scholarly journals Formation of Nickel(II)Porphyrin and Its Interaction with DNA in Aqueous Medium

2021 ◽  
Author(s):  
Ahsan Habib ◽  
Salma Serniabad ◽  
Mohammad Shamim Khan ◽  
Rokayea Islam ◽  
Mrittika Chakraborty ◽  
...  
Keyword(s):  
Aqueous Medium ◽  
Reaction Rate ◽  
Hydroxyl Group ◽  
Solution Ph ◽  
Net Charge ◽  
Ionic Strength Effect ◽  
Dependent Rate ◽  
Speciation Diagram ◽  
Kinetics Of Formation ◽  
Kinetics Of

In this work, kinetics of the reaction between 5,10,15,20-tetrakis(N-methylpyridium-4-yl)porphyrin and Ni2+ species were investigated in aqueous solution at 25 ±1 ºC in I = 0.10 M (NaNO3). Speciation of Ni2+ was carried out in I = 0.10 M (NaNO3) in order to provide the distribution of the Ni2+ species with different solution pH. The experimental data have been compared with the speciation diagram constructed from the values of hydrolysis constants of Ni2+ ion. Speciation data showed that the hexaaquanickel(II), [Ni(H2O)6]2+, ions take place in hydrolysis reactions through formation of [Ni(OH2)6-n(OH)n]2-n species with solution pH. Based on the speciation of Ni2+ and pH dependent rate constants, rate expression can be written as: d[Ni(TMPyP)4+]/dt = (k1[Ni2+(aq)] + k2[Ni(OH)+(aq)] + k3[Ni(OH)2o(aq)] + k4[Ni(OH)3-(aq)])[H2TMPyP4+], where k1, k2, k3 and k4 were found to be k1 = (0.62 ± 0.22) × 10-2; k2 = (3.60 ± 0.40) × 10-2; k3 = (2.09 ± 0.52) × 10-2, k4 = (0.53 ± 0.04) × 10-2 M-1s-1 at 25 ±1 °C, respectively. Kinetic results showed that monohydroxo, [Ni(H2O)5(OH)]+, is the most reactive among the [Ni(OH2)6-n(OH)n]2-n species. The enhanced reactivity has been ascribed to the formation of hydrogen bonding between oxygen atom of hydroxyl group of the [Ni(H2O)5(OH)]+ species and the pyrrolic hydrogen atom of the [H2TMPyP]4+. The rate of formation of [Ni(II)TMPyP]4+ complex was to be 3.99 × 10-2 M-1s-1 in I = 0.10 M, NaNO3 (25 ± 1 ºC). Ionic strength effect on the reaction rate is suggested that the net charge of the tetracationic porphyrin is to be +3.6 on the basis of Brønsted-Bjerrum equation. The UV-Vis and fluorescence data revealed that [Ni(II)TMPyP]4+ and H2(TMPyP)4+ interact with DNA, and UV-Vis results suggest that Ni(II)-porphyrin and free base porphyrin interact with DNA via outside binding with self-stacking and intercalation, respectively. Mechanism of kinetics of formation of the [Ni(II)TMPyP]4+ complex in aqueous medium is discussed. An investigation of application of the [Ni(II)TMPyP]4+ complex along with other metalloporphyrins such as Zn2+-, Ru2+-, Pt2+-, [Au(III)TMPyP]5+ as anti-COVID-19 agents is now in progress under international collaboration.

Cyclization and acid-catalyzed hydrolysis of O-benzoylbenzamidoximes

1986 ◽  
Vol 51 (12) ◽  
pp. 2786-2797
Author(s):  
František Grambal ◽  
Jan Lasovský
Keyword(s):  
Reaction Rate ◽  
Kinetic Isotope ◽  
Acid Base Equilibrium ◽  
Mineral Acids ◽  
Kinetics Of Formation ◽  
Acid Catalyzed ◽  
Ph Scale ◽  
Kinetics Of ◽  
Hydrolysis Of ◽  
Derivatives Of

Kinetics of formation of 1,2,4-oxadiazoles from 24 substitution derivatives of O-benzoylbenzamidoxime have been studied in sulphuric acid and aqueous ethanol media. It has been found that this medium requires introduction of the Hammett H0 function instead of the pH scale beginning as low as from 0.1% solutions of mineral acids. Effects of the acid concentration, ionic strength, and temperature on the reaction rate and on the kinetic isotope effect have been followed. From these dependences and from polar effects of substituents it was concluded that along with the cyclization to 1,2,4-oxadiazoles there proceeds hydrolysis to benzamidoxime and benzoic acid. The reaction is thermodynamically controlled by the acid-base equilibrium of the O-benzylated benzamidoximes.

Kinetics and mechanism of gold(III) incorporation into tetrakis(1-methylpyridium-4-yl)porphyrin in aqueous solution

2004 ◽  
Vol 08 (11) ◽  
pp. 1269-1275 ◽  
Author(s):  
Ahsan Habib ◽  
Masaaki Tabata ◽  
Ying Guang Wu
Keyword(s):  
Aqueous Solution ◽  
Rate Constants ◽  
Kinetic Data ◽  
Ph Dependence ◽  
Equilibrium Constants ◽  
Hydroxyl Group ◽  
Net Charge ◽  
First Order ◽  
Kinetics Of ◽  
Hydrolysis Of

The kinetics of the reaction of the tetrakis(1-methylpyridium-4-yl)porphyrin tetracation, [ H 2( TMPyP )]4+, with gold(III) ions were studied along with equilibria of gold(III) species in aqueous medium at 25°C, I = 0.10 M ( NaNO 3). The equilibrium constants for the formation of [ AuCl 4-n( OH ) n ]- ( n = 0,…,4), defined as β n = [ AuCl 4- n ( OH ) n ]- [ Cl -] n / [ AuCl 4-][ OH -] n were found to be that log β1 = 7.94 ± 0.03, log β2 = 15.14 ± 0.03, log β3 = 21.30 ± 0.05 and log β4 = 26.88 ± 0.05. The overall reaction was first order with respect to each of the total [ Au (III)] and [ H 2 TMPyP 4+]. On the basis of pH dependence on rate constants and the hydrolysis of gold(III), the rate expression can be written as d [ Au ( TMPyP )5+]/ dt = ( k 1[ AuCl 4-] + k2[ AuCl 3( OH )-] + k3[ AuCl 2( OH )2-] + k4[ AuCl ( OH )3-])[ H 2 TMPyP 4+], where k1, k2, k3 and k4 were found to be (2.16 ± 0.31) × 10-1, (6.56 ± 0.19) × 10-1, (1.07 ± 0.24) × 10-1, and (0.29 ± 0.21) × 10-1 M -1. s -1, respectively. The kinetic data revealed that the trichloromonohydroxogold(III) species, [ AuCl 3( OH )]-, is the most reactive. The higher reactivity of [ AuCl 3( OH )]- is explained by hydrogen bonding formation between the hydroxyl group of [ AuCl 3( OH )]- and the pyrrole hydrogen atom of [ H 2( TMPyP )]4+. Furthermore, applying the Fuoss equation to the observed rate constants at different ionic strengths, the apparent net charge of [ H 2( TMPyP )]4+ was calculated to be +3.5.

Oxidation of DL-penicillamine by chromium(VI). Kinetics of formation of the thioester intermediate

1994 ◽  
Vol 72 (7) ◽  
pp. 1637-1644 ◽  
Author(s):  
Joaquin F. Perez-Benito ◽  
Driss Lamrhari ◽  
Conchita Arias
Keyword(s):  
Reaction Rate ◽  
Aqueous Media ◽  
Bimolecular Reaction ◽  
Spectrophotometric Detection ◽  
State Behavior ◽  
Chromium Vi ◽  
Specific Effects ◽  
Kinetics Of Formation ◽  
Kinetics Of ◽  
Catalytic Power

The kinetics of formation of the thioester involved as an intermediate in the reaction between chromium(VI) and DL-penicillamine in aqueous media (pH = 1–8) containing different buffers (acetate, citrate, and phosphate) has been studied by monitoring the disappearance of chromium(VI) at 370 nm and application of the initial-rates method. The initial rate is directly proportional to the initial concentrations of both oxidant and reductant, and the rate vs. pH plots show bell-shaped profiles. The reaction is catalyzed by the buffer present in the medium, the catalytic power of each buffer increasing in the order acetate < citrate < phosphate. This is explained in terms of a mechanism involving the formation of a complex between the acidic form of the buffer and HCrO4− previous to the formation of the thioester. Potassium chloride and sodium sulfate do not seem to have important specific effects on the reaction rate, their effect being that of an acceleration of the reaction as the ionic strength increases. On the contrary, the sulfates of magnesium, manganese(II), and zinc (the latter only in the presence of acetate buffer) have specific effects, indicating the probable formation of several complexes. The spectrophotometric detection of the thioester at 430 nm has allowed to confirm some of the conclusions extracted from the measurement of initial rates, and suggests that this intermediate might approach a steady-state behavior in the three buffers at pH > 6.25, and also that a bimolecular reaction with DL-penicillamine might be involved in its destruction.

Kinetics of the anation reaction of nickel(II) and 1,10-phenanthroline in methanol–water mixtures

1969 ◽  
Vol 47 (20) ◽  
pp. 3773-3778 ◽  
Author(s):  
M. L. Sanduja ◽  
W. MacF. Smith
Keyword(s):  
Ionic Strength ◽  
Rate Constant ◽  
Rate Constants ◽  
Solvent Composition ◽  
Solvent Mixtures ◽  
Methanol Content ◽  
Dependent Rate ◽  
Kinetics Of Formation ◽  
Kinetics Of ◽  
Anation Reaction

The kinetics of formation of the monophenanthroline complex of nickel(II) has been studied spectrophotometrically in water–methanol mixtures of 0 to 97 weight % of methanol, at ionic strength 0.050, at varying acidities at 25 °C. Values for the rate constants for the acid independent and acid dependent reactions together with values for the equilibrium acid ionization quotient of phenanthrolium ion over the range of solvent mixtures have been determined. The values of the acid independent rate constant show little dependence on solvent compositions up to 76% methanol, then decrease and show no correlation with trends in the ionization quotient of phenanthrolium ion. The acid dependent rate constant shows only a modest dependence on solvent composition over most of the range of solvent compositions except in the range of highest methanol content where it is not significantly different from zero.

scholarly journals The kinetics and mechanism of the ligand substitution reaction of aquapentacyanoruthenate(II) with d-penicillamine in aqueous medium

2020 ◽  
pp. 174751982096101
Author(s):  
Rupal Yadav ◽  
Radhey Mohan Naik
Keyword(s):  
Aqueous Medium ◽  
Reaction Rate ◽  
Electronic Effect ◽  
Ligand Substitution ◽  
Order Conditions ◽  
Reaction Parameters ◽  
First Order ◽  
Coloured Complex ◽  
Kinetics Of ◽  
Ligand Substitution Reaction

The kinetics of the formation of the light orange–coloured complex [Ru(CN)5D-PA]3− are studied spectrophotometrically through substitution of a coordinated H2O molecule in aquapentacyanoruthenate(II) [Ru(CN)5OH2]3− by interaction with D-penicillamine [D-PA] in aqueous medium at 490 nm (λmax of [Ru(CN)5D-PA]3−). The reaction is monitored under pseudo-first-order conditions, taking [D-PA] in excess over [Ru(CN)5OH23−]. The effects of various reaction parameters on the rate of the reaction are investigated. Experimental observations reveal that the variation in [D-PA] obeyed the first-order rate law while it is found to be invariant with [Ru(CN)5OH23−] in the whole experimental range. With ionic strength variation, as the reaction advances a decrease in the reaction rate is noticed. The product stoichiometry is assigned as 1:1. The ease of substitution at an H2O molecule in [Ru(CN)5OH23−] is considered on the basis of the electronic effect generated through interactions of the M–OH2 bond. A provisional mechanism based on the calculated results is proposed based on the slowest step of the reaction.

Kinetics of formation of silicides: A review

1986 ◽  
Vol 1 (1) ◽  
pp. 205-221 ◽  
Author(s):  
F. M. d'Heurle ◽  
P. Gas
Keyword(s):  
Phase Formation ◽  
Reaction Rate ◽  
Diffusion Control ◽  
Specific Effects ◽  
Diffusion Controlled ◽  
Kinetics Of Formation ◽  
Amorphous Compounds ◽  
Silicide Growth ◽  
Rate Controlled ◽  
Kinetics Of

The kinetics of silicide growth are classified into three different categories: (a) diffusion controlled, (b) nucleation controlled, (c) others (reaction rate controlled). These are analyzed with the aim of understanding both the phenomenology of growth and the specific atomic mechanisms of phase formation. Diffusion-controlled growth is discussed with respect to the Nernst-Einstein equation. Stress relaxation is considered as a possible cause of reaction-rate control. The relative merits of two different types of marker experiments are compared. A few silicides are discussed in terms of what can be inferred about diffusion mechanisms. The competition between reaction-rate and diffusion control phenomena is shown to have specific effects on the sequence of phase formation; it is also related to the formation of some amorphous compounds. Reactions between silicon and alloyed metal films are used to illustrate the respective influences of mobility and driving force factors on the kinetics of silicide growth; they can also be used to underline the dominance of nucleation over diffusion in some silicide formation processes.

scholarly journals Bulk Polymerization Kinetics of Hydroxy Terminated Polybutadiene and Toluene Diisocyanate with Infrared Spectroscopy

2018 ◽  
Vol 18 (3) ◽  
pp. 552 ◽  
Author(s):  
Heri Budi Wibowo ◽  
Widhi Cahyo ◽  
Ratih Sanggra
Keyword(s):  
Reaction Temperature ◽  
Rate Constants ◽  
Reaction Rate ◽  
Bulk Polymerization ◽  
Isocyanate Group ◽  
Toluene Diisocyanate ◽  
Hydroxyl Group ◽  
Molar Ratio ◽  
Reaction Rate Constants ◽  
Kinetics Of

A study on bulk polymerization kinetics of HTPB (Hydroxy Terminated Polybutadiene) and TDI (Toluene Diisocyanate) with infrared (IR) spectroscopy has been conducted. The investigations included the molar ratio of 2,4-TDI to 2,6-TDI isomers, the initial molar ratio of isocyanate group to a hydroxyl group, and the reaction temperature. The polymerization rate constant was calculated based on the decrease rate of TDI. Kinetics model had been evaluated through the following reaction steps: (1) 2,4-urethane production, (2) 2,6-urethane production, (3) the reaction between 2,4-urethane and the isocyanate group of 2,4-TDI, (4) the reaction between 2,4-urethane and the isocyanate group of 2,4-TDI, (5) the reaction between 2,6-urethane and isocyanate group of 2,4-TDI, and (6) the reaction between 2,6-urethane and the isocyanate group of 2,6-TDI. Those reaction steps were assumed to be the first order reaction with the reaction rate constants k1, k2, k3, k4, k5, and k6, respectively. The reaction rate constants obtained at molar ratio of 2,4-TDI to 2,6-TDI of 80:20, isocyanate group to hydroxyl group (RNCO/OH) initial molar ratio of 1:1, and reaction temperature of 40 °C were 6.2 × 10-5, 5.8 × 10-5, 3.1 × 10-5, 2.8 × 10-5, and 2.5 × 10-5 L.mole-1.min-1 for k1, k2, k3, k4, k5, and k6, respectively, with the activation energy of 1152, 952, 1001, 656, and 1001 kJ/mole for reaction (1)–(6), respectively. The results show that the polymerization reaction rate-determining step was the reaction of 2,6-urethane and isocyanate group of 2,6-TDI (reaction (6)).

STUDYING THE KINETIC CHARACTERISTICS OF THE EXTRACTION OF ANTHOCYANINS FROM THE SQUEEZE OF KRASNOSTOP ZOLOTOVSKY

2020 ◽  
Author(s):  
M.A. Egyan ◽  
Keyword(s):  
Reaction Rate ◽  
Sugar Content ◽  
Extraction Process ◽  
Efficiency Coefficient ◽  
Kinetic Characteristics ◽  
Reaction Rate Constants ◽  
Solids Content ◽  
Kinetics Of ◽  
Process Speed

The article shows studies characterizing the quality of the squeeze: the mechanical composition of the squeeze is determined, the structural moisture of each component is determined, the sugar content in the formed process of sedimentation of the juice and its acidity are determined refractometrically. The kinetics of anthocyanins extraction was determined in two ways, the solids content in the extract was calculated, and the reaction rate constants of the extraction process and the efficiency coefficient of ultrasonic amplification of the extraction process speed were calculated.

Thermal Decomposition Kinetics of Glyphosate (GP) and its Metabolite Aminomethylphosphonic Acid (AMPA)

2019 ◽  
Author(s):  
Milad Narimani ◽  
Gabriel da Silva
Keyword(s):  
Thermal Decomposition ◽  
Reaction Rate ◽  
Decomposition Kinetics ◽  
Rate Theory ◽  
Thermal Decomposition Mechanism ◽  
Treatment Processes ◽  
Aminomethylphosphonic Acid ◽  
Reaction Rate Theory ◽  
Decomposition Chemistry ◽  
Kinetics Of

Glyphosate (GP) is a widely used herbicide worldwide, yet accumulation of GP and its main byproduct, aminomethylphosphonic acid (AMPA), in soil and water has raised concerns about its potential effects to human health. Thermal treatment processes are one option for decontaminating material containing GP and AMPA, yet the thermal decomposition chemistry of these compounds remains poorly understood. Here, we have revealed the thermal decomposition mechanism of GP and AMPA by applying computational chemistry and reaction rate theory methods. <br>

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