Highly photostable near-infrared fluorescent pH indicators and sensors based on BF2-chelated tetraarylazadipyrromethene dyes

Anal Chem. 2012 Aug 7;84(15):6723-30. doi: 10.1021/ac3011796. Epub 2012 Jul 12.

Abstract

In this study, a series of new BF(2)-chelated tetraarylazadipyrromethane dyes are synthesized and are shown to be suitable for the preparation of on/off photoinduced electron transfer modulated fluorescent sensors. The new indicators are noncovalently entrapped in polyurethane hydrogel D4 and feature absorption maxima in the range 660-710 nm and fluorescence emission maxima at 680-740 nm. Indicators have high molar absorption coefficients of ~80,000 M(-1) cm(-1), good quantum yields (up to 20%), excellent photostability and low cross-sensitivity to the ionic strength. pK(a) values of indicators are determined from absorbance and fluorescence measurements and range from 7 to 11, depending on the substitution pattern of electron-donating and -withdrawing functionalities. Therefore, the new indicators are suitable for exploitation and adaptation in a diverse range of analytical applications. Apparent pK(a) values in sensor films derived from fluorescence data show 0.5-1 pH units lower values in comparison with those derived from the absorption data due to Förster resonance energy transfer from protonated to deprotonated form. A dual-lifetime referenced sensor is prepared, and application for monitoring of pH in corals is demonstrated.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Chelating Agents / chemistry*
  • Dental Cements / chemistry*
  • Electron Transport
  • Fluorescent Dyes / chemistry*
  • Fluorides, Topical / chemistry*
  • Hydrogen-Ion Concentration
  • Indicators and Reagents / chemistry
  • Kinetics
  • Porphobilinogen / analogs & derivatives*
  • Porphobilinogen / chemical synthesis
  • Porphobilinogen / chemistry
  • Spectrometry, Fluorescence*

Substances

  • Chelating Agents
  • Dental Cements
  • Fluorescent Dyes
  • Fluorides, Topical
  • FluoroBond
  • Indicators and Reagents
  • dipyrromethene
  • Porphobilinogen