A continuous-flow instrument for the determination of linear polyacrylamide stability

Alkaline hydrolysis of high-molecular-mass (10 MDa) linear polyacrylamide, a widely used replaceable sieving medium for the capillary electrophoresis of DNA fragments and proteins, was investigated. The release rate of ammonia, a product of amide group hydrolysis, was monitored by a high-sensitivity continuous-flow system. The experimental results show a rapid onset of hydrolysis at a temperature of 70 degrees C. While the degree of 1 h hydrolysis was evaluated to reach about 16% at 70 degrees C and pH 13, it drops to 5% at 50 degrees C and pH 12.5.     

Unsteady transport phenomena in free-flow electrophoresis--prerequisite of ultrafast sample cleaning in microfluidic devices

The evolution partial differential equations describing the transport processes induced by hydrodynamic flow in free-flow electrophoresis (FFE) are solved by the generalized dispersion theory. Our theoretical analysis demonstrates that the central injection of solutes into a relatively fast hydrodynamic flow enables to transport them to the channel outlet well before they are spread through the width of the channel and their migration is negatively affected by a contact with walls. In this case, the axial zone spreading decreases by increasing the linear velocity of hydrodynamic flow. The resulting dependencies of convective and dispersion coefficients on the velocity of flow and parameters of the separation channel show the optimum separation conditions with respect to resolution and analysis time. Due to the unsteady character of transport processes, effective FFE separations can potentially be performed in a microfluidic device in seconds. This is a reasonable time to separate low-molecular mass impurities in the electric field. Thus, a fast and efficient sample cleaning before subsequent analysis by electrospray ionization-mass spectrometry (ESI-MS) or another separation method can be performed.     

Optimization of a pressurized liquid junction nanoelectrospray interface between CE and MS for reliable proteomic analysis

A pressurized liquid junction nanoelectrospray interface was designed and optimized for reliable on-line CE-MS coupling. The system was constructed as an integrated device for highly sensitive and selective analyses of proteins and peptides with the separation and spray capillaries fixed in a pressurized spray liquid reservoir equipped with the electrode for connection of the electrospray potential. The electrode chamber on the injection side of the separation capillary and the spray liquid reservoir were pneumatically connected by a Teflon tube filled with pressurized nitrogen. This arrangement provided precisely counterbalanced pressures at the inlet and outlet of the separation capillary. The pressure control system was driven by an electrically operated valve and maintained the optimum flow rate for the electrospray stability. All parts of the interface being in contact with the CEBGE, spray liquid and/or sample were made of glass or Teflon. The use of these materials minimized the electrospray chemical noise often caused by plastic softeners or material degradation. During optimization, the transfer of the separated zones between the separation and electrospray capillaries was monitored by UV absorbance and contactless conductivity detectors placed at the outlet of the separation capillary and inlet of the electrospray tip, respectively. This arrangement allowed independent monitoring of the effects of pressure, CE voltage and geometry of the liquid junction on the spreading and dilution of the separated zones after passage through the interface.     

Analytic mappings between noncommutative pencil balls

In this paper, we analyze problems involving matrix variables for which we use a noncommutative algebra setting. To be more specific, we use a class of functions (called NC analytic functions) defined by power series in noncommuting variables and evaluate these functions on sets of matrices of all dimensions; we call such situations dimension-free. These types of functions have recently been used in the study of dimension-free linear system engineering problems (Helton et al. (2009) [10], de Oliviera et al. (2009) [8]). In the earlier paper (Helton et al. (2009) [9]) we characterized NC analytic maps that send dimension-free matrix balls to dimension-free matrix balls and carry the boundary to the boundary; such maps we call “NC ball maps”. In this paper we turn to a more general dimension-free ball BL, called a “pencil ball”, associated with a homogeneous linear pencil

     

Capillary electrophoresis immunoassays with conjugated quantum dots

Water-soluble CdTe quantum dots (QDs) and their conjugates with antibodies and antigenes were prepared by optimized procedures for applications in CE immunoassays. The QD size of 3.5 nm, excitation spectrum in the range of 300-500 nm, the maximum wavelength of the emission spectrum at 610 nm, quantum yield of 0.25 and luminescence lifetimes in the range of 3.6-43 ns were determined. The 0.1 M solution of TRIS/TAPS (pH 8.3) was found to be the optimum buffer for the separation of the antiovalbumin-ovalbumin immunocomplex from the free conjugates of QDs.     

Theoretical background for clinical and biomedical applications of electromigration techniques

This review presents the theoretical principles of analytical electrophoresis. The basic rules which control the movement of ionic species in electrostatic fields, together with the phenomenological theory of the resulting mass transport are analysed. The separation principles and capabilities of zone electrophoresis, isotachophoresis, isoelectric focusing, micellar electrokinetic chromatography and gel electrophoresis are evaluated. The most important effects accompanying electrophoresis, such as the production of Joule heat, electroosmosis and diffusion are discussed.     

Etherification of glycerol with tert-butyl alcohol catalysed by ion-exchange resins

The reaction of glycerol with tert-butyl alcohol in the liquid phase on acid Amberlyst-type ion-exchange resins was studied. The influence of temperature, mole ratio n(TBA)/n(G), water and swelling of gel, and macroreticular type of polymer catalysts on etherification reaction was investigated. The most favourable reaction temperature is 75°C. The conversion of glycerol and yield of glycerol tert-butyl ethers has increased with the mole ratio n(TBA)/n(G). Dry form of macroreticular catalysts provided the best results. Etherification reaction of glycerol with isobutylene in non-aqueous conditions gives the highest yield of desired ethers. The influence of water was studied. The gel forms of ion-exchange resins have very low catalytic activity. It can be concluded that water has an inhibition effect on ion-exchange resins. By comparing the gel and macroreticular forms of Amberlyst ion-exchange resins it can be concluded that very acid forms of macroreticular ion-exchange resins with a high degree of crosslinking are more active catalysts for the studied reaction due to their pores which are sufficiently large so that the voluminous tert-butyl ethers of glycerol can be formed. It was estimated that tert-butyl alcohol as tert-butylation agent is not suitable for etherification of glycerol with the formation of di-and triethers.