis and chemistry.

A novel 1,3-dioxopyrrolo[3,4-b]porphyrin (2) has been synthesized in 70% yield following a [4 + 2] cycloaddition reaction of pyrrolo[3,4-b]porphyrin 1 with (1)O(2). The new imide was used as a template to other 1,3-dioxopyrrolo[3,4-b]porphyrins and to the corresponding open counterparts. The UV/vis absorption spectra of the new compounds show significant red-shifts when compared with those of the nonsubstituted analogues. The structure of an imide derivative was confirmed by single-crystal X-ray diffraction.

Optimization of an anion-exchange high performance liquid chromatography-inductively coupled plasma-mass spectrometric method for the speciation analysis of oxyanion-forming metals and metalloids in leachates from cement-based materials.

A method was developed for the speciation analysis of the oxyanions of As(III), As(V), Cr(VI), Mo(VI), Sb(III), Sb(V), Se(IV), Se(VI) and V(V) in leachates from cement-based materials, based on anion-exchange HPLC coupled with ICP-MS. The method was optimized in a two-step multivariate approach: the effect of sample pH and mobile phase composition on resolution, peak symmetry and analysis time was studied. Optimum conditions were then identified for the significant experimental factors by studying their interdependence. A mobile phase composition of 20 mM ammonium nitrate, 50 mM ammonium tartrate and pH 9.5 was found to be a compromise optimum for the separation of the target analytes using isocratic elution. The optimum condition provided separation of the analytes in less than 6 min, at a mobile phase flow rate of 1.0 mL/min. The signal intensities of the analytes were improved by adding 1% methanol to the mobile phase. The limit of detection of the method was in the range 0.2-2.2 µg/L for the various species. The effect of sample constituents was studied using spiked concrete leachates. The method was used to determine the target oxyanionic species in leachates generated from a concrete material in the pH range 3.5-12.4; CrO(4)(2-), MoO(4)(2-) and VO(4)(3-) were detected in most of the leachates.

Electron attachment to sulfur oxyhalides: SOF2, SOCl2, SO2F2, SO2Cl2, and SO2FCl attachment rate coefficients, 300-900 K.

Electron attachment to SOF(2), SOCl(2), SO(2)F(2), SO(2)FCl, and SO(2)Cl(2) was studied with two flowing-afterglow Langmuir-probe apparatuses over the temperature range 300-900 K. Attachment rate coefficients at 300 K are k(a) = 2.6+/-0.8x10(-10)(SOF(2)), 1.8+/-0.5x10(-8)(SOCl(2)), 4.8+/-0.7x10(-10)(SO(2)F(2)), 2.4+/-0.7x10(-9)(SO(2)Cl(2)), and 2.0+/-0.6x10(-7) cm(3) s(-1)(SO(2)FCl). Arrhenius plots of the data imply activation energies of 56+/-22 meV(SOF(2)), 92+/-40(SO(2)F(2)), 44+/-22 meV(SOCl(2)), and 29+/-15 meV(SO(2)Cl(2)). The rate coefficients for SO(2)FCl decrease slightly with temperature, commensurate with the decrease in the capture rate coefficient. Electron attachment to SOF(2) and SO(2)F(2) is nondissociative, while reaction with SOCl(2), SO(2)FCl, and SO(2)Cl(2) is dissociative. Dissociative attachment is dominated by channels arising from S-Cl bond cleavage but also includes a minor channel forming a dihalide product ion. Branching fraction data are reported for the dissociative attachment channels.

[Formation of flavor of dry champignons (Agaricus bisporus)].

The composition of aroma compounds of dry champignons (Agaricus bisporus L.) were identified using capillary gas chromatography and chromatography-mass spectrometry. In total, 56 compounds were identified. It was found that the flavor of dry mushrooms was formed by the volatile compounds produced as a result of enzymatic and oxidative conversion of unsaturated fatty acids as well as in the Maillard reaction. Unsaturated alcohols and ketones containing eight carbon atoms determined the mushroom note of the product. The specific aroma of dry mushrooms was determined by a complex composition of substituted sulfur-, oxygen-, and nitrogen-containing heterocyclic compounds as well as by aliphatic carbonyl compounds and methional. It was found that the concentrations of volatile carbonylic and heterocyclic compounds increased after the addition of a mixture of amino acids to mushrooms before drying. As a result, the intensity of the aroma of dry mushrooms increased.