Untersuchung des Phospholipase-C-γ-2-Gens auf genetische Variabilität

Wir untersuchten die PLCgamma2 in 95 Patienten der ECTIM-Studie mittels SSCP und Sequenzierung auf genetische Varianten. Es wurden 58 genetische Varianten identifiziert, 26 im Promotorbereich, 14 in Exons und 18 in Introns. Die SNPs A80369511G und T80369776C verändern die Vorhersage für TFBS der NF-kappaB-Familie. Die Varianten A80370272G und C80370273G liegen im PLCgamma2-Promotorbereich mit hoher Aktivität. In der Nähe einer AP-1- und NF-kappaB-TFBS befinden sich die Varianten T80368661G, G80368898C, C80369484A, G80369737A und A80369893G. In den kodierenden Bereichen wurden die genetischen Varianten A80377177T, A80480282T, C80480314T und C80510742T als Missensevarianten identifiziert. Die Varianten A80480282T und C80480314T befinden sich in der EF-hand-like-Domäne der PLCgamma2 und könnten zu einer veränderten Kalziumionenaffinität des Proteins führen. Diese Ergebnisse sollen als Grundlage für weitere molekular- und zellbiologische Analysen im PLCgamma2-Gen dienen.<br/

Induced selectivity in the photochemistry of estrone derivatives in sustainable and micellar environment: preparative and mechanistic studies

In this study, we carried out preparative and mechanistic studies on the photochemical reaction of a series of 3-acylestrone derivatives in confined and sustainable micellar environment under steady-state conditions and the results were compared with those obtained in cyclohexane solution. Theaim of this work is mainly focused to show whether the nature of the surfactant (cationic, neutral and anionic) leads to noticeable selectivity in the photoproduct formation. The 3-acylestrone derivatives underwent the photo-Fries rearrangement, with concomitant homolytic fragmentation of the ester group and [1;3]-acyl migration. This pathway afforded the ortho-acyl estrone derivatives, the main photoproducts together with estrone. However, epimerization of the ortho regioisomer 2-acetylestrone and estrone through Norrish Type I photoreaction occurred involving the fragmentation of the C-alpha at the carbonyl group (C-17) of the steroid. UV-visible and 2D-NMR (NOESY) spectroscopies have been employed to measure the binding constant Kb and the location of the steroids within the hydrophobic core of the micelle.Fil: Quindt, Matías Iván. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; ArgentinaFil: Gola, Gabriel Francisco. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; ArgentinaFil: Ramirez, Javier Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; ArgentinaFil: Bonesi, Sergio Mauricio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; Argentin

A New Highly Selective Chromogenic and Fluorogenic Chemosensor for Copper (II)

[EN] A new fluorogenic and chromogenic probe (L) for the selective, sensitive and naked-eye detection of Cu2+ is reported. Complexation constant, complex stoichiometry and quantum chemical (DFT) calculation for Cu2+ complex has been determined. Also, detection limits and the selectivity in front of other divalent and trivalent cations have been evaluated.This research was supported by the Agencia Nacional de Ciencia y Tecnologia (ANCyT) of Argentina-PICT 2014 No. 1587 and by the Universidad Nacional del Litoral, Santa Fe, Argentina.Quindt, MI.; Gutiérrez, LG.; Kneeteman, MN.; Mancini, P.; Parra Alvarez, M.; Gil Grau, S.; Costero, AM. (2018). A New Highly Selective Chromogenic and Fluorogenic Chemosensor for Copper (II). Letters in Organic Chemistry. 15(8):659-664. https://doi.org/10.2174/1570178615666180102155804S65966415

Mono- and Bis-Alkylated Lumazine Sensitizers: Synthetic, Molecular Orbital Theory, Nucleophilic Index and Photochemical Studies

Mono- and bis-decylated lumazines have been synthesized and characterized. Namely, mono-decyl chain [1-decylpteridine-2,4(1,3H)-dione] 6a and bis-decyl chain [1,3-didecylpteridine-2,4(1,3H)-dione] 7a conjugates were synthesized by nucleophilic substitution (SN 2) reactions of lumazine with 1-iododecane in N,N-dimethylformamide (DMF) solvent. Decyl chain coupling occurred at the N1 site and then the N3 site in a sequential manner, without DMF condensation. Molecular orbital (MO) calculations show a p-orbital at N1 but not N3 , which along with a nucleophilicity parameter (N) analysis predict alkylation at N1 in lumazine. Only after the alkylation at N1 in 6a, does a p-orbital on N3 emerge thereby reacting with a second equivalent of 1-iododecane to reach the dialkylated product 7a. Data from NMR (1 H, 13 C, HSQC, HMBC), HPLC, TLC, UV-vis, fluorescence and density functional theory (DFT) provide evidence for the existence of mono-decyl chain 6a and bis-decyl chain 7a. These results differ to pterin O-alkylations (kinetic control), where N-alkylation of lumazine is preferred and then to dialkylation (thermodynamic control), with an avoidance of DMF solvent condensation. These findings add to the list of alkylation strategies for increasing sensitizer lipophilicity for use in photodynamic therapy.Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicada

Photochemical Behavior of Some Estrone Aryl and Methyl Sulfonates in Solution: Preparative and Mechanistic Studies

Direct irradiation of estrone aryl and methyl sulfonates in different organic solvents under nitrogen atmosphere was investigated under steady-state conditions. The estrone derivatives reacted efficiently through the photo-Fries rearrangement reaction involving [1;3]-sulfonyl migration providing the ortho-sulfonyl estrone derivatives and estrone as the photoproducts. In addition, estrone and 2-arylsulfonyl estrone derivatives were epimerized involving a Norrish Type-I reaction. Chemical quenching and photosensitization experiments on the photoreaction have been also carried out to establish the photoreactive excited state. Likewise, the solvent effect and the nature of the sulfonyl group on the photoreactions have been also studied.Fil: Quindt, Matías Iván. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; ArgentinaFil: Gola, Gabriel Francisco. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; ArgentinaFil: Ramirez, Javier Alberto. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; ArgentinaFil: Bonesi, Sergio Mauricio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentin

Photohomolysis and Photoheterolysis in Aryl Sulfonates and Aryl Phosphates

The photochemical behaviour of selected aryl sulfonates and phosphates (ArOX) in polar and nonpolar media has been investigated by laser flash photolysis (LFP) experiments. Two main pathways have been identified, namely the photohomolysis of the ArO−X bond or the photoheterolysis of the Ar−OX bond depending on the nature of the leaving group (OX) and on the nature of the substituents on the aromatic ring. In nonpolar solvents the esters are quite photostable due to an efficient triplet deactivation. In polar solvents, the homolytic fragmentation of the ArO−S bond from the exited singlets was found in aryl sulfonates bearing moderately electron-donating groups as well as electron-withdrawing groups. In electron-rich aryl phosphates and sulfonates photoheterolysis of the Ar−OP/Ar−OS bond took place as the exclusive pathway.Fil: Bonesi, Sergio Mauricio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; ArgentinaFil: Protti, Stefano. Universita degli Studi di Pavia; ItaliaFil: Fagnoni, M.. Universita degli Studi di Pavia; Itali

Photochemistry of para substituted benzanilides in solution:Preparative and mechanistic studies

Preparative and mechanistic studies on the photochemical reaction of a series of p-substituted benzanilides in polar and nonpolar solvents have been carried out. The aim of this work is mainly focused to show whether the reaction solvent and the electronic effects of the substituents affect the product distribution, the chemical yields and the rate of formation of the 5-substituted-2-aminobenzophenone derivatives. Application of the Hammett linear free energy relationship (LFER) on the rate of formation of 2-aminobenzophenone derivatives, on the lower energy band of the UV–visible absorption spectra of the benzanilides and 5-substituted-2-aminobenzophenone derivatives allows a satisfactory quantification of the substituent effects. Furthermore, the solvent effect was also analyzed on the photoreaction by means of the Reichardt’s solvent parameter (ET(30). Finally, (TD-) DFT calculations have been carried out to support the trends observed experimentally. Graphical abstract: [Figure not available: see fulltext.]

Unstable impedance of a single electrode contact resulting in loss of DBS therapya case report

yy Open and short circuits of electrode contacts are important technical dysfunctions of DBS. Here, we report on another type of dysfunction restricted to a single electrode contact: impedance instability within regular absolute values. After 9-year subthalamic DBS, a Parkinson patient developed unilateral motor symptoms and intermittent dysaesthesia due to impedance instability of the active contact. DBS efficacy could be restored without surgical revision by activation of the neighboring contact. During 3-year-follow-up, impedances of the dysfunctional contact varied between 1 and 3k whereas the other three contacts remained stable. Impedance documentation is crucial to identify such dysfunctions