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showing 10 items of 1641 documents
Open-air Conservation of Ruins and the Concept of “Non-Dislocation”
2012
Most of the on-going debate is about “how” to protect archaeological ruins, whilst at the same time allowing the general public to enjoy them. Today it is clear how important it is, from the actual planning stages of excavations, to interact with experts from other disciplines, who are working on their own findings and offering them up for collective enjoyment. Whatever might be feasible for an indoor museum is not always feasible with an architectonic ruin, as regards both presenting objects with explicative apparatus that determines their significance, and exploring them in a new way when interpretations change or new ideologies are introduced. First of all, conserving excavations is the …
Uncapping the N-terminus of a ubiquitous His-tag peptide enhances its Cu2+ binding affinity
2019
Metal complexes with an N-terminally free and N-terminally acetylated polyhistidine region of Echis ocellatus venom, with an interesting His-rich motif present in numerous metal binding proteins from all kingdoms of life (DHDHDHHHHHHPGSSV-NH2 and Ac-DHDHDHHHHHHPGSSV-NH2) show the role of the free amino group in the thermodynamic enhancement of Cu2+, Ni2+ and Zn2+ binding. In the studied sequences, Cu2+ can be coordinated by different sets of imidazole rings, and a 3–10 helix is detected in close proximity of Cu2+ binding sites. The complexes are more stable than those with a typical His6-tag, despite a similar copper(II) coordination mode in both cases.
Allosteric regulation by Mg2+ of the vacuolar H(+)-PPase from Acer pseudoplatanus cells. Ca2+/Mg2+ interactions.
1996
The tonoplast H(+)-PPase was previously characterized in Acer pseudoplatanus cells (Pugin et al (1991) Plant Sci 73, 23-34; Fraichard et al (1993) Plant Physiol Biochem 31, 349-359). Tonoplast vesicles were obtained from vacuoles isolated from protoplasts of A pseudoplatanus suspension cultures and used to study kinetic effects of Mg2+ and Ca2+ on PPi hydrolysis. The concentrations of ionic species (free Mg2+, free PPi, and MgPPi complexes) were calculated with apparent dissociation constants of 55.3 microM for MgPPi and 59.6 microM for CaPPi. Our results indicated that the substrate of the tonoplast PPase was a MgPPi complex and that free Mg2+ was essential for PPi hydrolysis. With fixed f…
Pneumococcal histidine triads – involved not only in Zn2+, but also Ni2+ binding?
2018
Polyhistidine triad proteins, which participate in Zn2+ uptake in Streptococcus pneumoniae, contain multiple copies of the HxxHxH (histidine triad motif) sequence. We focus on three such motifs from one of the most common and well-conserved polyhistidine triad proteins, PhtA, in order to understand their bioinorganic chemistry; particular focus is given to (i) understanding which of the PhtA triads binds Zn2+ with the highest affinity (and why) and (ii) explaining whether Ni2+ (also crucial for bacterial survival and virulence) could potentially outcompete Zn2+ at its native binding site. There is no significant difference in the stability of zinc(II) complexes with the three studied protei…
Cytochrome-P450 phosphorylation as a functional switch
2002
Xenobiotic metabolizing cytochromes P450 (CYP) were shown to be phosphorylated in vitro (using purified protein kinases together with purified CYPs), in intact cells (in V79 cells after transfection of cDNAs coding for individual CYPs, in diagnostic mutants, in hepatocytes), and in whole organisms (rats). CYP phosphorylation is highly isoenzyme selective in that only some CYPs are phosphorylated. Protein kinase A (PKA) was identified as a major catalyst for the phosphorylation of CYPs. The PKA recognition motif Arg-Arg-X-Ser is present in several members of the CYP2 family, but is used by only some of them, most notably by CYP2B1/2B2 and CYP2E1. For CYP2B1 it was shown that a substantial po…
Multi-channel receptors based on thiopyrylium functionalised with macrocyclic receptors for the recognition of transition metal cations and anions.
2010
We report herein the synthesis and characterization of a family of ligands containing different cation binding sites covalently connected to a thiopyrylium signalling reporter. The receptors L1–L6 are able to signal the presence of certain metal cations via three different channels; i.e. electrochemically, fluorogenically and chromogenically. An acetonitrile solution of L1–L6 shows a bright blue colour due to a charge-transfer band in the 575–585 nm region. The colour variation in acetonitrile of L1–L6 in the presence of the metal cations Ag+, Cd2+, Cu2+, Fe3+, Hg2+, Ni2+, Pb2+ and Zn2+ has been studied. A selective hypsochromic shift of the blue band was found for the systems L4-Pb2+ and L…
4,4′-bis(dimethylamino)biphenyl containing binding sites. A newfluorescent subunit for cation sensing
2002
The emission behaviour of the 4,4′-bis(dimethylamino)biphenyl subunit covalently attached to aza-crown ethers is studied. Some new ligands have been synthesised in order to test the properties of this new fluorophore. The fluorescence of these new ligands and some other compounds previously described has been studied in acetonitrile in the presence of Ni2+, Cu2+, Zn2+, Hg2+, Pb2+, Cd2+ and also in the presence of some alkali and alkaline-earth cations.
The reduction of molecular oxygen by iron porphyrins
2002
Abstract Molecular assemblies have been synthesised to reproduce the structure of the cytochrome c oxidase (C c O) active site and to explore the roles played by its different features. It was discovered that a single iron porphyrin, adsorbed at the surface of a graphite electrode, is a selective catalyst for the four-electron reduction of dioxygen to water, at pH 7. To cite this article: D. Ricard et al., C. R. Chimie 5 (2002) 33–36
DFT insights into the oxygen-assisted selective oxidation of benzyl alcohol on manganese dioxide catalysts
2020
Abstract The reactivity pattern of the MnO2 catalyst in the selective aerobic oxidation of benzyl alcohol is assessed by density functional theory (DFT) analysis of adsorption energies and activation barriers on a model Mn4O8 cluster. DFT calculations predict high reactivity of defective Mn(IV) sites ruling a surface redox mechanism, L-H type, involving gas-phase oxygen. Bare and promoted (i.e., CeOx and FeOx) MnOx materials with high surface exposure of Mn(IV) sites were synthesized to assess kinetic and mechanistic issues of the selective aerobic oxidation of benzyl alcohol on real catalysts (T, 333–363 K). According to DFT predictions, the experimental study shows: i) comparable activity…
closo-borane conjugated regulatory peptides retain high biological affinity: synthesis of closo-borane conjugated Tyr(3)-octreotate derivatives for B…
2008
Despite the improvements in cancer therapy during the past years, high-grade gliomas and many other types of cancer are still extremely resistant to current forms of therapy. Boron neutron capture therapy (BNCT) provides a promising way to destroy cancer cells without damaging healthy tissue. However, BNCT in practice is still limited due to the lack of boron-containing compounds that selectively deliver boron to cancer cells. Since many neuroendocrine tumors show an overexpression of the somatostatin receptor, it was our aim to synthesize compounds that contain a large number of boron atoms and still show high affinity toward this transmembrane receptor. The synthetic peptide Tyr (3)-octre…