Reactions of the radical cation derived from 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS·+) with amino acids. Kinetics and mechanism

2000 ◽  
Vol 78 (8) ◽  
pp. 1052-1059 ◽  
Author(s):  
C Aliaga ◽  
E A Lissi
Keyword(s):  
Amino Acids ◽  
Radical Cation ◽  
Sulfonic Acid ◽  
Biological Fluids ◽  
Reaction Rates ◽  
Kinetics And Mechanism ◽  
Specific Rate ◽  
Wide Range ◽  
Initial Ph ◽  
Secondary Reactions

Stable free radicals derived from 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS·+) have been extensively employed to monitor the antioxidant capacity of biological fluids and beverages. Besides reacting with typical antioxidants (such as phenols or thiols) these radicals react with a variety of hydrogen or electron donors. The present work reports on the kinetics and mechanism of these radical reactions with several amino acids. Reaction rates notably increase when the pH of the media increases and, when measured under similar conditions, follows the ordercysteine > > tryptophan > tyrosine > histidine > cystineThe kinetics of the process is interpreted in terms of a mechanism comprising an initial pH dependent reversible step, followed by secondary reactions of the substrate derived radical with itself or with another ABTS·+; this simple three-step mechanism leads to very complex kinetic expressions. The specific rate constants of several of the elementary steps were determined by working under a wide range of substrate, radical, and ABTS concentrations. The values obtained for the initial interaction between the ABTS derived radical and the substrate range from 0.5 M–1 s–1 to 1.9 × 106 M–1 s–1 for histidine and cysteine, respectively.Key words: ABTS radical cation, 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid), amino acids, kinetics.

p-Sulfonic acid calix[n]arene catalyzed synthesis of bioactive heterocycles: A review

2020 ◽  
Vol 24 ◽  
Author(s):  
Bubun Banerjee ◽  
Gurpreet Kaur ◽  
Navdeep Kaur
Keyword(s):  
Supramolecular Chemistry ◽  
Sulfonic Acid ◽  
Catalytic Efficiency ◽  
The Other ◽  
Reaction Conditions ◽  
Metal Free ◽  
Bioactive Scaffolds ◽  
Wide Range ◽  
Efficient Alternative ◽  
Bioactive Heterocycles

: Metal-free organocatalysts are becoming an important tool for the sustainable developments of various bioactive heterocycles. On the other hand, during last two decades, calix[n]arenes have been gaining considerable attention due to their wide range of applicability in the field of supramolecular chemistry. Recently, sulfonic acid functionalized calix[n] arenes are being employed as an efficient alternative catalyst for the synthesis of various bioactive scaffolds. In this review we have summarized the catalytic efficiency of p-sulfonic acid calix[n]arenes for the synthesis of diverse biologically promising scaffolds under various reaction conditions. There is no such review available in the literature showing the catalytic applicability of p-sulfonic acid calix[n]arenes. Therefore, we strongly believe that this review will surely attract those researchers who are interested about this fascinating organocatalyst.

scholarly journals Autophagy Deficiency by Atg4B Loss Leads to Metabolomic Alterations in Mice

Metabolites ◽  
2021 ◽  
Vol 11 (8) ◽  
pp. 481
Author(s):  
Gemma G. Martínez-García ◽  
Raúl F. Pérez ◽  
Álvaro F. Fernández ◽  
Sylvere Durand ◽  
Guido Kroemer ◽  
...  
Keyword(s):  
Skeletal Muscle ◽  
Amino Acids ◽  
Mammalian Cells ◽  
Tissue Homeostasis ◽  
In Vivo Studies ◽  
Protective Mechanism ◽  
Cardiac Damage ◽  
Wide Range ◽  
First Time

Autophagy is an essential protective mechanism that allows mammalian cells to cope with a variety of stressors and contributes to maintaining cellular and tissue homeostasis. Due to these crucial roles and also to the fact that autophagy malfunction has been described in a wide range of pathologies, an increasing number of in vivo studies involving animal models targeting autophagy genes have been developed. In mammals, total autophagy inactivation is lethal, and constitutive knockout models lacking effectors of this route are not viable, which has hindered so far the analysis of the consequences of a systemic autophagy decline. Here, we take advantage of atg4b−/− mice, an autophagy-deficient model with only partial disruption of the process, to assess the effects of systemic reduction of autophagy on the metabolome. We describe for the first time the metabolic footprint of systemic autophagy decline, showing that impaired autophagy results in highly tissue-dependent alterations that are more accentuated in the skeletal muscle and plasma. These changes, which include changes in the levels of amino-acids, lipids, or nucleosides, sometimes resemble those that are frequently described in conditions like aging, obesity, or cardiac damage. We also discuss different hypotheses on how impaired autophagy may affect the metabolism of several tissues in mammals.

scholarly journals High-resolution particle separation by inertial focusing in high aspect ratio curved microfluidics

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Javier Cruz ◽  
Klas Hjort
Keyword(s):  
High Resolution ◽  
Aspect Ratio ◽  
High Aspect Ratio ◽  
Biological Fluids ◽  
Essential Feature ◽  
Particle Separation ◽  
Size Difference ◽  
Inertial Focusing ◽  
Complex Samples ◽  
Wide Range

AbstractThe ability to focus, separate and concentrate specific targets in a fluid is essential for the analysis of complex samples such as biological fluids, where a myriad of different particles may be present. Inertial focusing is a very promising technology for such tasks, and specially a recently presented variant, inertial focusing in High Aspect Ratio Curved systems (HARC systems), where the systems are easily engineered and focus the targets together in a stable position over a wide range of particle sizes and flow rates. However, although convenient for laser interrogation and concentration, by focusing all particles together, HARC systems lose an essential feature of inertial focusing: the possibility of particle separation by size. Within this work, we report that HARC systems not only do have the capacity to separate particles but can do so with extremely high resolution, which we demonstrate for particles with a size difference down to 80 nm. In addition to the concept for particle separation, a model considering the main flow, the secondary flow and a simplified expression for the lift force in HARC microchannels was developed and proven accurate for the prediction of the performance of the systems. The concept was also demonstrated experimentally with three different sub-micron particles (0.79, 0.92 and 1.0 µm in diameter) in silicon-glass microchannels, where the resolution in the separation could be modulated by the radius of the channel. With the capacity to focus sub-micron particles and to separate them with high resolution, we believe that inertial focusing in HARC systems is a technology with the potential to facilitate the analysis of complex fluid samples containing bioparticles like bacteria, viruses or eukaryotic organelles.

scholarly journals Mass and Heat Transfer Coefficients in Automotive Exhaust Catalytic Converter Channels

Catalysts ◽  
2019 ◽  
Vol 9 (6) ◽  
pp. 507
Author(s):  
Chrysovalantis C. Templis ◽  
Nikos G. Papayannakos
Keyword(s):  
Heat Transfer ◽  
Flow Reactor ◽  
Catalytic Converter ◽  
Reaction Rates ◽  
Cfd Model ◽  
Automotive Exhaust ◽  
Transfer Coefficients ◽  
Heat Transfer Coefficients ◽  
Wide Range ◽  
Mass And Heat Transfer

Mass and heat transfer coefficients (MTC and HTC) in automotive exhaust catalytic monolith channels are estimated and correlated for a wide range of gas velocities and prevailing conditions of small up to real size converters. The coefficient estimation is based on a two dimensional computational fluid dynamic (2-D CFD) model developed in Comsol Multiphysics, taking into account catalytic rates of a real catalytic converter. The effect of channel size and reaction rates on mass and heat transfer coefficients and the applicability of the proposed correlations at different conditions are discussed. The correlations proposed predict very satisfactorily the mass and heat transfer coefficients calculated from the 2-D CFD model along the channel length. The use of a one dimensional (1-D) simplified model that couples a plug flow reactor (PFR) with mass transport and heat transport effects using the mass and heat transfer correlations of this study is proved to be appropriate for the simulation of the monolith channel operation.

scholarly journals Destruxin A Interacts with Aminoacyl tRNA Synthases in Bombyx mori

2021 ◽  
Vol 7 (8) ◽  
pp. 593
Author(s):  
Jingjing Wang ◽  
Alexander Berestetskiy ◽  
Qiongbo Hu
Keyword(s):  
Amino Acids ◽  
Protein Synthesis ◽  
Bombyx Mori ◽  
Metarhizium Anisopliae ◽  
Free Amino ◽  
Molecular Target ◽  
Trna Synthetases ◽  
Interaction Mode ◽  
Aminoacyl Trna Synthetases ◽  
Wide Range

Destruxin A (DA), a hexa-cyclodepsipeptidic mycotoxin produced by the entomopathogenic fungus Metarhizium anisopliae, exhibits insecticidal activities in a wide range of pests and is known as an innate immunity inhibitor. However, its mechanism of action requires further investigation. In this research, the interactions of DA with the six aminoacyl tRNA synthetases (ARSs) of Bombyx mori, BmAlaRS, BmCysRS, BmMetRS, BmValRS, BmIleRS, and BmGluProRS, were analyzed. The six ARSs were expressed and purified. The BLI (biolayer interferometry) results indicated that DA binds these ARSs with the affinity indices (KD) of 10−4 to 10−5 M. The molecular docking suggested a similar interaction mode of DA with ARSs, whereby DA settled into a pocket through hydrogen bonds with Asn, Arg, His, Lys, and Tyr of ARSs. Furthermore, DA treatments decreased the contents of soluble protein and free amino acids in Bm12 cells, which suggested that DA impedes protein synthesis. Lastly, the ARSs in Bm12 cells were all downregulated by DA stress. This study sheds light on exploring and answering the molecular target of DA against target insects.

scholarly journals Determination of amino acids in human biological fluids by high-performance liquid chromatography: critical review

Amino Acids ◽  
2021 ◽  
Author(s):  
Grażyna Gałęzowska ◽  
Joanna Ratajczyk ◽  
Lidia Wolska
Keyword(s):  
Amino Acids ◽  
Amino Acid ◽  
High Performance ◽  
Hplc Analysis ◽  
Limit Of Detection ◽  
Biological Fluids ◽  
Analytical Techniques ◽  
Epidemiological Studies ◽  
Preparation Conditions

AbstractThe quantitation and qualification of amino acids are most commonly used in clinical and epidemiological studies, and provide an excellent way of monitoring compounds in human fluids which have not been monitored previously, to prevent some diseases. Because of this, it is not surprising that scientific interest in evaluating these compounds has resurfaced in recent years and has precipitated the development of a multitude of new analytical techniques. This review considers recent developments in HPLC analytics on the basis of publications from the last few years. It helps to update and systematize knowledge in this area. Particular attention is paid to the progress of analytical methods, pointing out the advantages and drawbacks of the various techniques used for the preparation, separation and determination of amino acids. Depending on the type of sample, the preparation conditions for HPLC analysis change. For this reason, the review has focused on three types of samples, namely urine, blood and cerebrospinal fluid. Despite time-consuming sample preparation before HPLC analysis, an additional derivatization technique should be used, depending on the detection technique used. There are proposals for columns that are specially modified for amino acid separation without derivatization, but the limit of detection of the substance is less beneficial. In view of the fact that amino acid analyses have been performed for years and new solutions may generate increased costs, it may turn out that older proposals are much more advantageous.

scholarly journals Gradient HPLC in the determination of drug lipophilicity and acidity

2001 ◽  
Vol 73 (9) ◽  
pp. 1465-1475 ◽  
Author(s):  
Roman Kaliszan ◽  
Piotr Haber ◽  
Tomasz Baczek ◽  
Danuta Siluk
Keyword(s):  
Mobile Phase ◽  
High Performance ◽  
Standard Procedure ◽  
Gradient Elution ◽  
Log P ◽  
Retention Data ◽  
Organic Modifier ◽  
Wide Range ◽  
Aqueous Component ◽  
Initial Ph

The linear-solvent strength (LSS) model of gradient elution in high-performance liquid chromatography (HPLC) has been demonstrated to provide parameters of lipophilicity and acidity of analytes. pKa and log kw values are determined in three gradient runs. The first two experiments use an aqueous buffered eluent with a wide-range organic modifier gradient at pH of buffer, providing suppression of ionization of the analyte. That experiment allows an estimate of contents of the organic modifier in the mobile phase (%B), producing requested retention coefficient, k, for the nonionized form of the analyte. The next experiment is carried out with the latter %B and a pH-gradient of the aqueous component of the eluent that is sufficient to overlap possible pKa value of the analyte. The initial pH of the buffer used to make the mobile phase is selected to insure that the analyte is in nonionized form. The resulting retention time allows an estimate of pKa in a solvent of the given %B.The log kw parameter obtained correlated well with the corresponding value obtained by the standard procedure of extrapolation of retention data determined in a series of isocratic measurements. The correlation between log kw and the reference parameter of lipophilicity, log P, was very good for a series of test analytes. The values of pKa were found to correlate with the literature pKa data determined in water for a set of aniline derivatives studied.

scholarly journals Ureido Functionalization through Amine-Urea Transamidation under Mild Reaction Conditions

Polymers ◽  
2021 ◽  
Vol 13 (10) ◽  
pp. 1583
Author(s):  
Natalia Guerrero-Alburquerque ◽  
Shanyu Zhao ◽  
Daniel Rentsch ◽  
Matthias M. Koebel ◽  
Marco Lattuada ◽  
...  
Keyword(s):  
Aqueous Media ◽  
Reaction Times ◽  
Reaction Rates ◽  
Secondary Amines ◽  
Isocyanic Acid ◽  
Advantages And Disadvantages ◽  
Major Disadvantage ◽  
Wide Range ◽  
Potential Alternative ◽  
Full Conversion

Ureido-functionalized compounds play an indispensable role in important biochemical processes, as well as chemical synthesis and production. Isocyanates, and KOCN in particular, are the preferred reagents for the ureido functionalization of amine-bearing compounds. In this study, we evaluate the potential of urea as a reagent to graft ureido groups onto amines at relatively low temperatures (<100 °C) in aqueous media. Urea is an inexpensive, non-toxic and biocompatible potential alternative to KOCN for ureido functionalization. From as early as 1864, urea was the go-to reagent for polyurea polycondensation, before falling into disuse after the advent of isocyanate chemistry. We systematically re-investigate the advantages and disadvantages of urea for amine transamidation. High ureido-functionalization conversion was obtained for a wide range of substrates, including primary and secondary amines and amino acids. Reaction times are nearly independent of substrate and pH, but excess urea is required for practically feasible reaction rates. Near full conversion of amines into ureido can be achieved within 10 h at 90 °C and within 24 h at 80 °C, and much slower reaction rates were determined at lower temperatures. The importance of the urea/amine ratio and the temperature dependence of the reaction rates indicate that urea decomposition into an isocyanic acid or a carbamate intermediate is the rate-limiting step. The presence of water leads to a modest increase in reaction rates, but the full conversion of amino groups into ureido groups is also possible in the absence of water in neat alcohol, consistent with a reaction mechanism mediated by an isocyanic acid intermediate (where the water assists in the proton transfer). Hence, the reaction with urea avoids the use of toxic isocyanate reagents by in situ generation of the reactive isocyanate intermediate, but the requirement to separate the excess urea from the reaction product remains a major disadvantage.

scholarly journals Impact of Foliar Application of Amino Acids on Total Phenols, Phenolic Acids Content of Different Mints Varieties under the Field Condition

Plants ◽  
2021 ◽  
Vol 10 (3) ◽  
pp. 599
Author(s):  
Živilė Tarasevičienė ◽  
Aloyzas Velička ◽  
Aurelija Paulauskienė
Keyword(s):  
Amino Acids ◽  
Phenolic Compounds ◽  
Phenolic Acids ◽  
Foliar Application ◽  
Mentha Piperita ◽  
Total Phenolic ◽  
Total Phenol Content ◽  
Individual Response ◽  
Total Phenols ◽  
Wide Range

Phenolic compounds have a number of benefits to human health and can be used as preventive compounds for the development of some chronic diseases. Mentha plants are not only a good source of essential oils, but also contain significant levels of wide range of phenolic compounds. The aim of this research was to investigate the possibility to increase phenols content in Mentha plants under the foliar application with L-phenylalanine, L-tryptophan, L-tyrosine at two concentrations (100 mg L−1 and 200 mg L−1) and to create preconditions for using this plant for even more diverse purposes. Quantitative and qualitative analyses of phenols in mints were performed by HPLC method. Foliar application of amino acids increased the total phenol content from 1.22 to 3.51 times depending on the treatment and mint variety. The most pronounced foliar application to total phenols content was tryptophane especially in Mentha piperita “Swiss”. Mentha piperita “Swiss” was affected most by foliar application and the amount of total phenolic acids depending on the treatment ranged from 159.25 to 664.03 mg 100 g−1 (DW), respectively, non-sprayed and sprayed with tryptophane 100 mg L−1. Our results suggest that the biophenol content varies according to such factors as foliar application and variety, and every single mint variety has individual response to different applications of amino acids.

Thorium oxide dissolution in HNO3-HF mixture: kinetics and mechanism

2019 ◽  
Vol 107 (4) ◽  
pp. 289-297 ◽  
Author(s):  
Marie Simonnet ◽  
Nicole Barré ◽  
Romuald Drot ◽  
Claire Le Naour ◽  
Vladimir Sladkov ◽  
...  
Keyword(s):  
Experimental Data ◽  
Dissolution Rate ◽  
Hydrofluoric Acid ◽  
Kinetics And Mechanism ◽  
Dissolution Mechanism ◽  
Oxide Dissolution ◽  
Thorium Oxide ◽  
Specific Focus ◽  
Acid Effect ◽  
Wide Range

Abstract This paper is an attempt to find out thorium oxide dissolution mechanism in HNO3-HF mixture. In a previous paper, several parameters effects on thorium oxide dissolution have been described, with specific focus on hydrofluoric acid effect, which can lead to an increase of the dissolution rate if present in small amount, but precipitates as ThF4 at higher content. Based on this previous study, experimental data were fitted using several dissolution models in order to find out the best one. Finally, a revisited model based on literature and considering the ThF4 formation was proposed. It describes the main steps of dissolution and is able to fit the experimental data for a wide range of solution compositions. This point is crucial since it allows considering an extrapolation of the established model to not-yet-studied conditions.

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