Oldószerrel hangolható foszforeszcenciájú, többmagvú ruténium(II)komplexek előállítása és jellemzése = Synthesis and characterization of polynuclear ruthenium(II) complexes of solvent tunable phosphorescence

A vízben oldódó 5,10,15,20-tetrakisz(paraszulfonato-fenil)porfirin (H2P4-) síkon kívüli (OOP: out-of-plane) fémkoplexeinek képződést vizsgáltuk Tl(III) és Hg(II) ionokkal. Azonosítottuk és jellemeztük a TlP3-, HgP4-, Hg2P28-, and Hg3P26- komplexeket spektrális, fotofizikai és fotokémiai sajátságaik alapján. Két [Ru(LL)(CN)4]2- típusú komplex sorozatot szintetizáltunk (LL=2,2’-bipiridin (bpy), 1,10-fenantrolin (phen), szubsztituált és deuterált származékaik) és jellemeztünk UV-Vis, IR, Raman spektroszkópiával, fotofizikai és fotokémiai sajátságaik alapján. Meghatároztuk a [Ru(dcb)(CN)4]4- és [Ru(dpp)(CN)4]2- protonálódási állandóit (dcb=4,4’dikarboxi-bpy és dpp=2,3-bis-2-piridil-pyrazin). Elméleti számításokat végeztünk a [Ru(bpy)2(CN)2] és [Ru(LL)(CN)4]2- komplexekre (LL= -CH3, -C6H5 és COO- csoportokkal szimmetrikusan 4,4’ szubsztituált bpy)). A [Ru(x,x’-dmb)(CN)4]2- (ahol x=3,4,5,6 és dmb=dimetil-bpy) komplexekre elméleti számításokkal kapott jellemző szerkezeti, fotofizikai és fotokémiai sajátságokat kísérleti eredményekkel igazoltuk. Új kétcentrumú Ru(II)-alapú komplexek prototípusát a [(bpy)2Ru(µ-bppz)Ru(CN)4] komplexet és metilált származékát a állítottuk elő és jellemeztük különböző spektroszkópiai módszerekkel (UV-Vis elnyelési és lumineszcencia, IR, NMR) módszerekkel. A komplexek két-két izomerét azonosítottuk NMR spektroszkópiai valamint az elméleti számítások eredményeinek összevetésével. | Formation of out-of-plane (OOP) metalloporphyrins of thallium(III) and mercury(II) with water soluble 5,10,15,20-tetrakis(parasulfonato-phenyl)porphyrin (H2P4-) was investigated. Spectral, photophysical and photochemical characteristics of TlP3-, HgP4-, Hg2P28-, and Hg3P26- complexes have been determined. Two series of [Ru(LL)(CN)4]2- complexes have been synthesized (LL=2,2’-bipyridine (bpy), 1,10-phenanthroline, and their substituted derivatives and several deuteriated isotopologues) and characterized by UV-Vis, IR, Raman, NMR spectroscopy, and photophysical and photochemical properties were measured. Stepwise protonation constants of [Ru(dcb)(CN)4]4- and [Ru(dpp)(CN)4]2- have been determined (dcb=4,4’dicarboxy-bpy, bpp=2,3-bis(2-pyridyl)-pyrazine). Theoretical calculations have been performed on [Ru(bpy)2(CN)2] and [Ru(LL)(CN)4]2- complexes (where LL is 4,4’ disubstituted bpy with -CH3, -C6H5 and COO- groups). All significant structural, photophysical and photochemical properties of [Ru(x,x’-dmb)(CN)4]2- (where x=3,4,5,6 and dmb=dimethyl-bpy) predicted by the theoretical calculations have been supported by the experiments. The [(bpy)2Ru(µ-bppz)Ru(CN)4] complex as prototype of new dinuclear Ru(II)-based complexes and its methylated derivative have been synthesized and characterized by various adequate spectroscopic (UV-Vis absorption and emission, IR, NMR) methods. Two isomers of the complexes have been assigned by NMR spectroscopy and theoretical calculations

Mit tudunk meg Klimó püspök hagyatéki irataiból könyvtárára vonatkozólag

Közlemények a Pécsi Erzsébet-Tudományegyetem Könyvtárából. 37. szám. 1937. január

Evaluation of the Internal Control System at Central Budgetary Institutions

During the audit on the final accounts for 2011, the State Audit Office of Hungary (SAO) reported on the operation of internal controls in a separate report, the background and results of which are presented in the present paper. The assessment of the operation of the internal control system was conducted using a 400-question questionnaire, which in turn was evaluated by a proprietary algorithm, generating the qualification of the components and the whole of the internal control system. Based on the summary and evaluation of results, it was determined that in 2011, the development and operation of the internal control system of central budgetary institutions fundamentally fulfilled its function. The operation of internal controls proved to be 85 per cent partially or entirely compliant at the 28 institutions and chapter-managed appropriations audited. The assessment proved that if internal controls were missing or not adequately established at the budgetary institutions audited, the deficiencies in their operation could be linked to the errors uncovered in the budget reports; furthermore, a correlation could be observed between the quality of internal audit activity and the compliance of the operation of the internal control system

ACTH- and cortisol-associated neutrophil modulation in coronary artery disease patients undergoing stent implantation

BACKGROUND: Psychosocial stress and activation of neutrophil granulocytes are increasingly recognized as major risk factors of coronary artery disease (CAD), but the possible relationship of these two factors in CAD patients is largely unexplored. Activation of neutrophils was reported to be associated with stenting; however, the issue of neutrophil state in connection with percutaneous coronary intervention (PCI) is incompletely understood from the aspect of stress and its hypothalamic-pituitary-adrenal axis (HPA) background. Thus, we aimed to study cortisol- and ACTH-associated changes in granulocyte activation in patients undergoing PCI. METHODOLOGY/PRINCIPAL FINDINGS: Blood samples of 21 stable angina pectoris (SAP) and 20 acute coronary syndrome (ACS) patients were collected directly before (pre-PCI), after (post-PCI) and on the following day of PCI (1d-PCI). Granulocyte surface L-selectin, CD15 and (neutrophil-specific) lactoferrin were analysed by flow cytometry. Plasma cortisol, ACTH, and lactoferrin, IL-6 were also assayed. In both groups, pre- and post-PCI ratios of lactoferrin-bearing neutrophils were relatively high, these percentages decreased substantially next day; similarly, 1d-PCI plasma lactoferrin was about half of the post-PCI value (all p</=0.0001). Post-PCI ACTH was reduced markedly next day, especially in ACS group (SAP: p<0.01, ACS: p</=0.0001). In ACS, elevated pre-PCI cortisol decreased considerably a day after stenting (p<0.01); in pre-PCI samples, cortisol correlated with plasma lactoferrin (r approximately 0.5, p<0.05). In 1d-PCI samples of both groups, ACTH showed negative associations with the ratio of lactoferrin-bearing neutrophils (SAP: r = -0.601, p<0.005; ACS: r = -0.541, p<0.05) and with plasma lactoferrin (SAP: r = -0.435, p<0.05; ACS: r = -0.609, p<0.005). CONCLUSIONS/SIGNIFICANCE: Pre- and post-PCI states were associated with increased percentage of activated/degranulated neutrophils indicated by elevated lactoferrin parameters, the 1d-PCI declines of which were associated with plasma ACTH in both groups. The correlation of plasma cortisol with plasma lactoferrin in the extremely stressed ACS before stenting, however, suggests an association of cortisol with neutrophil activation

Activation of AtMPK9 through autophosphorylation that makes it independent of the canonical MAPK cascades.

Mitogen activated protein kinases (MAPKs) are part of conserved signal transduction modules in eukaryotes that are typically organised into three-tiered kinase cascades. The activation of MAPKs in these pathways is fully dependent on the bisphosphorylation of the TXY motif in the T-loop by the pertinent dual-specificity MAPK kinases (MAPKKs). The plant AtMPK9 is a member of an atypical class of MAPKs. Representatives of this MAPK family have TDY phosphoacceptor site, a long C-terminal extension, and lack the common MAPKK binding docking motif. Here, we present multiple in vitro and in vivo data that AtMPK9 is activated independently of any upstream MAPKKs but it is activated through autophosphorylation. We mapped the autophosphorylation sites by mass spectrometry to the TDY motif and to the C-terminal regulatory extension. We mutated the phosphoacceptor sites on the TDY, which confirmed the requirement for bisphorylation at this site for full kinase activity. Next, we demonstrated that the kinase inactive mutant form of AtMPK9 is not transphosphorylated on the TDY site when mixed with an active AtMPK9, implying that the mechanism of the autocatalytic phosphorylation is intramolecular. Furthermore, we show that in vivo AtMPK9 is activated by salt and is regulated by okadaic acid-sensitive phosphatases. We conclude that the plant AtMPK9 shows similarities to the mammalian atypical MAPKs, ERK7/8 in terms of MAPKK-independent activation mechanism