Aluminium monoacetate complex formation reaction studied by the pressure-jump method

One of two pressure-jump relaxation processes observed in Al(III) acetate aqueous solution, the slow one, was studied kinetically. The relaxation was ascribed to the Al(III) monoacetate complex formation reaction. The detailed reaction mechanism, including the hydrolysis process, was revealed, and the rate constants were obtained.     

Interfacial nucleic acid chemistry studied by acoustic shear wave propagation

Acoustic wave devices have continued to gain attention as biosensor structures because of their relative ease of operation and sensitivity to interfacial biochemical events. In the present paper, we review the use of the thickness-shear mode device for the label-free detection of processes involving nucleic acid moieties that are imposed at the sensor-liquid interface. Following a concise discussion of the theory and technology connected to the operation of the sensor in liquids, we outline a number of protocols that have been adopted for the attachment of oligonucleotides to sensor surfaces, many of which have been employed in ultrasonic biosensing. The various categories of applications are then surveyed in some detail. By far, the largest group is the study of duplex formation at the sensor surface, involving a compendium of experiments involving complementary and mismatched sequences. Considerably less attention has been paid to the detection of interaction of surface-bound nucleic acids with small molecules such as specific-binding peptides and drugs.A comprehensive appraisal of the literature in this field strongly suggests that acoustic coupling phenomena are particularly sensitive to interfacial physical chemistry. Accordingly, acoustic shear wave technology offers unique advantages over other sensor configurations because of its ability to produce multidimensional information through the recording of various parameters obtained from acoustic network analysis.     

Interfacial reactivity of monolayer-protected clusters studied by scanning electrochemical microscopy

Solutions of monodisperse monolayer-protected clusters (MPCs) of gold can be used as multivalent redox mediators in electrochemical experiments due to their quantized double-layer charging properties. We demonstrate their use in scanning electrochemical microscopy (SECM) experiments wherein the species of interest (up to 2-electron reduction or 4-electron oxidation from the native charge-state of the MPCs) is generated at the tip electrode, providing a simple means to adjust the driving force of the electron transfer (ET). Approach curves to perfectly insulating (Teflon) and conducting (Pt) substrates are obtained. Subsequently, heterogeneous ET between MPCs in 1,2-dichloroethane and an aqueous redox couple (Ce(IV), Fe(CN)63-/4-, Ru(NH3)63+, and Ru(CN)64-) is probed with both feedback and potentiometric mode of SECM operation. Depending on the charge-state of the MPCs, they can accept/donate charge heterogeneously at the liquid-liquid interface. However, this reaction is very slow in contrast to ET involving MPCs at the metal-electrolyte interface.     

Intercomparison of slip flow velocity measurements of filled polymers by capillary extrusion rheometry

Slip flow can complicate both the measurement of the shear flow behaviour of polymers and the modelling of moulding processes. However, the understanding of the reliability of methods for measuring slip flow behaviour is limited. The results of an intercomparison on the measurement of slip flow behaviour by capillary extrusion rheometry of two polymer melts—a filled high-density polyethylene and a filled ethylene–vinyl acetate copolymer—are reported. Slip velocities were calculated, following the Mooney method, from the dependence of the shear stress–shear rate behaviour on the extrusion die diameter. Both compounds exhibited wall slip: in one case the slip velocity accounted for ≈80% of the total flow rate. Slip velocity results were typically within ≈±20% of the average values for the materials, although scatter up to ≈±40% was obtained for one material at high shear stresses. An analysis of slip velocity measurements indicated that uncertainties of 40–50% are typical (95% confidence level) although significantly higher uncertainties could result if testing conditions (primarily die diameters) are not optimised.     

Bovine serum albumin unfolding at the air/water interface as studied by dilational surface rheology

Measurements of the surface dilational elasticity close to equilibrium did not indicate significant distinctions in the surface conformation of different forms of bovine serum albumin (BSA) in a broad pH range. At the same time, the protein denaturation in the surface layer under the influence of guanidine hydrochloride led to strong changes in the kinetic dependencies of the dynamic surface elasticity if the denaturant concentration exceeded a critical value. It was shown that the BSA unfolding at the solution surface occurred at lower denaturant concentrations than in the bulk phase. In the former case, the unfolding resulted in the formation of loops and tails at surface pressures above 12 mN/m. The maximal values of the dynamic surface elasticity almost coincided with the corresponding data for the recently investigated solutions of β-lactoglobulin, thereby indicating a similar unfolding mechanism.     

Strong complex formation of carbohydrates with metal ions at alkaline pH studied by ligand exchange chromatography

Summary At alkaline pH, carbohydrates are highly retained on a sulphonated polystyrene resin loaded with rare earth or uranyl metal ions. The complex formation is governed by the ionization of the carbohydrate moiety. pH and the type of metal ion were found to have a decisive influence on the complex formation. Binding of the metal ion to the cation exchanger and to different carbohydrates is described. The competitive complexation between solute and hydroxide to the metal ions is described as a ligand exchange reaction and a retention model is proposed. The ligand exchange column was used as precolumn in a coupled column separation system and the high selectivity is demonstrated by the separation of paracetamol glucuronide from a urine sample after filtration and direct injection.     

Interfacial polycondensation of nylon-6,6 in microgravity as studied by free-fall experiments

Nylon-6,6 vesicles are synthesized by the interfacial polycondensation of hexamethylenediamine and adipoyl chloride in microgravity, and their size and shape are compared with those formed in normal gravity. Two methods are applied for the nylon syntheses. First, a carbon tetrachloride solution of adipoyl chloride (AC) is sprayed into an aqueous solution of hexamethylenediamine (HD) in a reaction column from the nozzle at the bottom of the column, and inversely HD solution is sprayed into the AC solution column. Nylon vesicles containing the solvent inside are formed. In the second method, both of the reaction solutions are sprayed in an air column and the reaction proceeds by the collision of both mists. For both methods, the reaction is followed by the transmitted-light intensity of the reaction mixture. Furthermore, the products are analyzed by microscopic observation. The nylon vesicles were not completely spherical in most cases, even if formed in microgravity. However, the size and the aspect ratio of the vesicles in microgravity are always smaller than those in normal gravity.     

Interfacial electron transfer energetics studied by high spatial resolution tip-enhanced Raman spectroscopic imaging

Interfacial electron transfer (ET) in TiO?-based systems is important in artificial solar energy harvesting systems, catalysis, and in advanced oxidative waste water treatment. The fundamental importance of ET processes and impending applications make the study of interfacial ET a promising research area. Photoexcitation of dye molecules adsorbed on the surface of wide band gap semiconductors, such as TiO?, results in the injection of electrons from the dye molecules to the conduction band of the semiconductor or energetically accessible surface electronic states. Using Raman spectroscopy and ensemble-averaging approaches,t he chemical bonding and vibrational relaxation of the ET processes have been extensively studied. However, due to the complexity of the interfacial ET energetics and dynamics, significant questions remain on characterizing the source of the observed complexities. To address these important issues, we have applied advanced spectroscopic and imaging techniques such as confocal and tip-enhanced near-field Raman as well as photoluminescence spectroscopic and topographic imaging. Here we explore single surface states on TiO? as well as the interfacial electronic coupling of alizarin to TiO? single crystalline surfaces.     

Interfacial dilational rheology properties of films formed at the oil/water interface by reaction between tetrameric acid and calcium ion

This article aims to determine the applicability of interfacial dilational rheology to study the formation of viscoelastic film at the oil/water interface by reaction between tetrameric acids ARN and calcium ions, and to determine the influence of asphaltenes and naphthenic acids (NA) on this film. It was first found that the formation of viscoelastic film by reaction between ARN and calcium ions is easily observed by dilational rheology: Significantly high values of E′ (130?mN/m) were measured for this system at low ARN concentration (10?µM). These values are at least 5 to 10 times higher than values obtained for ARN without Ca²⁺ or other crude oil components such as asphaltenes and naphthenic acids.

The influence of asphaltenes and NA on the viscoelastic film formation has been studied. When asphaltenes or NA are present, the interfacial viscoelastic film is weakened: There is a gradual decrease of E′ and E″ when the asphaltenes or NA concentration increases. These two components can therefore inhibit the ARN/Ca²⁺ film formation. This decrease is similar to the one previously observed by shear rheology. Several explanations are proposed.     

The interfacial dilational properties of hydrophobically modified associating polyacrylamide studied by the interfacial tension relaxation method at an oil-water interface

The interfacial dilational viscoelastic properties of hydrophobically associating block copolymer composed of acrylamide (AM) and a low amount of 2-phenoxylethyl acrylate (POEA) (<1.0 mol%) at the octane-water interfaces were studied by means of the interfacial tension relaxation method. The dependencies of interfacial dilational elasticity and viscous component on the dilational frequency were investigated. The interaction of hydrophobically associating block copolymer [P(AM/POEA)] with sodium dodecyl sulfate (SDS) has been explored. The results show that at lower frequency, the dilational elasticity for different concentration copolymer is close to zero; at higher frequency, the dilational elasticity shows no change with increased frequency; At moderate frequency (10(-3)-1 Hz), the dilational elasticity decreased with a decrease in the dilational frequency. The results show that the hydrophobic groups of [P(AM/POEA)] chains can be associated by inter- or intrachain liaisons in water solution. The dilational viscous component for P(AM/POEA) comes forth a different maximum value at different frequencies when the polymer concentration is different. It is generally believed that the dilational viscous component reflects the summation of the various microscopic relaxation processes at and near the interface and different relaxation processes have different characteristic frequencies. The spectrum of dilational viscous component may appear more than once maximum values at different frequencies. The influence of SDS on the limiting dilational elasticity and viscous component for polymer solution was elucidated. For 5000 ppm polymer solution, the limiting dilational elasticity decreased with an increase in SDS concentration. The dilational viscous component passed through a maximum value with a rise in the dilational frequency, which appeared at different frequency when SDS concentration is different; and the higher is the concentration, the lower is the dilational frequency. It can be explained that macromolecules may be substituted by SDS molecules in the interface and the interaction of molecules decrease, which makes the limiting dilational elasticity decrease. For 200 ppm polymer solution, the limiting dilational elasticity increased firstly and then decreased with SDS concentration increasing. This may be explained that the interfacial polymer concentration is so low that SDS molecules absorbed in the interface dominate dilational properties of the interfacial film even at very low SDS concentration. However, SDS molecules can gradually substitute the polymer molecules in the interface with a rise in SDS concentration, which results in the decrease in the limiting dilational elasticity.     

Determination of citric acid by means of competitive complex formation in a flow injection system

A photometric method for the determination of citrate and other organic acids based on their ability to complex Fe³⁺-ions is presented. The red colored complex of [Fe(SCN)₂]⁺, used as reagent, is destroyed upon contact with the sample because the organic acid complexes the Fe³⁺-ion. The decrease in absorption is monitored at 460 nm. The reaction is carried out in a simple flow injection system either in single or preferably double channel configuration.The influence of pH was investigated. Best results were obtained by adjusting the carrier stream to pH 2.0–2.5 with a KCl/HCl-buffer. With an increasing concentration of reagent the linear range is shifted to higher citrate concentrations. The slope of the calibration graph and the linear range are influenced by the sample volume. Other variations of parameters include flow rate, reactor volume and diameter of tubing. Generally speaking, optimum conditions for the flow system are not specified because they vary with the application.The typical conditions for a calibration graph from 1 to 8 mmol/l citrate were a reagent concentration of 2.6 mmol/l [Fe(SCN)₂]⁺, a flow rate of 2.4 ml/ min, a reactor length of 50 cm with tubing of 0.97 mm inner diameter and a sample volume of 100 l. At these system settings the coefficients of variation were 2.5% and 1.6% for eight replicate measurements of samples containing 4 mmol/l and 8 mmol/l citrate, respectively. Up to 180 samples can be analyzed per hour.Naturally the method is disturbed by all other ions that form complexes or precipitates with Fe³⁺-ions. Therefore its application is limited to samples with a known matrix, which was given in the analysis of citrate in lemon flavored soft drinks, where the citric acid usually accounts for 95 to 99% of the total acidity and other interfering ions are absent.     

Interfacial electron transfer dynamics in dye-modified graphene oxide nanosheets studied by single-molecule fluorescence spectroscopy

Graphene oxide (GO) nanosheets have received a great deal of attention for a wide range of applications from optoelectronic devices to biological sensors. We now report a mechanistic study of the interfacial electron transfer (ET) processes between organic dye molecule, 9-phenyl-2,3,7-trihydroxy-6-fluorone (PF), and nanometre-sized GO sheets using ensemble-averaged and single-molecule spectroscopies. The ET dynamics was characterized by the direct observation of the PF radical cation during the laser flash photolysis, and its reaction rate was determined to be ~10(11) s(-1). The single-molecule fluorescence spectroscopy was utilized to clarify the heterogeneous nature of the interfacial ET within individual composites. Their fluorescence lifetimes and spectra were found to vary from composite to composite, possibly due to the different local structures and molecular interactions. The autocorrelation analysis of fluorescence intensity trajectories also revealed the temporal fluctuation of the ET reactivity.     

Thermal behaviour of carbohydrates studied by heat flow calorimetry

The technique of heat flow calorimetry was used to study the thermal behaviour of different carbohydrates between 20°C and 270°C. The samples were analyzed by heating in sealed cells. The temperature range in which exothermic reactions, due to thermal decomposition, occurred varied widely depending on the type of carbohydrate investigated. Reaction enthalpies of 44 sugars and polysaccharides are given. Endothermic phenomena, such as fusion or vaporization of crystallized water, were also observed: fusion temperatures and enthalpies of 34 sugars and sugar alcohols are listed. Calorimetric curves showing crystallization of amorphous sucrose, cellobiose and lactose are also presented.

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Zusammenfassung Die Technik der Wärmeleitungs-Kalorimetrie wurde zur Untersuchung des thermischen Verhaltens von verschiedenen Kohlenhydraten zwischen 20°C und 270°C eingesetzt. Die Muster wurden in dicht verschlossenen Kapseln erhitzt. Der Temperaturbereich, in welchem exotherme Reaktionen infolge thermischer Zersetzung abliefen, änderte sich stark in Abhängigkeit vom untersuchten Kohlenhydrattyp. Reaktionsenthalpien von 44 Zuckern und Polysacchariden wurden ermittelt. Endotherme Phänomene, wie das Schmelzen oder das Verdampfen von Kristallwasser wurden auch beobachtet. Schmelztemperaturen und Schmelzenthalpien von 34 Zuckern und Zuckeralkoholen sind tabelliert. Kalorimetrische Daten der Kristallisation amorpher Saccharose, Cellobiose und Lactose werden diskutiert.

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20 270°C. . , . 44 . , . 34 . , , .

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The authors greatly acknowledge many discussions with P. Würsch, R. F. Hurrell and J. Löliger and the technical assistance of F. Michel, Ph. Roulet and S. Reimann.     

Optical resolution by inclusion complex formation

Novel optical resolutions of guest compounds by inclusion complex formation with optically active host compound are reviewed. Tertiary acetylenic alcohols, cyanohydrins, and secondary alcohols were resolved by complexation with alkaloids such as brucine or sparteine. Cycloalkanones, 2,3-epoxycyclohexanones, and some other neutral compounds were resolved by complex formation with optically active diacetylenic diol. Mutual optical resolution of bis--naphthol and sulfoxides by complex formation was also reviewed.     

Gelation in aqueous solutions of carboxylated polyacrylamide in the presence of chromium(III) acetate,studied by oscillation rheometry

The time dependences of the elastic moduli and loss moduli of aqueous solutions of Alcoflood-254S carboxylated polyacrylamide, containing chromium(III) acetate as a cross-linking agent, were studied by oscillation rheometry in the temperature interval 50–80°?. The gel time increases with a decrease in the temperature, as well as in the concentration of the polymer and cross-linking agent. The elastic properties of hydrogels at the moment of the onset of their formation, characterizing the concentration of cross-links between the macromolecules, are due to the polymer concentration in the solution and are independent of the chromium(III) acetate concentration and temperature. Presumably, equal degree of conversion in the reaction between carboxylate groups of the polymer and chromium(III) ion, leading to cross-linking of macromolecules of carboxylated polyacrylamide, allows determination of the kinetic parameters of the gelation from data obtained by oscillation rheometry under nonisothermal conditions.     

Inclusion complex formation of α- and β-cyclodextrins with aminobenzoic acids in aqueous solution studied by 1H NMR

Complex formation of α- and β-cyclodextrins with para- and meta-aminobenzoic acids in water at 298.15 K was studied by ¹H NMR. The formation of 1:1 inclusion complexes in all systems under consideration was observed. Stability constants of the complexes and chemical shift difference induced by 100% complex formation were calculated. The obtained results were discussed in terms of influence of the cyclodextrin cavity size and position of the side amino group in the aromatic ring of aminobenzoic acid molecule on the binding mode and the complex stability.