Recent highlights in stationary phase design for open-tubular capillary electrochromatography

This review examines the most recent innovations made to achieve high performance in open-tubular capillary electrochromatography (OT-CEC) separations, focusing on the ingenious chemical and physical solutions made to increase the surface area and equip the stationary phase with exploitable selectivity. Among the approaches taken are chemically bonded ligands, etching with chemical bonding, sol-gels, molecularly imprinted polymers, porous layers, physically attached or adsorbed phases, and nanoparticle coatings. Particularly noteworthy are modern developments with macrocyclic receptor ligands, nanoparticles and open channel electrochromatography on-chip.     

Effect of temperature on n-tetradecane emulsion in the presence of phospholipid DPPC and enzyme lipase or phospholipase A2

Zeta potentials and effective diameters of n-tetradecane emulsions in 1 M ethanol were investigated in the presence of 1,2-dipalmitoyl- sn-glycero-3-phosphocholine (DPPC) (1 mg/100 mL), Candida cylindracea lipase (CCL), and phospholipase PLA2 (1 mg/100 mL) at 20, 37, and 45 degrees C. The enzyme was added at the beginning of mechanical emulsion homogenization or 1 min before the end of stirring for 10 min at 10,000 rpm. It was found that DPPC decreases the negative zeta potentials at all three temperatures. The decrease was largest at 20 degrees C and smallest at 45 degrees C. The influence of the enzymes on the zeta potentials depended on the enzyme kind, time of its injection, and temperature. More negative values of the zeta potentials relative to n-C14H30/DPPC droplets were obtained if the lipase was present. Generally, the effective diameters correlate with the zeta potentials, i.e., lower zeta potential corresponds with bigger effective diameter. Possible reasons for the observed changes of the measured parameters are discussed.     

Supramolecular assemblies built with host-stabilized charge-transfer interactions

Host-stabilized charge-transfer (CT) interactions and supramolecular assemblies built with these interactions are described. A variety of supramolecular assemblies including polyrotaxanes, molecular necklaces, and rotaxane dendrimers were synthesized through the intramolecular or intermolecular host-stabilized CT complex formation using cucurbit[8]uril (CB[8]) and D-A molecules having both electron-donor and electron-acceptor units connected by various types of linkers. Applications, including the design and synthesis of redox-driven molecular machines such as molecular loop locks, development of redox-controllable vesicles and detection of biologically important molecules, are also described.     

Potentiometric titrations in methanol/water medium: Intertitration variability

Homogeneous sets of data from strong acid-strong base potentiometric titrations in a mixed solvent medium (9:1 v/v methanol/water), performed by means of the glass electrode, at various constant ionic strengths and with different reference electrodes, have been analysed by statistical criteria. A standardized procedure has been established to obtain reliable potentiometric data in mixed solvents. It has been demonstrated how, with the aid of a proper linearized model, analysis of variance (ANOVA) applied to the standardization titrations can be used to test the reliability of a potentiometric chain in a medium other than pure water. The error expected in the stability constants thus evaluated is related to the intertitration error of the operational pK*(')(w), for the same medium and the same chain. The results obtained by applying ANOVA to the mixed solvent data substantially confirm the trend found for aqueous media, the intertitration error being larger than the intratitration error for all the parameters investigated (E(')(0), pK*(')(w), mean equivalence volume). The stochastic error thus obtained depends on the ionic medium used and on the kind of reference electrode employed in the electrochemical chain.     

Simple radiochemical neutron-activation method for the determination of uranium in ultramafic rocks

A radiochemical neutron-activation method for the determination of trace concentrations of uranium in rocks is described. The method is based on separation of 23·5-min ²³⁹U after alkaline fusion by extraction with tri-n-butyl phosphate from moderately concentrated nitric acid, followed by measurement of the 74-keV γ-ray with a Ge(Li) detector. The limit of detection is 0·2 ng of U under the present conditions, and the precision at the 0·005 ppm level is about 10%. The method is especially useful for determination of uranium in ultramafic rocks.     

Mean activity coefficient of electrolyte solutions

In this paper, we deal with the mean activity coefficient, gamma, of electrolyte solutions. The case gamma < or = 1 is investigated. As is generally recognized, the most accepted models (specific ion interaction/Pitzer theory) have the disadvantage of the dependence on semiempirical parameters. These are not directly accessible from experimental measurements, but can only be estimated by means of best-fitting numerical techniques from experimental data. In the general context of research devoted to the achievement of some reduction of complexity, we propose a model of electrolyte solution that allows us to calculate gamma without using fitting parameters where the (upper) concentration exists at which the electrolyte solution exhibits gamma = 1 (molality scale). In the remaining cases, we show that a unique parameter is required, that is, the concentration that should ideally give gamma = 1 for the electrolyte. Compared to other models that do not require adjustable parameters, the present one is generally applicable over a wider range of concentrations; moreover, it does not impose any restriction on the ion-size variations. Our model follows a pseudolattice approach, starting from the primitive idea of a disordered lattice of solute ions within a continuous solvent at extremely dilute solutions and coming to a disordered lattice of local arrangements of both solute ions and solvent dipoles at higher concentrations. Compared to other theories based on lattice models, this work stresses the role of statistical deviations from any time-averaged (lattice) configuration. All formulas in this paper are applied for 1:1, 2:2, 1:2, and 2:1 aqueous electrolytes at 25 degrees C.     

Co- and counter-current spontaneous imbibition into groups of capillary tubes with lateral connections permitting cross-flow

A model for co- and counter-current imbibition through independent capillaries has already been developed and experiments conducted to verify the theory [E. Unsal, G. Mason, N.R. Morrow, D.W. Ruth, J. Colloid Interface Sci. 306 (2007) 105]. In this paper, the work is extended to capillaries which are connected laterally and in which cross-flow can take place. The fundamental pore geometry is a rod in an angled round-bottomed slot with a gap between the rod and a capping glass plate. The surfaces of the slot, rod and plate form capillaries and interconnecting passages which have non-axisymmetric cross-sections. Depending on the gap size either (i) a large single meniscus, (ii) two menisci one on each side of the rod, or (iii) three menisci, one between the rod and the glass additional to the ones on each side can be formed. A viscous refined oil was applied to one end of the capillaries and co-current and counter-current spontaneous imbibition experiments were performed. The opposite end was left open to the atmosphere for co-current experiments. When the gap between the rod and the plate was large, the imbibing oil advanced into the tubes with the meniscus in the largest capillary always lagging behind the two menisci in the other two smaller capillaries. For counter-current imbibition experiments the open end was sealed and connected to a sensitive pressure transducer. In some experiments, the oil imbibed into the smaller capillaries and expelled air as a series of bubbles from the end of the largest capillary. In other experiments, the oil was allowed to imbibe part way into the tubes before counter-current imbibition was started. The meniscus curvatures of the capillaries have been calculated using the Mayer and Stowe-Princen method for different cell slot angles and gap sizes using a value of zero for the contact angle. These values have been compared with actual values by measuring the capillary rise in the tubes; agreement was very close. A model for co-current and counter-current imbibition has also been developed. The significance of this model is that some hydraulic/capillary properties are common for both co-current and counter-current imbibition. The experiments give an illustration of behavior expected in a real porous material and verify the importance of the 'perfect cross-flow' modification to the 'bundle of parallel tubes' model.     

Bifurcation diagrams and Turing patterns in a chemical self-replicating reaction-diffusion system with cross diffusion

Chemical self-replication of oligonucleotides and helical peptides exhibits the so-called square root rate law. Based on this rate we extend our previous work on ideal replicators to include the square root rate and other possible nonlinearities, which we couple with an enzymatic sink. For this generalized model, we consider the role of cross diffusion in pattern formation, and we obtain exact general relations for the Poincare-Adronov-Hopf and Turing bifurcations, and our generalized results include the Higgins, Autocatalator, and Templator models as specific cases.     

Structure of incommensurate gold sulfide monolayer on Au(111)

We develop an atomic-scale model for an ordered incommensurate gold sulfide (AuS) adlayer which has previously been demonstrated to exist on the Au(111) surface, following sulfur deposition and annealing to 450 K. Our model reproduces experimental scanning tunneling microscopy images. Using state-of-the-art Wannier-function-based techniques, we analyze the nature of bonding in this structure and provide an interpretation of the unusual stoichiometry of the gold sulfide layer. The proposed structure and its chemistry have implications for related S-Au interfaces, as in those involved in self-assembled monolayers of thiols on Au substrates.