Spectroelectrochemical Sensing Based on Multimode Selectivity Simultaneously Achievable in a Single Device. 19. Preparation and Characterization of Films of Quaternized Poly(4‐vinylpyridine)‐silica

Conklin, Sean D.; Heineman, William R.; Seliskar, Carl J.

doi:10.1002/elan.200603796

Cited by 15 publications

(17 citation statements)

References 31 publications

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“…[10][11][12][13][14][15][16][17][18][19][20][21][22] and two commonly used model analytes: ferrocyanide, [Fe(CN) 6 ] 4-, and ruthenium-tris(2,2'-bipyridyl), [Ru(bpy) 3 ] 2+ , ions ( Figure 2). 17,23 These analytes absorb at similar wavelengths, however they are oppositely charged and the redox potentials are far apart ( Figure 3).…”

Section: Demonstration Of Spectroelectrochemical Sensormentioning

confidence: 99%

Spectroelectrochemistry as a strategy for improving selectivity of sensors for security and defense applications

Heineman¹,

Seliskar²,

Morris³

et al. 2012

SPIE Proceedings

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Spectroelectrochemistry provides improved selectivity for sensors by electrochemically modulating the optical signal associated with the analyte. The sensor consists of an optically transparent electrode (OTE) coated with a film that preconcentrates the target analyte. The OTE functions as an optical waveguide for attenuated total reflectance (ATR) spectroscopy, which detects the analyte by absorption. Alternatively, the OTE can serve as the excitation light for fluorescence detection, which is generally more sensitive than absorption. The analyte partitions into the film, undergoes an electrochemical redox reaction at the OTE surface, and absorbs or emits light in its oxidized or reduced state. The change in the optical response associated with electrochemical oxidation or reduction at the OTE is used to quantify the analyte. Absorption sensors for metal ion complexes such as [Fe(CN) 6 ] 4-and [Ru(bpy) 3 ] 2+ and fluorescence sensors for [Ru(bpy) 3 ] 2+ and the polycyclic aromatic hydrocarbon 1-hydroxypyrene have been developed. The sensor concept has been extended to binding assays for a protein using avidin-biotin and 17β-estradiol-anti-estradiol antibodies. The sensor has been demonstrated to measure metal complexes in complex samples such as nuclear waste and natural water. This sensor has qualities needed for security and defense applications that require a high level of selectivity and good detection limits for target analytes in complex samples. Quickly monitoring and designating intent of a nuclear program by measuring the Ru/Tc fission product ratio is such an application.

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Section: Demonstration Of Spectroelectrochemical Sensormentioning

confidence: 99%

Spectroelectrochemistry as a strategy for improving selectivity of sensors for security and defense applications

Heineman¹,

Seliskar²,

Morris³

et al. 2012

SPIE Proceedings

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“…Other investigations on such complex films are known [448,449]. The electroactivity in nonpolar solvent is then very dependent on the water content of the organic solvent, which allows the construction of a water sensor [233].…”

Section: Electrochemically Induced Complexationmentioning

confidence: 99%

Porous Carbons – Hyperbranched Polymers – Polymer Solvation

Long

Voit

Okay

2015

Advances in Polymer Science

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“…Two materials were investigated during this period: quaternized poly(4-vinylpyridine) (QPVP) in its pure form 32 and immobilized in porous silica. 39 and partially sulfonated polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene (SSEBS). 33 Quaternized poly (4-vinylpyridine) (QPVP).…”

Section: Development and Characterization Of New Materials For Preconmentioning

confidence: 99%

“…33 Quaternized poly (4-vinylpyridine) (QPVP). QPVP has been used as an anion exchanger alone 32 as well as incorporated into sol-gel derived silica films (QPVP-silica) 39 for the spectroelectrochemical sensor. The preparation, characteristics and performance of these films were determined.…”

Section: Development and Characterization Of New Materials For Preconmentioning

confidence: 99%

Spectroelectrochemical Sensor for Pertechnetate Applicable to Hanford and Other DOE Sites

Heineman¹,

Seliskar²,

Bryan³

et al. 2009

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RESULTS TO DATE:Task 1: Refinement of the chemically-selective film for pertechnetate New film materials for pertechnetate: A new film material comprised of quaternized poly(4-vinylpyridine) cross-linked with 1,10-diiododecane has been developed for use in the spectroelectrochemical sensor. Films were prepared in a one-pot synthesis by stirring poly(4-vinylpyridine), cross-linker and methyl iodide in 1-butanol for 1 h, after which the solution was spincoating onto ITO-glass. Film thickness was varied either by changing the spin rate or by dilution of the original precursor solution. The thinnest film prepared was 30 nm; the thickest 930 nm. Spectroscopic ellipsometry was used to study the dynamics of film changes on soaking in aqueous salt solution and on preconcentrating model analyte ferrocyanide. The results document that, on hydration, films expanded by almost 90% in 0.1 M KNO3, then contracted slightly when ferrocyanide solution was introduced probably due to electrostatic cross-linking. IR spectroscopy was used to determine the extent of quaternization of the film. For a polymer solution stirred for 1 h, films were about 20% quaternized. This can be increased to ~30% by adding more solvent to the precursor solution and stirring for an additional hour. Solubility of the partially cross-linked material was a factor that limited the quaternization process. Use of a more appropriate solvent may enable greater quaternization. A more quaternized film should preconcentrate more pertechnetate by virtue of having a higher density of charged binding sites. Film ruggedness is critical. To investigate this, films on ITO-glass were soaked in methanol and butanol overnight, in 0.1M KNO3, and in 0.1M KNO3 adjusted to pH 12 and pH 2 for 30 days. Each film was then tested as a spectroelectrochemical sensor for model analyte ferrocyanide. The results showed only the pH 2 conditioned sensor behaved abnormally. The film soaked in pH 2 electrolyte delaminated but did not dissolve. Delamination was most likely due to the acid digestion of the ITO layer of the sensor and not to any film-based process. We have also shown that it is possible to regenerate the film by flushing with 1M KNO3 solution. Response curves were prepared from a single sensor by injecting different concentrations of ferrocyanide, monitoring the uptake, then regenerating the film and injecting the next concentration. To check reproducibility, a film was regenerated 10 times with almost no change in response. Film selectivity was demonstrated by adding a model cationic species, Ru(bipy)32+ to the ferrocyanide sample. Even at 10 times the ferrocyanide concentration, only a very small electrochemical signal and no optical signal due to the cation were observed. Additionally a competitive anion Ru(CN)64-could be distinguished from Fe(CN)64-based on the redox potential and absorbance spectrum differences between the two anions. Both species were preconcentrated into the film, and both could be electrochemically modulated simultaneously or individually. The films e...

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Spectroelectrochemical Sensing Based on Multimode Selectivity Simultaneously Achievable in a Single Device. 19. Preparation and Characterization of Films of Quaternized Poly(4‐vinylpyridine)‐silica

Cited by 15 publications

References 31 publications

Spectroelectrochemistry as a strategy for improving selectivity of sensors for security and defense applications

Spectroelectrochemistry as a strategy for improving selectivity of sensors for security and defense applications

Porous Carbons – Hyperbranched Polymers – Polymer Solvation

Spectroelectrochemical Sensor for Pertechnetate Applicable to Hanford and Other DOE Sites

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