Fluorinated ethylenepropylene copolymer as a potential capillary material in CE

In this work, a new generation UV-transparent polymer, fluorinated ethylenepropylene copolymer (FEP) exhibiting a low degree of crystallinity, extruded in dimensions similar to the most commonly used CE capillaries of approximately 80 mum id and about 360 mum od was investigated for its use as a CE capillary. FEP is transparent down to the low-UV region, and as fluorinated polymers in general are good electrical insulators and exhibit reasonable heat conductivity, it has considerable potential as a material for electrodriven analysis in capillary or microchip formats. The FEP capillary has been characterised with regard to some important aspects for its use as a CE capillary, including its profile of EOF versus pH, as well as procedures for manipulating EOF by coating the inner capillary wall with various semipermanent and dynamic layers. The FEP capillaries were tested and compared with fused-silica capillary for the separation of inorganic and small organic ions using conditions involving direct and indirect detection in the low-UV region. Finally, advantages of the use of the FEP capillary for simultaneous detection of a mixture containing nine inorganic cations and anions using indirect photometric detection with a movable light-emitting diode (LED) detector and a novel electrolyte are demonstrated.     

Forming biocompatible and nonaggregated nanocrystals in water using amphiphilic polymers

High-quality nanocrystals formed in organic solvents can be completely solubilized in water using amphiphilic copolymers containing poly(ethylene glycol) or PEG. These copolymers are generated using a maleic anhydride coupling scheme that permits the coupling of a wide variety of PEG polymers, both unfunctionalized and functionalized, to hydrophobic tails. Thermogravimetric analysis, size exclusion chromatography, cryogenic transmission electron microscopy, and infrared spectroscopy all indicate that the copolymers effectively coat the nanocrystals surfaces. The composite nanocrystal-polymer assemblies can be targeted to recognize cancer cells with Her2 receptor and are biocompatible if their surface coatings contain PEG. In the particular case of semiconductor nanocrystals (e.g., quantum dots), the materials in water have the same optical spectra as well as quantum yield as those formed initially in organic solutions.     

Validation of NMR relaxation exchange time measurements in porous media

Two-dimensional T(2)-T(2) NMR relaxation exchange spectroscopy has been applied to model porous media composed of mixtures of nonporous borosilicate and soda lime glass spheres in water. The spheres had a mean diameter of 100 microm, thus providing an approximately constant characteristic pore dimension throughout the structures, while the use of two glass types ensured that water in different pore-space regions had significantly different T(2) relaxation rates. The packed beds were constructed in various ways with controlled glass type domain sizes to rigorously validate a model for region-to-region exchange of water. From the determined exchange times, the corresponding length scales were calculated based on the molecular self-diffusion of water; these agreed to better than +/-25% with the expected domain sizes. Furthermore, exchange distances on the order of the pore size were observed in thoroughly mixed systems. Depending on the relaxation rates present in the sample, this technique can provide estimates of length scales ranging from microns to millimeters.     

Direct determination of methionine sulfoxide in milk proteins by enzyme hydrolysis/high-performance liquid chromatography

A direct and simultaneous HPLC/UV determination of methionine and methionine sulfoxide in enzyme-hydrolyzed milk proteins is described. Protein hydrolysis is accomplished by a three-enzyme (pronase, leucine aminopeptidase, prolidase) 20-h/37 degrees C digestion. A gradient elution reversed-phase HPLC system with UV detection at 214 nm and 280 nm is then used to determine the quantitative releases of methionine sulfoxide, methionine, tyrosine, and tryptophan. The ease of methionine oxidation by a wide variety of oxidants, coupled with the quantitative release of both methionine and its sulfoxide by the three-enzyme hydrolysis, renders the approach valuable for identifying oxidized milk proteins. The relatively simple method proved accurate and precise in its application to commercial milk products, finding methionine sulfoxide levels as high as 74% of the total methionine.     

Emulsion droplet sizing using low-field NMR with chemical shift resolution and the block gradient pulse method

Pulsed Field Gradient (PFG) measurements are commonly used to determine emulsion droplet size distributions based on restricted self-diffusion within the emulsion droplets. Such measurement capability is readily available on commercial NMR bench-top apparatus. A significant limitation is the requirement to selectively detect signal from the liquid phase within the emulsion droplets; this is currently achieved using either relaxation or self-diffusion contrast. Here we demonstrate the use of a 1.1 T bench-top NMR magnet, which when coupled with an rf micro-coil, is able to provide sufficient chemical shift resolution such that unambiguous signal selection is achieved from the dispersed droplet phase. We also improve the accuracy of the numerical inversion process required to produce the emulsion droplet size distribution, by employing the Block Gradient Pulse (bgp) method, which partially relaxes the assumptions of a Gaussian phase distribution or infinitely short gradient pulse application inherent in current application. The techniques are successfully applied to size 3 different emulsions.     

Quantification of the velocity acceleration factor for colloidal transport in porous media using NMR

Nuclear magnetic resonance (NMR) techniques were used to quantify the transport of colloids through porous media. This was achieved via the application of chemically-resolved pulsed field gradient (PFG) methods, hence probing the displacement (probability distribution) propagators of both the colloidal and continuous liquid phase. A dilute decane-in-water emulsion was used with flow through a random glass sphere packing being considered. The acquired propagators allowed for quantification of both colloidal entrapment and the velocities of both the continuous phase and the flowing colloids. The flowing colloids were found to experience a velocity acceleration factor (VAF) increase of 1.08 relative to the continuous phase. This was found to be independent of displacement observation time or flowrate. It was speculated to be a consequence of radial exclusion due to the finite size of the colloids. Simulations of the colloidal transport were also performed using a lattice Boltzmann platform and a Lagrangian particle-tracking algorithm which incorporated colloidal radial exclusion. Reasonable agreement was observed between the simulation and the experimental data.     

Assignments and predictions of far-infrared laser lines in methyl alcohol

In this work, the results of detailed spectroscopic analyses of the high-resolution Fourier transform infrared (IR) C-O stretch and far-infrared (FIR) torsion-rotation bands of methyl alcohol are applied to assign and predict FIR laser lines optically pumped by a CO₂ laser in the dense Q-branch region of the C-O stretch band. The assignments are supported by means of closed combination loops of accurately measured transition frequencies. For the predicted FIR lines, the frequencies are deduced with an accuracy of ±0.001 cm⁻¹, which is at least an order of magnitude better than can be obtained from direct wavelength measurements. The IR and FIR spectroscopic data relevant to the assignments are included.