Determination of heavy metal concentrations in plants exposed to different degrees of pollution using ICP-AES

Plant samples (Plantago lanceolata - narrow leaf plantain and Cichorium endiviae - endive) were collected in the surroundings of heavy metal emission sources and in other less contaminated areas. After digestion in a closed microwave system using HNO(3), the concentrations of Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, and Zn were determined using ICP-AES. Detection limits for all the elements of interest are given. Differences in heavy metal uptake rate between both plant species were observed. The uptake is more intensive for endive than for narrow leaf plantain. High concentrations of some heavy metals were determined in the unwashed plant samples as a result of exposure to aerosols. Tukey's statistical test was used to confirm the discrepancy of Cr concentration in plant samples from various areas. Washing the leaves with water was found to remove a large amount of water-soluble aerosols.     

Gas-phase structure of protonated histidine and histidine methyl ester: combined experimental mass spectrometry and theoretical ab initio study

Gas-phase H/D exchange experiments with CD3OD and D2O and quantum chemical ab initio G3(MP2) calculations were carried out on protonated histidine and protonated histidine methyl ester in order to elucidate their bonding and structure. The H/D exchange experiments show that both ions have three equivalent fast hydrogens and one appreciably slower exchangeable hydrogen assigned to the protonated amino group participating in a strong intramolecular hydrogen bond (IHB) with the nearest N(sp2) nitrogen of the imidazole fragment and to the distal ring NH-group, respectively. It is taken for granted that the proton exchange in the IHB is much faster than the H/D exchange. Unlike in other protonated amino acids (glycine, proline, phenylalanine, tyrosine, and tryptophan) studied earlier, the exchange rate of the carboxyl group in protonated histidine is slower than that of the amino group. The most stable conformers and the enthalpies of neutral and protonated histidine and its methyl ester are calculated at the G3(MP2) level of theory. It is shown that strong intramolecular hydrogen bonding between the amino group and the imidazole ring nitrogen sites is responsible for the stability and specific properties of the protonated histidine. It is found that the proton fluctuates between the amino and imidazole groups in the protonated form across an almost vanishing barrier. Proton affinity (PA) of histidine calculated by the G3(MP2) method is 233.2 and 232.4 kcal mol(-1) for protonation at the imidazole ring and at the amino group nitrogens, respectively, which is about 3-5 kcal mol(-1) lower than the reported experimental value.     

Existence d'isomeres e et z d'ylures de cycloimmonium

E and Z isomers of p-nitrobenzoyl, 4-p-tolyl[1-2-4]triazolum methylide 5b and p-nitrobenzoyl, 4-p-phenyl[1-2-4]triazolium methylide 5e, have been characterised.     

Optimal orthogonalization processes

Two optimal orthogonalization processes are devised toorthogonalize,possibly approximately,the columns of a very large and possiblysparse matrix A∈C^n×k.Algorithmically the aim is,at each step,to optimallydecrease nonorthogonality of all the columns of A.One process relies on using translated small rank corrections.Another is a polynomial orthogonalization process forperforming the L?wdin orthogonalization.The steps rely on using iterative methods combined,preferably,with preconditioning which can have a dramatic effect on how fast thenonorthogonality decreases.The speed of orthogonalization depends on howbunched the singular values of A are,modulo the number of steps taken.These methods put the steps of the Gram-Schmidt orthogonalizationprocess into perspective regardingtheir(lack of)optimality.The constructions are entirely operatortheoretic and can be extended to infinite dimensional Hilbert spaces.     

UV-VIS and CD-spectroscopic investigations of intermolecular interactions of bile pigments with small proteins

Summary The intermolecular complex formation of bilirubin and biliverdin with two proteins (basic pancreatic trypsin inhibitor and lysozyme) were studied by optical and chiroptical methods. Evidence for specific intermolecular interactions of biliverdin with both proteins was found. Bilirubin forms a soluble complex only with lysozyme.

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UV-VIS und CD-spektroskopische Untersuchungen intermolekularer Wechselwirkungen von Gallenpigmenten mit kleinen Proteinen

Zusammenfassung Die intermolekulare Komplexbildung von Bilirubin und Biliverdin mit zwei Proteinen (basischer pankreatischer Trypsininhibitor und Lysozym) wurden mittels optischer und chiroptischer Spektroskopie untersucht. Für Biliverdin konnten intermolekulare Wechselwirkungen mit beiden Proteinen nachgewiesen werden. Bilirubin bildet nur mit Lysozym einen löslichen Komplex.

     

Beiträge zur Chemie der Pyrrolpigmente, 82. Mitt.: Wasserlösliche Polymere mit kovalent gebundenen violinoiden und 2,3-dihydro-verdinoiden Gallenfarbstoffen

Summary A violinoid and a 2,3-dihydrobilindione chromophore is attachedvia an appendix anchored at rings A of the pigments by means of reacting them with the polyacryl-N-acryloxysuccinimid copolymer to yield water-soluble chromopolymers. They are characterized by a molecular mass of about 4000 to 6000 and a relation of one chromophoric unit per 6 to 22 monomers. Their absorption spectra and circular dichroism recorded in water and dimethylsulfoxide as solvents are discussed with respect to structural aspects, and in comparison with monomeric chromophore derivatives.

Herrn Prof. Dr. K. Schlögl mit den besten Wünschen zum 65. Geburtstag gewidmet     

Local dissipation and coupling properties of cellular oscillators: a case study on calcium oscillations

Synchronised signal transduction between cells is crucial, since it assures fast and immutable information processing, which is vital for flawless functioning of living organisms. The question arises how to recognise the ability of a cell to be easily coupled with other cells. In the present paper, we investigate the system properties that determine best coupling abilities and assure the most efficient signal transduction between cells. A case study is done for intercellular calcium oscillations. For a particular diffusion-like coupled system of cellular oscillators, we determined the minimal gap-junctional permeability that is necessary for synchronisation of initially asynchronous oscillators. Our results show that dissipation is a crucial system property that determines the coupling ability of cellular oscillators. We found that low dissipation assures synchronisation of coupled cells already at very low gap-junctional permeability, whereas highly dissipative oscillators require much higher gap-junctional permeability in order to synchronise. The results are discussed in the sense of their biological importance for systems where the synchronous responses of cells were recognised to be indispensable for appropriate physiological functioning of the tissue.