Delphinidin–Aluminum(III) Complexes in Aqueous and Non-Aqueous Media: Spectroscopic Characterization and Theoretical Study

Summary. The study of delphinidin complexation with trivalent aluminum in acidic aqueous buffered (pH 3.0 and 3.8) and methanolic solutions was performed utilizing electronic absorption spectroscopy and quantum chemical calculations. In its structure delphinidin possesses several chelating sites in competition towards aluminum(III). Molar ratio plots denoted the formation of only one aluminum(III):delphinidin complex of stoichiometry of 1:1 in both investigated media. Semiempirical calculations, performed at the restricted HF AM1 level, enabled the determination of the structural features of free delphinidin and structural modifications caused by chelation of aluminum(III). Considering the pigment molecular structure and the results of the theoretical calculations it is possible to equally implicate C3′–C4′ and C4′–C5′ hydroxyl groups as those with the predominant chelating power.     

Signed graphs with at most three eigenvalues

Czechoslovak Mathematical Journal - We investigate signed graphs with just 2 or 3 distinct eigenvalues, mostly in the context of vertex-deleted subgraphs, the join of two signed graphs or...     

Estimation and setting starting values in ARMA algorithms

For the given observations set of the ARMA (autoregressive moving average) process, the likelihood function depends, not only on model parameters, but on the starting values of the input and output. Therefore, it is called theconditional likelihood function. Theunconditional likelihood function can be obtained in two ways. The first is to set the starting values to zero, as is often done, and the second is to set them to the properly estimated values. The difference between these two types of likelihood functions is significant when the given data sequence is short, and any of the zeros of the moving average part is close to the boundary of the unit circle.In this paper the direct method of starting value estimation and its application to two off-line ARMA estimation algorithms, the maximum likelihood (ML) algorithm and the iterative inverse filtering (ITIF) algorithm, is proposed. Experimental results prove both increased efficiency and stability of these algorithms.The importance of setting the starting values properly is also significant when the recursive algorithm, with previously estimated parameters, has to be restarted. The advantage of the proposed reinitialization method is shown on the recursive lattice algorithm working in the block mode.     

Determination of pefloxacin in serum and pharmaceutical forms by derivative spectrophotometry

A method for the direct determination of pefloxacin in serum and pharmaceutical forms (tablets and ampoules) has been developed, based on the use of second-order derivative ultraviolet spectra. Spectrophotometric assay of pefloxacin in tablets and ampoules was carried out in 0.1 mol/L NaOH, while in serum it was performed in 0.1 mol/L NaOH with the addition of sodium dodecylsulfate, in 337–347 nm wavelength range. Linear calibration curves were obtained in the concentration ranges 2–30g/mL pefloxacin for tablets and ampoules and 0.12–5 g/ mL for serum samples. Relative error of determination, as criterion for accuracy, was less than 1%, while the precision was better than 4 ng/ml. The minimum detectable concentration of pefloxacin in serum was 15 ng/mL.     

Gold(III) complexes with imidazole,benzoxazole, purine and pyrimidine derivatives

Summary The synthesis and characterization of Au^III complexes with several heterocyclic ligands are reported. The compounds have general formula [AuX₃(L)], where L =N-methylimidazole (N-MeIz),N-ethylimidazole (N-EtIz),N-propylimidazole (N-PrIz), benzoxazole (BO), 2-methylbenzoxazole (2-MeBO), 2,5-dimethylbenzoxazole (2,5-diMeBO), 2-amino-pyrimidine (2-APm), 4(6) -hydroxy-pyrimidine [4(6)-hydrPm] or hypoxanthine (Hypox) and X = Cl or Br. Elemental analysis, conductivity measurements and spectral studies were used for the characterization of the complexes. A square-planar geometry withN-bonded heterocyclic ligands is suggested.     

A DFT study of pyramidalized alkenes: 7-oxasesquinorbornenes and 7,7′-dioxasesquinorbornenes

  DFT calculations of 7′–oxasesquinorbornenes and 7,7′-dioxasesquinorbornenes using the B3LYP/6–31G* method are reported. All the investigated structures (syn- and anti- derivatives) showed significant non-planarity of the central double bond, with the exception of those anti-derivatives possessing symmetrical structures. The influence of the replacement of the methylene groups at position 7- of the norbornene fragment with oxygen and the introduction of second and third (peripheral) double bonds and benzene rings on the molecular and electronic structures of these molecules have also been investigated. Received: 11 November 2002 / Accepted: 6 June 2002 / Published online: 29 April 2003     

A characterization of brownian motion in a lipschitz domain by its killing distributions

Let (Y _t, Q^x) be a strong Markov process in a bounded Lipschitz domainD with continuous paths up to its lifetime , and let (X _t, P^x) be a Brownian motion inD. IfY _– exists in D andQ ^x(Y_– C)=P^x(X_– C) for all Borel subsetsC of D and allx, thenY is a time change ofX.     

Synergy between thermal analysis and simulation

Available databases presently used by commercial simulation software packages for the aluminum casting industry are usually armed with material properties for only a few selected standard alloys. In the case of other alloys with different chemical compositions and refinement or modification treatment, thermal analysis could be an invaluable tool to gain necessary properties. The aim of this article is to demonstrate the potential application of the cooling curve analysis in the existing simulation software by improving its accuracy.     

Advances in positron and electron scattering*

The topical issue on Advances in Positron and Electron Scattering” combines contributionsfrom POSMOL 2015 together with others devoted to celebrate the unprecedented scientificcareers of our loyal colleagues and trusted friends Steve Buckman (Australian NationalUniversity, Australia) and Michael Allan (University of Fribourg, Switzerland) on theoccasion of their retirements. POSMOL 2015, the XVIII International Workshop on Low-EnergyPositron and Positronium Physics and the XIX International Symposium on Electron-MoleculeCollisions and Swarms, was held at Universidade NOVA de Lisboa, Lisboa, Portugal, from17–20 July 2015. The international workshop and symposium allowed to achieve a veryprivileged forum of sharing and developing our scientific expertise on current aspects ofpositron, positronium and antiproton interactions with electrons, atoms, molecules andsolid surfaces, and related topics, as well as electron interactions with molecules inboth gaseous and condensed phases. Particular topics include studies of electroninteractions with biomolecules, electron induced surface chemistry and the study of plasmaprocesses. Recent developments in the study of swarms are also fully addressed.