Electrochemical reduction of tricarbonyl compounds: Reduction mechanism of alloxan on a mercury electrode

A study has been carried out on the reduction mechanism of alloxan over a DME corresponding to the first two-electron transfer over the pH range 0–12.Polarographic and voltammetric results show the reduction process to be kinetically controlled. Rate and equilibrium constant data for the prior chemical reaction have been evaluated and several reaction mechanisms for different pH zones have been proposed.     

Interaction of acrylodan with human serum albumin. A fluorescence spectroscopic study

The binding of the fluorescent probe acrylodan (AC) to human serum albumin (HSA) was studied by fluorescence spectroscopy. The binding isotherms could be fitted to two types of sites. Competition experiments using iodoacetamide suggested that AC binds tightly on HSA by the cysteine-34. Attempts were made to find the location of the second site using high concentrations of warfarin, phenylbutazone, diazepam, indomethacin, palmitic acid or bilirubin in order to displace the bound AC to the HSA. Bilirubin was the only ligand able to displace the bound AC. This result suggests that AC, which is a very hydrophobic molecule also capable of labeling lysine residues, should also bind the human albumin in the primary site of bilirubin, but with less affinity than to the cysteine-34.     

Electronic structure and spectra of CuO

We report the electronic structure of monoclinic CuO as obtained from first principles calculations utilizing density functional theory plus effective Coulomb interaction (DFT + U) method. In contrast to standard DFT calculations taking into account electronic correlations in DFT + U gave antiferromagnetic insulator with energy gap and magnetic moment values in good agreement with experimental data. The electronic states around the Fermi level are formed by partially filled Cu 3d _x²?y² orbitals with significant admixture of O 2p states. Theoretical spectra are calculated using DFT + U electronic structure method and their comparison with experimental photoemission and optical spectra show very good agreement.     

Pt]2Pb trinuclear systems: impact of the anionic platinum fragment on the lead environment and photoluminescence

A comparison of the solid structures of three novel trinuclear sandwich Pt 2Pb systems (NBu 4) 2[{Pt(C identical withCTol) 4} 2Pb(OH 2) 2] 1, [{Pt(bzq)(C identical withCPh) 2} 2Pb] 2, and (NBu 4)[{Pt(bzq)(C identical withCC 6H 4-CF 3-4) 2} 2Pb(O 2ClO 2)] 4 (NBu 4[ 3.(O 2ClO 2)]) with that of the previously reported (NBu 4) 2[{Pt(C 6F 5) 4} 2Pb] 5 showed that the local environment of Pb (II) is highly sensitive to the nature of the anionic platinate(II) precursors. The photoluminescence (PL) studies of all 1- 5 complexes revealed a dependence of PL on the structure type. Thus, complexes 1 and 5 exhibit metal centered emissions ( 1, 497 nm, 77 K; 5, 539 nm, varphi = 0.43, 298 K) related to the linear ( 5) or bent ( 1 Pt-Pb-Pt 149.9 degrees ) trinuclear entities. However, in complexes 2- 4, that have unprecedented Pb (II)...eta (1)(C identical withCR) bonding interactions and very short Pt...Pb and Pt...Pt distances, the emissive state in solid state (77 K) is attributed to a (3)MLM'CT [Pt(1)pi(C identical withCR)-->Pt(2)/Pb(sp)pi*(C identical withCR)] state mixed with some pipi* excimeric character in neutral complexes 2 (R = Ph) and 3 (R = C 6H 4-CF 3-4), and in the case of the adduct (NBu 4)[{Pt(bzq)(C identical withCC 6H 4-CF 3-4) 2} 2Pb(O 2ClO 2)] 4 modified also by Pb (II)...O (O 2ClO 2 (-)) contacts.     

Measurement of spatial gain distribution for a neonlike germanium 19.6-nm laser

We measure the transverse spatial distribution of the gain region for the 19.6-nm neonlike germanium laser line by use of a short amplifier, which is backlit by a longer laser, both of which are created by illumination of a germanium slab target with a series of short 100-ps pulses from the Nova laser. The backlighting technique enables us to reduce greatly the refraction effects that dominated previous imaging experiments and made direct gain measurements impossible. Measurements are made with a two-dimensional high-resolution spatial-imaging diagnostic, and simulations of the gain are compared with experiments.     

Rotations of Periodic Strings and Short Superstrings

This paper presents two simple approximation algorithms for the shortest superstring problem with approximation ratios 2 ( ≈ 2.67) and( ≈ 2.596). The framework of our improved algorithms is similar to that of previous algorithms in the sense that they construct a superstring by computing some optimal cycle covers on the distance graph of the given strings and then break and merge the cycles to finally obtain a Hamiltonian path, but we make use of new bounds on the overlap between two strings. We prove that for each periodic semiinfinite string α = a₁a₂··· of periodq, there exists an integerk, such that forany(finite) stringsof periodpwhich isinequivalentto α, the overlap betweensand therotationα[k] = a_ka_{k + 1}··· is at mostp + q. Moreover, ifp ≤ q, then the overlap betweensand α[k] is not larger than (p + q). The bounds are tight. In the previous shortest superstring algorithmsp + qwas used as the standard (tight) bound on overlap between two strings with periodspandq.     

A multi-orbital iterated perturbation theory for model Hamiltonians and real material-specific calculations of correlated systems

The dynamical mean field theory (DMFT) has emerged as one of the most importantframeworks for theoretical investigations of strongly correlated lattice models and realmaterial systems. Within DMFT, a lattice model can be mapped onto the problem of amagnetic impurity embedded in a self-consistently determined bath. The solution of thisimpurity problem is the most challenging step in this framework. The available numericallyexact methods such as quantum Monte Carlo, numerical renormalization group or exactdiagonalization are naturally unbiased and accurate, but are computationally expensive.Thus, approximate methods, based e.g. on diagrammatic perturbation theory have gainedsubstantial importance. Although such methods are not always reliable in various parameterregimes such as in the proximity of phase transitions or for strong coupling, theadvantages they offer, in terms of being computationally inexpensive, with real frequencyoutput at zero and finite temperatures, compensate for their deficiencies and offer aquick, qualitative analysis of the system behavior. In this work, we have developed such amethod, that can be classified as a multi-orbital iterated perturbation theory (MO-IPT) tostudy N-folddegenerate and non degenerate Anderson impurity models. As applications of the solver, wehave embedded the MO-IPT within DMFT and explored lattice models like the single orbitalHubbard model, covalent band insulator and the multi-orbital Hubbard model fordensity-density type interactions in different parameter regimes. The Hund’s couplingeffects in case of multiple orbitals is also studied. The limitations and quality ofresults are gauged through extensive comparison with data from the numerically exactcontinuous time quantum Monte Carlo method (CTQMC). In the case of the single orbitalHubbard model, covalent band insulators and non degenerate multi-orbital Hubbard models,we obtained an excellent agreement between the Matsubara self-energies of MO-IPT andCTQMC. But for the degenerate multi-orbital Hubbard model, we observe that the agreementwith CTQMC results gets better as we move away from particle-hole symmetry. We have alsointegrated MO-IPT+DMFT with density functional theory based electronic structure methodsto study real material systems. As a test case, we have studied the classic, stronglycorrelated electronic material, SrVO₃. A comparison of density of states and photo emissionspectrum (PES) with results obtained from different impurity solvers and experimentsyields good agreement.     

Uranyl complexes of alpha-carboxypolymethylenediaminetetra-acetic acids

The uranyl complexes of N,N,N',N'-tetrakis(carboxymethyl)-2,3-diaminopropionic acid, N,N,N',N'-tetrakis(carboxymethyl)diaminobutyric acid, N,N,N',N'-tetrakis(carboxymethyl)ornithine and N,N,N',N'-tetrakiscarboxymethyl)lysine have been studied by potentiometry, with computer evaluation of the titration data by the MINIQUAD program. Stability constants of the 1:1 and 2:1 metal:ligand chelates have been determined as well as the hydrolysis and polymerization constants at 25 degrees in 0.1M potassium nitrate. Results are compared with those obtained for the uranyl complexes of the corresponding members of the series of the polymethylenediaminetetra-acetic acids.