On the Mechanism of the Acridine Orange Sensitized Photodynamic Inactivation of Lysozyme

1976 ◽  
Vol 31 (1-2) ◽  
pp. 29-39 ◽  
Author(s):  
Peter Rosenkranz ◽  
I. Basic Kinetics ◽  
Hartmut Schmidt
Keyword(s):  
Singlet Oxygen ◽  
Acridine Orange ◽  
Ph Value ◽  
Photodynamic Inactivation ◽  
Rate Process ◽  
First Order ◽  
Quenching Process ◽  
Pseudo First Order ◽  
Kinetics Of ◽  
Excited Oxygen

The kinetics of the photodynamic desactivation of lysozyme in presence of acridine orange as the sensitizer have been investigated in detail varying oxygen, protein, dye concentration, ionic strength and pH value. The kinetics can be approximately described as an over all pseudo-first- order rate process. Changing the solvent from water to D2O or by quenching experiments in pres­ence of azide ions it could be shown that the desactivation of lysozyme is caused exclusively by singlet oxygen. The excited oxygen occurs via the triplet state of the dye with a rate constant considerably lower than that to be expected for a diffusionally controlled reaction. Singlet oxygen reacts chemically (desactivation, k=2.9 × 107 ᴍ-1 sec-1) and physically (quenching process, k = 4.1 × 108 ᴍ-1sec-1) with the enzyme. The kinetical analysis shows that additional chemical reactions between singlet oxygen and lysozyme would have only little influence on the kinetics of the desactivation as long as their products would be enzymatically active and their kinetical constants would be less than about 1 × 108 ᴍ-1 sec-1.

scholarly journals Kinetics of diatrizoate degradation by ozone and the formation of disinfection by-products in the sequential chlorination

2021 ◽  
Author(s):  
Chen-Yan Hu ◽  
Si-Cheng Ren ◽  
Yi-Li Lin ◽  
Ji-Chen Zhang ◽  
Ye-Ye Zhu ◽  
...  
Keyword(s):  
Ozone Concentration ◽  
Ph Value ◽  
Degradation Kinetics ◽  
Order Rate Constant ◽  
Order Kinetic ◽  
Solution Ph ◽  
First Order ◽  
Pseudo First Order ◽  
Kinetics Of ◽  
By Products

Abstract In this study, we studied the degradation kinetics of a common iodine contrast agent, diatrizoate, by ozone and the formation of disinfection by-products (DBPs) in the sequential chlorination. Effects of ozone concentration, solution pH, and bromide concentration on diatrizoate degradation were evaluated. The results indicate that diatrizoate can be effectively degraded (over 80% within 1 h) by ozone, and the degradation kinetics can be well described using the pseudo-first-order kinetic model. The pseudo-first-order rate constant (kobs) of diatrizoate degradation significantly increased with increasing ozone concentration and decreasing bromide concentration. The kobs kept increasing with the increase of pH value and reached a maximum of 6.5 (±0.05) × 10−2 min−1 at pH 9. As the ozone concentration gradually increased from 0.342 to 1.316 mg/L, the corresponding kobs of diatrizoate degradation increased from 1.76 (±0.20) × 10−3 to 4.22 (±0.3) × 10−2 min−1. The bromide concentration exhibited a strong inhibitory effect on diatrizoate degradation because of the competition for ozone with diatrizoate. Trichloromethane was the only detected DBP in the subsequent chlorination in the absence of bromide. However, in the presence of bromide, six other DBPs were detected, and bromochloroiodomethane and tribromomethane became the major products with concentrations 1–2 orders higher than those of the other DBPs. In order to provide safe drinking water to the public, water should be maintained at circumneutral pH values and low bromine concentrations (<5 μM) before reaching the chlorine disinfection process to effectively control the formation of DBPs.

Degradation Kinetics of Reactive Brilliant Red X-3B Dye by UV/Mn2+/H2O2/Micro-Aeration

2012 ◽  
Vol 441 ◽  
pp. 549-554
Author(s):  
Ying Jie Cai ◽  
Xiao Jun Yang ◽  
Dong Sheng Xia ◽  
Qing Fu Zeng
Keyword(s):  
Degradation Rate ◽  
Ph Value ◽  
Degradation Kinetics ◽  
H2o2 Concentration ◽  
Kinetics Equation ◽  
Linear Least Squares ◽  
First Order ◽  
First Order Kinetics ◽  
Pseudo First Order ◽  
Kinetics Of

Abstract. Degradation of reactive brilliant red X-3B (X-3B) by a UV/Mn2+/H2O2/micro- aeration method was investigated. The influencing factors of degradation of X-3B including UV irradiation, aeration, pH value, H2O2 concentration and X-3B concentration were examined. The results show that X-3B was effectively degraded by the UV/Mn2+/H2O2/micro-aeration method. The degradation rate of X-3B was obtained from weighted linear least squares analysis of the experimental data, and accorded with the pseudo-first order kinetics equation.

On the Mechanism of the Acridine Orange Sensitized Photodynamic Inactivation of Lysozyme II. Kinetics in Presence of N-Acetylglucosamine

1976 ◽  
Vol 31 (11-12) ◽  
pp. 679-682 ◽  
Author(s):  
Peter Rosenkranz ◽  
Hartmut Schmidt
Keyword(s):  
Amino Acid ◽  
Triplet State ◽  
Singlet Oxygen ◽  
Acridine Orange ◽  
Rate Constant ◽  
Enzymatic Reaction ◽  
Photodynamic Inactivation ◽  
Tryptophan Residues ◽  
Amino Acid Side Chains ◽  
Kinetics Of

Abstract The photodynamic deactivation of lysozyme in presence of acridine orange is caused by a reaction between singlet oxygen formed via the dye triplet state and the protein. In order to identify the region where the singlet oxygen reacts with the protein we have investigated the kinetics of the deactivation in presence of the inhibitor of the enzymatic reaction N-acetylglucosamine (GlcNAc). The overall experimental rate constant becomes slower with increasing saccharide concentrations. As we can exclude experimentally that this kinetical effect is caused in presence of the saccharide by a physical quenching of singlet oxygen or of the dye triplet state it has to be assumed that GlcNAc protects the surrounding of its binding place at subsite C of the enzymatic center sterically against an attack of singlet oxygen. In this region three tryptophan residues are located, which could be sensitive against singlet oxygen. Surprisingly, however, it has been found that only those species are protected, in which a second saccharide molecule is bound to the protein, probably at subsite E at the enzymatic center, where no sensitive amino acid side chains are located.

Efficient adsorption of chlorpyrifos onto modified activated carbon by gamma irradiation; a plausible adsorption mechanism

2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Mohamed S. Yahia ◽  
Ahmed S. Elzaref ◽  
Magdy B. Awad ◽  
Ahmed M. Tony ◽  
Ahmed S. Elfeky
Keyword(s):  
Gamma Irradiation ◽  
Area Measurement ◽  
Maximum Adsorption Capacity ◽  
X Ray Diffraction ◽  
X Ray ◽  
First Order ◽  
Pseudo Second Order ◽  
Ft Ir ◽  
Pseudo First Order ◽  
Kinetics Of

Abstract Commercial Granulated Active Carbon (GAC) has been modified using 10 Gy dose Gamma irradiation (GAC10 Gy) for increasing its ability of air purification. Both, the raw and treated samples were applied for removing Chlorpyrifos pesticide (CPF) from ambient midair. Physicochemical properties of the two materials were characterized by Fourier Transform Infrared (FT-IR) and Raman spectroscopy. The phase formation and microstructure were monitored using X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), supported with Energy-Dispersive X-ray (EDX). The Surface area measurement was detected using BET particle size prosometry. Obtained outcomes showed that, the maximum adsorption capacity, given by Langmuir equations, was greatly increased from 172.712 to 272.480 mg/g for GAC and GAC10 Gy, respectively, with high selectivity. The overall removal efficiency of GAC10 Gy was notably comparable to that of the original GAC-sorbent. The present study indicated that, gamma irradiation could be a promising technique for treating GAC and turned it more active in eliminating the pesticides pollutants from surrounding air. The data of equilibrium has been analyzed by Langmuir and Freundlich models, that were considerably better suited for the investigated materials than other models. The process kinetics of CPF adsorbed onto both tested carbon versions were found to obey the pseudo first order at all concentrations with an exception at 70 mg/l using GAC, where, the spontaneous exothermic adsorption of Chlorpyrifos is a strong function for the pseudo-first order (PFO) and pseudo second order (PSO) kinetics.

scholarly journals Kinetics and mechanism of sol-gel transformation between some trivalent- and tetravalent-metal ions and Sodium alginate Anionic polyelectrolyte with formation of coordination Biopolymeric structure polymembranes Hydrogels of Capillary Structures Ex

2007 ◽  
Vol 3 (1) ◽  
pp. 133-142 ◽  
Author(s):  
Ishaq Abdullah Zaafarany
Keyword(s):  
Sodium Alginate ◽  
Metal Ion ◽  
Sol Gel ◽  
Coordination Geometry ◽  
Large Excess ◽  
First Order ◽  
Pseudo First Order ◽  
The Stability ◽  
Kinetics Of ◽  
Overall Kinetics

Abstract          The kinetics of sol-gel transformation between A13+, La 3+ and Th4+ metal ion electrolytes and sodium alginate sol have been studied complexometrically at various  temperatures. In the presence of a large excess of sodium alginate sol concentration over that of metal ion electrolyte, the pseudo first–order plots of exchange showed sigmoidal curves with two distinct stages. The initial part was relatively fast and curved significantly at early times, followed by a slow decrease in the rates of exchange over longer time periods. The rate constants of gelation showed second-order overall kinetics which was first order in the concentration of both reactants. The thermodynamic parameters have been evaluated and tentative gelation mechanisms consistent with the kinetic results of gelation are suggested. The stability of these ionotropic metal-alginate complexes has been discussed in terms of the coordination geometry and strength of chelated bonds.

Kinetics and Activation Parameters for the Alkaline Aqueous Rearrangement of Trichorfon [O,O-Dimethyl-(2,2,2-Trichloro-1-Hydroxyethyl) Phosphonate] to Dichlorvos [O,O-Dimethyl-O-(2,2-Dichloroethenyl)Phosphate]

2001 ◽  
Vol 36 (3) ◽  
pp. 589-604 ◽  
Author(s):  
Julian M. Dust ◽  
Christopher S. Warren
Keyword(s):  
Activation Energy ◽  
High Pressure ◽  
Activation Parameters ◽  
Base Catalysis ◽  
Rearrangement Product ◽  
Exponential Factor ◽  
First Order ◽  
Pseudo First Order ◽  
Order Plot ◽  
Kinetics Of

Abstract The kinetics of the alkaline rearrangement of O,O-dimethyl-(2,2,2-trichloro-1- hydroxyethyl)phosphonate, (trichlorfon, 1), the active insecticidal component in such formulations as Dylox, was followed at 25±0.5°C by high pressure liquid chromatography (UV-vis detector, 210 nm). The rearrangement product, O,Odimethyl- O-(2,2-dichloroethenyl)phosphate (dichlorovos, 2), which is a more potent biocide than trichlorfon, undergoes further reaction, and the kinetics, consequently, cannot be treated by a standard pseudo-first-order plot. A two-point van't Hoff (initial rates) method was used to obtain pseudo-first-order rate constants (kѱ) at 25, 35 and 45°C: 2.6 × 10-6, 7.4 × 10-6 and 2.5 × 10-5 s-1, respectively. Arrhenius treatment of this data gave an activation energy (Ea) of 88 kJ·mol-1 with a pre-exponential factor (A) of 5.5 × 109 s-1. Kinetic trials at pH 8.0 using phosphate and tris buffer systems show no buffer catalysis in this reaction and indicate that the rearrangement is subject to specific base catalysis. Estimates are reported for pseudo-first-order half-lives for trichlorfon at pH 8.0 for environmental conditions in aqueous systems in the Corner Brook region of western Newfoundland, part of the site of a recent trichlorfon aerial spray program.

Kinetics of reconstitution of apotyrosinase by copper

1990 ◽  
Vol 68 (2) ◽  
pp. 476-479
Author(s):  
Donald C. Wigfield ◽  
Douglas M. Goltz
Keyword(s):  
Rate Constant ◽  
Copper Concentration ◽  
Copper Ions ◽  
Copper Ion ◽  
Order Rate Constant ◽  
First Order ◽  
Order Rate ◽  
Pseudo First Order ◽  
Rate Limiting ◽  
Kinetics Of

The kinetics of the reconstitution reaction of apotyrosinase with copper (II) ions are reported. The reaction is pseudo first order with respect to apoenzyme and the values of these pseudo first order rate constants are reported as a function of copper (II) concentration. Two copper ions bind to apoenzyme, and if the second one is rate limiting, the kinetically relevant copper concentration is the copper originally added minus the amount used in binding the first copper ion to enzyme. This modified copper concentration is linearly related to the magnitude of the pseudo first order rate constant, up to a copper concentration of 1.25 × 10−4 M (10-fold excess), giving a second order rate constant of 7.67 × 102 ± 0.93 × 102 M−1∙s−1.Key words: apotyrosinase, copper, tyrosinase.

Evidence for the formation of lignin-hexenuronic acid-xylan complexes during modified kraft pulping processes

Holzforschung ◽  
2006 ◽  
Vol 60 (2) ◽  
pp. 137-142 ◽  
Author(s):  
Zhi-Hua Jiang ◽  
Jean Bouchard ◽  
Richard Berry
Keyword(s):  
Acid Hydrolysis ◽  
Kraft Pulp ◽  
Kraft Pulping ◽  
Order Kinetic ◽  
Kraft Pulps ◽  
First Order ◽  
Pseudo First Order ◽  
Hexenuronic Acid ◽  
Kinetics Of ◽  
Hydrolysis Of

Abstract The finding that hexenuronic acid (HexA) groups can be selectively removed from kraft pulps by acid hydrolysis has provided an opportunity to reduce bleaching chemicals. However, there is evidence that the acid hydrolysis is not uniform. In this report, we evaluate the kinetics of acid hydrolysis of HexA in a xylan sample enriched with HexA, a conventional kraft pulp, and three modified kraft pulps: anthraquinone pulp (Kraft-AQ), polysulfide pulp (PS), and polysulfide-anthraquinone pulp (PS-AQ). We found that HexA present in the xylan and conventional kraft pulp behaved similarly toward the acid hydrolysis throughout. On the other hand, HexA present in the Kraft-AQ, PS-AQ and PS pulps was heterogeneous toward acid hydrolysis and the reaction can be separated into two pseudo-first-order kinetic phases, each of which has a different rate constant. The kinetic data provide evidence for the formation of lignin-HexA-xylan complexes during modified kraft pulping processes.

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