Alkaline side-coordination strategy for the design of nickel(II) and nickel(III) bis(1,2-diselenolene) complex based materials

The deprotonated form of the pyrazine-2,3-diselenol (pds) ligand, pds(2-), reacts with Ni(II) inorganic salts to form the nickel compounds [Ni(II)(pds)(2)](nBu(4)N)(2) (1), [Ni(II)(pds)(2)]Na(2).2H(2)O (2), and [Ni(III)(pds)(2)](2)Na(2).4H(2)O (3), depending on the reaction conditions. They are characterized by NMR, EPR, UV-vis, and IR spectroscopies, elemental analysis, cyclic voltammetry, and X-ray crystallography. The crystal structure of compound 3 shows the formation of segregated stacks of Ni(pds)(2-) units, with a strong dimerization along the stacks. The stacked fashion of the crystal packing was expected since the supramolecular forces of the alkaline side coordination to the pyrazine moieties dominate, as happens in the recently reported analogous copper system [Cu(III)(pds)(2)]Na.2H(2)O. The structure of 2 further emphasizes the alkaline coordination as the dominating supramolecular event, and an orthogonal array of 2D layers is observed. The absence of alkaline cations in complex 1 is reflected in a crystal packing with isolated complex Ni(pds)(2)(2-) units. The dimerization found in the paramagnetic Ni(III) complex 3 promotes a very strong antiferromagnetic interaction, leading to a singlet ground state.     

The Smallest Regular Semigroups with all Four Skew Pairs of Idempotents

An ordered pair (e, f) of idempotents of a regular semigroup is called a skew pair if ef is not idempotent whereas fe is idempotent. We have shown previously that there are four distinct types of skew pairs of idempotents. Here we consider the smallest regular semigroups that contain precisely one of each of these four types. We show that, to within isomorphism and dualisomorphism, there are six such semigroups and characterise them as quotient semigroups of certain regular Rees matrix semigroups.     

Scars of the Wigner Function

We propose a picture of Wigner function scars as a sequence of concentric rings along a two-dimensional surface inside a periodic orbit. This is verified for a two-dimensional plane that contains a classical hyperbolic orbit of a Hamiltonian system with 2 degrees of freedom. The stationary wave functions are the familiar mixture of scarred and random waves, but the spectral average of the Wigner functions in part of the plane is nearly that of a harmonic oscillator and individual states are also remarkably regular. These results are interpreted in terms of the semiclassical picture of chords and centers.     

Atomic transport and chemical stability during annealing of ultrathin Al2O3 films on Si

Ultrathin films of Al2O3 deposited on Si were submitted to rapid thermal annealing in vacuum or in oxygen atmosphere, in the temperature range from 600 to 800 degrees C. Nuclear reaction profiling with subnanometric depth resolution evidenced mobility of O, Al, and Si species, and angle-resolved x-ray photoelectron spectroscopy revealed the formation of Si-Al-O compounds in near-surface regions, under oxidizing atmosphere at and above 700 degrees C. Under vacuum annealing all species remained essentially immobile. A model is presented based on diffusion-reaction equations capable of explaining the mobilities and reproducing the obtained profiles.     

A phase I, randomized study of combined IL-2 and therapeutic immunisation with antiretroviral therapy

Background  

Fully functional HIV-1-specific CD8 and CD4 effector T-cell responses are vital to the containment of viral activity and disease progression. These responses are lacking in HIV-1-infected patients with progressive disease. We attempted to augment fully functional HIV-1-specific CD8 and CD4 effector T-cell responses in patients with advanced chronic HIV-1 infection.     

Linked scans of peptides and protein digests: amino acid sequence determination of components of complex mixtures

Two-sector linked-scan analysis of an unpurified proteolytic digest of a pyruvate decarboxylase enzyme (60,000 Da) has allowed the discovery and assignment of an amino-terminal post-translational modification and processing event. A difference in amino acid sequence from that predicted by a recently published nucleotide sequence has also been found. These results illustrate both the use and considerable potential of linked-scan methods for the analysis of complex biopolymer mixtures.     

A three-phase algorithm for the cell suppression problem in two-dimensional statistical tables

To obtain full cooperation from respondents, statistical offices must guarantee that confidential data will not be disclosed when their reports are published. For tabular data, cell suppression is one of the preferred techniques to control statistical disclosure. When suppressing only confidential values does not guarantee the desired data protection, it is also necessary to suppress the values in some non-confidential cells. The problem of finding an optimal set of complementary suppressions—the cell suppression problem (CSP)—is NP-hard. We present a three-phase algorithm for the CSP based on a binary relaxation derived from row and column protection conditions. To enforce violated single cell conditions, integer cuts are added to the CSP relaxation. The numerical results obtained in 1410 instances with up to more than 250?000 cells, which were generated to reproduce two classes of real-world data, indicate that the algorithm is quite effective for both classes of instances and that it outperforms state-of-the-art algorithms for one of them.     

Inversion of the Bessel potential operator in weighted variable Lebesgue spaces

We study the inversion problem of the Bessel potential operator within the frameworks of the weighted Lebesgue spaces with variable exponent. The inverse operator is constructed by using approximative inverse operators. This generalizes some classical results to the variable exponent setting.     

An integrated experimental and theoretical investigation of the vibrational modes and molecular structure of a new Cu(II)–phosphocreatine complex

A new complex of Cu(II) of stoichiometry [Cu(PCr)(H₂O)] was prepared from aqueous solution at pH 6. Its synthesis, characterization, thermogravimetric, vibrational spectroscopy, and electron paramagnetic resonance analyses were described and suggest that phosphocreatine (PCr) in solid state is acting as a tridentate ligand (the nitrogen atom of the guanidine group and the oxygen atoms of the phosphate group and the carboxylate group being the donor atoms). The fourth position is occupied by a water molecule. These results were confirmed through computational calculations (DFT/B3LYP:6-311G theoretical procedure). The tetra coordination of Cu(II) arranged in a quadratic planar geometry was found to be more stable in the DFT calculations. The calculated vibrational spectrum agrees well with the FT-IR experimental spectrum.