The preparation of a sol–gel glass oxygen sensor incorporating a covalently bound fluorescent dye

Malins, Chris; Glever, H.G; MacCraith, Brian D.; Fanni, Stefano; Vos, Johannes G.

doi:10.1039/a808731h

Cited by 56 publications

(28 citation statements)

References 14 publications

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“…23), rather than the glass substrate, provides the advantage of a more homogeneous and well-defined distribution of the dye in the glass film. [175,184] Moreover, the covalent coupling of the dye to the substrate allows prevention of any dye leaching and thus improves the sensor performance. Immobilization by chemical bonding is more appropriate for small indicators and sterically hindered analyte molecules.…”

Section: Hybrid Optical Sensorsmentioning

confidence: 99%

Optical Properties of Functional Hybrid Organic–Inorganic Nanocomposites

et al. 2003

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Functional hybrids are nanocomposite materials lying at the interface of organic and inorganic realms, whose high versatility offers a wide range of possibilities to elaborate tailor‐made materials in terms of chemical and physical properties. Because they present several advantages for designing materials for optical applications (versatile and relatively facile chemistry, easy shaping and patterning, materials having good mechanical integrity and excellent optical quality), numerous silica or/and siloxane based hybrid organic–inorganic materials have been developed in the past few years. The most striking examples of functional hybrids exhibiting emission properties (solid‐state dye lasers, rare‐earth doped hybrids, electroluminescent devices), absorption properties (photochromic), nonlinear optical (NLO) properties (second‐order NLO properties, photochemical hole burning (PHB), photorefractivity), and sensing are summarized in this review.

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Section: Hybrid Optical Sensorsmentioning

confidence: 99%

Optical Properties of Functional Hybrid Organic–Inorganic Nanocomposites

et al. 2003

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“…[50,51] Despite the growing interest in functionalized sol-gel materials, only a few examples are known for gas separation through the formation of chemical bonds between gas molecules and coordination complexes immobilized in an inorganic matrix by way of chemisorption, [39, 40, 52 53] and their use as gas sensors is still scarce. Mainly optical O 2 sensors based on fluorescence quenching have been studied, [50,51,[54][55][56][57] but a lack of selectivity [58] is generally observed when there is no covalent binding of the gas molecule to the active species.…”

Section: -Peroxodicopper(ii) and Bisa C H T U N G T R E N N U N G (M-mentioning

confidence: 99%

Exceptional Affinity of Nanostructured Organic–Inorganic Hybrid Materials towards Dioxygen: Confinement Effect of Copper Complexes

Brandès

David

Suspène

et al. 2007

Chemistry A European J

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We report the exceptional reactivity towards dioxygen of a nanostructured organic-inorganic hybrid material due to the confinement of copper cyclam within a silica matrix. The key step is the metalation reaction of the ligand, which can occur before or after xerogel formation through the sol-gel process. The incorporation of a Cu(II) center into the material after xerogel formation leads to a bridged Cu(I)/Cu(II) mixed-valence dinuclear species. This complex exhibits a very high affinity towards dioxygen, attributable to auto-organization of the active species in the solid. The remarkable properties of these copper complexes in the silica matrix demonstrate a high cooperative effect for O(2) adsorption; this is induced by close confinement of the two copper ions leading to end-on mu-eta(1):eta(1)-peroxodicopper(II) complexes. The anisotropic packing of the tetraazamacrocycle in a lamellar structure induces an exceptional reactivity of these copper complexes. We show for the first time that the organic-inorganic environment of copper complexes in a silica matrix fully model the protecting role of protein in metalloenzymes. For the first time an oxygenated dicopper(II) complex can be isolated in a stable form at room temperature, and the reduced Cu(2) (I,I) species can be regenerated after several adsorption-desorption cycles. These data also demonstrate that the coordination scheme and reactivity of the copper cyclams within the solid are quite different from that observed in solution.

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“…Either of these changes can be quantified and provide the basis for a relatively simple, inexpensive analysis method. In homogeneous media with a single-exponential decay, oxygen quenching of the intensity and lifetime of this kind of oxygen sensor is described by the Stern-Volmer equation: [28] I 0 /I = s 0 /s = 1 + K SV p O 2 = 1 + js 0 p O 2 (1) where I and s are the luminescence intensity and excited-state lifetime of the luminophore, respectively, the subscript 0 denotes the absence of oxygen, K SV is the Stern-Volmer constant, j is the bimolecular quenching constant, and p O 2 is the partial pressure of oxygen at 1 atm (1 atm = 101 325 Pa) pressure. A plot of I 0 /I or s 0 /s versus oxygen concentration should give a straight-line relationship with slope K SV , and an intercept of Novel oxygen sensors consisting of a [Ru(bpy) 2 phen] 2+ (bpy: 2,2′-bipyridyl, phen: phenathroline) portion covalently grafted to a mesostructured silica-based network are prepared in situ via a sol-gel approach with the help of cetyltrimethylammoniumbromide (CTAB) surfactant.…”

Section: Introductionmentioning

confidence: 99%

Mesostructured Silica Chemically Doped with Ru^II as a Superior Optical Oxygen Sensor

Lei

Zhang

et al. 2006

Adv Funct Materials

198

199

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Novel oxygen sensors consisting of a [Ru(bpy)2phen]2+ (bpy: 2,2′‐bipyridyl, phen: phenathroline) portion covalently grafted to a mesostructured silica‐based network are prepared in situ via a sol–gel approach with the help of cetyltrimethylammoniumbromide (CTAB) surfactant. 1,10‐Phenanthroline covalently grafted to 3‐(triethoxysilyl)propyl isocyanate is used as not only the sol–gel precursor but also as the second ligand of the Ru(bpy)2Cl2 · 2H2O complex to prepare the sol–gel‐derived mesostructured silicates for an oxygen sensor. For comparison purposes, the oxygen sensors in which [Ru(bpy)2phen]Cl2 is conventionally physically incorporated into the matrix are also prepared. Elemental analysis, NMR, Fourier transform IR, UV‐vis electronic absorption, luminescence‐intensity quenching Stern–Volmer plots, and excited‐state decay analysis are used to characterize the obtained oxygen sensors. These obtained bulk xerogels and spin‐coated thin films show that the homogeneity and the sensitivity of the covalently grafted samples are superior to those of the physically incorporated ones, and the highest sensitivity is obtained in the mesostructured bulk xerogel. This improvement in oxygen sensitivity is attributed to the increased diffusivity of oxygen in the uniform and nearly parallel porous structure of the Mobil Catalytic Material 41 mesostructured matrix, the enhanced homogeneity results from the covalently grafted propyl group in –Si–(CH2)3– that acts as the fundamental spacer which prevents interaction between the attached RuII complex and the silica matrix, and optimal dispersion in the mesopores during the sol–gel polycondensation. Furthermore, the greatly minimized leaching effect of the sensing molecules could be observed in the covalently grafted system. The covalent grafting strategy presented in this paper provides superior optical oxygen sensors with homogeneous distribution, improved sensitivity, and simplified calibration plots.

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The preparation of a sol–gel glass oxygen sensor incorporating a covalently bound fluorescent dye

Cited by 56 publications

References 14 publications

Optical Properties of Functional Hybrid Organic–Inorganic Nanocomposites

Optical Properties of Functional Hybrid Organic–Inorganic Nanocomposites

Exceptional Affinity of Nanostructured Organic–Inorganic Hybrid Materials towards Dioxygen: Confinement Effect of Copper Complexes

Mesostructured Silica Chemically Doped with Ru^II as a Superior Optical Oxygen Sensor

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The preparation of a sol–gel glass oxygen sensor incorporating a covalently bound fluorescent dye

Cited by 56 publications

References 14 publications

Optical Properties of Functional Hybrid Organic–Inorganic Nanocomposites

Optical Properties of Functional Hybrid Organic–Inorganic Nanocomposites

Exceptional Affinity of Nanostructured Organic–Inorganic Hybrid Materials towards Dioxygen: Confinement Effect of Copper Complexes

Mesostructured Silica Chemically Doped with RuII as a Superior Optical Oxygen Sensor

Contact Info

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Mesostructured Silica Chemically Doped with Ru^II as a Superior Optical Oxygen Sensor