Search results for "Equilibrium constant"
showing 10 items of 79 documents
Statistics of reversible bond dynamics observed in force-clamp spectroscopy
2010
We present a detailed analysis of two-state trajectories obtained from force-clamp spectroscopy (FCS) of reversibly bonded systems. FCS offers the unique possibility to vary the equilibrium constant in two-state kinetics, for instance the unfolding and refolding of biomolecules, over many orders of magnitude due to the force dependency of the respective rates. We discuss two different kinds of counting statistics, the event-counting usually employed in the statistical analysis of two-state kinetics and additionally the so-called cycle-counting. While in the former case all transitions are counted, cycle-counting means that we focus on one type of transitions. This might be advantageous in p…
Atom transfer radical polymerization with different halides (F, Cl, Br, and I): Is the process "living" in the presence of fluorinated initiators?
2016
Atom transfer radical polymerization (ATRP) is often used for grafting from fluorinated polymers. Nevertheless, the possibility to initiate an ATRP from a C-F functionality and the activity of the catalysts in the presence of fluoride anions are essentially unexplored. Therefore, we investigated the thermodynamics and kinetics of C-F bond activation by ATRP catalysts and compared it with other halide systems. The ATRP equilibrium constant was estimated to be small for the reaction between [CuITPMA]+ and benzyl fluoride (TPMA = tris(2-pyridylmethyl)- amine). However, [CuITPMA] + could react with the more active initiator diethyl fluoromalonate (DEFM). With DEFM as initiator and CuIBr/TPMA as…
Examination of the least-squares method applied to the evaluation of physicochemical parameters with linearized equations
1989
Physicochemical parameters are frequently evaluated by the least-squares method after linearization of the equation which relates the experimental variables to the parameters of interest. When a given set of data is treated to evaluate (n+1) parameters. (n+2) nominally identical linearized equations are possible; each of these leads to different sets of values of the parameters which are also affected by different variances. These differences are also observed when statistical weights are used. Two methods for establishing which one of the (n+2) equations is best for fitting the data, i.e., simulation of experiments and propagation of errors, are discussed, compared and applied to a potenti…
Bohr-effect and buffering capacity of hemocyanin from the tarantula E. californicum.
2003
A previous report showed that binding of oxygen to the 24-meric hemocyanin from E. californicum does not correlate linearly with the release of protons as known from hemoglobin. However, this unusual complex phenomenological observation could not be explained at that time. Here, I present a full analysis of the thermodynamic coupling between protons and oxygen for the 24-meric tarantula hemocyanin in Ringer-solution based on the Nested-MWC-model. A strategy is presented which allows to reduce the number of free parameters when fitting the model to the data by including explicitly the equilibrium constants for binding of protons to the different conformations. The results show that the Neste…
Intermolecular coupling influence on conformations of molecules in solution
1994
Abstract The influence of non-specific intermolecular interactions on conformational equilibria of organic molecules is investigated with the help of the London-Debye-Keesom pair coupling potentials. It is shown that in a series of apolar solvents equilibrium constant logarithms are proportional to ζα ≡ Z αs/ R 6s,d, and in a series of polar solvents equilibrium constants logarithms are proportional to ζμ ≡ Z μ2s/ R 6s,d, where Z is the average number of neighbours of a solute molecule in the first coordination sphere, αs is the polarizability, μs the dipole moment of solvent molecules, and R s,d = R s + R d is the sum of the radii of spherical volumes per molecule of solvent (s) and dissol…
Dynamic force spectroscopy: analysis of reversible bond-breaking dynamics
2008
The problem of diffusive bond-dissociation in a double well potential under application of an external force is scrutinized. We compute the probability distribution of rupture forces and present a detailed discussion of the influence of finite rebinding probabilities on the dynamic force spectrum. In particular, we focus on barrier crossing upon extension, i.e. under linearly increased load, and upon relaxation starting from completely separated bonds. For large loading rates the rupture force and the rejoining force depend on the loading rate in the expected manner determined by the shape of the potential. For small loading rates the mean forces obtained from pull and relax modes approach …
Calculation of the rate constants for hydrogen abstraction reactions by Hydroperoxyl radical from Methanol, and the investigation of stability of CH3…
2020
Abstract Master equation (ME) with Lennard-Jones potential utilized to simulate the collision between CH3OH and HO2 radical in the presence of bath gas. The reaction mechanism explored through the lowest doublet potential energy surface at CCSD(T)/aug-cc-pVTZ//B3LYP/aug-cc-pVTZ level of theory that is barrierless and forms shallow energized intermediate at the entrance channel. The investigation of the fractional population showed that lifetime of CH3OH.HO2 intermediate (INT*) is fairly short due to its shallow depth, and at the low temperature, most reaction takes place by re-dissociation back to reactants and also when the pressure is high enough, the INT* is thermalized and comes into eq…
Adsorption of Heavy Metals from Aqueous Solutions onto Activated Carbon in Single Cu and Ni Systems and in Binary Cu-Ni, Cu-Cd and Cu-Zn Systems
1997
Single copper and nickel adsorption from aqueous solutions onto a granular activated carbon is reported. Metal removals increase on raising pH and temperature, and decrease on raising the initial metal concentration at constant carbon dose. The adsorption processes are modelled using the surface complex formation (SCF) Triple Layer Model (TLM) with an overall surface bidentate species. A dependence of the SCF constant on pH, initial molar metal/carbon ratio and temperature is observed, and a correlation for log Kads is determined. The SCF model successfully predicts copper and nickel removals in single metal solutions. Adsorption in the binary metal systems copper–nickel, copper–cadmium and…
Efficiency of dihydroxamic and trihydroxamic siderochelates to extract uranium and plutonium from contaminated soils
2021
International audience; Actinide-based mineral phases occurring in contaminated soils can be solubilized by organic chelators excreted by plants, such as citrate. Herein, the efficiency of citrate towards U and Pu extraction is compared to that of siderophores, whose primary function is the acquisition of iron(III) as an essential nutrient and growth factor for many soil microorganisms. To that end, we selected desferrioxamine B (DFB) as an emblematic bacterial trishydroxamic siderophore and a synthetic analog, abbreviated (LCy,Pr)H2, of the tetradentate rhodotorulic acid (RA) produced by yeasts. Firstly, the uranyl speciation with both ligands was assessed in the pH range 2–11 by potentiom…
Untersuchung des Solvatationsgleichgewichts im ternären system Tetrachlormethan/Polymethylmethacrylat/Benzol durch kernmagnetische relaxation
1971
Im ternaren System CCl4/Polymethacrylate(PMMA)/Benzol tritt praferentielle Solvatation auf, Benzol ist in der Solvathulle des Polymeren angereichert. Es genugt eine Solvatationsgleichgewichtskonstante, um die praferentielle Solvatation bei variablen Konzentrationsverhaltnissen zu beschreiben. Gemessen wurde die Kernmagnetische Relaxationszeit T1 von Benzol in Abhangigkeit von der Polymerkonzentration. Der Vergleich mit analogen Messungen im System C6D6/PMMA/C6H6 ergibt fur die Solvatationsgleichgewichtskonstante K = (c32 · c10)/(c12 · c30) = 2,5 ± 0,5. Hierbei bedeuten: c10 die CCl4-Konzentrationen im „freien” Losungsmittel, c30 die Benzolkonzentrationen im „freien” Losungsmittel, c12 und c…