ENDOR signal of hydrogen physically adsorbed on activated MgO

A matrix ENDOR signal has been observed for physisorbed molecular hydrogen interacting with trapped-hole surface paramagnetic centres on MgO. The localization of the physisorbed molecules is derived from the matrix ENDOR lineshape.     

Spontaneous desorption of vibrationally excited molecules physically adsorbed on surfaces

The energy within a vibrationally excited physisorbed molecule often exceeds that needed to break its bond to the surface. Energy transfer from the vibrating chemical bond to the surface bond causes the surface bond to rupture and the vibrationally relaxed adsorbate is released from the surface. We present a theoretical model which allows an estimation of the residence time of a vibrationally excited adsorbate on a surface. Because of uncertainties in the nature of the surface bond, the lifetimes obtained from the analytical expressions presented have only qualitative significance. The results are interpreted in terms of Franck-Condon overlaps between the wavefunctions which describe the adsorbate-substrate complex and the released adsorbate. Lifetimes are calculated for hydrogen isotopes adsorbed on sapphire surfaces. Guide-lines are given for estimating lifetimes of other systems in terms of a few easily calculated parameters.Let us summarize this guide to spontaneous desorption of physically adsorbed vibrationally excited molecules. The most efficient desorption processes will occur for adsorbates with a small number of bound states (d₀ small) and when released the adsorbate has small translational momentum (small q_m). This momentum gap correlation is most succinctly revealed by fig. 3. Smaller translational momentum will be achieved if the adsorbate can take up energy into its internal motions. Absorption of energy into lattice modes of the substrate will also serve to reduce the translational momentum and provide for more efficient desorption. However, if the vibrational frequency of the adsorbate is in near resonance with surface polarons or plasmons of the substrate, energy transfer to the solid will be so efficient that desorption will be quenched.A test of these possible relaxation channels awaits the first experimental measurements of desorption of vibrationally excited molecules.     

Flow-injection spectrophotometric determination of paraoxon by its inhibitory effect on the enzyme acetylcholinesterase.

A spectrophotometric enzymatic flow injection (FI) system for the determination of diethyl-p-nitrophenylphosphate (paraoxon) is proposed. The method was based on the determination of the acetic acid formed by the enzymatic reaction of the acetylcholinesterase, immobilized on glass beads, with the substrate acetylcholine. The acetic acid formed permeates through a PTFE membrane and is received by a solution (pH 7.0) containing the acid-base indicator Bromocresol Purple (B.C.P.), leading to a pH change and therefore to a color change. The variation of the absorbance of the solution is detected spectrophotometrically at 400 nm. The determination of paraoxon is related to its inhibitory action on the enzyme. Therefore the analytical signal is the difference between the signal that corresponds to the free and the one that corresponds to the inhibited enzyme, considering a fixed acetylcholine concentration. The correlation between the peak height and paraoxon concentration at a given acetylcholine concentration is linear in the range from 5.0 x 10(-7) mol L-1 to 5.0 x 10(-5) mol L-1 (r = 0.998) of paraoxon, with a relative estimated standard deviation (R.S.D.) of +/- 1.7% (n = 10) considering a solution containing 5.0 x 10(-6) mol L-1 of paraoxon and a solution containing 5.0 x 10(-3) mol L-1 of acetylcholine. Therefore, the quantitative limit detection is about 2.5 x 10(-7) of paraoxon (3 sigma). A 1,1'-trimethylene-bis(4-formylpyridinium bromide)dioxime (TMB-4) solution was used to reactivate the enzyme.     

Determination of carbaryl pesticide using amperometric acetylcholinesterase sensor formed by electrochemically deposited chitosan

A sensitive, fast and cheap sensor for quantitative determination of carbaryl pesticide using amperometric acetylcholinesterase (AChE) sensor based on electrochemically deposited chitosan was reported. From a mildly acidic chitosan solution, a chitosan film is electrochemically deposited on Au electrode surface via a negative voltage bias, leading to a stable AChE sensor. The characteristics of the deposited layer were observed to be dependent upon the deposition time, pH, and the chitosan concentration. Fourier-transform infrared spectra proved that the immobilized enzyme could preserve their native structure due to the excellent biocompatibility and non-toxicity of chitosan. Under the optimal experimental conditions, the carbaryl inhibition on AChE-CHIT/Au was proportional to its concentration in two ranges, from 0.005 to 0.1 μg/ml and 0.5 to 5 μg/ml, with the correlation coefficients of 0.9966 and 0.9982, respectively. The detection limit was 0.003 μg/ml taken as the concentration equivalent to a 10% decrease in signal. The determination of carbaryl in garlic samples obtained from export of farm base showed acceptable accuracy. The developed sensor exhibited good fabrication reproducibility and acceptable stability, which provided a new promising tool for pesticide analysis.     

Fast and easy coating for capillary electrophoresis based on a physically adsorbed cationic copolymer

In this work, a new copolymer synthesized in our laboratory is used as physically adsorbed coating for capillary electrophoresis (CE). The copolymer is composed of ethylpyrrolidine methacrylate (EPyM) and methylmethacrylate (MMA). The capillary coating is easily obtained by simply flushing into the tubing an EPyM/MMA solution. It is demonstrated that the composition of the EPyM/MMA copolymer together with the selection of the background electrolyte (BGE) and pH allow tailoring the direction and magnitude of the electroosmotic flow (EOF) in CE. It is also shown that the EOF obtained for the EPyM/MMA-coated capillaries was reproducible in all cases independently on pH or polymer composition. Thus, RSD values lower than 1.9% (n=5) for the same capillary and day were obtained for the migration time, while the repeatability interdays (n=5) was observed to provide RSD values lower than 0.5%. The stability of the coating procedure was also tested between capillaries (n=3) obtaining RSD values lower than 0.6%. It is demonstrated with several examples that the use of EPyM/MMA coatings in CE can drastically reduce the analysis time and/or to improve the resolution of the separations. It is shown that EPyM/MMA-coated capillaries allow the separation of basic proteins by reducing their adsorption onto the capillary wall. Also, EPyM/MMA-coated capillaries provide a faster separation of samples containing simultaneously positive and negative analytes. Moreover, it is demonstrated that the use of EPyM/MMA-coated capillaries can incorporate an additional chromatographic-like interaction with nucleosides that highly improves the separation of this group of solutes.     

Redox reactions of dissolved substances on amalgamated platinum electrode modified with adsorbed porphyrin

In order to develop the electrodes convenient for investigating the high-rate redox reactions not distorted by a reagent adsorption, the modification of amalgamated Pt electrodes with a monolayer of irreversibly adsorbed porphyrin is studied. A specific feature of applied procedure is that the adsorption was performed at a controlled electrode potential from the aqueous solution, in which porphyrin in a low concentration was solubilized. The adsorbed porphyrin monolayer prevents immediate contact of dissolved reagent with the metal. At the same time, due to a strong electronic interaction of the system of conjugate π-electrons with the metal, the monolayer does not hamper the electronic transfer between the reagent and the electrode.     

The effect of surfactants on adsorbed layers of a cationic polyelectrolyte

A comparative study of the influence of anionic (sodium dodecyl sulfate, SDS), cationic (tetradecyltrimethylammonium bromide, TTAB) and non-ionic (penta-ethyleneglycol mono n-dodecyl ether, C₁₂E₅) surfactants on the structure and composition of adsorbed layers of cationic hydrophobically modified hydroxyethylcellulose (Quatrisoft LM 200) on hydrophilic surfaces (mica and silica) was carried out using surface force apparatus andin situ null ellipsometry. It is shown that a complex interplay of electrostatic, hydrophobic, and steric effect govern polymer/surfactant/surface interactions and that the effect of surfactant addition strongly depends on its nature and concentration.Both anionic and non-ionic surfactants exhibit aggregation on the polymer hydrophobes. SDS has the most profound influence on Quatrisoft interfacial behavior due to the changes in electrostatics accompanying formation of the polymer/surfactant complex. In the case of C₁₂E₅, large surfactant clusters bound to the polymer affect the macromolecules' conformation in the adsorbed layer via steric effects. In contrast to SDS and C₁₂E₅, no evidence of interaction between the polycation and a like-charged surfactant, TTAB, was obtained. At the same time, TTAB adsorbs on the surface in competition with the polyelectrolyte. This results in partial displacement of the latter and its looser attachment to the surface.     

Stable physically adsorbed coating of poly-vinyl alcohol for the separation of basic proteins

In aqueous capillary electrophoresis, the electroosmotic flow can be strongly suppressed by coating the inner surface of the capillary. In the present work hydrophilic coating of 4% polyvinyl alcohol (PVA) has been used for the analysis of basic proteins. The coating is simple and easy to obtain. The separation of ribonuclease and α-chymotrypsin has been uniquely done with other three basic proteins (lysozyme, cytochrome-c and trypsin) using a buffer 11.60 mM sodium acetate and 18.40 mM acetic acid at pH 4.5 in addition to positive power supply of 20 kV at 25°C. Detection was performed using UV detector at 230 nm. The proposed PVA coated capillary provides reproducible separation of five basic proteins within 10 min with RSD values for mobility bellow 1.4% (n = 6) for all the five basic proteins. The stability of coated capillary has been checked up to 40 runs. The viscosity measurement for 4% PVA have been studied and scanning electron microscope (SEM) images obtained to make it compatible with future micro-chip applications.     

Influence of physically adsorbed oxygen on the separation of electron-hole pairs on anatase irradiated by visible light

ESR studies on the formation and properties of O ₂ ^– and [O^–·O₂] ion-radicals under photo-irradiation of oxidized anatase have been performed. The role of physically adsorbed oxygen in the separation of electrone-hole pairs is shown.

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- O ₂ ^– [O^–·O₂], . - .

     

The hydrolysis of phosphoranes in aqueous dioxane

The entropy of activation for the hydrolysis of pentaphenoxyphosphorane in 25% aqueous dioxane is ?188 J/mol deg. The enthalpy of activation is 22.5 kJ/mol, which is small for the relatively slow reaction. This suggests that the reaction is a multistep process having a preliminary equilibrium with a negative heat of reaction. This conclusion is supported by the results obtained for the hydrolysis of C₆H₅ [OCH(CF₃)₂]₂. A kinetic isotope effect k_H2O/k_D2O of 3.46 was found for the latter reaction. Orders in water were obtained, and a mechanism of hydrolysis is proposed.     

Synthesis of benzofuran derivatives via rearrangement and their inhibitory activity on acetylcholinesterase

During a synthesis of coumarins to obtain new candidates for treating Alzheimer's Disease (AD), an unusual rearrangement of a benzopyran group to a benzofuran group occurred, offering a novel synthesis pathway of these benzofuran derivatives. The possible mechanism of the novel rearrangement was also discussed. All of the benzofuran derivatives have weak anti-AChE activities compared with the reference compound, donepezil.     

The effect of polyamidoamine dendrimers on human erythrocyte membrane acetylcholinesterase activity

Polyamidoamine (PAMAM) dendrimers impact on activity of acetylcholinesterase was studied. It has been shown that dendrimers induce a biphasic effect: depending on their concentrations they increase or decrease enzyme activity. It may be due to two types of interactions: direct--between dendrimers and the enzyme; indirect--via a modification of the physical state of membrane phospholipids affecting the acetylcholinesterase.     

Differential-pulse anodic voltammetric determination of dissolved and adsorbed phosphate in turbid natural waters

Orthophosphate in turbid natural waters exists in dissolved and adsorbed forms. Phosphate adsorbed on suspended matter in turbid waters is difficult to determine spectrophotometrically. In the voltammetric method, the peak current is related to the reoxidation of the molybdophosphate complex at a glassy-carbon electrode. This allows the determination of dissolved and adsorbed phosphate at micromolar levels in natural waters, especially turbid waters, with good precision and accuracy.     

Evaluation of the dioxane effect on the dipole moment of malonic acid

The dipole moment of malonic acid has been calculated taking into account its high conformational flexibility. The use of the MNDO method yields, at 25 °C, a value of 2.07 D, which is approximately 0.5 D lower than the values observed in dilute solution in liquid dioxane. A greater difference is obtained at higher temperatures. This result, which can be interpreted in terms of solute-solvent interactions, confirms the tendency of dioxane to increase the dipole moment of compounds dissolved in it. In the present case, the change in the conformational equilibria of malonic acid seems to be the main cause of this difference, whereas the effect of hydrogen bonding between the solute and the solvent is found to be of minor importance.     

The effect of nanopore shape on the structure and isotherms of adsorbed fluids

A Grand Canonical Monte Carlo simulation method is used to determine the adsorption isotherms, interaction energies, entropies, and density distribution of a Lennard-Jones fluid adsorbed in smooth-walled nanopores of varying size and shape. We specifically include very crowded pores, where packing effects are important. Differences in the isotherms of slit, cylindrical, and spherical nanopores of varying sizes can be explained in terms of the adsorbate-adsorbate interaction energy, the adsorbate-pore interaction energy, and the density profiles, which influence the balance between the former and the latter energy contributions. The expectation from low loading studies that the most energetically favorable adsorbate-pore interactions maximize adsorption is not borne out at intermediate and higher loadings. Instead, the relationships between adsorbed amounts and pore size and shape are found to be strong functions of the depth and steepness of the external potential, the extent to which adsorbate-adsorbate repulsion establishes short range fluid order, and the accessible pore volume. This study has implications for high pore density processes in nanoporous materials, such as zeolite catalysis, separations, and templating in zeolite synthesis.     

Connections between structure and performance of four cationic copolymers used as physically adsorbed coatings in capillary electrophoresis

In this work, the properties of four cationic copolymers synthesized in our laboratory are studied as physically adsorbed coatings for capillary electrophoresis (CE). Namely, the four copolymers investigated were poly(N-ethyl morpholine methacrylamide-co-N,N-dimethylacrylamide), poly(N-ethyl pyrrolidine methacrylate-co-N,N-dimethylacrylamide), poly(N-ethyl morpholine methacrylate-co-N,N-dimethylacrylamide) and poly(N-ethyl pyrrolidine methacrylamide-co-N,N-dimethylacrylamide). Capillaries were easily coated using these four different macromolecules by simply flushing into the tubing an aqueous solution containing the copolymer. The stability and reproducibility of each coating were tested for the same day, different days and different capillaries. It is demonstrated that the use of these coatings in CE can drastically reduce the analysis time, improve the resolution of the separations or enhance the analysis repeatability at very acidic pH values compared to bare silica columns. As an example, the analysis of an organic acids test mixture revealed that the analysis time was reduced more than 6-times whereas the separation efficiency was significantly increased to nearly 10-times attaining values up to 595,000 plates/m using the coated capillaries. Moreover, it was shown that all the copolymers used as coatings for CE allowed the separation of basic proteins by reducing their adsorption onto the capillary wall. Links between their molecular structure, physicochemical properties and their performance as coatings in CE are discussed.     

The effect of engineered disulfide bonds on the stability of Drosophila melanogaster acetylcholinesterase

Background  

Acetylcholinesterase is irreversibly inhibited by organophosphate and carbamate insecticides allowing its use in biosensors for detection of these insecticides. Drosophila acetylcholinesterase is the most sensitive enzyme known and has been improved by in vitro mutagenesis. However, its stability has to be improved for extensive utilization.