The structure and synthesis of plutonium(III) chlorides from aqueous solution

The preparation and structure of three trivalent plutonium chloride compounds from aqueous solution is reported. Two of the three are plutonium tetraaquatetrachloro complexes exhibiting a cis and a trans arrangement of Cl about the Pu. The identification of the coordination number of 4 with respect to Cl and the isomerism are both unprecedented in actinide solution chemistry. The third complex is a hexaaquadichloro complex of Pu(III), predicted by available thermodynamic data.     

The correlation-consistent composite approach: application to the G3/99 test set

The correlation-consistent composite approach (ccCA), an ab initio composite technique for computing atomic and molecular energies, recently has been shown to successfully reproduce experimental data for a number of systems. The ccCA is applied to the G3/99 test set, which includes 223 enthalpies of formation, 88 adiabatic ionization potentials, 58 adiabatic electron affinities, and 8 adiabatic proton affinities. Improvements on the original ccCA formalism include replacing the small basis set quadratic configuration interaction computation with a coupled cluster computation, employing a correction for scalar relativistic effects, utilizing the tight-d forms of the second-row correlation-consistent basis sets, and revisiting the basis set chosen for geometry optimization. With two types of complete basis set extrapolation of MP2 energies, ccCA results in an almost zero mean deviation for the G3/99 set (with a best value of -0.10 kcal mol(-1)), and a 0.96 kcal mol(-1) mean absolute deviation, which is equivalent to the accuracy of the G3X model chemistry. There are no optimized or empirical parameters included in the computation of ccCA energies. Except for a few systems to be discussed, ccCA performs as well as or better than Gn methods for most systems containing first-row atoms, while for systems containing second-row atoms, ccCA is an improvement over Gn model chemistries.     

Ocean acoustic hurricane classification

Theoretical and empirical evidence are combined to show that underwater acoustic sensing techniques may be valuable for measuring the wind speed and determining the destructive power of a hurricane. This is done by first developing a model for the acoustic intensity and mutual intensity in an ocean waveguide due to a hurricane and then determining the relationship between local wind speed and underwater acoustic intensity. From this it is shown that it should be feasible to accurately measure the local wind speed and classify the destructive power of a hurricane if its eye wall passes directly over a single underwater acoustic sensor. The potential advantages and disadvantages of the proposed acoustic method are weighed against those of currently employed techniques.     

Multidimensional liquid chromatography for sample characterisation

While LC finds enormously widespread use in almost all areas of chemical science, the technique is limited as a means of identification because compounds do not elute with unique retention times. This limitation spurred the growth of hyphenated instrumental methods of analysis, such as LC-MS/MS, which because of the MS/ MS detection became a method of identification. However, techniques like LC-MS/ MS are specialised and require high initial purchase and running costs, inhibiting the more widespread growth of the technique. In an attempt to increase the separation power of LC, multi-dimensional LC was developed. This expanded the separation space and subsequently has allowed the development of methods with fingerprinting ability due to the lower probability of component overlap. The work in this study illustrates the application of 2-D LC as a means of chemical fingerprinting. We employed a sample base of various low molecular weight oligostyrenes and their diastereomers that represent a population of compounds whose selectivities in a one-dimensional separation are almost unity and hence essentially impossible to separate. Yet in a 2-D domain almost all individual components occupy unique 2-D retention times.     

Determination of the titanium content of human transferrin by inductively-coupled plasma-atomic-emission spectroscopy

We report a simple method that combines dialysis, as a purification method, with the multielement capability of ICP to determine the titanium-to-transferrin mole ratio at physiological pH, under buffer conditions. The method, by means of which titanium and transferrin are determined simultaneously, enabled us to assess the binding capacities of different titanocene complexes. Figure Titanocene dichloride     

Application of perceptual difference model on regularization techniques of parallel MR imaging

Parallel magnetic resonance imaging through sensitivity encoding using multiple receiver coils has emerged as an effective tool to reduce imaging time or to improve image SNR. The quality of reconstructed images is limited by the inaccurate estimation of the sensitivity map, noise in the acquired k-space data and the ill-conditioned nature of the coefficient matrix. Tikhonov regularization is a popular method to reduce or eliminate the ill-conditioned nature of the problem. In this approach, selection of the regularization map and the regularization parameter is very important. Perceptual difference model (PDM) is a quantitative image quality evaluation tool that has been successfully applied to varieties of MR applications. High correlation between the human rating and PDM score shows that PDM should be suitable to evaluate image quality in parallel MR imaging. By applying PDM, we compared four methods of selecting the regularization map and four methods of selecting the regularization parameter. We found that a regularization map obtained using generalized series (GS) together with a spatially adaptive regularization parameter gave the best reconstructions. PDM was also used as an objective function for optimizing two important parameters in the spatially adaptive method. We conclude that PDM enables one to do comprehensive experiments and that it is an effective tool for designing and optimizing reconstruction methods in parallel MR imaging.     

Koszulity of splitting algebras associated with cell complexes

We associate to a good cell decomposition of a manifold M a quadratic algebra and show that the Koszulity of the algebra implies a restriction on the Euler characteristic of M. For a two-dimensional manifold M the algebra is Koszul if and only if the Euler characteristic of M is two.     

An application of Fourier transforms on finite Abelian groups to an enumeration arising from the Josephus problem

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We analyze an enumeration associated with the Josephus problem by applying a Fourier transform to a multivariate generating function. This yields a formula for the enumeration that reduces to a simple expression under a condition we call local prime abundance. Under this widely held condition, we prove (Corollary 3.4) that the proportion of Josephus permutations in the symmetric group Sn that map t to k (independent of the choice of t and k) is 1/n. Local prime abundance is intimately connected with a well-known result of S.S. Pillai, which we exploit for the purpose of determining when it holds and when it fails to hold. We pursue the first case where it fails, reducing an intractable DFT computation of the enumeration to a tractable one. A resulting computation shows that the enumeration is nontrivial for this case.

Video

For a video summary of this paper, please click here or visit http://www.youtube.com/watch?v=DnZi-Znuk-A.     

Prediction of catastrophes in space over time

Predicting rare events, such as high level up-crossings, for spatio-temporal processes plays an important role in the analysis of the occurrence and impact of potential catastrophes in, for example, environmental settings. Designing a system which predicts these events with high probability, but with few false alarms, is clearly desirable. In this paper an optimal alarm system in space over time is introduced and studied in detail. These results generalize those obtained by de Maré (Ann. Probab. 8, 841–850, 1980) and Lindgren (Ann. Probab. 8, 775–792, 1980, Ann. Probab. 13, 804–824, 1985) for stationary stochastic processes evolving in continuous time and are applied here to stationary Gaussian random fields.