title: Optical determination of low-level water concentrations in organic solvents using fluorescent acridinyl dyes and dye-immobilized polymer membranes.
abstract: The fluorescent acridinyl indicators 4-(9-acridinyl)-N-(5-hexenyl)-N-methylaniline (KD-F0011), 6-(9-acridinyl)-1,2,2,3-tetramethyl-2,3-dihydro- 1H-perimidine (KD-F0021), and 6-(9-acridinyl)-2-(3-butenyl)-1,2,3-trimethyl-2,3-dihydro-1H-perimidine (KD-F0022) were designed, synthesized, and applied for highly sensitive optical determination of low-level water in organic solvents. All these dyes were found useful as fluorescence indicators for the detection of water below 1% (v/v) in different solvent media with a low detection limit of 0.002% (v/v) or 20 mg/L (22 ppm by weight) for KD-F0021 in THF solution. Sensing membranes made from poly(ethylene glycol) dimethacrylate by photocopolymerization with the indicator KD-F0011 were also prepared. Using the membrane sensor, the lowest detection limit of 0.001% (v/v) or 14 mg/L (20 ppm) water was achieved in diethyl ether samples. This system enables the continuous monitoring of the water content in a flow-through arrangement, where single-wavelength excitation (404 nm) and single-wavelength detection (532 mm) can be used for the fluorescence determination, allowing a simple measurement setup. In a continuous-flow experiment using THF samples, fully reversible and fast signal changes with t95% = 1-2 min for water concentrations up to 0.50% (v/v) were observed. A detection limit of 0.004% (v/v) or 40 mg/L (45 ppm) water in THF was achieved. These characteristics make this type of sensor a useful tool for the online continuous monitoring of water present as an impurity in organic media, which is difficult to achieve using a Karl Fischer instrument.
authors.affiliation: Department of Applied Chemistry, Keio University, Yokohama, Japan.
authors.forename: D
authors.initials: D
authors.lastname: Citterio
authors.forename: T K
authors.initials: TK
authors.lastname: Minamihashi
authors.forename: Y
authors.initials: Y
authors.lastname: Kuniyoshi
authors.forename: H
authors.initials: H
authors.lastname: Hisamoto
authors.forename: S
authors.initials: S
authors.lastname: Sasaki
authors.forename: K
authors.initials: K
authors.lastname: Suzuki