Coil to extended coil transition in polygalacturonic acid: Conductometric titration and monte carlo simulations

The conformational transition from coil to extended coil for polygalacturonic acid has been studied by conductometric titrations and Monte Carlo simulations. The results of conductometric titrations at different polymer concentrations have been analyzed using the model proposed by Manning,1 which describes the conductivity of polyelectrolitic solutions. This experimental approach provides the transport factor and the average distance between charged groups at different degrees of ionization (α). The mean distances between charged groups have been compared with the values obtained by Monte Carlo simulations. In these simulations the polymer chain is modeled as a self-avoiding random walk in a cubic lattice. The monomers interact through the unscreened Coulombic potential. The ratio between the end-to-end distance and the number of ionized beads provides the average distance between charged monomers. The experimental and theoretical values are in good agreement for the whole range of ionization degrees accessed by conductometric titrations. These results suggest that the electrostatic interactions seem to be the major contribution for the coil to extended coil conformational change. The small deviations for α ≤ 0.5 suggests that the stiffness of the chain, associated with local interactions, becomes increasingly significant as the fraction of charged groups is decreased. © 2000 American Chemical Society.

Non-aqueous Titration of Gatifloxacin in Pharmaceutical Formulations using Perchloric Acid

An inexpensive, simple, precise and rapid method for the determination of fluoroquinolone gatifloxacin in tablets is described. The procedure is based on the use of volumetric dosage in a non-aqueous medium in glacial acetic acid with 0.1 M perchloric acid. The method validation yielded good results and included the precision, recovery and accuracy. It was also found that the excipients in the commercial tablet preparation did not interfere with the assay.

A novel potentiometric naproxenate ion sensor immobilized in a graphite matrix for determination of naproxen in pharmaceuticals

The characteristics, performance, and application of an electrode, namely, Pt|Hg|Hg 2(NAP) 2| Graphite, where NAP stands for naproxenate ion, are described. This electrode responds to NAP with sensivity of (58.1± 0.9) mV decade -1 over the range 5.0 × 10 -5 - 1.0 × 10 -2 mol L -1 at pH 6.0-9.0 and a detection limit of 3.9 × 10 -5 mol L -1. The electrode is easily constructed at a relatively low cost with fast response time (within 10-35 s) and can be used for a period of 6 months without any considerable divergence in potentials. The proposed sensor displayed good selectivity for naproxen in the presence of several substances, especially concerning carboxylate and inorganic anions. It was used for the direct assay of naproxen in commercial tablets by means of the standard additions method. The analytical results obtained by using this electrode are in good agreement with those given by the United States Pharmacopeia procedure. ©2006 Sociedade Brasileira de Química.

Potentiometric determination of phosphorus in biodiesel using chemically modified electrode with cobalt film

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Simple and direct potentiometric determination of potassium ions in biodiesel microemulsions at a glassy carbon electrode modified with nickel(II) hexacyanoferrate nanoparticles

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Effects of Positive End-expiratory Pressure Titration and Recruitment Maneuver on Lung Inflammation and Hyperinflation in Experimental Acid Aspiration-induced Lung Injury

Background: In acute lung injury positive end-expiratory pressure (PEEP) and recruitment maneuver are proposed to optimize arterial oxygenation. The aim of the study was to evaluate the impact of such a strategy on lung histological inflammation and hyperinflation in pigs with acid aspiration-induced lung injury. Methods: Forty-seven pigs were randomly allocated in seven groups: (1) controls spontaneously breathing; (2) without lung injury, PEEP 5 cm H2O; (3) without lung injury, PEEP titration; (4) without lung injury, PEEP titration + recruitment maneuver; (5) with lung injury, PEEP 5 cm H2O; (6) with lung injury, PEEP titration; and (7) with lung injury, PEEP titration + recruitment maneuver. Acute lung injury was induced by intratracheal instillation of hydrochloric acid. PEEP titration was performed by incremental and decremental PEEP from 5 to 20 cm H2O for optimizing arterial oxygenation. Three recruitment maneuvers (pressure of 40 cm H2O maintained for 20 s) were applied to the assigned groups at each PEEP level. Proportion of lung inflammation, hemorrhage, edema, and alveolar wall disruption were recorded on each histological field. Mean alveolar area was measured in the aerated lung regions. Results: Acid aspiration increased mean alveolar area and produced alveolar wall disruption, lung edema, alveolar hemorrhage, and lung inflammation. PEEP titration significantly improved arterial oxygenation but simultaneously increased lung inflammation in juxta-diaphragmatic lung regions. Recruitment maneuver during PEEP titration did not induce additional increase in lung inflammation and alveolar hyperinflation. Conclusion: In a porcine model of acid aspiration-induced lung injury, PEEP titration aimed at optimizing arterial oxygenation, substantially increased lung inflammation. Recruitment maneuvers further improved arterial oxygenation without additional effects on inflammation and hyperinflation.

Structural, spectral and potentiometric characterization, and antimicrobial activity studies of [Zn(phen)(2)(cnge)(H2O)](NO3)(2)∙H2O

An octahedral Zn complex with o-phenanthroline (o-phen) and cyanoguanidine (cnge) has been synthesized and characterized. The crystal structural data show the formation of a ZnN5O core where the metal coordinates to two mutually perpendicular o-phenanthrolines as bidentate ligands [Zn-N bond lengths in the 2.124(2)-2.193(2) angstrom range], the cyanide nitrogen of a cnge [d(Zn-N) = 2.092(2) angstrom, angle(Zn-N-C) = 161.1(2)degrees], and a water molecule [d(Zn-Ow) = 2.112(2) angstrom]. Spectral data (FT-IR, Raman, and fluorescence) and speciation studies are in agreement with the structure found in the solid state and the one proposed to exist in the solution. To evaluate the changes in the microbiological activity of Zn, antibacterial studies were carried out by observing the changes in minimum inhibitory concentration of the complex, the ligands, and the metal against five different bacterial strains. The antibacterial activity of Zn improved upon complexation in three of the tested strains.

Heats of mixing using an isothermal titration calorimeter: Associated thermal effects

[EN] The correct determination of the energy generated or absorbed in the sample cell of an Isothermal Titration Calorimeter (ITC) requires a thorough analysis of the calorimetric signal. This means the identification and quantification of any thermal effect inherent to the working method. In this work, it is carried out a review on several thermal effects, studied by us in previous work, and which appear when an ITC is used for measuring the heats of mixing of liquids in a continuous mode. These effects are due to: (i) the difference between the temperature of the injected liquid and the temperature of the mixture during the mixing process, (ii) the increase of the liquid volume located in the mixing cell and (iii) the stirring velocity. Besides, methods for the identification and quantification of the mentioned effects are suggested.

Direct electron transfer to cytochrome c oxidase investigated by electrochemistry and time-resolved surface-enhanced infrared absorption spectroscopy

Cytochrom c Oxidase (CcO), der Komplex IV der Atmungskette, ist eine der Häm-Kupfer enthaltenden Oxidasen und hat eine wichtige Funktion im Zellmetabolismus. Das Enzym enthält vier prosthetische Gruppen und befindet sich in der inneren Membran von Mitochondrien und in der Zellmembran einiger aerober Bakterien. Die CcO katalysiert den Elektronentransfer (ET) von Cytochrom c zu O2, wobei die eigentliche Reaktion am binuklearen Zentrum (CuB-Häm a3) erfolgt. Bei der Reduktion von O2 zu zwei H2O werden vier Protonen verbraucht. Zudem werden vier Protonen über die Membran transportiert, wodurch eine elektrochemische Potentialdifferenz dieser Ionen zwischen Matrix und Intermembranphase entsteht. Trotz ihrer Wichtigkeit sind Membranproteine wie die CcO noch wenig untersucht, weshalb auch der Mechanismus der Atmungskette noch nicht vollständig aufgeklärt ist. Das Ziel dieser Arbeit ist, einen Beitrag zum Verständnis der Funktion der CcO zu leisten. Hierzu wurde die CcO aus Rhodobacter sphaeroides über einen His-Anker, der am C-Terminus der Untereinheit II angebracht wurde, an eine funktionalisierte Metallelektrode in definierter Orientierung gebunden. Der erste Elektronenakzeptor, das CuA, liegt dabei am nächsten zur Metalloberfläche. Dann wurde eine Doppelschicht aus Lipiden insitu zwischen die gebundenen Proteine eingefügt, was zur sog. proteingebundenen Lipid-Doppelschicht Membran (ptBLM) führt. Dabei musste die optimale Oberflächenkonzentration der gebundenen Proteine herausgefunden werden. Elektrochemische Impedanzspektroskopie(EIS), Oberflächenplasmonenresonanzspektroskopie (SPR) und zyklische Voltammetrie (CV) wurden angewandt um die Aktivität der CcO als Funktion der Packungsdichte zu charakterisieren. Der Hauptteil der Arbeit betrifft die Untersuchung des direkten ET zur CcO unter anaeroben Bedingungen. Die Kombination aus zeitaufgelöster oberflächenverstärkter Infrarot-Absorptionsspektroskopie (tr-SEIRAS) und Elektrochemie hat sich dafür als besonders geeignet erwiesen. In einer ersten Studie wurde der ET mit Hilfe von fast scan CV untersucht, wobei CVs von nicht-aktivierter sowie aktivierter CcO mit verschiedenen Vorschubgeschwindigkeiten gemessen wurden. Die aktivierte Form wurde nach dem katalytischen Umsatz des Proteins in Anwesenheit von O2 erhalten. Ein vier-ET-modell wurde entwickelt um die CVs zu analysieren. Die Methode erlaubt zwischen dem Mechanismus des sequentiellen und des unabhängigen ET zu den vier Zentren CuA, Häm a, Häm a3 und CuB zu unterscheiden. Zudem lassen sich die Standardredoxpotentiale und die kinetischen Koeffizienten des ET bestimmen. In einer zweiten Studie wurde tr-SEIRAS im step scan Modus angewandt. Dafür wurden Rechteckpulse an die CcO angelegt und SEIRAS im ART-Modus verwendet um Spektren bei definierten Zeitscheiben aufzunehmen. Aus diesen Spektren wurden einzelne Banden isoliert, die Veränderungen von Vibrationsmoden der Aminosäuren und Peptidgruppen in Abhängigkeit des Redoxzustands der Zentren zeigen. Aufgrund von Zuordnungen aus der Literatur, die durch potentiometrische Titration der CcO ermittelt wurden, konnten die Banden versuchsweise den Redoxzentren zugeordnet werden. Die Bandenflächen gegen die Zeit aufgetragen geben dann die Redox-Kinetik der Zentren wieder und wurden wiederum mit dem vier-ET-Modell ausgewertet. Die Ergebnisse beider Studien erlauben die Schlussfolgerung, dass der ET zur CcO in einer ptBLM mit größter Wahrscheinlichkeit dem sequentiellen Mechanismus folgt, was dem natürlichen ET von Cytochrom c zur CcO entspricht.

Adsorption of macromolecules on interfaces studied by isothermal titration calorimetry

The mixing of nanoparticles with polymers to form composite materials has been applied for decades. They combine the advantages of polymers (e.g., elasticity, transparency, or dielectric properties) and inorganic nanoparticles (e.g., specific absorption of light, magneto resistance effects, chemical activity, and catalysis etc.). Nanocomposites exhibit several new characters that single-phase materials do not have. Filling the polymeric matrix with an inorganic material requires its homogeneous distribution in order to achieve the highest possible synergetic effect. To fulfill this requirement, the incompatibility between the filler and the matrix, originating from their opposite polarity, has to be resolved. A very important parameter here is the strength and irreversibility of the adsorption of the surface active compound on the inorganic material. In this work the Isothermal titration calorimetry (ITC) was applied as a method to quantify and investigate the adsorption process and binding efficiencies in organic-inorganic–hybrid-systems by determining the thermodynamic parameters (ΔH, ΔS, ΔG, KB as well as the stoichiometry n). These values provide quantification and detailed understanding of the adsorption process of surface active molecules onto inorganic particles. In this way, a direct correlation between the adsorption strength and structure of the surface active compounds can be achieved. Above all, knowledge of the adsorption mechanism in combination with the structure should facilitate a more rational design into the mainly empirically based production and optimization of nanocomposites.

Simulation of titration experiments

Nowadays computer simulation is used in various fields, particularly in laboratories where it is used for the exploration data which are sometimes experimentally inaccessible. In less developed countries where there is a need for up to date laboratories for the realization of practical lessons in chemistry, especially in secondary schools and some higher institutions of learning, it may permit learners to carryout experiments such as titrations without the use of laboratory materials and equipments. Computer simulations may also permit teachers to better explain the realities of practical lessons, given that computers have now become very accessible and less expensive compared to the acquisition of laboratory materials and equipments. This work is aimed at coming out with a virtual laboratory that shall permit the simulation of an acid-base titration and an oxidation-reduction titration with the use of synthetic images. To this effect, an appropriate numerical method was used to obtain appropriate organigram, which were further transcribed into source codes with the help of a programming language so as to come out with the software.

Titration and implementation of neurally adjusted ventilatory assist in critically ill patients

BACKGROUND: Neurally adjusted ventilatory assist (NAVA) delivers assist in proportion to the patient's respiratory drive as reflected by the diaphragm electrical activity (EAdi). We examined to what extent NAVA can unload inspiratory muscles, and whether unloading is sustainable when implementing a NAVA level identified as adequate (NAVAal) during a titration procedure. METHODS: Fifteen adult, critically ill patients with a Pao(2)/fraction of inspired oxygen (Fio(2)) ratio < 300 mm Hg were studied. NAVAal was identified based on the change from a steep increase to a less steep increase in airway pressure (Paw) and tidal volume (Vt) in response to systematically increasing the NAVA level from low (NAVAlow) to high (NAVAhigh). NAVAal was implemented for 3 h. RESULTS: At NAVAal, the median esophageal pressure time product (PTPes) and EAdi values were reduced by 47% of NAVAlow (quartiles, 16 to 69% of NAVAlow) and 18% of NAVAlow (quartiles, 15 to 26% of NAVAlow), respectively. At NAVAhigh, PTPes and EAdi values were reduced by 74% of NAVAlow (quartiles, 56 to 86% of NAVAlow) and 36% of NAVAlow (quartiles, 21 to 51% of NAVAlow; p < or = 0.005 for all). Parameters during 3 h on NAVAal were not different from parameters during titration at NAVAal, and were as follows: Vt, 5.9 mL/kg predicted body weight (PBW) [quartiles, 5.4 to 7.2 mL/kg PBW]; respiratory rate (RR), 29 breaths/min (quartiles, 22 to 33 breaths/min); mean inspiratory Paw, 16 cm H(2)O (quartiles, 13 to 20 cm H(2)O); PTPes, 45% of NAVAlow (quartiles, 28 to 57% of NAVAlow); and EAdi, 76% of NAVAlow (quartiles, 63 to 89% of NAVAlow). Pao(2)/Fio(2) ratio, Paco(2), and cardiac performance during NAVAal were unchanged, while Paw and Vt were lower, and RR was higher when compared to conventional ventilation before implementing NAVAal. CONCLUSIONS: Systematically increasing the NAVA level reduces respiratory drive, unloads respiratory muscles, and offers a method to determine an assist level that results in sustained unloading, low Vt, and stable cardiopulmonary function when implemented for 3 h.