Organic-doped fluorescent polyethylenimine composites
have been
prepared by incorporating three commercially available aldehydessalicylaldehyde
(SA-PEI), 4-hydroxybenzaldehyde (PHB–PEI), and 2-hydroxynaphthaldehyde (NP-PEI)in PBS
buffer solution (pH = 7.4). The polymers derived from salicylaldehyde
and 4-hydroxybenzaldehyde exhibited opposite responses (turn-on with SA-PEI and turn-off with PHB–PEI) to pyrophosphate
(PPi), whereas NP-PEI showed a negligible response. Mechanistic
investigations indicated that the electrostatic interaction supplemented
by hydrogen bonding is responsible for the phosphate-specific optical
response. However, the mode of interaction and fluorescence response
depended on the nature of the organic dopant to the PEI polymeric
backbone. Mechanistic investigation suggested that the SA-PEI composite showed turn-on response due to the restricted intramolecular
motion and enhancement of hydrophobicity surrounding the probe due
to PPi addition, and PHB–PEI showed turn-off response
due to higher hydrogen-bonding interaction leading to more nonradiative
decay by charge transfer. Not only this but also the entanglement
of polymer chains, leading to aggregated structures, depends on the
degree of anionic charges on phosphate analytes. Further, a similar
idea was extended for analysis of biogenic phosphates like Calf Thymus
DNA (CT DNA) and adenosine triphosphate (ATP), which was relevant
for clinical diagnosis.