Small molecule adsorption on to polyester capillary‐channeled polymer fibers: Frontal analysis of naphthalene and naphthol (naphthalene and naphthol adsorption on capillary‐channeled polymer fibers)

Frontal analysis was carried out employing poly(ethylene‐terephthalate) capillary‐channeled polymer fibers as the stationary phase for the immobilization of low‐molecular‐weight polycyclic aromatic hydrocarbon compounds (naphthol and naphthalene) from 2% methanol/water solutions. The effects of several experimental parameters on the frontal profile, the breakthrough volume, and the equilibrium parameters were determined for each solute. The amount adsorbed at exhaustion of naphthalene and naphthol was also compared. The kinetics and thermodynamics were maintained at relatively fast flow rates/linear velocities (～6–18 mm/s). Comparisons of dynamic capacity revealed that naphthalene was more retained than naphthol, in most situations more than five times that of the naphthol adsorption. This increase in capacity is most likely due to the multilayering of naphthalene on the surface of the fibers through π–π interactions between the solute and the fiber surface and successive layering of solute molecules. The extent of layering is a function of the flow, with faster flow rates (and subsequent shear forces) reducing the extent of adsorbate–adsorbate interactions. Although the overall loading capacity of the capillary‐channeled polymer fibers is far below porous phases, there are a number of attractive attributes that support further development.     

Capillary zone electrophoresis: Effect of physical parameters on separation efficiency and quantitation

Separation efficiency in capillary zone electrophoresis was examined as a function of capillary length and diameter as well as solute concentration for a borosilicate glass capillary/phosphate buffer system. Electroosmotic flow coefficients in borosilicate, fused silica, and teflon capillaries were measured over the useful operating pH range of 3–8 at constant applied power (0.333 W). Sample introduction by a simple, low-dispersion electromigration method was found to be a reliable procedure for solute quantitation.     

Solute distribution coupled with laminar flow in wide-bore capillaries: what can be separated without chemical or physical fields?

Solute diffusion coupled with an orthogonal laminar flow has been systematically studied with wide-bore capillaries to establish its limitations and reveal its potentials as separation methodology requiring neither chemical nor physical interactions. Simulations based on the advection-diffusion equation in a cylindrical coordinate system indicate several important features of this potentially useful method: (1) if a solute diffuses over the entire cross-section of the capillary before it is eluted from the capillary, it behaves as a diffusive solute and gives a Gaussian-shaped peak (diffusion peak) having an apex at the traveling time of the average flow; (2) when a solute is poorly (or not) diffusive, a new peak appears with an apex at the elution time of the maximum flow (non-diffusion peak); (3) these two peaks are simultaneously detected for intermediately diffusive solutes; (4) the transformation from the diffusion to non-diffusion peak occurs when the solute diffuses over the distance 0.86 times as large as the capillary radius before it leaves the capillary. These results of simulations are consistent with experimental results for selected solutes having various diffusivities. This method has proved useful particularly for the evaluation of diffusion coefficients of poorly diffusive solutes. Separation of PS particles having different sizes is also attempted.     

On the mathematical model of capillary electrophoresis

Summary The influence of the electroosmotic flow profile on the efficiency of capillary electrophoresis for a wide range of buffer concentrations and capillary diameters is studied. Thermal effects in the capillary, the finite size of solute molecules and their interactions with the capillary wall are also taken into consideration. The dependence of capillary electrophoresis efficiency and resolution on the zeta-potential values is investigated.Presented at the 19^th ISC, Aix-en-Provence, France, September 13–18, 1992.     

Characterization of a microscale cyclical electrical field flow fractionation system

A microscale cyclical electrical field flow fractionation (CyElFFF) channel is characterized with regard to the effect of various operating parameters and comparison made to recent theoretical developments. Challenges associated with various operating conditions are reported along with some of the optimized operating parameters. The effect of retention wall choice, an offset voltage, relaxation steps, and flow rates, along with the basic operating parameters of voltage, frequency, and electrophoretic mobility are reported. Retention of polystyrene nanoparticle standards is accomplished and the first separations using this technique in a microscale system are also demonstrated. Relaxation steps and offset voltages are found to be effective in eliminating early peaks and in improving plate heights. Plate heights were also found to decrease with increasing flow rates, which is the opposite of the behavior seen in most existing chromatographic systems. The experimental results are compared to the analytical and empirical models of CyElFFF and found to be compatible. Suggestions are made for improving the separation and analysis methods used with CyElFFF.     

Optimal separation times for electrical field flow fractionation with Couette flows

The prediction of optimal times of separation as a function of the applied electrical field and cation valence have been studied for the case of field flow fractionation [Martin M., Giddings J. C., J. Phys. Chem. 1981, 85, 727] with charged solutes. These predictions can be very useful to a priori design or identify optimal operating conditions for a Couette-based device for field flow fractionation when the orthogonal field is an electrical field. Mathematically friendly relationships are obtained by applying the method of spatial averaging to the solute species continuity equation; this is accomplished after the role of the capillary geometrical dimensions on the applied electrical field equations has been assessed [Oyanader M. A., Arce P., Electrophoresis 2005; 26, 2857]. Moreover, explicit analytical expressions are derived for the effective parameters, i.e. diffusivity and convective velocity as functions of the applied (orthogonal) electrical field. These effective transport parameters are used to study the effect of the cation valence of the solutes and of the magnitude of the applied orthogonal electrical field on the values of the optimal time of separation. These parameters play a significant role in controlling the optimal separation time, leading to a family of minimum values, for particular magnitudes of the applied orthogonal electrical field.     

Poly(vinyl alcohol) hydrogels: their synthesis and steps towards control of electroendosmosis

Poly(vinyl alcohol) (PVAl) hydrogel networks cross-linked with glutaraldehyde were prepared and their properties as membranes examined using a variety of techniques including preparative electrophoresis. Electroendosmosis (EEO) was observed and shown to be the result of charges on the membrane and of complexation with borate buffer ions. Investigation of "glutaraldehyde" solutions showed acid entities in, or formed in "glutaraldehyde" were responsible for EEO. Techniques for using "glutaraldehyde" which minimize EEO are described.     

Role of geometrical dimensions in electrophoresis applications with orthogonal fields

The role of geometrical dimensions in electrophoresis applications with axial and orthogonal (secondary) electric fields is investigated using a rectangular capillary channel. In particular, the role of the applied orthogonal electrical field in controlling key parameters involved in the effective diffusivity and effective (axial) velocity of the solute is identified. Such mathematically friendly relationships are obtained by applying the method of spatial averaging to the solute species continuity equation; this is accomplished after the role of the capillary geometrical dimensions on the applied electrical field equations has been studied. Moreover, explicit analytical expressions are derived for the effective parameters, i.e., diffusivity and convective velocity as functions of the applied (orthogonal) electric field. Previous attempts (see Sauer et al., 1995) have only led to equations for these parameters that require numerical solution and, therefore, limited the use of such results to practical applications. These may include, for example, the design of separation processes as well as environmental applications such as soil reclamation and wastewater treatment. An illustration of how a secondary electrical field can aid in reducing the optimal separation time is included.     

Formation of coffee stains on porous surfaces

During the drying of drops of nanoparticle suspensions, segregation can occur by internal fluid flows toward the contact line, if the contact line is pinned. This leads to a characteristic ring deposit or coffee stain. On solid substrates coffee staining can be eliminated through the use of solvent mixtures that promote Marangoni flows to oppose these drying-induced flows. Here it is shown that a suspension, optimized to eliminate the formation of coffee stains on a range of solid surfaces, shows coffee staining on a number of porous surfaces. This behavior is shown to be consistent with a mechanism of fluid removal through capillary flow (draining) of the solvent into the porous substrate, combined with filtration of the particles by the small pore size, in addition to the flow from solvent evaporation. The extent of capillary driven coffee staining is a function of substrate pore size: if the pore size is small, capillary flow is slow, reducing the observed coffee staining. However, if the pore size is too large, the nanoparticles are absorbed into the material along with the draining solute and no deposition of particles is observed.     

Modeling of combined electroosmotic and capillary flow in microchannels

In the present study, theoretical model for the transient response of a capillary flow under the combined effects of electroosmotic and capillary forces at low Reynolds number is presented. The governing equation is derived based on the balance among the electrokinetic, surface, viscous and gravity forces. A non-dimensional transient governing equation for the penetration depth as a function of time is obtained by normalizing the viscous, gravity and electroosmotic forces with surface tension force. A new non-dimensional group for the electroosmotic force, E_o, is obtained through the non-dimensional analysis. This new non-dimensional group is a representation of combined electroosmosis and surface tension, i.e., capillarity. The numerical solution of governing equation is obtained to study the effect of different operating parameters on the flow front transport. In a combined flow, it is observed that the flow with positive and low negative magnitude E_o numbers, the attainment of equilibrium penetration depth is similar to a capillary flow. In case of high negative magnitude E_o numbers, complete filling of the channel is observed. The electrolyte with lower permittivity delays the progress of the flow front whereas a large EDL transports the electrolyte quickly. Higher viscous and gravity forces also delay the transport process in the combined flow. This model suggests that in combined flow the electrokinetic parameters also play an important role on the capillary flow and experiments are required to confirm this electrokinetic effect on capillary transport.     

Capillary zone electrophoresis in laboratory-made fluorinated ethylene propylene capillaries

Capillaries made of fluorinated ethylene propylene (FEP) with an inner diameter of 50 microm have been employed in capillary zone electrophoresis with UV-Vis absorbance detection. The capillaries were made in the laboratory with a recently developed technique using fluoropolymer heat shrink/melt tubing and a tungsten wire as a template for the channel. An electroosmotic flow was obtained in the channels and it is shown that an FEP capillary is more effective for a cationic test solute than a fused-silica capillary. The compatibility of FEP capillaries with optical detection is evaluated briefly.     

弛豫理论对离子交换毛细管电色谱中峰压缩现象的研究

 在毛细管电色谱中,由于溶质在输运过程中所具有的电性质,常会产生一些特殊的现象。这些现象,如离子交换毛细管电色谱中产生超高柱效峰的现象,已经不能用一般的色谱理论加以解释。基于弛豫理论所建立的基本模型,在考虑溶质在两相中皆有可能发生正、反向迁移的情况下,得到了流出曲线一阶原点矩和二阶中心矩的理论表达式,并通过对溶质在两相中电扩散速率与电泳速率、电渗流速率关系的分析结果证实:溶质在固定相表面的电扩散行为可以使其保留变弱,出峰加快;而这种电扩散导致的超常柱效峰的出现具有不稳定性,只有在多方面因素综合影响匹配的情况下才可能出现。     

Capillary supercritical fluid chromatography-mass spectrometry

Capillary supercritical fluid chromatography and its combination with mass spectrometry (SFC-MS) is an important analytical methodology for the analysis of thermally labile and high molecular weight compounds. The mass spectrometer provides sensitive and highly selective detection for the chromatographic effluent. The same physical-chemical properties of supercritical fluids that provide important chromatographic advantages are also important for the transport and gas phase introduction of analyte molecules into the mass spectrometer. The low mobile phase flow rates of small diameter (< 100 μm i.d.) capillary columns allow the total chromatographic effluent to be introduced with conventional, but often slightly modified, ion source configurations for quadrupole mass spectrometers with either electron impact (EI) or chemical ionization (CI) detection. The full range of CI reagents can also be used to obtain additional selectivity and complementary structural data. The instrumentation and operating parameters for capillary SFC-MS methods are described. The applicability and usefulness of various SFC-MS analysis methods are demonstrated using a variety of samples.     

Instrument-induced effects in the analysis of polycyclic aromatic compounds by capillary gas chromatography with atomic emission detection (GC-AED)

Peak splitting of high molecular weight polycyclic aromatic compounds originating from the microwave plasma of an atomic emission detector (AED) coupled to a GC has been described and evaluated. The influence of the solute structure, solute concentration, and physical conditions in the AED (such as detector temperature, make-up gas flow, concentration of reagent gases and distance of column end from the plasma) have been studied. An explanation is presented for peak splitting, which is based on an insufficient solute decomposition and solute mass flow in the discharge tube. Modification of the instrument by introduction of additional make-up gas applied through the transfer line has been shown to improve peak shape and solute response.     

Parameters influencing separation and detection of anions by capillary electrophoresis

Electrolyte composition is critical in optimizing separation and detection of ions by capillary electrophoresis. The parameters which must be considered when designing an electrolyte system for capillary electrophoresis include electrophoretic mobility of electrolyte constituents and analytes, detection mode, and compatibility of electrolyte constituents with one another. An electrolyte system based on pyromellitic acid is well suited for use with indirect photometric detection, and provides excellent separations of anions. The ability to modify the electrophoretic mobility of pyromellitic acid as a function of ph provides flexibility in matching electrophoretic mobilities of analytes. Additionally, the use of alkyl amines as electroosmotic flow modifiers allows the rapid separation of anions by reversing the direction of electroosmotic flow in a fused-silica capillary. The optimization of a capillary electrophoresis electrolyte for anion analysis is also discussed in terms of pH, ionic strength and applied voltage. The effect of organic solvent on separation selectivity is also discussed.     

Supercritical fluid extraction-capillary gas chromatography: On-line coupling with a programmed temperature vaporizer

A simple and versatile system is described for the on-line coupling of SFE to capillary GC. The interfacing consists of a programmed temperature vaporizer (PTV) injector. With this injector it is possible to combine solute trapping, elimination of a high flow of extraction fluid, and quantitative transfer of solutes to the seperation column. The problems caused by impurities in the extraction fluid in on-line SFE-GC are discussed. Simple methods are described for the purification of commercially available carbon dioxide. The trapping efficiency of the PTV injector is studied. Applications of the SFE-PTV-GC system are given for the analysis of polymer anti-degradants, polar compounds, and samples with environmental relevance.     

Dual Adsorber-Capillary Column System for Gas Chromatographic Analysis of Air Samples

Abstract

An interface which allows thermal desorption and subsequent capillary gas chromatographic analysis of air samples is described. A small solid-sorbent trap is positioned between the sampling tube and capillary column. A sample thermally released from the sampling tube is transferred by a carrier gas at high flow rate to the trap and retained. From there it is again thermally released and transferred to the capillary column by carrier gas at a low flow rate, as required by capillary GC. The transfer and injection steps are effected by means of externally placed solenoid valves. The performance of the system depends on the desorption temperature and time allowed for transfer of the sample between the two adsorbers and the column. These parameters are programmable and can be changed to suit the requirements of a particular analysis. The system allows the analysis of sub-parts-per-billion concentrations of organic compounds in a comparatively simple and reproducible manner. Operation of the system does not require cryogenic cooling of either the trap or the GC oven. Chromatograms of a variety of air samples are presented and discussed.     

Enantiomer elution order reversal of fluorenylmethoxycarbonyl-isoleucine in high-performance liquid chromatography by changing the mobile phase temperature and composition

In this paper the elution order reversal of enantiomers of fluorenylmethoxycarbonyl- or FMOC-isoleucine is described depending on the separation temperature and composition of the mobile phase when using the polysaccharide-based chiral column Lux Cellulose-1 in HPLC with normal-phase eluent. Reversal of the enantiomer elution order (EEO) in HPLC depending on the column temperature and content of the polar modifier in the mobile phase has been reported before in the literature. However, EEO reversal by changing the content of acidic modifier in the mobile phase seems to be described for the first time in the present work.     

Quantitative gas chromatographic analysis of hydrocarbon systems using the lovelock diode detector and capillary columns

The application of gas chromatography using capillary columns and the lovelock diode detector to the quantitative analysis of a variety of hydrocarbons in the C₆—C₁₂ molecular weight range is described. The hydrocarbons studied include aliphatics, aromatics, alicyclics, and olefinics. With these molecules and in this molecular weight range, excellent quantitative results are easy to achieve. The response of the lovelock diode under the conditions employed is such that an excellent agreement between weight per cent in the sample and area per cent on the chromatogram exists. The operating parameters of the capillary-diode system have been studied. It has been found that sample size and scavenger flow rate are the only critical parameters controlling quantitative results.