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J W Grate

Publications and source records attributed to J W Grate.

9 recordsLinked to original sources

Selective stationary phase for solid-phase microextraction analysis of sarin (GB).

A number of critical field applications require monitoring air samples for trace levels of chemical warfare agents. Solid-phase microextraction (SPME) is a convenient format to conduct these analyses. Measurements could be significantly improved if a SPME phase selective for nerve agents were substituted for non-selective polymers typically used (e.g., polydimethylsiloxane). This paper evaluates a novel stationary phase, previously developed for methylphosphonate sensor applications, for use with SPME sampling. The phenol-based polymer, BSP3, was found to offer far higher selectivity toward sarin (GB) than polydimethylsiloxane due to a pronounced affinity toward the target analyte and a lower affinity toward hydrocarbons.

Air↗

Inverse least-squares modeling of vapor descriptors using polymer-coated surface acoustic wave sensor array responses.

In previous work, it was shown that, in principle, vapor descriptors could be derived from the responses of an array of polymer-coated acoustic wave devices. This new chemometric classification approach was based on polymer/vapor interactions following the well-established linear solvation energy relationships (LSERs) and the surface acoustic wave (SAW) transducers being mass sensitive. Mathematical derivations were included and were supported by simulations. In this work, an experimental data set of polymer-coated SAW vapor sensors is investigated. The data set includes 20 diverse polymers tested against 18 diverse organic vapors. It is shown that interfacial adsorption can influence the response behavior of sensors with nonpolar polymers in response to hydrogen-bonding vapors; however, in general, most sensor responses are related to vapor interactions with the polymers. It is also shown that polymer-coated SAW sensor responses can be empirically modeled with LSERs, deriving an LSER for each individual sensor based on its responses to the 18 vapors. Inverse least-squares methods are used to develop models that correlate and predict vapor descriptors from sensor array responses. Successful correlations can be developed by multiple linear regression (MLR), principal components regression (PCR), and partial least-squares (PLS) regression. MLR yields the best fits to the training data, however cross-validation shows that prediction of vapor descriptors for vapors not in the training set is significantly more successful using PCR or PLS. In addition, the optimal dimension of the PCR and PLS models supports the dimensionality of the LSER formulation and SAW response models.

Journal Article↗

Automated immunomagnetic separation and microarray detection of E. coli O157:H7 from poultry carcass rinse.

We describe the development and application of an electromagnetic flow cell and fluidics system for automated immunomagnetic separation (IMS) of Escherichia coli O157:H7 directly from poultry carcass rinse. We further describe the biochemical coupling of automated sample preparation with nucleic acid microarrays. Both the cell concentration system and microarray detection method did not require cell growth or enrichment from the poultry carcass rinse prior to IMS. Highly porous Ni foam was used to enhance the magnetic field gradient within the flow path, providing a mechanism for immobilizing immunomagnetic particles throughout the fluid rather than the tubing wall. A maximum of 32% recovery efficiency of non-pathogenic E. coli was achieved within the automated system with 6 s cell contact times using commercially available antibodies targeted against the O and K antigens. A 15-min protocol (from sample injection though elution) provided a cell recovery efficiency that was statistically similar to > I h batch captures. O157:H7 cells were reproducibly isolated directly from poultry carcass rinse with 39% recovery efficiency at 10(3) CFU ml(-1) inoculum. Direct plating of washed beads showed positive recovery of O157:H7 directly from poultry carcass rinse at an inoculum of 10 CFU ml(-1). Recovered beads were used for direct polymerase chain reaction (PCR) amplification and microarray detection, with a process-level detection limit (automated cell concentration though microarray detection) of < 10(3)CFU ml(-1) in poultry carcass rinse.

Animals↗

Rational design of a Nile Red/polymer composite film for fluorescence sensing of organophosphonate vapors using hydrogen bond acidic polymers.

The solvatochromic dye Nile Red dispersed in selected hydrogen bond acidic polymer matrixes demonstrated strong fluorescence enhancement at the presence of dimethyl methylphosphonate (DMMP) vapors. Two hydrogen bond acidic polymers were examined as dye matrixes, one with fluorinated alcohol groups on a polystyrene backbone (PSFA) and the other with fluorinated bisphenol groups alternating with oligo(dimethylsiloxane) segments (BSP3). The combination of hydrogen bond acidic polymer (a strong sorbent for DMMP) with the solvatochromic dye led to initial depression of the dye fluorescence and a significant red shift in the absorbance and fluorescence spectra. DMMP sorption changed the dye environment and dramatically altered the fluorescence spectrum and intensity, resulting in a strong fluorescence enhancement. It is proposed that this fluorescence enhancement is due to the competition set up between the dye and the sorbed vapor for polymeric hydrogen-bonding sites. The highest responses were obtained with BSP3. DMMP detection has been demonstrated at sub-ppm DMMP concentrations, indicating very low detection limits compared to previous Nile Red/polymer matrix fluorescence vapor sensors. Nile Red/poly(methyl methacrylate) films prepared for comparisons exhibited substantially lower response to DMMP. Rational selection of polymers providing high sorption for DMMP and competition for hydrogen-bonding interactions with Nile Red yielded flourescent films with high sensitivity.

Journal Article↗

A method for chemometric classification of unknown vapors from the responses of an array of volume-transducing sensors.

A method for the characterization and classification of unknown vapors based on the responses on an array of polymer-based volume-transducing vapor sensors is presented. Unlike conventional pattern recognition methods, the sensor array pattern vector is converted into another vector containing vapor descriptors. Equations are developed to show how this approach can be applied to arrays of sensors where each sensor responds to the fractional volume increase of the polymer upon vapor sorption. The vapor sorption step of the response is modeled with linear solvation energy relationships using solvation parameters as vapor descriptors. The response model also includes the vapor concentration, the sensitivity to fractional volume increases, and the specific volume of the vapor as a liquid. The response model can be solved for the vapor descriptors given the array responses and sensitivity factors, following an approach described previously for purely gravimetric sensors. The vapors can then be classified from a database of candidate vapor descriptors. Chemiresistor vapor sensors coated with composite polymer films containing conducting particles represent a volume-transducing sensor technology to which this new classification method should apply. Preliminary equations are also presented for sensors that respond on the basis of both the mass and the volume of a sorbed vapor. Surface acoustic wave sensors with acoustically thin polymer films that respond to both mass and modulus effects may fit this classification approach.

Journal Article↗

Rotating rod renewable microcolumns for automated, solid-phase DNA hybridization studies.

The development of a new temperature-controlled renewable microcolumn flow cell for solid-phase nucleic acid hybridization in an automated sequential injection system is described. The flow cell included a stepper motor-driven rotating rod with the working end cut to a 45 degrees angle. In one position, the end of the rod prevented passage of microbeads while allowing fluid flow; rotation of the rod by 180 degrees releases the beads. This system was used to rapidly test many hybridization and elution protocols to examine the temperature and solution conditions required for sequence-specific nucleic acid hybridization. Target nucleic acids labeled with a near-infrared fluorescent dye were detected immediately postcolumn during all column perfusion and elution steps using a flow-through fluorescence detector. Temperature control of the column and the presence of Triton X-100 surfactant were critical for specific hybridization. Perfusion of the column with complementary oligonucleotide (200 microL, 10 nM) resulted in hybridization with 8% of the DNA binding sites on the microbeads with a solution residence time of less than 1 s and a total sample perfusion time of 40 s. The use of the renewable column system for detection of an unlabeled PCR product in a sandwich assay was also demonstrated.

DNA↗

The fractional free volume of the sorbed vapor in modeling the viscoelastic contribution to polymer-coated surface acoustic wave vapor sensor responses.

Surface acoustic wave (SAW) vapor sensors with polymeric sorbent layers can respond to vapors on the basis of mass loading and modulus decreases of the polymer film. The modulus changes are associated with volume changes that occur as vapor is sorbed by the film. A factor based on the fractional free volume of the vapor as a liquid has been incorporated into a model for the contribution of swelling-induced modulus changes to observed SAW vapor sensor responses. In this model, it is not the entire volume added to the film by the vapor that contributes to the modulus effect; it is the fractional free volume associated with the vapor molecules that causes the modulus to decrease in a manner that is equivalent to free volume changes from thermal expansion. The amplification of the SAW vapor sensor response due to modulus effects that are predicted by this model has been compared to amplification factors determined by comparing the responses of polymer-coated SAW vapor sensors with the responses of similarly coated thickness shear mode (TSM) vapor sensors, the latter being gravimetric. Results for six to eight vapors on each of two polymers, poly(isobutylene) and poly(epichlorohydrin), were examined. The model predicts amplification factors of the order of about 1.5-3, and vapor-dependent variations in the amplification factors are related to the specific volume of the vapor as a liquid. The fractional free volume factor provides a physically meaningful addition to the model and is consistent with conventional polymer physics treatments of the effects of temperature and plasticization on polymer modulus.

Elasticity↗