Development of a Ratiometric Fluorescent Cu(II) Indicator Based on Poly(N-isopropylacrylamide) Thermal Phase Transition and an Aminopyridyl Cu(II) Ligand

Author:

Nyiranshuti Lea1,Andrews Emily R.1,Povolotskiy Leonid I.1,Gomez Frances M.1ORCID,Bartlett Nathan R.1,Royappa Arun Timothy2,Rheingold Arnold L.3,Seitz William Rudolf1,Planalp Roy P.1ORCID

Affiliation:

1. Department of Chemistry, University of New Hampshire, Durham, NH 03824, USA

2. Department of Chemistry, University of West Florida, Pensacola, FL 32514, USA

3. Department of Chemistry, University of California San Diego, La Jolla, CA 92093, USA

Abstract

An aqueous Cu2+ and Zn2+ indicator is reported based on copolymerizing aminopyridine ligands and the environment-sensitive dansyl fluorophore into the responsive polymer poly(N-isopropylacrylamide) (PNIPAm). The metal ion binding creates charge and solvation that triggers PNIPAm’s thermal phase transition from hydrophobic globule to hydrophilic open coil. As a basis for sensing the metal-binding, the dansyl fluorescence emission spectra provide a signal at ca. 530 nm and a signal at 500 nm for the hydrophobic and hydrophilic environment, respectively, that are ratiometrically interpreted. The synthesis of the title pyridylethyl-pyridylmethyl-amine ligand (acronym PEPMA) with a 3-carbon linker to the copolymerizable group, aminopropylacrylamide (PEPMA-C3-acrylamide), is reported, along with a nonpolymerizable model ligand derivative. The response of the polymer is validated by increasing temperature from 25 °C to 49 °C, which causes a shift in maximum emission wavelength from 536 nm to 505 nm, along with an increase in the ratio of emission intensity of 505 nm/536 nm from 0.77 to 1.22 (λex = 330 nm) as the polymer releases water. The addition of divalent Cu or Zn to the indicator resulted in a dansyl emission shift of 10 nm to a longer wavelength, accompanied by fluorescence quenching in the case of Cu2+. The addition of EDTA to the Cu2+-loaded indicator reversed the fluorescence shift at 25 °C to 35 °C. The affinities of Cu2+ and Zn2+ for the PEPMA derivatives are log Kf = 11.85 and log Kf = 5.67, respectively, as determined by potentiometric titration. The single-crystal X-ray structure of the Cu2+-PEPMA derivative is five-coordinate, of-geometry intermediate between square-pyramidal and trigonal-bipyramidal, and is comparable to that of Cu2+ complexes with similar formation constants.

Funder

National Science Foundation

Publisher

MDPI AG

Subject

Chemistry (miscellaneous),Analytical Chemistry,Organic Chemistry,Physical and Theoretical Chemistry,Molecular Medicine,Drug Discovery,Pharmaceutical Science

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