Molecular Fluorescence, Phosphorescence, and Chemiluminescence Spectrometry

Oldham, Philip B.; McCarroll, Matthew E.; McGown, Linda B.; Warner, Isiah M.

doi:10.1021/a1000017p

Cited by 55 publications

(37 citation statements)

References 132 publications

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“…38-41 Since 100 mol % borate is required to observe such behavior (or 100 mol % pH chromoionophore; see below), initial conditioning of the films in buffer leads to all of the TFPB anions serving as counter-ions to 100 % of the Al[OEP] in monomeric form (as Al[OEP] + ) and hence the very sharp Soret band expected for the monomer species. As fluoride is added to the buffer, fluoride is extracted to serve as an axial ligand to the Al[OEP] + species; however, to maintain charge neutrality in the polymeric film, a dimer in which two fluoride ions are bridging two Al[OEP] complexes appears to form (Al[OEP] F) 2 . If only a single fluoride bridging species were responsible for the dramatic change in UV-VIS spectrum, then 50 mol% TFPB would be the optimal level to stabilize a positively charged (Al[OEP]) 2 F + dimer.…”

Section: Spectral Properties Of Films Doped With Al[oep]mentioning

confidence: 99%

“…Interestingly, we found that the experimental data obtained for different film compositions and measured at different pH-values or different buffer systems fit very well with the general optode response function assuming a 1 Figures 5A, B, C, and D, as well as Figure 6B for Film-7 formulated with DOS). The theoretical curves in this case can be calculated based on the following general anion-optode response function 13 : (2) where (K ) corresponding to the overall coextraction constant, and α -value (the degree of deprotonation) is the fraction of the total indicator present in the deprotonated form. 13 Although it appears from the spectral data that the Al[OEP]-fluoride interaction is not as simple as that observed for other porphyrin systems, and possibly involves multiple equlibria including the formation of a bis-fluoride bridged porphyrin dimer, the fluoride ion response of the optical sensitive films based on Al[OEP] does follow the classical optode response function for a 1:1 complex formation.…”

Section: Optical Response Of Al[oep]/eth-7075 To Fluoride Ionmentioning

confidence: 99%

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Fluoride-Selective Optical Sensor Based on Aluminum(III)−Octaethylporphyrin in Thin Polymeric Film: Further Characterization and Practical Application

Badr

Meyerhoff

2005

Anal. Chem.

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More detailed analytical studies of a new fluoride selective optical sensor based on the use of aluminum(III)-octaethylporphyrin and a lipophilic pH indicator (4′,5′-dibromofluorescein octadecyl ester; ETH-7075) within a thin plasticized poly(vinyl chloride) film are reported. The sensor exhibits extraordinary optical selectivity for fluoride over a wide range of other anions, including anions with far more positive free energies of hydration (e.g., perchlorate, thiocyanate, nitrate, etc.). UV-VIS spectrophotometric studies of the sensing films indicate that fluoride interacts with the Al(III) center of the porphyrin structure, yielding both a change in the Soret band λ max of the porphyrin as well as a change in the protonation state of the pH indicator within the film. The same change in spectral properties of the metalloporphyrin occurs in the absence of added pH indicator or with added tetraphenylborate derivative anionic sites, but optical responses to fluoride in these cases are shown to be irreversible. The presence of the pH indicator and the simultaneous fluoride/proton coextraction equilibrium chemistry is shown to greatly enhance the reversibility of fluoride binding to the Al(III) porphyrin. Optical response toward fluoride can be observed in the range of 0.1 μM to 1.6 mM. Optical selectivity coefficients of < 10 −6 for common anions (e.g., sulfate, chloride, nitrate etc.) and < 10 −4 for perchlorate and thiocyanate are obtained. Measurements of fluoride in drinking water via the new optical sensor are shown to correlate well with values obtained for the same samples using a classical LaF 3 based fluoride ion-selective electrode method.

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Section: Spectral Properties Of Films Doped With Al[oep]mentioning

confidence: 99%

Section: Optical Response Of Al[oep]/eth-7075 To Fluoride Ionmentioning

confidence: 99%

Fluoride-Selective Optical Sensor Based on Aluminum(III)−Octaethylporphyrin in Thin Polymeric Film: Further Characterization and Practical Application

Badr

Meyerhoff

2005

Anal. Chem.

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“…6 Chemiluminescence (CL) has been exploited with a wide range of applications in different fields, such as biotechnology, pharmacology, molecular biology, and clinical and environmental chemistries. [7][8][9][10] However, only one CL method was reported for the determination of MP, which was based on reactions among tris-(2,2′-bipyridine)ruthenium(II), MP, hydrogen peroxide, Tween 20 and hydroxide ion. 11 In this method, the mixing order of the reagents considerably affects the CL signal.…”

Section: Introductionmentioning

confidence: 99%

Simple Chemiluminescence Method for the Determination of Mercaptopurine

Lau

Yagisawa

et al. 2002

ANAL. SCI.

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IntroductionMercaptopurine (MP) belongs to a general group of drugs known as antimetabolites, and is used to treat several types of cancers, including leukemia. MP interferes with the synthesis of nucleic acids, and thus disrupts the growth of cancer cells, which are then destroyed. However, because this drug can not distinguish cancer and normal cells, it causes side effects, since some normal cells are affected. Therefore, it is important to develop sensitive quantitative methods for controlling its administration.A number of spectrometric and fluorometric methods have already been successfully used for determining MP. For example, Tawa et al. developed a sensitive fluorometric method, based on the enzymatic oxidation of MP with xanthine oxidase to the oxypurine, followed by oxidation with acidic chromate to the corresponding fluorescent sulfonate. 1 Several liquid chromatographic methods have also been described. [2][3][4][5][6] Jonkers et al. determined MP in human plasma using HPLC, including post-column derivatization and fluorometric detection. 4 Van Os et al. measured MP using solid-phase extraction and reversed-phase HPLC. 5 Georget et al. determined MP in capsules prepared for paediatric patients by capillary zone electrophoresis. 6 Chemiluminescence (CL) has been exploited with a wide range of applications in different fields, such as biotechnology, pharmacology, molecular biology, and clinical and environmental chemistries.7-10 However, only one CL method was reported for the determination of MP, which was based on reactions among tris-(2,2′-bipyridine)ruthenium(II), MP, hydrogen peroxide, Tween 20 and hydroxide ion. 11 In this method, the mixing order of the reagents considerably affects the CL signal. Still, a simple and convenient method to measure mercaptopurine would be highly desirable.Here, we report on such a simple and convenient CL method for the determination of MP. We found that weak CL emitted after mixing H2O2 and luminol under alkaline conditions could be greatly enhanced by MP. Most importantly, this new reaction had a longer light signal, which was very convenient for routine applications, especially with a simple setup, since the mixing of CL reagents could generally be performed outside of the measuring device. Based on this fact, a simple and robust technique for the convenient measurement of MP was developed. The linear range was 1.5 mM -5 µM with a detection limit of 1 µM. Overall, the proposed CL method was simple, convenient and sufficiently sensitive for the determination of MP in the drug powder. Experimental ChemicalsA stock solution for 10 -2 M MP (Wako, Japan) was prepared by dissolving in 0.1 M NaOH. Other standard solutions were made by gradually diluting relative stock solutions with 0.1 M NaOH containing 2.5 mM EDTA. Hydrogen peroxide, luminol and other organic compounds were also purchased from Wako, Japan. An MP-containing drug, Leukerin, was obtained from Takeda Pharmaceutical Company, Japan. CL detection proceduresLight-producing reactions were carried out in 12 ×...

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“…Nevertheless, the advantages of LEDs are compelling. LEDs have now been used in a wide range of optical-sensing devices (Oldham et al 2000;Agbaria et al 2002;Powe et al 2004;Fletcher et al 2006;Lowry et al 2008;Powe et al 2010), and researchers have begun to demonstrate field-capable instruments. For example, Obeidat et al (2008) describe a 1.5 kg spectrofluorometer for analyzing plant and animal feed in the field, using excitation sources ranging from 405 to 640 nm; power is supplied by a laptop computer which also captures, stores, and analyzes the resulting EEMs.…”

mentioning

confidence: 99%

A multi‐platform optical sensor for in situ sensing of water chemistry

Senft-Grupp

Hemond

2012

Limnology & Ocean Methods

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A compact field-deployable optical instrument using fluorescence, absorbance, and scattering to identify and quantify contaminants and natural substances in water bodies is described. The instrument is capable of deployment on autonomous underwater and surface vehicles, manned vehicles, fixed platforms such as buoys, or access points in water supply or drainage networks. The instrument comprises (1) a flowcell, (2) multiple optical systems, (3) a data logger, (4) a power control board and computer, and (5) a battery. The instrument has been packaged in a cylindrical pressure case of 200 mm diameter and 300 mm length for electrically and mechanically seamless insertion as a STARFISH AUV payload module. The same module can be fitted with watertight end caps for use aboard other platforms, or simpler packaging can be employed for use in less demanding environments. For spectrofluorometry, the system uses six (expandable to twelve) electronically switchable excitation sources, allowing the construction of fluorescence excitation-emission matrices (EEMs). A deuterium-tungsten light source (185 to 1100 nm) is used in making UV-VIS absorbance measurements. Turbidity can be measured by nephelometry, using observations of light scattering at each excitation wavelength. The absorbance and turbidity capabilities provide useful water quality information and can also be used for correction of inner shielding effects. Validation of the instrument includes (1) comparison with a commercial luminescence spectrometer in measuring both standards and field samples, (2) comparisons of observed spectra with published optical characteristics for several chemicals, and (3) field demonstration aboard an AUV.

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Molecular Fluorescence, Phosphorescence, and Chemiluminescence Spectrometry

Cited by 55 publications

References 132 publications

Fluoride-Selective Optical Sensor Based on Aluminum(III)−Octaethylporphyrin in Thin Polymeric Film: Further Characterization and Practical Application

Fluoride-Selective Optical Sensor Based on Aluminum(III)−Octaethylporphyrin in Thin Polymeric Film: Further Characterization and Practical Application

Simple Chemiluminescence Method for the Determination of Mercaptopurine

A multi‐platform optical sensor for in situ sensing of water chemistry

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