Kinetics and Thermodynamics of Amine and Diamine Signaling by a Trifluoroacetyl Azobenzene Reporter Group

Abstract

[reaction: see text] (Trifluoroacetyl)azobenzene dyes were previously employed as amine reporter groups (chemosensors) in a dendrimer-based monomolecular imprinting system. Kinetic and binding studies with a range of amines and diamines show that the highly selective signaling observed for alkane diamines by these imprinted dendrimers arises from a kinetic effect due to intramolecular general base-catalyzed carbinolamine formation with the dye itself. The relationship between diamine structure and carbinolamine stability and rate of formation is described.

Star‐Shaped Tripodal Chemosensors for the Detection of Aliphatic Amines

“…These solvent-dependent emission properties are typically observed in the case of donor-acceptor-substituted stilbenes. [22,23] The excited state is stabilized by more polar solvents, thus leading to a bathochromic shift of the emission wavelength and additionally to a decrease in emission intensity.…”

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.…”

“…In one specific example, (trifluoreacetyl) azobenzene dye (10, Scheme 3.3) was reported to change chromophoric properties upon reaction with an amine. This allows 10 to be used for the detection of amine-containing compounds [133]. Specifically, reactions between 10 and an amino compound led to the formation of aminol 11.…”

“…Another example of amine sensor was developed by the Zimmerman laboratory by integrating the chromogenic reporter 10 into imprinting polymers [132,133]. The subject of molecular imprinting is discussed in detail in Chapter 7 and therefore not discussed in detail in this chapter.…”

Fluorescence Enhancement Detection of Underivatized Amino Acids Using a Trifluoroacetophenone-Based Tripodal Fluoroionophore

“…We have recently demonstrated that well-designed trifluoroacetophenone derivatives including compound 1 are applicable to ISEs as ionophores for the determination of phenylalanine with a monoanionic Nernstian response [29]. Trifluoroacetophenone is known to form adducts with amines [31][32][33][34] or alcohols [35], and almost all ISEs for carbonate sensing utilize trifluoroacetophenone derivatives as ionophores [36] [37]. To bind the amino and the carboxylate groups of an amino acid in the anionic form simultaneously, more than one trifluoroacetophenone group should be included in one molecule.…”