A Personal Account on Inorganic Reaction Mechanisms.

The presented Review is focused on the latest research in the field of inorganic chemistry performed by the van Eldik group and his collaborators. The first part of the manuscript concentrates on the interaction of nitric oxide and its derivatives with biologically important compounds. We summarized mechanistic information on the interaction between model porphyrin systems (microperoxidase) and NO as well as the recent studies on the formation of nitrosylcobalamin (CblNO). The following sections cover the characterization of the Ru(II)/Ru(III) mixed-valence ion-pair complexes, including Ru(II)/Ru(III)(edta) complexes. The last part concerns the latest mechanistic information on the DFT techniques applications. Each section presents the most important results with the mechanistic interpretations.

A Systematic Review of Methods Used to Determine the Work of Breathing during Exercise.

INTRODUCTION: Measurement of the work of breathing (Wb) during exercise provides useful insights into the energetics and mechanics of the respiratory muscles across a wide range of minute ventilations. The methods and analytical procedures used to calculate the Wb during exercise have yet to be critically appraised in the literature. PURPOSE: The aim of this systematic review was to evaluate the quality of methods used to measure the Wb during exercise in the available literature. METHODS: We conducted an extensive search of three databases for studies that measured the Wb during exercise in adult humans. Data were extracted on participant characteristics, flow/volume and pressure devices, esophageal pressure (P oes ) catheters, and methods of Wb analysis. RESULTS: A total of 120 articles were included. Flow/volume sensors used were primarily pneumotachographs ( n = 85, 70.8%), whereas the most common pressure transducer was of the variable reluctance type ( n = 63, 52.5%). Esophageal pressure was frequently obtained via balloon-tipped catheters ( n = 114, 95.0%). Few studies mentioned calibration, frequency responses, and dynamic compensation of their measurement devices. The most popular method of measuring the Wb was pressure-volume integration ( n = 51, 42.5%), followed by the modified Campbell ( n = 28, 23.3%) and Dean & Visscher diagrams ( n = 26, 21.7%). Over one-third of studies did not report the methods used to process their pressure-volume data, and the majority (60.8%) of studies used the incorrect Wb units and/or failed to discuss the limitations of their Wb measurements. CONCLUSIONS: The findings of this systematic review highlight the need for the development of a standardized approach for measuring Wb, which is informative, practical, and accessible for future researchers.

Consequences of Preterm Birth: Knowns, Unknowns, and Barriers to Advancing Cardiopulmonary Health.

Preterm birth occurs in 10% of all live births and creates challenges to neonatal life, which persist into adulthood. Significant previous work has been undertaken to characterize and understand the respiratory and cardiovascular sequelae of preterm birth, which are present in adulthood, i.e., "late" outcomes. However, many gaps in knowledge are still present and there are several challenges that will make filling these gaps difficult. In this perspective we discuss the obstacles of studying adults born preterm, including (1) the need for invasive (direct) measures of physiologic function; (2) the need for multistate, multinational, and diverse cohorts; (3) lack of socialized medicine in the United States; (4) need for detailed and better-organized birth records; and (5) transfer of neonatal and pediatric knowledge to adult care physicians. We conclude with a discussion on the "future" of studying preterm birth in regards to what may happen to these individuals as they approach middle and older age and how the improvements in perinatal and postnatal care may be changing the phenotypes observed in adults born preterm on or after the year 2000.

A comparison of methods used to quantify the work of breathing during exercise.

The mechanical work of breathing (Wb) is an insightful tool used to assess respiratory mechanics during exercise. There are several different methods used to calculate the Wb, however, each approach having its own distinct advantages/disadvantages. To date, a comprehensive assessment of the differences in the components of Wb between these methods is lacking. We therefore sought to compare the values of Wb during graded exercise as determined via the four most popular methods: 1) pressure-volume integration; 2) the Hedstrand diagram; 3) the Otis diagram; and the 4) modified Campbell diagram. Forty-two participants (30 ± 15 yr; 16 women) performed graded cycling to volitional exhaustion. Esophageal pressure-volume loops were obtained throughout exercise. These data were used to calculate the total Wb and, where possible, its subcomponents of inspiratory and expiratory, resistive and elastic Wb, using each of the four methods. Our results demonstrate that the components of Wb were indeed different between methods across the minute ventilations engendered by graded exercise. Importantly, however, no systematic pattern in these differences could be observed. Our findings indicate that the values of Wb obtained during exercise are uniquely determined by the specific method chosen to compute its value-no two methods yield identical results. Because there is currently no "gold-standard" for measuring the Wb, it is emphasized that future investigators be cognizant of the limitations incurred by their chosen method, such that observations made by others may be interpreted with greater context, and transparency.NEW & NOTEWORTHY The measurement of the work of breathing (Wb) during exercise provides us with deep insights into respiratory (patho)physiology, and sheds light on the putative factors which lead to respiratory muscle fatigue. There are 4 popular methods available to determine the Wb. Our study demonstrates that no two of these methods produce identical values of Wb during exercise. This paper also discusses the practical and theoretical limitations of each method.

Inorganic reaction mechanisms. A personal journey.

This review covers highlights of the work performed in the van Eldik group on inorganic reaction mechanisms over the past two decades in the form of a personal journey. Topics that are covered include, from NO to HNO chemistry, peroxide activation in model porphyrin and enzymatic systems, the wonder-world of RuIII(edta) chemistry, redox chemistry of Ru(iii) complexes, Ru(ii) polypyridyl complexes and their application, relevant physicochemical properties and reaction mechanisms in ionic liquids, and mechanistic insight from computational chemistry. In each of these sections, typical examples of mechanistic studies are presented in reference to related work reported in the literature.

Understanding chemical reaction mechanisms in ionic liquids: successes and challenges.

The focus of this article is an examination of chemical reaction mechanisms in ionic liquids. These mechanisms are compared with those pertaining to the same reactions carried out in conventional solvents. In cases where the mechanisms differ, attempts to provide an explanation in terms of the chemical and physicochemical properties of the reactants and of the components of the ionic liquids are described. A wide range of reactions from different branches of chemistry has been selected for this purpose. A sufficient background for student readers has been included. This tutorial review should also be of interest to kineticists, and to both new and experienced investigators in the ionic liquids field.

Structural, Spectroscopic, Thermodynamic and Kinetic Properties of Copper(II) Complexes with Tripodal Tetraamines.

Spectroscopic, thermodynamic, and kinetic measurements have been made on aqueous solutions of copper(II) complexes of hexamethylated tren and trimethylated tren (one methylation per primary amine group of tren) with the objective of correlating the influence of geometry (trigonal bipyramidal, evident from UV/vis spectroscopy) and N-alkyl substitution in the ligand on these inherent properties. At 25.0 degrees C the protonation constants of Me(3)tren are not significantly different from those of tren and Me(6)tren, and the stability constant for the Cu(II) complex is of the same order of magnitude as that for the [Cu(tren)(H(2)O)](2+) complex ion. The pK(a) for deprotonation of the coordinated water molecule of [Cu(Me(3)tren)(H(2)O)](2+) is intermediate between the values for the complexes containing the unsubstituted and the fully substituted tren ligand. Substitution (pyridine for water) kinetics measurements employing stopped-flow and temperature-jump methods revealed different patterns of reactivity: pyridine replaces water in [Cu(Me(3)tren)(H(2)O)](2+) with a second-order rate constant of (4.4 +/- 0.8) x 10(2) M(-)(1) s(-)(1) at 25.0 degrees C, whereas the corresponding process for [Cu(Me(6)tren)(H(2)O)](2+) is relatively complex and is discussed in more detail. Substitution in the former complex ion is characterized in the forward and reverse directions, by DeltaH() = 60 +/- 8 and 51.9 +/- 0.9 kJ mol(-)(1), DeltaS() = 5 +/- 27 and -23 +/- 3 J mol(-)(1) K(-)(1), and DeltaV() = -8.7 +/- 4.6 and -6.2 +/- 1.1 cm(3) mol(-)(1), respectively. It is concluded that this reaction follows an I(a) mechanism, similar to that reported for the comparable reaction of [Cu(tren)(H(2)O)](2+). An X-ray structural determination on a crystal of [Cu(2)(Me(3)tren)(2)(CN)](ClO(4))(3).2CH(3)CN demonstrated trigonal bipyramidal geometry about each copper(II) center. As has been found in comparable complexes of tren and Me(6)tren, the axial nitrogen to copper bond is shorter than the equatorial nitrogen-copper bonds, and the angle made by N(axial)-Cu-N(equatorial) is less than 90 degrees (84.6-85.4 degrees ), signifying that each copper ion lies below the plane of the equatorial nitrogen atoms.