Greg E. Collins

A chip-based capillary electrophoresis-contactless conductivity microsystem for fast measurements of low-explosive ionic components.

A miniaturized analytical system for separating and detecting inorganic explosive residues, based on the coupling of a micromachined capillary electrophoresis (CE) chip with a contactless conductivity detector is described. The low electroosmotic flow (EOF) of the poly(methylmethacrylate) (PMMA) chip material facilitates the rapid switching between analyses of cations and anions using the same microchannel and run buffer (and without an EOF modifier), and hence offers rapid (< 1 min) measurement of seven explosive-related cations and anions. Experimental parameters relevant to the separation and detection processes have been optimized. Addition of a 18-crown-6 ether modifier has been used for separating the peaks of co-migrating potassium and ammonium ions. The ionic-explosive microchip system combines the distinct advantages of contactless conductivity detection with the attractive features of plastic CE microchips. The new microsystem offers great promise for monitoring explosive-related ions at the sample source, with significant advantages of speed/warning, efficiency, cost, or sample size.

Selective metals determination with a photoreversible spirobenzopyran

The photoreversible metal-ion complexation behavior of nitroquinolinospiropyranindoline (NQSP) was studied in combination with the selective identification of six different transition-metal ions, Zn(2+), Co(2+), Hg(2+), Cu(2+), Cd(2+), and Ni(2+), in single- and binary-component mixtures via partial least squares discriminant (PLSD) analysis. The plasticizer, dicapryl phthalate, was chosen as the support medium for this study on the basis of (1) its enhancement of the photoreversibility and hypsochromic shifts seen in metal complexation and (2) its potential application to supported liquid membranes for eventual sensor applications. Complexation of divalent transition-metal ions by NQSP in dicapryl phthalate produced variable hypsochromic shifts in the absorption spectra (30-60 nm), requiring chemometric techniques in order to overcome the spectral overlaps. PLSD analysis was used to build classification analysis models to differentiate between the six divalent transition-metal ions. The feasibility of performing mixture analysis was studied using the concept of net analyte signal prior to experimental verification. Single- and binary-component mixtures of metals were identified with 100 and 97.4% accuracy, respectively, which included no false positives in either the training or prediction sets.

Electroosmotic Flow-Based Pump for Liquid Chromatography on a Planar Microchip

An electroosmotic flow (EOF)-based pump, integrated with a sol-gel stationary phase located in the electric field-free region of a microchip, enabled the separation of six nitroaromatic and nitramine explosives and their degradation products via liquid chromatography (LC). The integrated pump and LC system were fabricated within a single quartz substrate. The pump region consisted of a straight channel (3.0 cm x 230 microm x 100 microm) packed with 5-microm porous silica beads. The sol-gel stationary phase was derived from a precursor mixture of methyltrimethoxy- and phenethyltrimethoxysilanes and was synthesized in the downstream, field-free region of the microchip, resulting in a stationary-phase monolith with dimensions of 2.6 cm x 230 microm x 100 microm. Fluid dynamic design considerations are discussed, especially as they relate to integrating the EOF pump with the LC system. Pump and separation performance, as characterized by flow rate measurements, injection, elution, separation, and detection, point to a viable analytical chemistry platform that encompasses all of the benefits expected of portable, laboratory-on-chip systems, including reduced sample requirements and small packaging.

Orientation and structure of monolayer →→ multilayer phthalocyanine thin films on layered semiconductor (MoS2 and SnS2) surfaces

Thin films of both chloroindium and copper pthalocyanines have been vacuum deposited onto metal dichalcogenide surfaces such as MoS2 and SnS2, with ordering achieved for these four‐fold symmetric molecules ranging from below monolayer to multilayers. Reflection high‐energy electron diffraction suggests that square lattice geometries are adopted for low coverages of each phthalocyanine (Pc), but with multiple domains. Low‐energy electron diffraction confirms the presence of three square lattice domains, each domain rotated by 60° with respect to the other. Basal plane defects, and especially terrace sites in the metal dichalcogenide surface, are implicated as the nucleation sites for the growth of these square lattice domains. Optical spectroscopies have been used to characterize submonolayer to multilayer deposits of chloroindium phthalocyanine on SnS2 thin films, where the packing geometries of the adjacent Pcs cause perceptible changes in the position and width of the absorbance band in the visible/near...

Microchip separations of transition metal ions via LED absorbance detection of their PAR complexes.

Micellar electrokinetic chromatography was utilized in the electrophoretic separation of seven transition metal ions, colorimetrically complexed by 4-(2-pyridylazo)resorcinol (PAR) on a glass capillary electrophoresis microchip. Detection of the PAR metal chelates was demonstrated using a green light emitting diode (540 nm) and a miniature photomultiplier tube. Parameters investigated included the effect of buffer type, pH and surfactant concentration (sodium dodecyl sulfate, SDS) on the separation efficiency. The optimally determined background electrolyte contained 10 mM ammonium phosphate buffer (pH 7.5), 1 mM PAR to prevent kinetic lability problems and 75 mM SDS for enhanced resolution. The separation of seven transition metal ions, Co2+, V3+, Ni2+, Cu2+, Fe2+, Mn2+ and Cd2+, was achievable in under 65 s, with the resolution of each metal ion in excess of 1.60. Detection limits obtained ranged from 400 ppb for Ni2+ to 1.2 ppm for Mn2+.

Microchip micellar electrokinetic chromatography separation of alkaloids with UV-absorbance spectral detection.

A microchip device is demonstrated for the electrophoretic separation and UV‐absorbance spectral detection of four toxic alkaloids: colchicine, aconitine, strychnine, and nicotine. A fused‐silica (quartz) microchip containing a simple cross geometry is utilized to perform the separations, and a miniature, fiber‐optic CCD spectrometer is coupled to the microchip for detection. Sensitive UV‐absorbance detection is achieved via the application of online preconcentration techniques in combination with the quartz microchip substrate which contains an etched bubble‐cell for increased pathlength. The miniature CCD spectrometer is configured to detect light between 190 and 645 nm and LabView programming written in‐house enables absorbance spectra as well as separations to be monitored from 210 to 400 nm. Consequently, the configuration of this microchip device facilitates qualitative and quantitative separations via simultaneous spatial and spectral resolution of solutes. UV‐absorbance limits of quantification for colchicine, 20 μM (8 mg/L); strychnine, 50 μM (17 mg/L); aconitine, 50 μM (32 mg/L); and nicotine, 100 μM (16 mg/L) are demonstrated on the microchip. With the exception of aconitine, these concentrations are ≥20‐times more sensitive than lethal dose monitoring requirements. Finally, this device is demonstrated to successfully detect each toxin in water, skim milk, and apple juice samples spiked at sublethal dose concentrations after a simple, SPE procedure.

Microscale Solid-Phase Extraction System for Explosives

A simple, semi-automated, microcolumn solid-phase extraction (SPE) system is optimized for the extraction, preconcentration and HPLC analysis of seven different explosives and explosive derivatives contaminating seawater, river water and well water samples. The microcolumns were constructed from 1/16 in. O.D. PTFE tubing (1 in.=2.54 cm) packed with 0.5-1.5 mg of SPE material. LiChrolut EN or Porapak R. The extraction system consisted of two syringe pumps and several solenoid valves. Optimal detection limits were realized when the sample water flow-rate was maximally increased within the limits of the pump, 5-10 ml/min (despite exceeding the breakthrough threshold of the SPE microcolumn), and when the eluate volume collected from the column was minimized, <5 microl (despite very low recovery percentages).

Nonaqueous based microchip separation of toxic metal ions using 2-(5-bromo-2-pyridylazo)-5-(N-propyl-N-sulfopropylamino)phenol

The colorimetric metal chelating agent, 2-(5-bromo-2-pyridylazo)-5-(N-propyl-N-sulfopropylamino)phenol (5-Br-PAPS), was demonstrated on a capillary electrophoresis microchip in the separation and detection of six metal ions of environmental concern, Cd2+, Pb2+, Cu2+, Co2+, Ni2+, and Hg2+. The inclusion of methanol in the buffer was found to improve both the separation efficiency and sensitivity, in addition to making the technique directly amenable to the application of solid-phase extraction. The combination of metal chelation with solid-phase extraction on a C18 silica gel microcolumn gave several hundred fold improvements in detection limits for the CE microchip measurements of toxic metal ions in water and extracted from a solid Plexiglas surface.

Separation of uranium(VI) and transition metal ions with 4-(2-thiazolylazo)resorcinol by capillary electrophoresis.

A capillary electrophoresis method utilizing 4-(2-thiazolylazo)resorcinol (TAR) was developed to separate uranium, cobalt, cadmium, nickel, titanium and copper metal ions. TAR was chosen as the visible absorbing chelating ligand because of its ability to form stable complexes with a wide variety of metals. Several parameters that included pH, electrophoretic run buffer concentration, buffer type and the influence of chelating ligand in the electrophoretic run buffer were examined to determine the best separating conditions. Optimum separation of the six metal chelates was achieved in a 15 mM Na2B4O7-NaH2PO4, pH 8.3 buffer containing 0.1 mM TAR. Method validation included injection and method precision studies as well as detection limit and linear dynamic range determination. High-ppb to low-ppm (w/w ratio) detection limits were achieved with linear dynamic ranges between 0.1 and 75 ppm.

Chemiluminescence detection of hydrazine vapor

An efficient, real-time chemiluminescence detector for hydrazine vapor, N(2)H(4)(g), is described, capable of monitoring sub part-per-billion levels of hydrazine in air. The catalytic oxidation of hydrazine by colloidal platinum forms an intermediate, oxidizing agent (e.g. OH or OOH) which subsequently oxidizes luminol, generating a chemiluminescence signal that is proportional to the hydrazine concentration. Major components of the instrument include a photomultiplier tube (PMT), a short length of glass tubing coiled directly in front of the PMT cathode surface, a vacuum pump for sampling the air, and a peristaltic pump for circulating the liquid reagent. The liquid reagent, a basic solution (pH 13) of luminol and colloidal platinum, is continuously recycled. The detection sequence is initiated by pumping the hydrazine vapor through a short length of teflon tubing that is concurrently transporting the liquid reagent. The liquid is separated from the gas stream in an impinger and quickly pumped to the PMT. We have evaluated the effect of solution pH, luminol and platinum concentrations, and air and liquid flow rates on the analytical characteristics of this system. A linear, dynamic detection range for hydrazine has been obtained from 1 to 2000 ppb in air, with an instrument response that is fully reversible and achieves plateau response in less than 2 min.