Flow counterbalanced capillary electrophoresis using packed capillary columns: resolution of enantiomers and isotopomers

A method with the ability to increase greatly both the resolution and efficiency of a given capillary electrophoretic system is described. This method differs from traditional capillary electrophoresis (CE) in that a counterflow is induced in the direction opposite to the electrokinetic migration of the analyte. This has the effect of extending not only the time the analytes migrate in the electric field but also the effective length and the effective applied voltage of the system. Previous work in our group with flow counterbalanced capillary electrophoresis has utilized an open tube of small inner diameter to reduce peak broadening caused by hydrodynamic flow. Narrow-diameter capillaries (5-10 microm) restricted analysis to fluorescent analytes and laser-induced fluorescence detection. The method described here uses a capillary of much larger inner diameter (75 microm) that has been packed with nonporous silica particles. The packing material reduces the amount of band broadening caused by pressure-induced flow relative to that experienced in an open tube. A larger diameter capillary allows the detection of analytes by UV absorption, not only eliminating the need to tag analytes with fluorescent tags but also allowing for the detection of a much broader range of analytes. The system was evaluated by studying the separations of several enantiomers using only beta-cyclodextrin as the chiral selector. The system was also used to resolve the two naturally occurring isotopes of bromine and to resolve phenylalanine from phenylalanine-d8. Relative to traditional CE, large improvements in resolution and separation efficiency have been achieved with this method.     

Modeling the dynamics of fermentation and respiratory processes in a groundwater plume of phenolic contaminants interpreted from laboratory- to field-scale

A biodegradation model with consecutive fermentation and respiration processes, developed from microcosm experiments and simulated mathematically with microbial growth kinetics, has been implemented into a field-scale reactive transport model of a groundwater plume of phenolic contaminants. Simulation of the anaerobic plume core with H2 and acetate as intermediate products of biodegradation allows the rates and parameter values forfermentation processes and individual respiratory terminal electron accepting processes (TEAPS) to be estimated using detailed, spatially discrete, hydrochemical field data. The modeling of field-scale plume development includes consideration of microbial acclimatization, substrate toxicity toward degradation, bioavailability of mineral oxides, and adsorption of biogenic Fe(ll) species in the aquifer, identified from complementary laboratory process studies. The results suggest that plume core processes, particularly fermentation and Fe(lll)-reduction, are more important for degradation than previously thought, possibly with a greater impact than plume fringe processes (aerobic respiration, denitrification, and SO4-reduction). The accumulation of acetate as a fermentation product within the plume contributes significantly to the mass balance for carbon. These results demonstrate the value of quantifying fermentation products within organic contaminant plumes and strongly suggest that the conceptual model selected for reactive processes plays a dominant role in the quantitative assessment of risk reduction by naturally occurring biodegradation processes.     

A comparison of the cell phone driver and the drunk driver

OBJECTIVE: The objective of this research was to determine the relative impairment associated with conversing on a cellular telephone while driving. BACKGROUND: Epidemiological evidence suggests that the relative risk of being in a traffic accident while using a cell phone is similar to the hazard associated with driving with a blood alcohol level at the legal limit. The purpose of this research was to provide a direct comparison of the driving performance of a cell phone driver and a drunk driver in a controlled laboratory setting. METHOD: We used a high-fidelity driving simulator to compare the performance of cell phone drivers with drivers who were intoxicated from ethanol (i.e., blood alcohol concentration at 0.08% weight/volume). RESULTS: When drivers were conversing on either a handheld or hands-free cell phone, their braking reactions were delayed and they were involved in more traffic accidents than when they were not conversing on a cell phone. By contrast, when drivers were intoxicated from ethanol they exhibited a more aggressive driving style, following closer to the vehicle immediately in front of them and applying more force while braking. CONCLUSION: When driving conditions and time on task were controlled for, the impairments associated with using a cell phone while driving can be as profound as those associated with driving while drunk. APPLICATION: This research may help to provide guidance for regulation addressing driver distraction caused by cell phone conversations.     

Terpenes of ponderosa pine and feeding preferences by pocket gophers

Yield and composition of essential oils were compared in foliage, stems, and roots of ponderosa pine seedlings, and preferences for the trees by pocket gophers were determined. Test seedlings represented nine widely separated provenances in the western United States. Seed source of the trees influenced gopher feeding preferences and resulted in varied tree damage. The damage ranged from 0 to 31%, suggesting that some sources might possess sufficient natural resistance to give trees practical protection from gophers in the field. There were no morphological differences among sources to explain differential tree damage. All sources contained essential oils in all tissues examined, but oil yield varied among and within tissue types. Oils were predominantly (76–97%) composed of monoterpene hydrocarbons. Oil composition varied by source, and different tissue types varied greatly in the yield and composition of their oils. Neither yield nor constituents of foliage oils were significantly correlated with gopher damage (or preference). In contrast, some components of stem and root oils were strongly related to preference. Results of correlation and discriminant analyses showed that some oil constituents could serve as indicators of resistance (or susceptibility) to gopher damage. Such important chemical variables, when verified, could be used in selections for ponderosa pine resistant to gophers.The authors thank Dr. K. Hungerford, University of Idaho, for supervising the gopher preference test under a cooperative-aid agreement with the U.S.D.A. Forest Service.     

Direct‐Write Formation and Dissolution of Silver Nanofilaments in Ionic Liquid‐Polymer Electrolyte Composites

Materials with reconfigurable optical properties are candidates for applications such as optical cloaking and wearable sensors. One approach to fabricate these materials is to use external fields to form and dissolve nanoscale conductive channels in well‐defined locations within a polymer. In this study, conductive atomic force microscopy is used to electrochemically form and dissolve nanoscale conductive filaments at spatially distinct points in a polyethylene glycol diacrylate (PEGDA)‐based electrolyte blended with varying amounts of ionic liquid (IL) and silver salt. The fastest filament formation and dissolution times are detected in a PEGDA/IL composite that has the largest modulus (several GPa) and the highest polymer crystal fraction. This is unexpected because filament formation and dissolution events are controlled by ion transport, which is typically faster within amorphous regions where polymer mobility is high. Filament kinetics in primarily amorphous and crystalline regions are measured, and two different mechanisms are observed. The formation time distributions show a power‐law dependence in the crystalline regions, attributable to hopping‐based ion transport, while amorphous regions show a normal distribution. The results indicate that the timescale of filament formation/dissolution is determined by local structure, and suggest that structure could be used to tune the optical properties of the film.     

Transient heat conduction in a medium with multiple spherical cavities

This paper considers a transient heat conduction problem for an infinite medium with multiple non‐overlapping spherical cavities. Suddenly applied, steady Dirichlet‐, Neumann‐ or Robin‐type boundary conditions are assumed. The approach is based on the use of the general solution to the problem of a single cavity and superposition. Application of the Laplace transform and the so‐called addition theorem results in a semi‐analytical transformed solution for the case of multiple cavities. The solution in the time domain is obtained by performing a numerical inversion of the Laplace transform. A large‐time asymptotic series for the temperature is obtained. The limiting case of infinitely large time results in the solution for the corresponding steady‐state problem. Several numerical examples that demonstrate the accuracy and the efficiency of the method are presented. Copyright © 2008 John Wiley & Sons, Ltd.     

Identification of the genes encoding Mn2+-dependent RNase HII and Mg2+-dependent RNase HIII from Bacillus subtilis: classification of RNases H into three families

Database searches indicated that the genome of Bacillus subtilis contains three different genes encoding RNase H homologues. The ypdQ gene encodes an RNase HI homologue with 132 amino acid residues, whereas the rnh and ysgB genes encode RNase HII homologues with 255 and 313 amino acid residues, respectively. RNases HI and HII show no significant sequence similarity. These genes were individually expressed in Escherichia coli; the recombinant proteins were purified, and their enzymatic properties were compared with those of E. coli RNases HI and HII. We found that the ypdQ gene product showed no RNase H activity. The 2.2 kb pair genomic DNA containing this gene did not suppress the RNase H deficiency of an E. coli rnhA mutant, indicating that this gene product shows no RNase H activity in vivo as well. In contrast, the rnh (rnhB) gene product (RNase HII) showed a preference for Mn2+, as did E. coli RNase HII, whereas the ysgB (rnhC) gene product (RNase HIII) exhibited a Mg2+-dependent RNase H activity. Oligomeric substrates digested with these enzymes indicate similar recognition of these substrates by B. subtilis and E. coli RNases HII. Likewise, B. subtilis RNase HIII and E. coli RNase HI have generated similar products. These results suggest that B. subtilis RNases HII and HIII may be functionally similar to E. coli RNases HII and HI, respectively. We propose that Mn2+-dependent RNase HII is universally present in various organisms and Mg2+-dependent RNase HIII, which may have evolved from RNase HII, functions as a substitute for RNase HI.