scholarly journals Models for enzyme superactivity in aqueous solutions of surfactants

1999 ◽  
Vol 344 (3) ◽  
pp. 765-773 ◽  
Author(s):  
Paolo VIPARELLI ◽  
Francesco ALFANI ◽  
Maria CANTARELLA
Keyword(s):  
Substrate Concentration ◽  
Surfactant Concentration ◽  
Reaction Rate ◽  
Reaction Medium ◽  
Bound Water ◽  
Free Water ◽  
Theoretical Models ◽  
Enzymic Activity ◽  
Equilibrium Relation ◽  
Micellar Aggregates

Theoretical models are developed here for enzymic activity in the presence of direct micellar aggregates. An approach similar to that of Bru et al. [Bru, Sánchez-Ferrer and Garcia-Carmona (1989) Biochem. J. 259, 355-361] for reverse micelles has been adopted. The system is considered to consist of three pseudo-phases: free water, bound water and surfactant tails. The substrate concentration in each pseudo-phase is related to the total substrate concentration in the reaction medium. In the absence of interactions between the enzyme and the micelles, the model predicts either monotonically increasing or monotonically decreasing trends in the calculated reaction rate as a function of surfactant concentration. With enzyme-micelle interactions included in the formulation (by introducing an equilibrium relation between the enzyme confined in the free water and in the bound water pseudo-phases, and by allowing for different catalytic behaviours for the two forms), the calculated reaction rate can exhibit a bell-shaped dependence on surfactant concentration. The effect of the partition of enzyme and substrate is described, as is that of enzyme efficiency in the various pseudo-phases.

scholarly journals The effect of substrate partitioning on the kinetics of enzymes acting in reverse micelles

1990 ◽  
Vol 268 (3) ◽  
pp. 679-684 ◽  
Author(s):  
R Bru ◽  
A Sánchez-Ferrer ◽  
F García-Carmona
Keyword(s):  
Reverse Micelle ◽  
Substrate Concentration ◽  
Reverse Micelles ◽  
Bound Water ◽  
Free Water ◽  
Enzymic Activity ◽  
Molar Ratio ◽  
Biphasic Model ◽  
Catalytic Constant ◽  
Kinetics Of

A theoretical model for the expression of enzymic activity in reverse micelles previously developed [Bru. Sánchez-Ferrer & García-Carmona (1989) Biochem. J. 259, 355-361] was extended in the present work. The substrate concentration in each reverse-micelle phase (free water, bound water and surfactant apolar tails) and the organic solvent was expressed as a function of the total substrate concentration, taking into account its partition coefficients, that is, partitioning of the substrate in a multiphasic system. In each phase the enzyme expresses a catalytic constant and a Km. Thus the whole reaction rate is the addition of the particular rates expressed in each domain. This model was compared with that developed for a biphasic system [Levashov, Klyachko, Pantin, Khmelnitski & Martinek (1980) Bioorg. Khim. 6, 929-943] by fitting the experimental results obtained with mushroom tyrosinase (working on both 4-t-butylcatechol and 4-methylcatechol) to the two models. The parameters which characterize reverse micelles, omega 0 (water/surfactant molar ratio) and theta (fraction of water) were investigated. The omega 0 profile was shown to be hyperbolic for both substrates. Activity towards 4-t-butylcatechol decreases as theta increases, this observation being attributable to a dilution of the substrate. A Km of 7.8 M for 4-t-butylcatechol could be calculated on the basis of the biphasic model, whereas it was 13.5 mM when calculating on the basis of our model. A new parameter, rho (= [substrate]/theta), was defined to characterize those substrates that mainly solubilize in the reverse micelle (‘micellar substrates’).

Chemical Transformation of Fe, Air & Water to Ammonia: Variation of Reaction Rate with Temperature, Pressure, Alkalinity and Iron

2018 ◽  
Author(s):  
Ping Peng ◽  
Fang-Fang Li ◽  
Xinye Liu ◽  
Jiawen Ren ◽  
jessica stuart ◽  
...  
Keyword(s):  
Particle Size ◽  
Reaction Rate ◽  
Electrolyte Concentration ◽  
Iron Concentration ◽  
Reaction Medium ◽  
Iron Particle ◽  
Intermediate Step ◽  
Ammonia Production ◽  
Pure Nitrogen ◽  
Alkaline Reaction

The rate of ammonia production by the <u>chemical </u>oxidation of iron, N<sub>2</sub>(from air or as pure nitrogen) and water is studied as a function of (1) iron particle size, (2) iron concentration, (3) temperature, (4) pressureand (5) concentration of the alkaline reaction medium. The reaction meduium consists of an aqueous solution of equal molal concentrations of NaOH and KOH (Na<sub>0.5</sub>K<sub>0.5</sub>OH). We had previously reported on the <u>chemical </u>reaction of iron and nitrogen in alkaline medium to ammonia as an intermediate step in the <u>electrochemical </u>synthesis of ammonia by a nano-sized iron oxide electrocatlyst. Here, the intermediate <u>chemical </u>reaction step is exclusively explored. The ammonia production rate increases with temperature (from 20 to 250°C), pressure (from 1 atm to 15 atm of air or N<sub>2</sub>), and exhibits a maximum rate at an electrolyte concentration of 8 molal Na<sub>0,5</sub>K<sub>0,5</sub>OH in a sealed N<sub>2</sub>reactor. 1-3 µm particle size Fe drive the highest observed ammonia production reaction rate. The Fe mass normalized rate of ammonia production increases with decreasing added mass of the Fe reactant reaching a maximum observed rate of 2.2x10<sup>-4</sup>mole of NH<sub>3</sub>h<sup>-1</sup>g<sup>-1</sup>for the reaction of 0.1 g of 1-3 µm Fe in 200°C 8 molal Na<sub>0.5</sub>K<sub>0.5</sub>OH at 15 atm. Under these conditions 5.1 wt% of the iron reacts to form NH<sub>3</sub>via the reaction N<sub>2</sub>+ 2Fe + 3H<sub>2</sub>O ®2NH<sub>3</sub>+ Fe<sub>2</sub>O<sub>3</sub>.

Determine the Moisture Distribution in Sewage Sludge by Drying Differential

2014 ◽  
Vol 665 ◽  
pp. 404-407 ◽  
Author(s):  
Wan Yu ◽  
Pei Sheng Li
Keyword(s):  
Sewage Sludge ◽  
Interstitial Water ◽  
Bound Water ◽  
Free Water ◽  
High Accuracy ◽  
Moisture Distribution ◽  
Municipal Sewage ◽  
Municipal Sewage Sludge ◽  
Hot Air ◽  
Critical Water Content

Moisture distribution in sewage sludge was considered as the essential of thermal drying. Some methods were given in literatures to test the moisture distribution, but there was no standard method to determine the critical water content between different kinds of water. The municipal sewage sludge was dried by hot air in this work. Based on the drying curve, the derivative of drying rate with respect to dry basis moisture content was brought out to analyze the moisture distribution in sewage sludge. Results show that this method can easily determine the free water, interstitial water, surface water and bound water with a high accuracy. The present work can provide new insight to determine the moisture distribution in sewage sludge, which was still lacking in the literatures.

scholarly journals The apparent Km is a misleading kinetic indicator

1986 ◽  
Vol 239 (1) ◽  
pp. 175-178 ◽  
Author(s):  
I W Plesner
Keyword(s):  
Substrate Concentration ◽  
Kinetic Data ◽  
Substrate Binding ◽  
Enzymic Activity ◽  
Free Enzyme ◽  
Ligand Concentration ◽  
Double Reciprocal Plot ◽  
Michaelis Constant ◽  
Formal Framework ◽  
Enzyme Species

When information concerning whether or not a ligand interacts with the same enzyme species as do the substrates, the variation of the Michaelis constant Km (for each substrate) with ligand concentration is sometimes used as a diagnostic. It is shown that the Michaelis constant is of no particular value in this respect and may be misleading. Thus, depending on the mechanism, Km may vary with ligand concentration even though the ligand interacts with species far removed in the mechanism from the substrate-binding steps, and it may stay constant in cases where the ligand competes directly for the free enzyme. In contrast, the slope of a double-reciprocal plot of the kinetic data (= Km/Vmax.) (or, equivalently, the ordinate intercept of a Hanes plot A/v versus A, where A is the substrate concentration) independently of the particular mechanism involved uniquely signifies whether or not such interaction occurs. The results clearly indicate that, for purposes other than communicating the substrate concentration yielding control of the enzymic activity, usage of Km and its variation with ligand concentration should be avoided and interest instead focused on the slope, in accordance with the long-established rules of Cleland [Biochim. Biophys. Acta (1963) 67, 188-196], for which the present analysis provides the formal framework.

scholarly journals Perborate Oxidation of Substituted 5-Oxoacids in Aqueous Acetic Acid Medium: A Kinetic and Mechanistic Study

2014 ◽  
Vol 2014 ◽  
pp. 1-7 ◽  
Author(s):  
S. Shree Devi ◽  
B. Muthukumaran ◽  
P. Krishnamoorthy
Keyword(s):  
Acetic Acid ◽  
Acid Medium ◽  
Reaction Rate ◽  
Reaction Medium ◽  
Activation Parameters ◽  
Reaction Rates ◽  
Mechanistic Study ◽  
Aqueous Acetic Acid ◽  
Sodium Perborate ◽  
Acetic Acid Medium

Kinetics and mechanism of oxidation of substituted 5-oxoacids by sodium perborate in aqueous acetic acid medium have been studied. The reaction exhibits first order both in [perborate] and [5-oxoacid] and second order in [H+]. Variation in ionic strength has no effect on the reaction rate, while the reaction rates are enhanced on lowering the dielectric constant of the reaction medium. Electron releasing substituents in the aromatic ring accelerate the reaction rate and electron withdrawing substituents retard the reaction. The order of reactivity among the studied 5-oxoacids is p-methoxy ≫ p-methyl > p-phenyl > –H > p-chloro > p-bromo > m-nitro. The oxidation is faster than H2O2 oxidation. The formation of H2BO3+ is the reactive species of perborate in the acid medium. Activation parameters have been evaluated using Arrhenius and Eyring’s plots. A mechanism consistent with the observed kinetic data has been proposed and discussed. Based on the mechanism a suitable rate law is derived.

Acceleration of Baylis-Hillman reaction using ionic liquid supported organocatalyst

2021 ◽  
Vol 08 ◽  
Author(s):  
Vivek Srivastava
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Reaction Rate ◽  
Reaction Medium ◽  
Catalyst Loading ◽  
Catalyst Recycling ◽  
Catalytic Systems ◽  
Heterogeneous Catalytic ◽  
Highly Active ◽  
Low Catalyst Loading

Background: Baylis-Hillman reaction suffers from the requirement of cheap starting materials, easy reaction protocol, possibility to create the chiral center in the reaction product has increased the synthetic efficacy of this reaction, and high catalyst loading, low reaction rate, and poor yield. Objective: The extensive use of various functional or non-functional ionic liquids (ILs) with organocatalyst increases the reaction rate of various organic transformations as a reaction medium and as a support to anchor the catalysts. Methods: In this manuscript, we have demonstrated the synthesis of quinuclidine-supported trimethylamine-based functionalized ionic liquid as a catalyst for the Baylis-Hillman reaction. Results: We obtained the Baylis-Hillman adducts in good, isolated yield, low catalyst loading, short reaction time, broad substrate scope, accessible product, and catalyst recycling. N-((E,3S,4R)-5-benzylidene-tetrahydro-4-hydroxy-6-oxo-2H-pyran-3-yl) palmitamide was also successfully synthesized using CATALYST-3 promoted Baylis-Hillman reaction. Conclusion: We successfully isolated the 25 types of Baylis-Hillman adducts using three different quinuclidine-supported ammonium-based ionic liquids such as Et3AmQ][BF4] (CATALYST-1), [Et3AmQ][PF6] (CATALYST-2), and [TMAAmEQ][NTf2](CATALYST-3) as new and efficient catalysts. Tedious and highly active N-((E,3S,4R)-5-benzylidene-tetrahydro-4-hydroxy-6-oxo-2H-pyran-3-yl) palmitamide derivative was also synthesized using CATALYST-3 followed by Baylis-Hillman reaction. Generally, all the responses demonstrated higher activity and yielded high competition with various previously reported homogenous and heterogeneous Catalytic systems. Easy catalyst and product recovery followed by six catalysts recycling were the added advantages of the prosed catalytic system.

scholarly journals Testing the effects of basic numerical implementations of water migration on models of subduction dynamics

Solid Earth ◽  
2014 ◽  
Vol 5 (1) ◽  
pp. 537-555 ◽  
Author(s):  
M. E. T. Quinquis ◽  
S. J. H. Buiter
Keyword(s):  
Upper Mantle ◽  
Water Distribution ◽  
Mantle Wedge ◽  
Bound Water ◽  
Free Water ◽  
Water Velocity ◽  
Water Migration ◽  
Creep Flow ◽  
Dehydration Reactions ◽  
Slab Dehydration

Abstract. Subduction of oceanic lithosphere brings water into the Earth's upper mantle. Previous numerical studies have shown how slab dehydration and mantle hydration can impact the dynamics of a subduction system by allowing a more vigorous mantle flow and promoting localisation of deformation in the lithosphere and mantle. The depths at which dehydration reactions occur in the hydrated portions of the slab are well constrained in these models by thermodynamic calculations. However, computational models use different numerical schemes to simulate the migration of free water. We aim to show the influence of the numerical scheme of free water migration on the dynamics of the upper mantle and more specifically the mantle wedge. We investigate the following three simple migration schemes with a finite-element model: (1) element-wise vertical migration of free water, occurring independent of the flow of the solid phase; (2) an imposed vertical free water velocity; and (3) a Darcy velocity, where the free water velocity is a function of the pressure gradient caused by the difference in density between water and the surrounding rocks. In addition, the flow of the solid material field also moves the free water in the imposed vertical velocity and Darcy schemes. We first test the influence of the water migration scheme using a simple model that simulates the sinking of a cold, hydrated cylinder into a dry, warm mantle. We find that the free water migration scheme has only a limited impact on the water distribution after 1 Myr in these models. We next investigate slab dehydration and mantle hydration with a thermomechanical subduction model that includes brittle behaviour and viscous water-dependent creep flow laws. Our models demonstrate that the bound water distribution is not greatly influenced by the water migration scheme whereas the free water distribution is. We find that a bound water-dependent creep flow law results in a broader area of hydration in the mantle wedge, which feeds back to the dynamics of the system by the associated weakening. This finding underlines the importance of using dynamic time evolution models to investigate the effects of (de)hydration. We also show that hydrated material can be transported down to the base of the upper mantle at 670 km. Although (de)hydration processes influence subduction dynamics, we find that the exact numerical implementation of free water migration is not important in the basic schemes we investigated. A simple implementation of water migration could be sufficient for a first-order impression of the effects of water for studies that focus on large-scale features of subduction dynamics.

Mono- and dinuclear CuII complexes of the benzyldipicolylamine (BDPA) ligand: crystal structure, synthesis and characterization

2017 ◽  
Vol 73 (11) ◽  
pp. 1024-1029
Author(s):  
Dharmalingam Sivanesan ◽  
Min Hye Youn ◽  
Ki Tae Park ◽  
Hak Joo Kim ◽  
Andrews Nirmala Grace ◽  
...  
Keyword(s):  
Hydrogen Bonds ◽  
Reaction Medium ◽  
Bound Water ◽  
Dinuclear Complex ◽  
Residual Moisture ◽  
Structure Synthesis ◽  
Distorted Octahedral ◽  
Vis Spectroscopy ◽  
Ft Ir ◽  
Solvent Molecules

The crystal structures of mono- and dinuclear CuII trifluoromethanesulfonate (triflate) complexes with benzyldipicolylamine (BDPA) are described. From equimolar amounts of Cu(triflate)2 and BDPA, a water-bound CuII mononuclear complex, aqua(benzyldipicolylamine-κ3 N,N′,N′′)bis(trifluoromethanesulfonato-κO)copper(II) tetrahydrofuran monosolvate, [Cu(CF3SO3)2(C19H19N3)(H2O)]·C4H8O, (I), and a triflate-bridged CuII dinuclear complex, bis(μ-trifluoromethanesulfonato-κ2 O:O′)bis[(benzyldipicolylamine-κ3 N,N′,N′′)(trifluoromethanesulfonato-κO)copper(II)], [Cu2(CF3SO3)4(C19H19N3)2], were synthesized. The presence of residual moisture in the reaction medium afforded water-bound complex (I), whereas dinuclear complex (II) was synthesized from an anhydrous reaction medium. Single-crystal X-ray structure analysis reveals that the CuII centres adopt slightly distorted octahedral geometries in both complexes. The metal-bound water molecule in (I) is involved in intermolecular O—H...O hydrogen bonds with triflate ligands and tetrahydrofuran solvent molecules. In (II), weak intermolecular C—H...F(triflate) and C—H...O(triflate) hydrogen bonds stabilize the crystal lattice. Complexes (I) and (II) were also characterized fully using FT–IR and UV–Vis spectroscopy, cyclic voltammetry and elemental analysis.

Characterization of thin water layers in pulp by tritium exchange. Part 1: Methods development

Holzforschung ◽  
2007 ◽  
Vol 61 (2) ◽  
pp. 115-119 ◽  
Author(s):  
Frances L. Walsh ◽  
Sujit Banerjee
Keyword(s):  
Water Content ◽  
Surface Area ◽  
Tritiated Water ◽  
Bound Water ◽  
Free Water ◽  
Fiber Surface ◽  
Bulk Water ◽  
Methods Development ◽  
A Value ◽  
A New Technique

Abstract A new technique for measuring the monolayer water content of fiber is presented. Tritiated water is added to a pulp/water suspension, whereupon the tritium partitions between the bulk water and the pulp. In the pulp phase the tritium can exchange with free water, bound water, and with hydroxyl and other protons present in the pulp matrix. The free water in the pulp is then removed by displacement with acetone. The tritium remaining in the pulp is mostly associated with tightly bound water, with a small fraction being tied up with the exchangeable hydrogen in pulp. The procedure provides a value of 10% for the tightly bound water content of hardwood or softwood fiber, either bleached or unbleached. If this water is assumed to cover the fiber surface as a monolayer, then an estimate of the wet surface area of the fiber can be obtained. This estimate compares well with independent measurements of surface area.

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