Solvent Polarity-Dependent Behavior of Aliphatic Thiols
and Amines toward Intriguingly Fluorescent AuAgGSH Assembly
Posted on 2017-11-17 - 19:21
Highly stable fluorescent glutathione
(GSH)-protected AuAg assembly
has been synthesized in water under UV irradiation. The assembly is
composed of small Ag2/Ag3 clusters. These clusters
gain stability through synergistic interaction with Au(I) present
within the assembly. This makes the overall assembly fluorescent.
Here, GSH acts as a reducing as well as stabilizing agent. The assembly
is so robust that it can be vacuum-dried to solid particles. The as-obtained
solid is dispersible in nonaqueous solvents. The interaction between
solvent and the assembly provides stability to the assembly, and the
assembly shows fluorescence. It is interesting to see that the behavior
of long-chain aliphatic thiols or amines toward the fluorescent assembly
is altogether a different phenomenon in aqueous and nonaqueous mediums.
The assembly gets ruptured in water due to direct interaction with
long-chain thiols or amines, whereas in nonaqueous medium, solvation
of added thiols or amines becomes pronounced, which hinders the interaction
of solvent with the assembly. However, the fluorescence of the assembly
is always quenched with thiols or amines no matter what the solvent
medium is. In aqueous medium, the fluorescence quenching by aliphatic
thiol or amine becomes pronounced with successive decrease in their
chain length, whereas in nonaqueous medium, the trend is just reversed
with chain length. The reasons behind such an interesting reversal
of fluorescence quenching in aqueous and nonaqueous solvents have
been discussed explicitly. Again, in organic solvents, thiol or amine-induced
quenched fluorescence is selectively recovered by Pb(II) ion without
any alteration of excitation and emission maxima. This phenomenon
is not observed in water because of the ruptured fluorescent assembly.
The fluorescence recovery by Pb(II) and unaltered emission peak only
in nonaqueous solvent unequivocally prove the engagement of Pb(II)
with thiols or amines, which in turn revert the original solvent-supported
stabilization of the assembly.
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Jana, Jayasmita; Aditya, Teresa; Negishi, Yuichi; Pal, Tarasankar (2017). Solvent Polarity-Dependent Behavior of Aliphatic Thiols
and Amines toward Intriguingly Fluorescent AuAgGSH Assembly. ACS Publications. Collection. https://doi.org/10.1021/acsomega.7b01560
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AUTHORS (4)
JJ
Jayasmita Jana
TA
Teresa Aditya
YN
Yuichi Negishi
TP
Tarasankar Pal