Evaluating uranium radiochronometry by single-collector mass spectrometry for nuclear forensics: a multi-instrument investigation

Radiochronometric data, a key signature in evaluating the provenance and process history of nuclear material out of regulatory control, are conventionally acquired via multi-collector mass spectrometry. Here we explore the potential of age-dating by single-collector mass spectrometry. To evaluate model age accuracy/precision across different instrument designs, we performed ²³⁰Th–²³⁴U and ²³¹Pa–²³⁵U radiochronometry of CRM 125-A using two single-collector and one multi-collector plasma source mass spectrometers. Single-collector instruments produce accurate model ages for this uranium standard and thus hold promise for nuclear forensics radiochronometry. Increased acquisition of age information via multiple instrument designs will bolster the global response to nuclear interdictions.

     

Solvent optimization and conformational flexibility effects on 1H and 13C NMR scaling factors

The effects of including (a) implicit solvent in geometry optimizations, (b) conformationally flexible molecules in test sets, and (c) empirical dispersion D3(BJ) on scaling factors for predicting ¹H and ¹³C NMR chemical shifts were explored. Scaling factors with optimizations performed in the gas phase and with a Polarizable Continuum Model (PCM) solvent model were obtained for 12 organic solvents, including 2,2,2-trifluroethanol and chlorobenzene, for which scaling factors have been developed for the first time. Scaling factors for aromatic solvents were split into primary and secondary scaling factors to account for CH–π effects. Including empirical dispersion D3(BJ) did not lead to significant improvement.     

A single-cell analysis of myogenic dedifferentiation induced by small molecules

An important direction in chemical biology is the derivation of compounds that affect cellular differentiation or its reversal. The fragmentation of multinucleate myofibers into viable mononucleates (called cellularization) occurs during limb regeneration in urodele amphibians, and the isolation of myoseverin, a trisubstituted purine that could apparently activate this pathway of myogenic dedifferentiation in mammalian cells, generated considerable interest. We have explored the mechanism and outcome of cellularization at a single-cell level, and we report findings that significantly extend the previous work with myoseverin. Using a panel of compounds, including a triazine compound with structural similarity and comparable activity to myoseverin, we have identified microtubule disruption as critical for activation of the response. Time-lapse microscopy has enabled us to analyze the fate of identified mononucleate progeny, and directly assess the extent of dedifferentiation.     

Single-crystalline vanadium dioxide nanowires with rectangular cross sections

We report the synthesis of single-crystalline VO2 nanowires with rectangular cross sections using a vapor transport method. These nanowires have typical diameters of 60 (+/-30) nm and lengths up to >10 mum. Electron microscopy and diffraction measurements show that the VO2 nanowires are single crystalline and exhibit a monoclinic structure. Moreover, they preferentially grow along the [100] direction and are bounded by the (01) and (011) facets. These VO2 nanowires should provide promising materials for fundamental investigations of nanoscale metal-insulator transitions.     

Resonance Raman studies of xanthine oxidase: The reduced enzyme-product complex with violapterin

A study of the molecular, electronic, and vibrational characteristics of the molybdenum-containing enzyme complex xanthine oxidase with violapterin has been carried out using density functional theory calculations and resonance Raman spectroscopy. The electronic structure calculations were carried out on a model consisting of the enzyme molybdopterin cofactor [in the four-valent, reduced state; Mo(IV)O(SH)] covalently linked to violapterin (1H,3H,8H-pteridine-2,4,7-trione in the neutral form) via an oxygen bridge, Mo-O-C7. Full geometry optimizations were performed for all models using the SDD basis set and the three-parameter exchange functional of Becke combined with the Lee, Yang, and Parr correlational functional. Harmonic vibrational frequencies were determined for a variety of isotopes in an attempt to correlate experimentally observed shifts upon 18O-labeling of the Mo-OR bridge to bound product as well as shifts seen upon substitution of solvent-exchangeable protons in samples prepared in D2O. The theoretical vibrational frequencies compared favorably with experimentally observed vibrational modes in the resonance Raman spectra of the reduced xanthine oxidase-violapterin complex prepared in H2O and D2O and with 18O-labeled product. Correlating the isotopic shifts from the calculations with those from the resonance Raman experiments resulted in complete normal mode assignments for all modes observed in the 350-1750 cm(-1) range. The present work demonstrates that a model in which the violapterin is coordinated to the molybdenum of the active site in a simple end-on manner via the hydroxyl group introduced by an enzyme accurately predicts the observed resonance Raman spectrum of the complex. Given the numerous modes involving the bridging oxygen, a side-on binding mode can be eliminated.     

Complex magnetic ordering in Eu3InP3: a new rare earth metal zintl compound

Eu3InP3 has been prepared as large single crystals with an indium flux reaction. The structure of the new compound is isotypic to Sr3InP3 and crystallizes in the orthorhombic space group Pnma with unit cell dimensions of a = 12.6517(15) A, b = 4.2683(5) A, and c = 13.5643(14) A (Z = 4, T = 140 K, R1 = 0.0404, wR2 = 0.0971 for all data). The structure consists of one-dimensional chains of corner-shared distorted [InP2P2/2]6- tetrahedra separated by rows of Eu2+ ions. Two of the three crystallographically distinct europium sites have a short Eu(1)-Eu(2) distance of 3.5954(7) A, which yields Eu-Eu dimers. The Eu-P bond distances range from 2.974(2) to 3.166(2) A. The temperature dependence of the conductivity indicates that Eu3InP3 is a small band gap semiconductor. Both magnetization and Eu-151 Mossbauer spectral measurements indicate that the europium in Eu3InP3 is divalent and that at least two magnetic transitions occur. Magnetization studies reveal magnetic transitions at 14, 10.4, and approximately 5 K. These transitions are also observed in heat capacity studies of Eu3InP3. The Mossbauer spectra indicate that the two europium sites are ordered at 12 K and that all three europium sites are ordered at 8 K.     

The copper chelator methanobactin from Methylosinus trichosporium OB3b binds copper(I)

The oxidation state of copper bound to methanobactin, a small siderophore-like molecule from the methanotroph Methylosinus trichosporium OB3b, was investigated. Purified methanobactin loaded with Cu(II) exhibits a weak EPR signal probably due to adventitious Cu(II). The EPR signal intensity increases significantly upon addition of the strong oxidant nitric acid. Features of the X-ray absorption near edge spectrum, including a 1s --> 4p transition at 8985 eV, further indicate the presence of Cu(I). EXAFS data were best fit using a multiple scattering model generated from previously reported crystallographic parameters. These results establish definitively that M. trichosporium OB3b methanobactin binds Cu(I) and suggest that methanobactin itself reduces Cu(II) to Cu(I).     

Effect of interfacial liquid structuring on the coherence length in nanolubrication

The degree of interfacial structuring of n-hexadecane and octamethylcyclotetrasiloxane (OMCTS) was measured within a nanometer boundary regime to silicon surfaces. Boundary-layer effects on lubricating sliding (in terms of a thermodynamic stress activation parameter) and the layer thickness were determined by scanning force microscopy. A 2.0+/-0.3 nm thick, entropically cooled layer was found for n-hexadecane. Measurements on spherically shaped OMCTS molecules exhibited only an interfacial "monolayer," and identified the molecular shape of n-hexadecane responsible for augmented interfacial structuring. Interfacial liquid structuring was found to reduce friction.     

Unusually long cooperative chain of seven hydrogen bonds. An alternative packing type for symmetrical phenols

Conformational flexibility in a symmetrical tris-phenol leads to close packed structures that are also characterised by an extended though finite cooperative chain of hydrogen bonds.     

The reaction mechanism of xanthine oxidase: evidence for two-electron chemistry rather than sequential one-electron steps

Current research on xanthine oxidase has favored a mechanism involving base-catalyzed proton abstraction from a Mo-OH group, allowing nucleophilic attack on the substrate and hydride transfer from the substrate to Mo=S group in the active site. During the course of this reaction mechanism, the molybdenum redox cycles from MoVI to MoIV, with reoxidation of the MoIV speices to form the EPR active MoV intermediate. However, it has also been suggested that the reaction occurs in two subsequent one-electron steps. We have determined kinetic parameters kred and kred/Kd for a variety of plausible substrates as well as the one-electron reduction potentials for these substrates. Our data indicate no correlation between these kinetic parameters and their one-electron reduction potentials, as would be expected if the enzyme were using two subsequent one-electron reduction steps. Our results provide additional support to current evidence for the favored two-electron reduction mechanism.