scholarly journals Computation of Oxidation Potentials of Solvated Nucleobases by Static and Dynamic Multilayer Approaches

2022 ◽  
Author(s):  
Jesús Lucia-Tamudo ◽  
Gustavo Cárdenas ◽  
Nuria Anguita-Ortiz ◽  
Sergio Díaz-Tendero ◽  
Juan J. Nogueira
Keyword(s):  
Experimental Studies ◽  
Direct Determination ◽  
Redox Properties ◽  
Marcus Theory ◽  
Thermodynamic Cycles ◽  
Dynamic Framework ◽  
Oxidation Potentials ◽  
The One ◽  
Implicit And Explicit

The determination of the redox properties of nucleobases is of paramount importance to get insight into the charge-transfer processes in which they are involved, as those occurring in DNA-inspired biosensors. Although many theoretical and experimental studies have been conducted, the value of the one-electron oxidation potentials of nucleobases is not well defined. Moreover, the most appropriate theoretical protocol to model the redox properties has not been established yet. In this work, we have implemented and evaluated different static and dynamic approaches to compute the one-electron oxidation potentials of solvated nucleobases. In the static framework, two thermodynamic cycles have been tested to assess their accuracy against the direct determination of oxidation potentials from the adiabatic ionization energies. Then, the introduction of vibrational sampling, the effect of implicit and explicit solvation models, and the application of the Marcus theory have been analyzed through dynamic methods. The results revealed that the static direct determination provides more accurate results than thermodynamic cycles. Moreover, the effect of sampling has not shown to be relevant, and the results are improved within the dynamic framework when the Marcus theory is applied, especially in explicit solvent, with respect to the direct approach. Finally, the presence of different tautomers in water does not affect significantly the one-electron oxidation potentials.

scholarly journals Interlaboratory study of the method for direct determination of volatile compounds in alcoholic products using ethanol as internal standard

2020 ◽  
pp. 74-87
Author(s):  
Siarhei V. Charapitsa ◽  
Svetlana N. Sytova ◽  
Anton L. Korban ◽  
Lidia N. Sobolenko ◽  
Vladimir V. Egorov ◽  
...  
Keyword(s):  
Volatile Compounds ◽  
Volatile Component ◽  
Experimental Studies ◽  
Internal Standard ◽  
Direct Determination ◽  
Interlaboratory Study ◽  
Significance Level ◽  
First Time ◽  
Standard Solutions

A collaborative interlaboratory study of the method of direct determination of volatile compounds in spirit drinks and alcoholic products was performed. The proposed method employs ethanol, the major volatile component of an alcoholic product, as an internal standard. For the experiment realization, 9 laboratories from 4 countries – Belarus, Czech Republic, Turkey, Russia – were supplied with standard solutions for gas chromatographic measurements. Five aqueous ethanol 40 % (v/v) standard solutions containing target compounds in concentrations ranging from 10 to 400 mg/L of absolute alcohol were gravimetrically prepared and delivered to the participants. The interlaboratory study was evaluated according to the ISO 5725 standards and the «EuroChem» guide. The repeatability limits (within-laboratory precision) varied between 0.4 and 7.5 % for all samples and compounds, showing a sufficiently high repeatability of the method. The reproducibility limits (between-laboratory precision) were found to vary within a satisfactory range of 0.5–10.0 %. Precision of the method was well within the range predicted by the Horwitz equation for all analytes. In the study experimental estimation of trueness was performed for the first time. Analysis of the obtained results showed that the bias of the method is insignificant at the significance level 5 %. The experimentally determined concentrations of the analytes compared well to the gravimetrical values, thus showing very satisfactory accuracy of the method. The results of the interlaboratory study confirmed that the method «ethanol as internal standard» is robust and reliable and can be used as a standard method for the determination of volatile compounds in water-ethanol samples. Moreover, this method can be validated in any one laboratory without performing additional experimental studies based on the results obtained by validation of the traditional method.

scholarly journals An experimental determination of the ionisation potential for electrons in helium

1919 ◽  
Vol 95 (671) ◽  
pp. 408-429 ◽  
Keyword(s):  
Direct Determination ◽  
Complete Removal ◽  
The Other ◽  
Ionisation Potential ◽  
Electron Collisions ◽  
Positive Ions ◽  
Positive Nucleus ◽  
Quantum Theory Of Radiation ◽  
The One

Bohr has developed a theory of atomic structure by applying a system of mechanics based on the quantum theory of radiation to the theory of the nucleus atom proposed by Rutherford. In the case of certain simple atoms he has calculated the minimum voltages through which an electron must fall in order to be able to produce ionisation by collision, and a comparison of the calculated values with those obtained experimentally serves as a check on the validity of the theory. Next to the hydrogen atom, that of helium has the simplest constitution, and this, for the normal atom, consists of two electrons rotating in non-radiating orbits round a doubly charged positive nucleus. The application of Bohr’s formula to helium indicates that the minimum velocity necessary to remove one electron from the helium atom is about 29 volts, but the direct experimental determinations of several observers agree in fixing the value at about 20 volts. Bohr has attempted to explain this by the assumption that the ionisation potential measured does not correspond to the complete removal of the electron from the atom, but only to a transition from the normal state of the atom to some other stationary state, where the one electron rotates outside the other. When the outer electron falls back to its original orbit, radiation of sufficiently high frequency to liberate electrons by photo-electric action from the metal parts of the apparatus is produced, and Bohr has suggested that such a secondary effect has been mistaken for a genuine ionisation of helium by electron collisions. The first direct determination of the minimum ionisation potential for helium was made by Franck and Hertz, using the method originally devised by Lenard. In their experiments, electrons from a glowing filament were accelerated towards a platinum gauze, on the other side of which they encountered an opposing field, which prevented any of them from reaching a collecting electrode. If, however, the electrons on passing through the gauze possessed sufficient energy to ionise the gas present by collisions, the positive ions liberated were driven towards the collecting electrode, and the ionisation was measured by an electrometer in connection with it. The experiment consisted in gradually increasing the potential difference accelerating the electrons until positive ions were detected by the electrometer. The accelerating voltage at which this occurred was increased by the experimentally determined velocity of emission of the electrons from the glowing filament, and the value 20·5 volts was obtained for the ionisation potential.

scholarly journals Determination of the Idle Mode of the Stage of Axial Turbine during Operation at Partial Loads

2020 ◽  
Vol 65 (1) ◽  
pp. 103-109
Author(s):  
Aleksandr Shubenko ◽  
Vladimir Goloshchapov ◽  
Daria Senetska ◽  
Oleksandr Senetskyi
Keyword(s):  
Experimental Studies ◽  
Rotor Blades ◽  
Working Fluid ◽  
Idle Mode ◽  
One Dimensional ◽  
Operating Modes ◽  
Wide Range ◽  
The One ◽  
Partial Loads

On the basis of the one-dimensional theory of calculating the operation of steam turbine stages the method for determining the idle mode, the initial data for which are the geometric characteristics of the blade rows is proposed. Formulas have been obtained that make it possible to calculate the efficiency in the proximity of Rotor Blades (RB) at operating modes from nominal to the idle mode, depending on the flow rate of the stage and taking into account the use of kinetic energy with the runaway velocity and losses arising at off-design angles of flow on the Rotor Blade (RB). The results of possible computational studies and their comparison for an incompressible working fluid with the results of experimental studies showed the good possibilities of the proposed method for determining the idle mode in a wide range of the characteristics of stages.

The Direct Determination of I131 in Heterogeneous Fecal Specimens

1961 ◽  
Vol 41 (4) ◽  
pp. 380-384 ◽  
Author(s):  
Arthur F. Dratz ◽  
James C. Coberly
Keyword(s):  
Direct Determination

Stories and the Self

2020 ◽  
Vol 32 (2) ◽  
pp. 47-58 ◽  
Author(s):  
Stefan Krause ◽  
Markus Appel
Keyword(s):  
Meta Analysis ◽  
The Self ◽  
The Other ◽  
Lower Degree ◽  
Contrast Effects ◽  
Self Perception ◽  
Self Perceptions ◽  
Other Hand ◽  
The One ◽  
Implicit And Explicit

Abstract. Two experiments examined the influence of stories on recipients’ self-perceptions. Extending prior theory and research, our focus was on assimilation effects (i.e., changes in self-perception in line with a protagonist’s traits) as well as on contrast effects (i.e., changes in self-perception in contrast to a protagonist’s traits). In Experiment 1 ( N = 113), implicit and explicit conscientiousness were assessed after participants read a story about either a diligent or a negligent student. Moderation analyses showed that highly transported participants and participants with lower counterarguing scores assimilate the depicted traits of a story protagonist, as indicated by explicit, self-reported conscientiousness ratings. Participants, who were more critical toward a story (i.e., higher counterarguing) and with a lower degree of transportation, showed contrast effects. In Experiment 2 ( N = 103), we manipulated transportation and counterarguing, but we could not identify an effect on participants’ self-ascribed level of conscientiousness. A mini meta-analysis across both experiments revealed significant positive overall associations between transportation and counterarguing on the one hand and story-consistent self-reported conscientiousness on the other hand.

Two-Stage Procedure for the Quantitative Determination of Autoprothrombin III Concentration and Some Applications

1967 ◽  
Vol 18 (01/02) ◽  
pp. 198-210 ◽  
Author(s):  
Ronald S Reno ◽  
Walter H Seegers
Keyword(s):  
Prothrombin Time ◽  
Factor Vii ◽  
Two Stage ◽  
Pronounced Increase ◽  
One Stage ◽  
Assay Procedure ◽  
Bovine Plasma ◽  
The One ◽  
Autoprothrombin C

SummaryA two-stage assay procedure was developed for the determination of the autoprothrombin C titre which can be developed from prothrombin or autoprothrombin III containing solutions. The proenzyme is activated by Russell’s viper venom and the autoprothrombin C activity that appears is measured by its ability to shorten the partial thromboplastin time of bovine plasma.Using the assay, the autoprothrombin C titre was determined in the plasma of several species, as well as the percentage of it remaining in the serum from blood clotted in glass test tubes. Much autoprothrombin III remains in human serum. With sufficient thromboplastin it was completely utilized. Plasma from selected patients with coagulation disorders was assayed and only Stuart plasma was abnormal. In so-called factor VII, IX, and P.T.A. deficiency the autoprothrombin C titre and thrombin titre that could be developed was normal. In one case (prethrombin irregularity) practically no thrombin titre developed but the amount of autoprothrombin C which generated was in the normal range.Dogs were treated with Dicumarol and the autoprothrombin C titre that could be developed from their plasmas decreased until only traces could be detected. This coincided with a lowering of the thrombin titre that could be developed and a prolongation of the one-stage prothrombin time. While the Dicumarol was acting, the dogs were given an infusion of purified bovine prothrombin and the levels of autoprothrombin C, thrombin and one-stage prothrombin time were followed for several hours. The tests became normal immediately after the infusion and then went back to preinfusion levels over a period of 24 hrs.In other dogs the effect of Dicumarol was reversed by giving vitamin K1 intravenously. The effect of the vitamin was noticed as early as 20 min after administration.In response to vitamin K the most pronounced increase was with that portion of the prothrombin molecule which yields thrombin. The proportion of that protein with respect to the precursor of autoprothrombin C increased during the first hour and then started to go down and after 3 hrs was equal to the proportion normally found in plasma.

Improvement Of Curvilinear Diagrams Of Concrete Deformation

2019 ◽  
pp. 99-104
Keyword(s):  
Reinforced Concrete ◽  
Peak Load ◽  
Experimental Studies ◽  
Concrete Structures ◽  
Deformation Model ◽  
Reinforced Concrete Structures ◽  
Significant Difference ◽  
Deformation Diagrams

Problems when calculating reinforced concrete structures based on the concrete deformation under compression diagram, which is presented both in Russian and foreign regulatory documents on the design of concrete and reinforced concrete structures are considered. The correctness of their compliance for all classes of concrete remains very approximate, especially a significant difference occurs when using Euronorm due to the different shape and sizes of the samples. At present, there are no methodical recommendations for determining the ultimate relative deformations of concrete under axial compression and the construction of curvilinear deformation diagrams, which leads to limited experimental data and, as a result, does not make it possible to enter more detailed ultimate strain values into domestic standards. The results of experimental studies to determine the ultimate relative deformations of concrete under compression for different classes of concrete, which allowed to make analytical dependences for the evaluation of the ultimate relative deformations and description of curvilinear deformation diagrams, are presented. The article discusses various options for using the deformation model to assess the stress-strain state of the structure, it is concluded that it is necessary to use not only the finite values of the ultimate deformations, but also their intermediate values. This requires reliable diagrams "s–e” for all classes of concrete. The difficulties of measuring deformations in concrete subjected to peak load, corresponding to the prismatic strength, as well as main cracks that appeared under conditions of long-term step loading are highlighted. Variants of more accurate measurements are proposed. Development and implementation of the new standard GOST "Concretes. Methods for determination of complete diagrams" on the basis of the developed method for obtaining complete diagrams of concrete deformation under compression for the evaluation of ultimate deformability of concrete under compression are necessary.

SIMPLIFIED DEXAMETHASONE SUPPRESSION TEST

1969 ◽  
Vol 61 (2) ◽  
pp. 219-231 ◽  
Author(s):  
V. H. Asfeldt
Keyword(s):  
Cushing’S Syndrome ◽  
Normal Subjects ◽  
Cushing's Syndrome ◽  
Dexamethasone Suppression Test ◽  
Clinical Value ◽  
Suppression Test ◽  
The One ◽  
Steroid Excretion ◽  
Dexamethasone Suppression

ABSTRACT This is an investigation of the practical clinical value of the one mg dexamethasone suppression test of Nugent et al. (1963). The results, evaluated from the decrease in fluorimetrically determined plasma corticosteroids in normal subjects, as well as in cases of exogenous obesity, hirsutism and in Cushing's syndrome, confirm the findings reported in previous studies. Plasma corticosteroid reduction after one mg of dexamethasone in cases of stable diabetes was not significantly different from that observed in control subjects, but in one third of the insulin-treated diabetics only a partial response was observed, indicating a slight hypercorticism in these patients. An insufficient decrease in plasma corticosteroids was observed in certain other conditions (anorexia nervosa, pituitary adenoma, patients receiving contraceptive or anticonvulsive treatment) with no hypercorticism. The physiological significance of these findings is discussed. It is concluded that the test, together with a determination of the basal urinary 17-ketogenic steroid excretion, is suitable as the first diagnostic test in patients in whom Cushing's syndrome is suspected. In cases of insufficient suppression of plasma corticosteroids, further studies, including the suppression test of Liddle (1960), must be carried out.

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