Title:
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Investigation of polyaniline derivatives and their optical sensing properties
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Chemically modified polyaniline (CMP) self doped derivatives were synthesised by
the diazotisation of polyaniline, copolyanilines and polyaniline-Ti02 nanoparticle
composites with diazonium salts and polymerising aniline diazo anilic or anthranilic
dyes. Oxidative chemical polymerisation in strong acidic aqueous media with the
help of (NH4)2S20a was employed to polymerise monomers or comonomers. The
diazotisation of polyanilines was proved to be the most promising and efficient to
incorporate sulphonic phenyl groups in polyanilines structure to form self doped
CMPs. The highest degree of self doping! suiphonation was achieved when
polyaniline- Ti02 composites were coupled with diazonium ion.
CMPs were investigated with the help of analytical techniques such as UVVis,
FT-IR, FT-NMR, fluorescence and elemental analysis. The spectroscopic and
physical data confirm the introduction of chemically linked sulphonic phenyl groups
and formation of triphenyl amine like fluorophores structures in them. They have the
fundamental polyaniline properties as they are green in acidic and blue in basic
media, pH sensitive, have reversible electrochromic and redox behaviour in different
environments. They are highly fluorescent, soluble in polar solvents (H20, R-OH,
NMP, DMSO, DMF) and optical metals ion sensor. Their solutions have persistent
fluorescence even after several months without significant changes in their spectra.
They can be immobilised directly and in the form of composites with other reagents
such as PMMA, PVA, nafion and sol gel on glass and polymeric substrates. Their
composite films are stable in ambient conditions and luminescent even after a
period of one year. Their solubility, fluorescence and optical metals ion sensing are
directly related to their degree of sulphonation! self doping. Consequently, SPPATi02
has better solubility, higher fluorescence intensity, stable optical pH response
and lower limit of detection for Cu2+ ion compared to that of SPPA and SPCPA.
Their UV-Vis absorption and emission spectra are pH sensitive with a linear
and quick optical response in the range of pH 5-8. They have excitations at 256-258
and 292-300 nm in acidic and basic media respectively while emissions at 423-
428nm. They have broad optimum pH ranges (pH 6-10) for their emission and metal
ions sensing. They can be used as pH sensor for a broad range of pH 3-8, out of
which the optical sensitivity of pH 3-6 is based on hypo! hyper chromic effects in
their fluorescence while of pH 5-8 in their UV-Vis absorption spectra. They are
optical metals ions sensors for higher concentrations (> 10-4M) of heavy metals ion
but are selective and sensitive to Cu2+ ion «10-4 M) lower concentrations. The
optimum pH ranges for their optical Cu2+ ion sensing are broad (pH 6-10). Their
LOO and LOa for Cu2+ ion on the basis of fluorescence quenching are in the ranges
3.96 x 10-7 - 4.5 x 10-7 and 1.3 x 10-6 - 1.5 x 10-6M respectively.
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