Determination of vapor pressure of low-volatility compounds using a method to obtain saturated vapor with coated capillary columns

The vapor pressures of O-ethyl S-2-diisopropylaminoethyl methylphosphonothiolate (VX), O-isobutyl S-2-diethylaminoethyl methylphosphonothiolate (RVX), and 2,4-dinitrotoluene (2,4-DNT) were determined with the gas saturation method in temperatures ranging from -12 to 103 degrees C. The saturated vapor was generated using a fused-silica column coated with the compound. This column was placed in a gas chromatograph, and the vapor pressure was determined directly from the detector signal or by sampling on Tenax tubes that were subsequently analyzed. From the linear relationships obtained by plotting log P vs 1/T, the enthalpies of vaporization (deltaHvap) and the vapor pressures at selected temperatures were determined. The vapor pressure of VX at 25 degrees C was 0.110 Pa and the deltaHvap 77.9 kJ x mol(-1). The corresponding results for RVX were 0.082 Pa and 76.6 kJ x mol(-1). The vapor pressure of 2,4-DNT at 72 degrees C (melting point) was determined to 6.0 Pa, and the enthalpies of the solid and the liquid state were 94.2 and 75.3 kJ x mol(-1), respectively. Using capillary columns to generate saturated vapors has three major advantages: short equilibrium time, low consumption of sample, and safe handling of toxic compounds.     

Peak capacity, peak-capacity production rate, and boiling point resolution for temperature-programmed GC with very high programming rates

Recent advances in column heating technology have made possible very fast linear temperature programming for high-speed gas chromatography. A fused-silica capillary column is contained in a tubular metal jacket, which is resistively heated by a precision power supply. With very rapid column heating, the rate of peak-capacity production is significantly enhanced, but the total peak capacity and the boiling-point resolution (minimum boiling-point difference required for the separation of two nonpolar compounds on a nonpolar column) are reduced relative to more conventional heating rates used with convection-oven instruments. As temperature-programming rates increase, elution temperatures also increase with the result that retention may become insignificant prior to elution. This results in inefficient utilization of the down-stream end of the column and causes a loss in the rate of peak-capacity production. The rate of peak-capacity production is increased by the use of shorter columns and higher carrier gas velocities. With high programming rates (100-600 degrees C/min), column lengths of 6-12 m and average linear carrier gas velocities in the 100-150 cm/s range are satisfactory. In this study, the rate of peak-capacity production, the total peak capacity, and the boiling point resolution are determined for C10-C28 n-alkanes using 6-18 m long columns, 50-200 cm/s average carrier gas velocities, and 60-600 degrees C/min programming rates. It was found that with a 6-meter-long, 0.25-mm i.d. column programmed at a rate of 600 degrees C/min, a maximum peak-capacity production rate of 6.1 peaks/s was obtained. A total peak capacity of about 75 peaks was produced in a 37-s long separation spanning a boiling-point range from n-C10 (174 degrees C) to n-C28 (432 degrees C).     

Control of electroosmotic flow and wall interactions in capillary electrophoresis capillaries by photografted zwitterionic polymer surface layers

A novel capillary with covalently bonded zwitterionic surface modification was prepared by photograft polymerization of the zwitterionic monomer N,N-dimethyl-N-methacryloxyethyl-N-(3-sulfopropyl)ammonium betaine, onto the inner surface of a UV-transparent fused-silica capillary. Although the zwitterionic moieties in the resulting polymeric "tentacles" comprise both a positive quaternary ammonium group and a negative sulfonate group, the coating has a net zero charge. The electroosmotic flow (EOF) was therefore extensively suppressed on the grafted capillary compared to the native silica capillary and to the silica capillary that had been activated for graft polymerization by reaction with 3-(methacryloyl)oxypropyltrimethoxysilane. It was also found that the EOF can be varied by adding chaotropic anions or divalent cations such as perchlorate ion and magnesium ion to the running buffer, due to the interaction between these ions and zwitterionic functional group. This provides a new way of altering the EOF and the wall interaction without changing the pH or the overall ionic strength of the separation buffer. The influence of pH and ionic strength of separation buffer on the EOF were also investigated to optimize the separation conditions. Good separations of a mixture containing eight inorganic anions were achieved within 5 min under optimal conditions by capillary zone electrophoresis. The newly prepared capillary was also well suited for the separation of peptides or proteins.     

An etched porous interface for on-line capillary electrophoresis-based two-dimensional separation system

The construction and evaluation of an on-column etched fused-silica porous junction for on-line coupling of capillary isoelectric focusing (CIEF) with capillary zone electrophoresis (CZE) are described. Where two separation columns were integrated on a single piece of fused-silica capillary through the etched approximately 4 to 5-mm length porous junction along the capillary. The junction is easily prepared by etching a short section of the capillary wall with HF after removing the polyimide coating. The etched section becomes a porous glass membrane that allows only small ions related to the background electrolyte to pass through when high voltage is applied across the separation capillary. The primary advantages of this novel porous junction interface over previous designs (in which the interface is usually formed by fracturing the capillary followed by connecting the two capillaries with a section of microdialysis hollow fiber membrane) are no dead volume, simplicity, and ruggedness, which is particularly well suited for an on-line coupling capillary electrophoresis-based multiple dimensional separation system. The performance of the 2D CIEF-CZE system constructed by such an etched porous junction was evaluated by the analyses of protein mixtures.     

Characterization of Nonbonded Poly(ethylene oxide) Coating for Capillary Electrophoresis via Continuous Monitoring of Electroosmotic Flow

We examined changes in a poly(ethylene oxide) (PEO) coating by continuously monitoring the electroosmotic flow (EOF) in a fused-silica capillary during electrophoresis. An imaging CCD camera was used to follow the motion of a fluorescent neutral marker zone along the length of the capillary. The PEO coating was shown to reduce the velocity of EOF by more than 1 order of magnitude compared to a bare capillary at pH 7.0. However, it did not reduce EOF efficiently at pH 8.2. The coating protocol was important, especially at an intermediate pH of 7.7. Capillary reconditioning with an acidified solution of PEO was necessary in order to create a stable and efficient coating. In all cases we observed a gradual increase of EOF during extended runs, suggesting that the coating is slowly being degraded. The increase of pH in the cathodic (detection-end) buffer reservoir beyond pH ～8.0, e.g., as a result of electrolysis, had a large impact on the stability of the coating. This phenomenon may be used for the efficient and fast regeneration of the column surface and provides a simpler and more reliable alternative to pressure flushing of the capillary.     

Monitoring temperature changes in capillary electrophoresis with nanoliter-volume NMR thermometry

Nanoliter-volume proton nuclear magnetic resonance (NMR) spectroscopy is used to monitor the electrolyte temperature during capillary electrophoresis (CE). By measuring the shift in the proton resonance frequency of the water signal, the intracapillary temperature can be recorded noninvasively with subsecond temporal resolution and spatial resolution on the order of 1 mm. Thermal changes of more than 65 degrees C are observed under both equilibrium and nonequilibrium conditions for typical CE separation conditions. Several capillary and buffer combinations are examined with external cooling by both liquid and air convection. Additionally, NMR thermometry allows nonequilibrium temperatures in analyte bands to be monitored during a separation. As one example, a plug of 1 mM NaCl is injected into a capillary filled with 50 mM borate buffer. Upon reaching the NMR detector, the temperature in the NaCl band is more than 20 degrees C higher than the temperature in the surrounding buffer. Such observations have direct applicability to a variety of studies, including experiments which utilize sample stacking and isotachophoresis.     

Speciation of mercury by hydrostatically modified electroosmotic flow capillary electrophoresis coupled with volatile species generation atomic fluorescence spectrometry

A novel method for speciation analysis of mercury was developed by on-line hyphenating capillary electrophoresis (CE) with atomic fluorescence spectrometry (AFS). The four mercury species of inorganic mercury Hg(II), methymercury MeHg(I), ethylmercury EtHg(I), and phenylmercury PhHg(I) were separated as mercury-cysteine complexes by CE in a 50-cm x 100-microm-i.d. fused-silica capillary at 15 kV and using a mixture of 100 mmol L(-1) of boric acid and 12% v/v methanol (pH 9.1) as electrolyte. A novel technique, hydrostatically modified electroosmotic flow (HSMEOF) in which the electroosmotic flow (EOF) was modified by applying hydrostatical pressure opposite to the direction of EOF was used to improve resolution. A volatile species generation technique was used to convert the mercury species into their respective volatile species. A newly developed CE-AFS interface was employed to provide an electrical connection for stable electrophoretic separations and to allow on-line volatile species formation. The generated volatile species were on-line detected with AFS. The precisions (RSD, n = 5) were in the range of 1.9-2.5% for migration time, 1.8-6.3% for peak area response, and 2.3-6.1% for peak height response for the four mercury species. The detection limits ranged from 6.8 to 16.5 microg L(-1) (as Hg). The recoveries of the four mercury species in the water samples were in the range of 86.6-111%. The developed technique was successfully applied to speciation analysis of mercury in a certified reference material (DORM-2, dogfish muscle).     

On-line temperature monitoring in a capillary electrochromatography frit using microcoil NMR

A new nuclear magnetic resonance (NMR) spectroscopy probe has been designed to measure the temperature of the water inside a capillary. The probe provides the ability to measure the temperature in a several hundred micrometer long capillary section, corresponding to liquid volumes in the picoliter to nanoliter range with a temperature monitoring accuracy of 0.2 degrees C. The NMR probe is based on a novel two-turn vertical solenoidal design, and its performance for capillary-scale temperature measurements is characterized. The temperature rise in a chromatographic frit of the type used in capillary electrochromatography is measured as a function of applied power, and temperature rises of more than 50 degrees C are observed. The temperature of the electrolyte cools rapidly after exiting the frit and can be followed as a function of distance from the frit. The ability to accurately monitor the temperature of water as it moves through porous materials such as packed chromatographic beds and frits is important to allow the effects of temperature on CEC separation performance to be determined.     

On-line concentration of acidic compounds by anion-selective exhaustive injection-sweeping-micellar electrokinetic chromatography

An easy, simple, and highly efficient on-line preconcentration method for acidic compounds in capillary electrophoresis was investigated. It combined two on-line concentration techniques, field-amplified sample injection (FASI) and sweeping. A low-pH (2.5) background electrolyte was used to suppress the electroosmotic flow (EOF), obviating the need of a coated capillary, as well as to neutralize the weakly acidic analytes. After injection of a plug of water inside the separation capillary, negative voltage was applied to initialize FASI for a much longer time than usual. The anions experienced a high electric field and moved quickly to the boundary of the water and the low-pH nonmicellar electrolyte. When the anions encountered the low-pH electrolyte, they were neutralized and a focused sample zone was formed. Then both inlet and outlet vials were changed to those containing the low-pH micellar background electrolyte. As negative voltage was applied, the anionic micelles moved into the capillary, and sweeping and separation began. The novelty in the present procedure is that a low-pH buffer is used to suppress the EOF and also the ionization of the analytes, without need of any other additives or use of a coated capillary. This method afforded 100,000-fold improvement in peak heights for some phenoxy acidic herbicides. The detection limits for these compounds could be low as 100 pg/mL     

Separation and biospecific identification of subviral particles of human rhinovirus serotype 2 by capillary zone electrophoresis.

During infection, human rhinoviruses undergo structural rearrangements of their capsid proteins from D-antigenic native virus (sedimenting at 150S upon sucrose density gradient centrifugation) to C-antigenic A-particles (sedimenting at 135S) and B-particles (sedimenting at 80S); the latter remain after release of the viral genomic RNA into the cytosol. Subviral particles with very similar properties can also be produced in vitro upon exposure to elevated temperatures or to low-pH buffers. This paper reports on the successful separation of native virus and 80S B-particles by capillary zone electrophoresis. Separation was carried out in an untreated fused-silica capillary (50 microns i.d., total length 50.0 cm, effective length 41.5 cm) at 20 degrees C and monitored with UV detection. The separation buffer was 100 mmol/L boric acid/borate (pH 8.3) and contained 0.5% sodium deoxycholate, 0.05% SDS, and 0.5% Triton X100R; the detergents were required to prevent viral aggregation and adsorption to the capillary wall. The analytes were identified from their characteristic spectra as determined by fast spectral scanning. Final confirmation was obtained by comparison of electropherograms from samples prior and after immunodeplition with antibodies specifically precipitating D- or C-antigen. The present method enables one to easily monitor and quantify these structural changes and thus to determine the most favorable conditions for complete conversion of native virus to 80S B-particles.     

Incorporation of single-wall carbon nanotubes into an organic polymer monolithic stationary phase for mu-HPLC and capillary electrochromatography

Single-wall carbon nanotubes (SWNT) were incorporated into an organic polymer monolith containing vinylbenzyl chloride (VBC) and ethylene dimethacrylate (EDMA) to form a novel monolithic stationary phase for high-performance liquid chromatography (HPLC) and capillary electrochromatography (CEC). The retention behavior of neutral compounds on this poly(VBC-EDMA-SWNT) monolith was examined by separating a mixture of small organic molecules using micro-HPLC. The result indicated that incorporation of SWNT enhanced chromatographic retention of small neutral molecules in reversed-phase HPLC presumably because of their strongly hydrophobic characteristics. The stationary phase was formed inside a fused-silica capillary whose lumen was coated with covalently bound polyethyleneimine (PEI). The annular electroosmotic flow (EOF) generated by the PEI coating allowed peptide separation by CEC in the counterdirectional mode. Comparison of peptide separations on poly(VBC-EDMA-SWNT) and on poly(VBC-EDMA) with annular EOF generation revealed that the incorporation of SWNT into the monolithic stationary phase improved peak efficiency and influenced chromatographic retention. The structures of pretreated SWNT and poly(VBC-EDMA-SWNT) monolith were examined by high-resolution transmission electron microscopy, Raman spectroscopy, scanning electron microscopy, and multipoint BET nitrogen adsorption/desorption.     

Behavior of cation-exchange materials in capillary electrochromatography

The behavior of a strong, cation-exchange material (propanesulfonic acid, SCX) has been studied in capillary electrophoresis (CE) and capillary electrochromatography (CEC) by the use of coated and packed capillaries. In aqueous electrolytes, the SCX-coated capillary showed a far more consistent electroosmotic flow over the pH range 3.6-10.5, compared to untreated fused silica. However, in similar electrolytes containing 80% (v/v) acetonitrile, both coated and untreated capillaries performed similarly, casting doubts upon the stability of the SCX coating. The effect of voltage and mobile-phase parameters such as pH, ionic strength, and organic content was studied in CEC for both 3-μm SCX and C(18) packing materials, and the results were compared in terms of linear velocities, currents, and conductivities. Only at pH 5 and below was a higher EOF velocity than expected observed for the SCX column. In accordance with theory, the EOF was seen to increase with decreasing ionic strength for the C(18) column. However, for the SCX column, this was not the case: the EOF showed a general reduction as the ionic strength was decreased. The greatest anomaly was observed on changing the acetonitrile composition: the EOF showed a consistent decline with increasing organic, whereas the EOF in both the open capillary and C(18) column decreased and then started to rise with acetonitrile contents above 70% (v/v).     

Sol-gel poly(ethylene glycol) stationary phase for high-resolution capillary gas chromatography

A sol-gel chemistry-based method was developed for the preparation of highly stable capillary gas chromatography (GC) columns with surface-bonded poly(ethylene glycol) (PEG) stationary phase. Through a single-step procedure, it concurrently provided column deactivation, stationary-phase coating, and chemical immobilization of the coated film. Sol-gel reactions were carried out within fused-silica capillaries that were filled with properly designed sol solutions containing two sol-gel precursors, two different triethoxysilyl-derivatized poly(ethylene glycol)s, two sol-gel catalysts, and a deactivation reagent. Hydrolytic polycondensation reactions led to the formation of a sol-gel coating chemically bonded to the inner walls of the capillary. A number of sol-gel coated fused-silica capillary columns were prepared using sol-gel-active PEG derivatives. These columns demonstrated many inherent advantages, the main being the strong anchoring of the coating to the capillary wall resulting from chemical bonding with the silanol groups on the fused-silica capillary inner surface. This chemical bonding yielded strongly immobilized PEG coatings with outstanding thermal stability (up to 320 degrees C). To our knowledge, such a high thermal stability has not been achieved so far on conventionally prepared PEG GC columns. Sol-gel PEG columns provided excellent chromatographic performances: high number of theoretical plates, excellent run-to-run and column-to-column reproducibility, and pronounced selectivity for a wide range of test solutes. Using n-octadecane as a test solute (k = 7.14), an efficiency value of 3200 theoretical plates/m was obtained on a 10 m x 0.25 mm i.d. fused-silica capillary column. Five sol-gel PEG columns provided RSD values of 1.09% for column efficiency (solute, n-octadecane), 1.37% for retention factor (solute, n-octadecane), and 0.9% for separation factor (for solute pair o- and p-xylene). In five replicate measurements using the same column, RSD values of less than 0.50% for the retention time and 1.36% for retention factor (k) were obtained.     

Immobilized ionic liquids as high-selectivity/high-temperature/high-stability gas chromatography stationary phases

Ionic liquids (ILs) are a class of nonmolecular solvents in which the cation/anion combination can be easily tuned to provide desired chemical and physical properties. When used as stationary phases in gas-liquid chromatography, ionic liquids exhibit dual nature retention selectivity. That is, they are able to separate polar molecules such as a polar stationary phase and nonpolar molecules such as a nonpolar stationary phase. However, issues such as optimization of the wetting ability of the ionic liquid on fused-silica capillaries, the maximum operating temperatures of the stationary phases, and nonuniform film thickness on the wall of the capillary at high temperatures have limited their use in gas chromatography. As described in this paper, these limitations are overcome by cross-linking a new class of ionic liquid monomers by free radical reactions to provide a more durable and robust stationary phase. By lightly cross-linking the ionic liquid stationary phase using a small amount of free radical initiator, high-efficiency capillary columns were produced that are able to endure high temperatures with little column bleed. Two types of cross-linked IL stationary phases are developed. A partially cross-linked stationary phase allows for high-efficiency separations up to temperatures of approximately 280 degrees C. However, by creating a more highly cross-linked stationary phase of geminal dicationic ILs, exclusively, an increase in efficiency is observed at high temperatures allowing for its use over 350 degrees C. In addition, through the use of solvation thermodynamics and interaction parameters, it was shown that the cross-linking/immobilization of the ionic liquid does not affect the selectivity of the stationary phase thereby preserving its dual nature retention behavior.     

Field-amplified sample injection combined with water removal by electroosmotic flow pump in acidic buffer for analysis of phenoxy acid herbicides by capillary electrophoresis

A procedure that combines two common stacking techniques, field-amplified sample injection and water removal, with an electroosmotic flow pump, is used to separate phenoxy acid herbicides by capillary zone electrophoresis. Before sample loading, a long plug of water was hydrodynamically injected into the capillary both to serve as the medium to permit a high electric field strength and to contain sample anions. Because of this long length of water, the number of ions injected into the capillary was greatly increased. Electrokinetic injection at reversed voltage was then used for introducing negatively charged ions from the diluted sample into the column. The water was removed from the capillary using the electroosmotic flow (EOF) pump when the EOF of the background electrolyte was suppressed. This method afforded a sensitivity enhancement of greater than 3,000 times. Combined with solid-phase extraction, detection limits for the phenoxy acid herbicides as low as 0.01 ng/mL could be achieved.     

Fritless packed columns for capillary electrochromatography: separation of uncharged compounds on hydrophobic hydrogels

A novel column is described that does not require frits to keep packing material within a capillary. A continuous bed is prepared in situ in aqueous solution by radical copolymerization of N-isopropylacrylamide and 2-acrylamido-2-methylpropanesulfonic acid (the resultant gel is denoted poly(AMPS-co-IPAAm). N,N'-Methylenebisacrylamide is used for cross-linking. On the application of an electrical field, electroosmotic flow (EOF) is developed in the bed along the capillary, where fluid propulsion would be otherwise difficult to achieve. The resultant EOF transports neutral compounds through the column without forcing the gel out of the capillary. Examination of the fluid motion in the continuous bed using a video microscope system and an image processor shows a relatively flat flow profile of EOF. The bed functions as the stationary phase for reversed-phase capillary electrochromatography (CEC). This new approach is an alternative to packed capillary columns which have been used previously in CEC. A high efficiency is obtained for a steroid which is separated on a 4.0% total monomer concentration (T), 10.0% degree of cross-linking (C), and 10.0% mole fraction of AMPS in the total monomer (S), poly(AMPS-co-IPAAm) column. A mixture of polyaromatic hydrocarbons is separated on a 6.9% T, 5.8% C, and 5.5% S poly(AMPS-co-IPAAm) column. The capacity factor of benzo[a]pyrene increases from 0.63 to 1.91 as the acetonitrile content in a Tris-boric acid buffer is decreased from 45 to 30% (v/v). The run-to-run RSD of analyte migration time is less than 0.73%, and the day-to-day RSD is acceptable. Potential benefits of this approach are also mentioned.     

A colloidal graphite-coated emitter for sheathless capillary electrophoresis/nanoelectrospray ionization mass spectrometry

A colloidal graphite-coated emitter is introduced for sheathless capillary electrophoresis/nanoelectrospray ionization time-of-flight mass spectrometry (CE/ESI-TOFMS). The conductive coating can be produced by brushing the capillary tip to construct a fine layer of 2-propanol-based colloidal graphite. The fabrication involves a single step and requires less than 2 min. Full cure properties develop in approximately 2 h at room temperature and then the tip is ready for use. The coated capillary tip is applied as a sheathless electrospray emitter. The emitter has proven to bear stable electrospray and excellent performance for 50 microm i.d. x 360 microm o.d. and 20 microm i.d. x 360 microm o.d. capillaries within the flow rate of 80-500 nL/min; continuous electrospray can last for over 200 h in positive mode. Baseline separation and structure elucidation of two clinically interesting basic drugs, risperidone and 9-hydroxyrisperidone, are achieved by coupling pressure-assisted CE to ESI-TOFMS using the described sheathless electrospray emitter with a bare fused-silica capillary at pH 6.7. It is found that the signal intensity of m/z in sheathless CE/ESI-TOFMS at pH 6.7 is approximately 50 times higher than that at pH 9.0 for the two analytes, although the electroosmotic flow (EOF) at pH 9.0 provides sufficient flow rate (approximately 150 nL/min) to maintain electrospray.     

Capillary electrochromatography with fused-silica capillaries packed with copolymeric reversed-phase adsorbent and ion exchangers

Macroporous poly(styrene-divinylbenzene) (PSDVB), PRP-1, a reversed-phase adsorbent, and PSDVB-based strong acid cation exchangers and strong base and weak base anion exchangers were evaluated as stationary phases for capillary electrochromatography (CEC). Electroosmotic flow (EOF) for adsorbent and exchanger packed fused-silica capillaries for acetone as the marker increases with increasing ion exchange capacity, buffer organic solvent concentration, and applied voltage, is nearly independent of pH, and decreases with increased buffer ionic strength. For anion exchangers, EOF is reversed. Thiourea, acetone, acrylamide, nitromethane, propanal, and acetic acid were evaluated as EOF markers and undergo weak interaction with the PSDVB-based stationary phases. EOF in a basic buffer is greater than or equal to silica-based C-18 and cation exchanger packed capillaries. For an acidic buffer, EOF for a PRP-1 capillary is almost twice the C-18 packed capillary. As analyte hydrophobicity increases, retention and migration time increases for the PSDVB-based stationary phases. As exchange capacity increases, availability of the polymeric matrix for analyte partitioning decreases, causing analyte migration time to decrease. Increasing buffer organic solvent concentration decreases analyte retention. The PSDVB-based stationary phases provide good resolving power and reproducibility and are applicable to the CEC separation of neutral, weakly acidic, and basic analytes. Efficiency, however, is less than obtained with silica-based stationary phases. Because of stability in a strong acid buffer, the CEC separation of weak acids, where dissociation is suppressed, and weak bases as cations is possible. Separations of short-chain alkyl aldehydes, methyl ketones, aromatic hydrocarbons, substituted benzene derivatives, and short-chain carboxylic acids are described.     

Universal method for determining electrolyte temperatures in capillary electrophoresis

Temperature increase in capillary electrophoresis (CE) due to Joule heating is an inherent limitation of this powerful separation technique. Active cooling systems can decrease the temperature of a large part of the capillary but they leave "hot spots" at the capillary ends which can completely ruin some CE analyses despite their short lengths. Here, we introduce a "universal method for determining electrolyte temperatures" (UMET) that can determine temperatures in both efficiently- and inefficiently-cooled parts of the capillary. UMET can be applied to all electrolytes, as it does not involve any probe; it requires only measuring current versus voltage for different voltages and processing the data using an iterative algorithm. To demonstrate the universality of UMET, we measured temperatures for electrolytes of different ionic strengths as well as for different capillary diameters. We further propose a "simplified universal method for predicting electrolyte temperatures" (SUMET) which only requires one measurement of current and voltage (that can be completed in 1 min) and uses two empirical equations to predict temperatures in the efficiently- and inefficiently-cooled parts of the capillary. The equations include several instrument-specific empirical parameters that are determined using a large set of current-voltage data obtained with UMET for a range of electrolytes and different capillaries. To demonstrate the utility of SUMET, we obtained the required data set for a Beckman MDQ CE instrument and produced all required empirical parameters that enable a user of this instrument to predict the temperature for every new experimental set in a matter of minutes. We confirmed the accuracy of SUMET by measuring the temperature-sensitive dissociation rate constant of a protein-DNA complex. We foresee that UMET will be used to produce instrument-specific empirical parameters for all CE instruments and then SUMET will be routinely used for temperature prediction in CE.     

Phase-transition temperatures and piezoelectric properties of (Bi1/2Na1/2)TiO3-(Bi1/2Li1/2)TiO3-(Bi1/2K1/2)TiO3 lead-free ferroelectric ceramics.

The phase-transition temperatures and piezoelectric properties of x(Bi(1/2)Na(1/2))TiO3-y(Bi(1/2)Li(1/2))TiO3-z(Bi(1/2)K(1/2))TiO3 [x + y + z = 1] (abbreviated as BNLKT100(y)-100(z)) ceramics were investigated. These ceramics were prepared using a conventional ceramic fabrication process. The phase-transition temperatures such as depolarization temperatures T(d), rhombohedraltetragonal phase transition temperature T(R-T), and dielectric-maximum temperature T(m) were determined using electrical measurements such as dielectric and piezoelectric properties. The X-ray powder diffraction patterns of BNLKT100(y)-100(z)) show the morphotropic phase boundary (MPB) between rhombohedral and tetragonal at approximately z = 0.20, and the piezoelectric properties show the maximum at the MPB. The electromechanical coupling factor k(33), piezoelectric constant d(33) and T(d) of BNLKT4-20 and BNLKT8-20 were 0.603, 176 pC/N, and 171 degrees C, and 0.590, 190 pC/N, and 115 degrees C, respectively. In addition, the relationship between d33 and Td of tetragonal side and rhombohedral side for BNLKT4-100z and BNLKT8-100z were presented. Considering both high Td and high d(33), the tetragonal side of BNLKT4-100z is thought to be the superior composition. The d(33) and T(d) of BNLKT4-28 were 135 pC/N and 218 degrees C, respectively. Moreover, this study revealed that the variation of T(d) is related to the variation of lattice distortion such as rhombohedrality 90-alpha and tetragonality c/a.