scholarly journals Rigorous equations for isothermal titration calorimetry: theoretical and practical consequences

2019 ◽  
Author(s):  
Philippe Dumas
Keyword(s):  
Isothermal Titration Calorimetry ◽  
Titration Calorimetry ◽  
Single Pair ◽  
Mathematical Methods ◽  
Injection Method ◽  
Titration Curves ◽  
Preliminary Version ◽  
One Step ◽  
The One ◽  
Step Mechanism

AbstractA preliminary version of this work, [doi.org/10.1101/512780], was deposited in bioRχiv on January 6, 2019, and in a revised form on May 15, 2019New mathematical methods have been developed for processing titration curves (TC) obtained from Isothermal Titration Calorimetry (ITC). Exact TC equations for the usual multi-injection method (MIM), or for the single-injection method (SIM) with continuous injection, were derived by taking into account rigorously the effect of dilution resulting from the titration process. Several practical consequences of these results are discussed. An exact fit of a TC can thus be obtained, even with large injected volumes leading to important dilution. All available programs show systematic differences with the exact results, NanoAnalyze from TA being significantly more accurate. A part of the results have been incorporated into AFFINImeter from S4SD. It is also examined how certain multi-step mechanisms are in fact thermodynamically equivalent to the one-step association/dissociation mechanism. They will thus never explain any “atypical” TC not showing the classical sigmoid shape. Although only a single pair of parameters (Kd and ΔH) can explain an experimental TC compatible with the one-step mechanism, an infinite number of parameters explain equally well the same data with such an equivalent multi-step mechanism. An explicit link between the two sets of parameters is given. A parallel with the concept of gauge invariance in physics is proposed.Statement of significanceThis work reconsiders in full the processing of ITC data by taking into account exactly the dilution due to the titration. New equations are obtained both for the single and multiple injection methods, which suppresses systematic problems in commonly used programs. The method is made practically available to everyone.

scholarly journals MNDO and DFT Computational Study on the Mechanism of the Oxidation of 1,2-Diphenylhydrazine by Iodine

2014 ◽  
Vol 2014 ◽  
pp. 1-8 ◽  
Author(s):  
Gideon A. Shallangwa ◽  
Adamu Uzairu ◽  
Victor O. Ajibola ◽  
Hamza Abba
Keyword(s):  
Reaction Mechanisms ◽  
Density Functional ◽  
Computational Study ◽  
The Other ◽  
Complex Mechanism ◽  
Functional Theory ◽  
One Step ◽  
The One ◽  
Activated Complex ◽  
Step Mechanism

The reaction mechanisms of the oxidation of 1,2-diphenylhydrazine by iodine have been examined using semiempirical and density functional theory methods, the oxidation proceeded via two independent pathways that can be separately monitored. One pathway involved the chain multistep mechanism. The other pathway occurred via a one-step mechanism in which a “cyclic” activated complex was formed which on disproportionation gave the products. The one-step “cyclic” activated complex mechanism proceeds more rapidly than the chain multistep mechanism. The results were explained by analyses based on computational energetics of the optimised reactants, intermediates, transition states, and products of the reaction of iodine with 1,2-diphenylhydrazine.

scholarly journals Atmospheric band fitting coefficients derived from a self-consistent rocket-borne experiment

2019 ◽  
Vol 19 (2) ◽  
pp. 1207-1220 ◽  
Author(s):  
Mykhaylo Grygalashvyly ◽  
Martin Eberhart ◽  
Jonas Hedin ◽  
Boris Strelnikov ◽  
Franz-Josef Lübken ◽  
...  
Keyword(s):  
Atomic Oxygen ◽  
Band Emission ◽  
Self Consistent ◽  
Volume Emission ◽  
Volume Measurements ◽  
One Step ◽  
The One ◽  
Background Air ◽  
Atomic Oxygen Concentration ◽  
Step Mechanism

Abstract. Based on self-consistent rocket-borne measurements of temperature, the densities of atomic oxygen and neutral air, and the volume emission of the atmospheric band (762 nm), we examined the one-step and two-step excitation mechanism of O2b1Σg+ for nighttime conditions. Following McDade et al. (1986), we derived the empirical fitting coefficients, which parameterize the atmospheric band emission O2b1Σg+-X3Σg-0,0. This allows us to derive the atomic oxygen concentration from nighttime observations of atmospheric band emission O2b1Σg+-X3Σg-0,0. The derived empirical parameters can also be utilized for atmospheric band modeling. Additionally, we derived the fit function and corresponding coefficients for the combined (one- and two-step) mechanism. The simultaneous common volume measurements of all the parameters involved in the theoretical calculation of the observed O2b1Σg+-X3Σg-0,0 emission, i.e., temperature and density of the background air, atomic oxygen density, and volume emission rate, is the novelty and the advantage of this work.

Analysis of mechanism of the catalytic effect of hydrogen on the decay of alkyl macroradicals in polyethylene

1986 ◽  
Vol 51 (6) ◽  
pp. 1279-1286 ◽  
Author(s):  
Josef Bartoš
Keyword(s):  
Activation Energy ◽  
Kinetic Model ◽  
Energy Barrier ◽  
Catalytic Effect ◽  
Molecular Model ◽  
Particle State ◽  
One Step ◽  
The One ◽  
Step Mechanism ◽  
Phase Proceeds

The suggested one-step and two-step mechanism of decay of alkyl macroradicals in polyethylene are analyzed in detail at the activation energy level. For the one-step mechanism, the BEBO method is modified for reactions proceeding via a three-particle state. For the two-step mechanism, a three-process kinetic model is used; the contributions to the total energy barrier are calculated by the original BEBO method for two-particle transition states and by a molecular model for the diffusion of simple penetrants in polymers. The results indicate that the catalytic effect of hydrogen on the migration of the alkyls in the amorphous phase proceeds by the two-step mechanism.

A Study on the Rearrangement of Dialkyl 1-Aryl-1-hydroxymethylphosphonates to Benzyl Phosphates

2020 ◽  
Vol 24 (4) ◽  
pp. 465-471 ◽  
Author(s):  
Zita Rádai ◽  
Réka Szabó ◽  
Áron Szigetvári ◽  
Nóra Zsuzsa Kiss ◽  
Zoltán Mucsi ◽  
...  
Keyword(s):  
Quantum Chemical ◽  
Room Temperature ◽  
Phase Transfer ◽  
One Pot ◽  
Substrate Dependence ◽  
Triethylbenzylammonium Chloride ◽  
One Step ◽  
The Pudovik Reaction ◽  
The One ◽  
Solid Liquid

The phospha-Brook rearrangement of dialkyl 1-aryl-1-hydroxymethylphosphonates (HPs) to the corresponding benzyl phosphates (BPs) has been elaborated under solid-liquid phase transfer catalytic conditions. The best procedure involved the use of triethylbenzylammonium chloride as the catalyst and Cs2CO3 as the base in acetonitrile as the solvent at room temperature. The substrate dependence of the rearrangement has been studied, and the mechanism of the transformation under discussion was explored by quantum chemical calculations. The key intermediate is an oxaphosphirane. The one-pot version starting with the Pudovik reaction has also been developed. The conditions of this tandem transformation were the same, as those for the one-step HP→BP conversion.

scholarly journals One-Year Clinical Evaluation of the Bonding Effectiveness of a One-Step, Self-Etch Adhesive in Noncarious Cervical Lesion Therapy

2015 ◽  
Vol 2015 ◽  
pp. 1-5 ◽  
Author(s):  
Babacar Faye ◽  
Mouhamed Sarr ◽  
Khaly Bane ◽  
Adjaratou Wakha Aidara ◽  
Seydina Ousmane Niang ◽  
...  
Keyword(s):  
Clinical Performance ◽  
Retention Rate ◽  
Recall Rate ◽  
Acid Etching ◽  
Significant Difference ◽  
Usphs Criteria ◽  
One Step ◽  
One Year ◽  
The One ◽  
Self Etch

This study evaluated the one-year clinical performance of a one-step, self-etch adhesive (Optibond All-in-One, Kerr, CA, USA) combined with a composite (Herculite XRV Ultra, Kerr Hawe, CA, USA) to restore NCCLs with or without prior acid etching. Restorations performed by the same practitioner were evaluated at baseline and after 3, 6, and 12 months using modified USPHS criteria. At 6 months, the recall rate was 100%. The retention rate was 84.2% for restorations with prior acid etching, but statistically significant differences were observed between baseline and 6 months. Without acid etching, the retention rate was 77%, and no statistically significant difference was noted between 3 and 6 months. Marginal integrity (93.7% with and 87.7% without acid etching) and discoloration (95.3% with and 92.9% without acid etching) were scored as Alpha or Bravo, with better results after acid etching. After one year, the recall rate was 58.06%. Loss of pulp vitality, postoperative sensitivity, or secondary caries were not observed. After one year retention rate was of 90.6% and 76.9% with and without acid conditioning. Optibond All-in-One performs at a satisfactory clinical performance level for restoration of NCCLs after 12 months especially after acid etching.

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