Design of oxygen sensors based on quenching of luminescent metal complexes: Effect of ligand size on heterogeneity

Sacksteder, LouAnn.; Demas, J. N.; DeGraff, Β. A.

doi:10.1021/ac00071a024

Cited by 131 publications

(79 citation statements)

References 7 publications

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“…The first model conceptualizes the embedded luminophores as occupying two, or more, sites within the foil. Each site is considered to have its own characteristic quenching constants (Carraway et al 1991;Sacksteder et al 1993). For an optode, if some fluorophores in the foil are accessible to oxygen by diffusion while others are not, fluorophores at both sites still fluoresce when stimulated with blue light, but only those sites accessible to oxygen contribute to a reduction in the intensity of the fluoresced red light.…”

Section: Non-linear Stern-volmer Relationshipmentioning

confidence: 99%

A calibration equation for oxygen optodes based on physical properties of the sensing foil

McNeil

D’Asaro

2014

Limnology & Ocean Methods

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We present a new physically based calibration equation for Aanderaa Inc. oxygen sensing optodes. We use the two site fluorescence quenching model of Demas et al. (1995) to describe the nonlinear Stern-Volmer response of the optode foil to oxygen partial pressure. Seven (minimally six) coefficients quantify foil response to oxygen and temperature; another quantifies response to hydrostatic pressure. These eight coefficients are related, theoretically, to basic physical properties of the foil. The equation provides a framework to study causes of variability and drift in optodes and to develop better quality control and handling procedures. We tested the equation using factory calibrations of 24 optode foils. When accurate multi-point calibration data are unavailable, two additional coefficients empirically correct the usually large differences observed between factory foil calibrations and post-factory laboratory/field calibrations; we cannot eliminate this major cause of uncertainty in optode calibrations. Excluding two potentially anomalous foils, the calibration equation fits 13 similarly calibrated foils, totaling 455 calibration points over 3 -40°C to -0.57 ± 1.48 mbar. Analysis of the resulting best fit coefficients reveals an underlying variability in optodes associated with variability in site 2 and site 1 Stern-Volmer coefficients of 32% and 20%, respectively. The fraction of unquenched fluorophores responding with the more accessible site 1 quenching characteristics varies by only 3%. The equation fits multi-point data for two optodes within manufacturer's specifications, the greater of ± 2.5 μmol . kg -1 and ± 1.5%. Detailed measurements of calibration changes over time will be required to understand the causes of optode drift.

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Section: Non-linear Stern-volmer Relationshipmentioning

confidence: 99%

A calibration equation for oxygen optodes based on physical properties of the sensing foil

McNeil

D’Asaro

2014

Limnology & Ocean Methods

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“…Recently, a variety of devices and sensors based on luminescent quenching of organic dyes have been developed to measure oxygen concentration on the solid surface. Many optical oxygen sensors are composed of organic dyes, such as polycyclic aromatic hydrocarbons (pyrene and its derivatives) [8][9][10][11][12][13][14], transition metal polypyridine complexes (ruthenium [15][16][17][18][19][20], osmium [21] or rhenium complexes [22]), and metalloporphyrins (platinum or palladium complexes [23][24][25]), immobilized in an oxygen permeable polymer (silicon polymer, polystyrene and so on). Among these dyes, platinum and palladium octaethylporphyrin (PtOEP and PdOEP) display strong room-temperature phosphorescence with high quantum yield and long lifetime (ca 100 ms for PtOEP and ca 770 ms for PdOEP) [26].…”

Section: Introductionmentioning

confidence: 99%

Metalloporphyrins immobilized in styrene–trifluoroethylmethacrylate copolymer film as an optical oxygen sensing probe

Amao¹,

Miyashita

Okura

2001

J. Porphyrins Phthalocyanines

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A series of new fluoropolymer, poly(styrene-co-trifluoroethylmethacrylate) (poly-Sty n -co-TFEM m ), with different composition ratios of Sty and TFEM units, is synthesized and applied to the matrix of an optical oxygen sensing probe using phosphorescence quenching of metalloporphyrins, platinum and palladium octaethylporphyrin (PtOEP and PdOEP), by oxygen. The phosphorescence intensity of PtOEP and PdOEP in poly-Sty n -co-TFEM m film decreased with increase of oxygen concentration. The ratio I 0 /I 100 is used as a sensitivity of the sensing film, where I 0 and I 100 represent the detected phosphorescence intensities from a film exposed to 100% argon and 100% oxygen, respectively. For PtOEP in poly-Sty n -co-TFEM m film, I 0 /I 100 ratios are more than 20.6 and large Stern-Volmer constants greater than 0.49% À1 are obtained compared with PtOEP in PS film. For PdOEP in poly-Sty n -co-TFEM m film, on the other hand, large I 0 /I 100 values greater than 188.7 are obtained. In both cases for PtOEP and PdOEP, I 0 / I 100 values increased with increase of the number of TFEM units in poly-Sty n -co-TFEM m . The response times of PtOEP and PdOEP immobilized in poly-Sty 1 -co-TFEM 2.50 films are 5.5 and 3.0 s on going from argon to oxygen and 90.0 and 143 s from oxygen to argon, respectively. These results show that PtOEP and PdOEP immobilized in polySty n -co-TFEM m films are highly sensitive devices for oxygen.

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“…Consequently, the material, along with platinum-porphyrin, is useful as a luminescence sensor for oxygen. [41][42][43][44] We incorporated ruthenium complexes in polymer nanosheets through polyion complex method 45 and examined the possibility of the luminescent polymer nanosheets for oxygen sensor applications. The luminescent polymer nanosheet provides smooth surface coating, and enables the surface oxygen concentration detection as the luminescence intensity changes.…”

Section: Spectroscopic Properties Of Metal Nanoparticles Assembled Wimentioning

confidence: 99%

Hybrid Polymer Nanoassemblies: Polymer Nanosheets Organized with Metal Nanoparticle Arrays for Surface Plasmon Photonics

Mitsuishi

Ishifuji

Endô

et al. 2007

Polym J

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ABSTRACT:The paper describes fabrication of hybrid polymer nanoassemblies possessing polymer nanosheets and metal nanoparticle arrays. Based on a bottom-up approach with ultrathin polymer Langmuir-Blodgett films (polymer nanosheets) and metal nanoparticles, we constructed hybrid nanoassemblies for opto/electric nanodevice applications: nanoscale positioning of metal nanoparticles, free-standing hybrid polymer nanosheets, hybrid polymer nanoassemblies for luminescence sensor application, and enhancement of nonlinear optical (NLO) efficiency via surface plasmon coupling. Assembling nanomaterials such as nanoparticles and organic functional molecules through a bottom-up approach makes it possible to strengthen free-standing nanofilm stability, enhance luminescence of luminescent molecules, and enhance second harmonic light from NLO molecules under the influence of localized surface plasmons. The high potential of hybrid polymer nanoassemblies for precise nanoscale design is also demonstrated.[doi:10.1295/polymj.PJ2006235] KEY WORDS Polymer / LB Film / Metal Nanoparticle / Surface Plasmon / Hybrid / Design of nanostructures using polymer materials has been widely explored and has now become prevalent. Bottom-up approaches such as layer-by-layer (LbL) adsorption, 1 surface-initiated polymerization exemplified by atom transfer radical polymerization (ATRP), 2 and Langmuir-Blodgett (LB) technique [3][4][5][6][7] make it possible to develop myriad nanoarchitectures on solid substrates. These approaches and their combinations offer a promising route to polymer nanoarchitectures for a wide variety of functional materials and surfaces. Using these nanostructures, for instance, the surface properties can be controlled uniformly, even on a nanoscale. These compelling qualities of ultrathin polymer films have been expanded to broad scientific fields. It is important to intensify the interdisciplinary interactions, for example, between polymer materials and inorganic nanoparticles in basic and application-oriented work.We have investigated functionalization of polymer LB films consisting of poly(alkylacrylamide)s. Poly-(N-dodecylacrylamide) (pDDA) proved to be excellent for LB assembly; the material provides a highly oriented and densely packed monolayer at the airwater interface. 8,9 Varying the side chain length, the film thickness is tuned at a nanometer scale (1-2 nm in length). Widely various functional molecules were incorporated and distributed uniformly in a two-dimensional (2D) field. The key factor is the existence of a 2D hydrogen-bonding network between polymer backbones, which enhances the monolayer stability at the air-water interface, leading to quantitative deposition onto solid substrates via vertical dipping. We recently designated polymer LB films consisting of alkyl acrylamide polymer as polymer nanosheets. Using these advantages, directional (vectorial) electron transfer between several redox components was achieved in multilayered polymer nanosheets, 10,11 extending to logic gate operations.12, 13 We have...

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Design of oxygen sensors based on quenching of luminescent metal complexes: Effect of ligand size on heterogeneity

Cited by 131 publications

References 7 publications

A calibration equation for oxygen optodes based on physical properties of the sensing foil

A calibration equation for oxygen optodes based on physical properties of the sensing foil

Metalloporphyrins immobilized in styrene–trifluoroethylmethacrylate copolymer film as an optical oxygen sensing probe

Hybrid Polymer Nanoassemblies: Polymer Nanosheets Organized with Metal Nanoparticle Arrays for Surface Plasmon Photonics

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