Investigations of actinides in the context of final disposal of high-level radioactive waste: trivalent actinides in aqueous solution

The speciation of redox sensitive trivalent actinides Pu(III), Np(III), and U(III) has been studied in aqueous solution. The redox preparation, stabilization, and speciation of these trivalent actinides in aqueous systems are discussed here. The reductants investigated were rongalite, hydroxylamine hydrochloride, and acetohydroxamic acid and the An(III) species have been characterized by UV–Vis and XANES spectroscopy. The results show that the effectiveness of stabilization decreases generally in the order Pu(III) > Np(III) > U(III) and that the effectiveness of each reducing agent depends on the experimental conditions. More than 80 % of Pu(III) aquo species have been stabilized up to pH 5.5, whereas the Np(III) aquo ion could be stabilized in a pH range 0–2.5, and U(III) aquo ion is sufficiently stable at pH 1.0 and below over time periods suitable for experiments. However, this study gives a basis for the characterisation of the trivalent lighter actinides involved in complexation, sorption, and solid formation reactions in the future.     

Ab initio calculations of the lowest electronic states in the CuNO system

The lowest singlet and triplet electronic levels of the A' and A" symmetry species of the neutral copper-nitrosyl (CuNO) system are calculated by ab initio methods at the multi-reference configuration interaction (MRCI) level of theory with single and double excitations, and at the coupled cluster level of theory with both perturbational (CCSD(T)) and full inclusion of triple excitations (CCSDT). Experimental data are difficult to obtain, hence the importance of carrying out calculations as accurate as possible to address the structure and dynamics of this system. This paper aims at validating a theoretical protocol to develop global potential energy surfaces for transition metal nitrosyl complexes. For the MRCI calculations, the comparison of level energies at linear structures and their values from C(2v) and C(s) symmetry restricted calculations has allowed to obtain clear settings regarding atomic basis sizes, active orbital spaces and roots obtained at the multi-configurational self-consistent field (MCSCF) level of theory. It is shown that a complete active space involving 18 valence electrons, 11 molecular orbitals and the prior determination of 12 roots in the MCSCF calculation is needed for overall qualitatively correct results from the MRCI calculations. Atomic basis sets of the valence triple-zeta type are sufficient. The present calculations yield a bound singlet A' ground state for CuNO. The CCSD(T) calculations give a quantitatively more reliable account of electronic correlation close to equilibrium, while the MRCI energies allow to ensure the qualitative assessment needed for global potential energy surfaces. Relativistic coupled cluster calculations using the Douglas-Kroll-Hess Hamiltonian yield a dissociation energy of CuNO into Cu and NO to be (59 ± 5) kJ mol(-1) ((4940 ± 400) hc?cm(-1)). Favorable comparison is made with some of previous theoretical results and a few known experimental data.     

An Improved Synthesis of 4-Cycloheptene-1-Carboxylic Acid

Modification of the method of Stork and Landesman (J. Am. Chem. Soc. 1956, 78, 5129) permitted the synthesis of the title acid (1) in 58% yield from a cyclopentanone enamine. Acid 1 is a useful intermediate for the preparation of 4-substituted cycloheptenes in good yields.     

Low-threshold optical parametric oscillations in a whispering gallery mode resonator

In whispering gallery mode (WGM) resonator light is guided by continuous total internal reflection along a curved surface. Fabricating such resonators from an optically nonlinear material one takes advantage of their exceptionally high quality factors and small mode volumes to achieve extremely efficient optical frequency conversion. Our analysis of the phase-matching conditions for optical parametric down-conversion (PDC) in a spherical WGM resonator shows their direct relation to the sum rules for photons' angular momenta and predicts a very low parametric oscillation threshold. We realized such an optical parametric oscillator (OPO) based on naturally phase-matched PDC in lithium niobate. We demonstrated a single-mode, strongly nondegenerate OPO with a threshold of 6.7 μW and linewidth under 10 MHz. This work demonstrates the remarkable capabilities of WGM-based OPOs.     

Oxidative DNA Damage in the Photolysis of Af-Hydroxy-2-Pyridone, a Specific Hydroxyl-Radical Source

Abstract The photooxidative DNA damage by iV-hydroxy-2-pyri-done (1) is caused by hydroxyl radicals, as confirmed by electron paramagnetic resonance studies with the spin trap 5,5-dimethylpyrroline JV-oxide. Irradiation of the pyridone 1 at 300 nm induced strand breaks in super-coiled pBR322 DNA, while in calf-thymus DNA and 2'-deoxyguanosine (dG), respectively, 8-oxoguanine and 8-oxo-7,8-dihydro-2'-deoxyguanosine were formed. Time-dependent control experiments disclosed that photoprod-ucts of pyridone 1, e.g. 2-pyridone (3), are not responsible for the modification of DNA. Also the photosensitization by the pyridine-2-one chromophore was excluded, because JV-methylpyridine-2-one (2), which cannot generate hydroxyl radicals, was ineffective in the photooxidation of DNA and dG. Thus, the photolysis of pyridone 1 serves as a specific source of hydroxyl radicals for DNA damage, both strand breaks and base modifications.     

Direct refinement against proton-proton dipolar couplings in NMR structure determination of macromolecules

The computational tools necessary for making use of (1)H-(1)H dipolar couplings in macromolecular structure refinement are presented. Potentials are described for direct refinement against (1)H-(1)H dipolar couplings of known sign as well as of unknown sign. In addition, a multiple potential is developed for prochiral protons whose stereospecific assignments are unknown. The utility of direct (1)H-(1)H dipolar coupling refinement is illustrated using the small protein ubiquitin. It is shown that direct (1)H-(1)H dipolar coupling refinement leads to improvements in the precision, accuracy, and quality of the resulting structures.     

Pseudorandom number generators based on random covers for finite groups

Random covers for finite groups have been introduced in Magliveras et?al. (J Cryptol 15:285–297, 2002), Lempken et?al. (J Cryptol 22:62–74, 2009), and Svaba and van Trung (J Math Cryptol 4:271–315, 2010) for constructing public key cryptosystems. In this article we describe a new approach for constructing pseudorandom number generators using random covers for large finite groups. We focus, in particular, on the class of elementary abelian 2-groups and study the randomness of binary sequences generated from these generators. We successfully carry out an extensive test of the generators by using the NIST Statistical Test Suite and the Diehard battery of tests. Moreover, the article presents argumentation showing that the generators are suitable for cryptographic applications. Finally, we include performance data of the generators and propose a method of using them in practice.     

Multi-sample loading technique for comparative physical property measurements in the diamond-anvil cell

ABSTRACT

We present a method to perform improved measurements of the effects of chemical variability on physical properties of single-crystal samples in the diamond-anvil cell by employing a multi-sample approach. By customizing the sizes and shapes of the samples using a focused ion beam machine the simultaneous loading of relatively large crystals into a single sample chamber becomes feasible. To illustrate the potential of this approach, elastic properties of four single crystals of ringwoodite with different chemical compositions have been measured at high pressure. Our results suggest that the multi-sample approach allows for the quantification of small effects of chemical variations, such as iron and hydrogen incorporation, on physical properties. Furthermore, we discuss the possibility of using the multi-sample approach to load several crystals with different crystallographic orientations of the same material into one sample chamber in order to map out the direction dependence of anisotropic physical properties.