Using N-Aminoperylene-3,4:9,10-tetracarboxylbisimide as a Fluorogenic Reactand in the Optical Sensing of Aqueous Propionaldehyde

Abstract

Aldehydes are usually determined via chemical derivatization using a chromogenic and fluorogenic reagent followed by chromatographic separation and UV-visible detection. As a consequence, continuous on-line monitoring is impossible. Following our concept of reversible chemical reactions as the basis of optical sensors, we have investigated N-amino-N'-(1-hexylheptyl)perylene-3,4:9,10-tetracarboxylbisimide for aldehyde sensing. The fluorogenic reactand has been embedded in plasticized PVC, and the resulting thin layers have been exposed to aqueous samples of aliphatic aldehydes and ketones. The reactand exhibits a pronounced increase in fluorescence upon interaction with aldehydes since the chemical reaction causes a dequenching of perylene fluorescence. Upon interaction with aqueous propionaldehyde, sensor layers typically exhibit a dynamic range from 5 to 100 mM propionaldehyde, and the limit of detection amounts to 0.08 mM. The forward and reverse response time (t95) for a decade change in activity is in the range of 2-7 min, when measured at pH 2.5. The selectivity of sensor layers toward aldehydes correlates with their lipophilicity in that aldehydes with higher lipophilicity are more efficiently extracted into the polymer layer.

Chromogenic and Fluorogenic Reactands: New Indicator Dyes for Monitoring Amines, Alcohols and Aldehydes

“…Again a dependence of the response on the lipophilicity of the respective aldehyde is found in that highest sensitivity is observed for butyraldehyde, followed by propionaldehyde, acetaldehyde, glutaraldehyde, formaldehyde and glyoxal [32]. The sensitivity to all investigated ketones is relatively small (Table 5).…”

Covalent Interactions in Chemosensor Design

“…This type of interaction has the advantage of being very strong, reversible, and functional in an aqueous or at least in a protic solvent. Quite a few optical sensors have been reported in recent years in this area [126][127][128][129][130][131][132][133][134][135][136][137][138][139][140][141]. In one specific example, (trifluoreacetyl) azobenzene dye (10, Scheme 3.3) was reported to change chromophoric properties upon reaction with an amine.…”

Chromo‐ and Fluororeactands: Indicators for Detection of Neutral Analytes by Using Reversible Covalent‐Bond Chemistry

“…The resulting electron de- [8] PVC/DOS decrease in absorbance at 305 ÀNH 2 (primary, secondary and tertiary amines, aniline) ETH T 4004 [10] PVC/DOS 453!373 ÀSH ETH T 4001 [10] PVC/DOS 497!424 CR-546 [18] PVC/NPOE 556!482 CR-573 [31] PVC/NPOE 577!546 ÀNH 2 (primary and secondary amines), OH -CR-593 [18] PVC/NPOE 642!468 ÀNHÀNH 2 (hydrazines) [20] Sol-gel (TEOS) increase in absorbance at 460 HSO 3 À , SO 2 , CN À , HCN CR-514 [19] PVC/NPOE 524!488 CR-590 [18] PVC/NPOE 582!524 cis-diols (glucose, fructose, mannose) [24] methanol/water (1:2, w/w) 564!509 ÀCHO (formaldehyde, acetaldehyde, acrolein, etc. ), CO 2 J-57 [26] PVC/TOP increase in fluorescence at 534 , 576 and 613 CR-418 [28] PVC/NPOE 438!449 pararosaniline [9] XAD-resin increase in absorbance at 560 CO 2 [29] DMSO increase in fluorescence at 380…”

“…The lone pair of the amino nitrogen quenches the fluorescence of the perylene dye, but when the amino group, upon reaction with aldehydes/ketones, is converted into a hemiaminal the quenching of fluorescence is reduced and an increase in fluorescence takes place. [26] Consequently, the optical transduction of the recognition process is comparable to the detection of saccharides, because changes in photoinduced energy transfer are observed. The fluorescence of sensor layers based on J-57 in plasticised PVC increases at the emission maxima of 534 nm, 576 nm, and 613 nm when exposed to aqueous aldehydes (Figure 4).…”