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Morphology-Directing Synthesis of Rhodamine-Based Fluorophore Microstructures and Application toward Extra- and Intracellular Detection of Hg2+
journal contribution
posted on 2015-04-15, 00:00 authored by Rahul Bhowmick, Rabiul Alam, Tarun Mistri, Debalina Bhattacharya, Parimal Karmakar, Mahammad AliA new,
easily synthesizable rhodamine-based chemosensor with potential N2O2 donor atoms, L3, has been characterized by single-crystal X-ray diffraction
together with 1H NMR and high-resolution mass spectrometry
(HRMS) studies. L3 was found to bind selectively and reversibly
to the highly toxic Hg2+ ion. The binding stoichiometry
and formation constant of the sensor toward Hg2+ were determined
by various techniques, including UV–vis, fluorescence, and
Job’s studies, and substantiated by HRMS methods. None of the
biologically relevant and toxic heavy metal ions interfered with the
detection of Hg2+ ion. The limit of detection of Hg2+calculated by the 3σ method was 1.62 nM. The biocompatibility
of L3 with respect to its good
solubility in mixed organic/aqueous media (MeCN/H2O) and
cell permeability with no or negligible cytotoxicity provides good
opportunities for in vitro/in vivo cell imaging studies. As the probe
is poorly soluble in pure water, an attempt was made to frame nano/microstructures
in the absence and in the presence of sodium dodecyl sulfate (SDS)
as a soft template, which was found to be very useful in synthesizing
morphologically interesting L3 microcrystals. In pure water, micro-organization of L3 indeed occurred with block-shaped morphology
very similar to that in the presence of SDS as a template. However,
when we added Hg2+ to the solution of L3 under the above two conditions, the morphologies
of the microstructures were slightly different; in the first case,
a flowerlike structure was observed, and in second case, a simple
well-defined spherical microstructure was obtained. Optical microscopy
revealed a dotlike microstructure for L3–SDS assemblies, which changed to a panicle microstructure
in the presence of Hg2+. UV–vis absorption and steady-state
and time-resolved fluorescence studies were also carried out in the
absence and presence of Hg2+, and also the SDS concentration
was varied at fixed concentrations of the receptor and guest. The
results revealed that the fluorescence intensity increased steadily
with [SDS] until it became saturated at ∼7 mM SDS, indicating
that the extent of perturbation to the emissive species increases
with the increase in [SDS] until it becomes thermodynamically stable.
There was also an increase in anisotropy with increasing SDS concentration,
which clearly manifests the restriction of movement of the probe in
the presence of SDS.