Temperature-dependent fluorescence lifetime of a fluorescent polymeric thermometer, poly(N-isopropylacrylamide), labeled by polarity and hydrogen bonding sensitive 4-sulfamoyl-7-aminobenzofurazan

J Phys Chem B. 2008 Mar 13;112(10):2829-36. doi: 10.1021/jp709810g. Epub 2008 Feb 16.

Abstract

Fluorescent molecular thermometers showing temperature-dependent fluorescence lifetimes enable thermal mapping of small spaces such as a microchannel and a living cell. We report the temperature-dependent fluorescence lifetimes of poly(NIPAM-co-DBD-AA), which is a random copolymer of N-isopropylacrylamide (NIPAM) and an environment-sensitive fluorescent monomer (DBD-AA) containing a 4-sulfamoyl-7-aminobenzofurazan structure. The average fluorescence lifetime of poly(NIPAM-co-DBD-AA) in aqueous solution increased from 4.22 to 14.1 ns with increasing temperature from 30 to 35 degrees C. This drastic change in fluorescence lifetime (27% increase per 1 degrees C) is the sharpest ever reported. Concentration independency, one of the advantages of fluorescence lifetime measurements, was seen in average fluorescence lifetime (13.7 +/- 0.18 ns) of poly(NIPAM-co-DBD-AA) at 33 degrees C over a wide concentration range (0.005-1 w/v%). With increasing temperature, polyNIPAM units in poly(NIPAM-co-DBD-AA) change their structure from an extended form to a globular form, providing apolar and aprotic environments to the fluorescent DBD-AA units. Consequently, the environment-sensitive DBD-AA units translate the local environmental changes into the extension of the fluorescence lifetime. This role of the DBD-AA units was revealed by a study of solvent effects on fluorescence lifetime of a model environment-sensitive fluorophore.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Acrylamides / chemistry*
  • Acrylic Resins
  • Benzoxazoles / chemistry*
  • Deuterium / chemistry
  • Fluorescent Dyes / chemistry*
  • Hydrogen Bonding
  • Molecular Structure
  • Oxides / chemistry
  • Photochemistry
  • Polymers / chemistry*
  • Sensitivity and Specificity
  • Solvents
  • Temperature*
  • Time Factors
  • Water / chemistry

Substances

  • 4-sulfamoyl-7-aminobenzofurazan
  • Acrylamides
  • Acrylic Resins
  • Benzoxazoles
  • Fluorescent Dyes
  • Oxides
  • Polymers
  • Solvents
  • Water
  • poly-N-isopropylacrylamide
  • Deuterium