Reconstitution of apomyoglobin with bile pigments

Summary Apomyoglobin was reconstituted with bile pigments of the verdinoid, 2,3-dihydroverdinoid, pterobilinoid, and violinoid type. Absorption and circular dichroism data as well as formation constants of the complexes were measured. From these results it was concluded that chromophore binding and induced chirality of these pigments are mainly governed by a lipophilic region opposite to the propionic side chain(s) and the asymmetric position of the hydrogen bonding acceptors of the propionic acid side chain(s) at the entrance of the protein pocket.Dedicated to Prof. Dr. A. Eschenmoser on occasion of his 65th birthday     

Zur Kenntnis des Lariciresinols

Ohne ZusammenfassungHerrn Prof. M. Bamberger, sage ich für seine freundliche Unterstützung bei Ausführung dieser Arbeit meinen aufrichtigsten Dank.     

Neuroprotection from NMDA excitotoxic lesion by Cu/Zn superoxide dismutase gene delivery to the postnatal rat brain by a modular protein vector

Background  

Superoxide mediated oxidative stress is a key neuropathologic mechanism in acute central nervous system injuries. We have analyzed the neuroprotective efficacy of the transient overexpression of antioxidant enzyme Cu/Zn Superoxide dismutase (SOD) after excitotoxic injury to the immature rat brain by using a recently constructed modular protein vector for non-viral gene delivery termed NLSCt. For this purpose, animals were injected with the NLSCt vector carrying the Cu/Zn SOD or the control GFP transgenes 2 hours after intracortical N-methyl-D-aspartate (NMDA) administration, and daily functional evaluation was performed. Moreover, 3 days after, lesion volume, neuronal degeneration and nitrotyrosine immunoreactivity were evaluated.     

Toward a Comparison of Classical and New Privacy Mechanism

In the last decades, the development of interconnectivity, pervasive systems, citizen sensors, and Big Data technologies allowed us to gather many data from different sources worldwide. This phenomenon has raised privacy concerns around the globe, compelling states to enforce data protection laws. In parallel, privacy-enhancing techniques have emerged to meet regulation requirements allowing companies and researchers to exploit individual data in a privacy-aware way. Thus, data curators need to find the most suitable algorithms to meet a required trade-off between utility and privacy. This crucial task could take a lot of time since there is a lack of benchmarks on privacy techniques. To fill this gap, we compare classical approaches of privacy techniques like Statistical Disclosure Control and Differential Privacy techniques to more recent techniques such as Generative Adversarial Networks and Machine Learning Copies using an entire commercial database in the current effort. The obtained results allow us to show the evolution of privacy techniques and depict new uses of the privacy-aware Machine Learning techniques.     

Synthesis of 5′-seleno-xylofuranosides

The synthesis of selenium derivatives of naturally occurring chiral molecules is becoming increasingly important in recent years. In this context, we describe herein an easy, straightforward synthetic route for the preparation of a series of chiral seleno-furanosides, starting from the readily available carbohydrate d-xylose. In addition, selected compounds were screened as inhibitors of the δ-aminolevulinate dehydratase (δ-ALA-D) enzyme. Diselenide 4 was found to reduce significantly the enzymatic activity, while seleno-furanoside 1a increased δ-ALA-D activity.     

The localized electrons detector as an ab initio representation of molecular structures

The local single particle momentum is proposed as a localized‐electrons detector (LED) that provides a direct three‐dimensional representation of bonding interactions in molecules. It is given exclusively in terms of the electron density and its gradient. We show that the graphical representation of bonding interactions given by LED is consistent with the local curvatures of the electron density as given by the eigenvalues of the Hessian matrix, according to a local symmetry classification of the critical points here introduced. LED consistently complements the topological analysis of the electron density given by the quantum theory of atoms in molecules, by providing a graphical representation of the symmetry of the bonding interactions in molecular systems. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem 110:2418–2425, 2010     

Long-term behaviour of GFRP pipes: Reducing the prediction test duration

The certification of glass-fibre reinforced plastic (GFRP) piping systems is regulated by normative standards in which test series of 10,000 h are required to estimate the residual properties at the end of the expected life (normally, 50 years). In this paper, the possibility to reduce the test duration, whilst maintaining an equivalent prediction of long-term properties, is discussed. Experimental results from standard test procedures conducted on GFRP pipes of four different types and respective data analysis support this possibility. The estimation error when using only data from shorter tests is consistently less than 10% if compared to the standard methods.     

Distribution of Chlorophyll- and Bacteriochlorophyll-derived Photosensitizers in Human Blood Plasma

Chlorophyll a and, in particular, bacteriochlorophyll a derivatives are promising candidates for photosensitizers in photodynamic therapy. The distribution of 21 (bacterio)chlorophyll derivatives among human blood plasma fractions was studied by iodixanol gradient ultracentrifugation and in situ absorption spectroscopy. Modifications of the natural pigments involved the central metal (Mg²⁺, Zn²⁺, Pd²⁺, none), the isocyclic ring (closed, open and taurinated), substituents at C-3 (vinyl, acetyl, 1-hydroxyethyl) and C-17³ (phytyl ester, free acid). Cellular blood components bound only a small fraction of the pigments. Distribution among low-density lipoproteins (LDL), high-density lipoproteins (HDL) and high-density proteins (HDP) of the plasma was influenced as follows: (1) application in Cremophor^® EL slightly altered pigment distribution by lipoprotein modification, (2) only very polar pigments with multiple hydrophilic substituents showed substantial HDP binding, (3) the presence of the esterifying alcohol at C-17³ caused enrichment in LDL, this was more pronounced with bacteriochlorophylls than with chlorophylls, (4) substituents at C-3 had only little influence on the distribution, (5) Zn²⁺-complexes were enriched in HDL compared to Mg²⁺ and Pd²⁺ complexes, indicating specific binding of the former. Equilibration of pigments among the different fractions was largely complete within 3 h.