NO* release from MbFe(II)NO and HbFe(II)NO after oxidation by peroxynitrite

In this work, we showed that the reaction of peroxynitrite with MbFe(II)NO, in analogy to the corresponding reaction with HbFe(II)NO (Herold, S. Inorg. Chem. 2004, 43, 3783-3785), proceeds in two steps via the formation of MbFe(III)NO, from which NO* dissociates to produce iron(III)myoglobin (Mb = myoglobin; Hb = hemoglobin). The second-order rate constants for the first steps are on the order of 10(4) and 10(3) M(-1) s(-1), for the reaction of peroxynitrite with MbFe(II)NO and HbFe(II)NO, respectively. For both proteins, we found that the values of the second-order rate constants increase with decreasing pH, an observation that suggests that HOONO is the species responsible for oxidation of the iron center. Nevertheless, it cannot be excluded that the pH-dependence arises from different conformations taken up by the proteins at different pH values. In the presence of 1.2 mM CO2, the values of the second-order rate constants are larger, on the order of 10(5) and 10(4) M(-1) s(-1), for the reaction of peroxynitrite with MbFe(II)NO and HbFe(II)NO, respectively. The pH-dependence of the values for the reaction with MbFe(II)NO suggests that ONOOCO2- or the radicals produced from its decay (CO3*-/NO2*) are responsible for the oxidation of MbFe(II)NO to MbFe(III)NO. In the presence of large amounts of nitrite (in the tens and hundreds of millimoles range), we observed a slight acceleration of the rate of oxidation of HbFe(II)NO by peroxynitrite. A catalytic rate constant of 40 +/- 2 M(-1) s(-1) was determined at pH 7.0. Preliminary studies of the reaction between nitrite and HbFe(II)NO showed that this compound also can oxidize the iron center, albeit at a significantly slower rate. At pH 7.0, we obtained an approximate second-order rate constant of 3 x 10(-3) M(-1) s(-1).     

Pulse radiolysis studies of the reactions of CO3*- and NO2* with nitrosyl(II)myoglobin and nitrosyl(II)hemoglobin

The reactions of carbonate radical anion [CO3*-, systematic name: trioxidocarbonate*1-] with nitrosyl(II)hemoglobin (HbFe(II)NO) and nitrosyl(II)myoglobin (MbFe(II)NO) were studied by pulse radiolysis in N2O-saturated 0.25 M sodium bicarbonate solutions at pH 10.0 and room temperature. The reactions proceed in two steps: outer-sphere oxidation of the nitrosyliron(II) proteins to their corresponding nitrosyliron(III) forms and subsequent dissociation of NO*. The second-order rate constants measured for the first reaction steps were (4.3 +/- 0.2) x 10(8) and (1.5 +/- 0.3) x 10(8) M(-1) s(-1), for MbFe(II)NO and HbFe(II)NO, respectively. The reactions between nitrogen dioxide and MbFe(II)NO or HbFe(II)NO were studied by pulse radiolysis in N2O-saturated 0.1 M phosphate buffer pH 7.4 containing 5 mM nitrite. Also for the reactions of this oxidant with the nitrosyliron(II) forms of Mb and Hb a two-step reaction was observed: oxidation of the iron was followed by dissociation of NO*. The second-order rate constants measured for the first reaction steps were (2.9 +/- 0.3) x 10(7) and (1.8 +/- 0.3) x 10(7) M(-1) s(-1), for MbFe(II)NO and HbFe(II)NO, respectively. Both radicals appear to be able to oxidize the iron(II) centers of the proteins directly. Only for the reactions with HbFe(II)NO it cannot be excluded that, in a parallel reaction, CO3*- and NO2* first react with amino acid(s) of the globin, which then oxidize the nitrosyliron(II) center.     

The consultation timetabling problem at Danish high schools

In the different stages of the educational system, the demand for efficient planning is increasing. This article treats the $\mathcal NP $ NP -hard Consultation Timetabling Problem, a recurrent planning problem for the high schools in Denmark, which has not been described in the literature before. Two versions of the problem are considered, the Parental Consultation Timetabling Problem (PCTP) and the Supervisor Consultation Timetabling Problem (SCTP). It is shown that both problems can be modeled using the same Integer Programming model. Solutions are found using the state-of-the-art MIP solver Gurobi and Adaptive Large Neighborhood Search (ALNS), and computational results are established using 300 real-life datasets. These tests show that the developed ALNS algorithm is significantly outperforming both Gurobi and a currently applied heuristic for the PCTP. For both the PCTP and the SCTP, it is shown that the ALNS algorithm in average provides results within 5 % of optimum. The developed algorithm has been implemented in the commercial product Lectio, and is therefore available for approximately 95 % of the Danish high schools.     

An ESR investigation of triple ions derived from 1,2,4,5-tetramesitoylbenzene

Stable triple ions were obtained in MTHF solution from the ion pairs of 1,2,4,5-tetramesitoylbenzene (TMB) radical anion and alkali metal cations by reaction with soluble alkali metal salts. Their ESR spectra are highly resolved. MO calculations with parameters which lead to spin density values as nearly as possible equal to the experimental ones allow estimates of the oxygen-metal distances. The relatively most stable triple ions are the ones with the smallest estimated oxygen metal distances.     

Intraventricular thrombus formation in the LVAD-assisted heart studied in a mock circulatory loop

Left ventricular assist devices (LVADs) are mechanical pumps that are surgically attached to the left ventricle and aorta. Clinical studies show that LVADs improve patient health and quality of life, and dramatically reduce the mortality of cardiac failure. During periods of high LVAD support, blood flow occurs entirely through the LVAD, the aortic valve is continuously closed, and the heart operates in series with the pump. Thus the normal fluid dynamics of intraventricular flow are altered and linked to the development of thrombus in both the native heart and LVAD. Our goal in this study was to simulate a patient with a recurring thrombus and quantify the variations in the flow field in the LV as the thrombus developed. Particle image velocimetry measurements of transparent silicone models were performed for a range of LVAD support conditions. Results show that the presence of a small thrombus in the LVOT creates a favorable condition for further growth, especially in the presence of high LVAD support. As the thrombus enlarges, it begins to affect the normal vortex-flow pattern, further reducing flow rate and pulsatility in the LVOT. Evaluation of vortex dynamics and stasis regions in both patients and experimental models of LVAD support yield quantitative metrics that can be used to assess the risk of thrombus and the development of strategies to reduce this risk in LVAD patients.     

Drift estimation for a periodic mean reversion process

In this paper we propose a periodic, mean-reverting Ornstein–Uhlenbeck process of the form

Quantitative Auswertung von Dünnschicht-Chromatogrammen: On line-Kopplung mit programmierbaren elektronischen Tischrechnern

The paper describes the coupling of TLC-photometer, electronic integrator and desk calculator for the determination of phthalic acid by measurement of the remission at 280.3 nm. The average of integrator counts by scanning in and against development of the plate avoids errors caused by base line-drifts. From standards on the plate results a straight line by least squares using the quadratic proportionality of peak area to concentration. From this straight line the concentrations will be determined. The error of this method is in the range of 2–2.5% (relative standard deviation).     

Nullstellen bei Lösungen komplexer linearer Differentialgleichungen 2. Ordnung

Ohne Zusammenfassung