A ratiometric fluorescent probe for Hg2+ ions in aqueous media based on organic/inorganic hybrid nanoparticles was prepared.Amphiphilic diblock copolymer
abbreviated as P (MPS-co-NBDAE)-b-P (NIPAM-co-RhBHA)
was firstly synthesized via consecutive reversible addition-fragmentation chain transfer (RAFT) polymerization of MPS and NIPAM monomer together with NBDAE and RhBHA respectively
where NBDAE and RhBHA were 7-nitro-2
1
3-benzoxadiazole (NBDAE)-based acrylic derivative monomer and Hg2+-reactive rhodamine B (RhB)-based acrylamide derivative monomer
respectively.Upon exposure to aqueous media
the amphiphilic diblock copolymer of P (MPS-co-NBDAE)-b-P (NIPAM-co-RhBHA) underwent self-assembly to form spherical nanoparticles with NBD-labeled PMPS cores and thermos-responsive PNIPAM coronas co-labeled with RhBHA moieties.Then a sol-to-gel process was conducted via addition of trimethylamine (TEA) into the micellar solution as the catalyst
resulting in core-crosslinked organic/inorganic hybrid nanoparticels.In the absence of Hg2+ ions
the micellar solution of the hybrid nanoparticles was solely green emissive under UV irradiation
which was originated from the NBD moieties trapped in the crosslinked PMPS micellar cores.However
upon addition of Hg2+ ions into the aqueous solution
Hg2+ induced ring-opening of the lactam ring in RhBHA moieties and thus generated RhB residues capable of fluorescence emission.Due to the fluorescence resonance energy transfer (FRET) between NBD and RhB moieties that were located in the micellar cores and coronas and acted as FRET donors and acceptors respectively
when the aqueous micellar solution was exposed to UV irradiation
a drastically green-to-orange emission transition was facilely discerned by both naked eye and fluorescence spectrometry
thus allowing for probing Hg2+ ions in a ratiometric manner.Moreover
because of the thermos-responsiveness of PNIPAM blocks
the collapse of PNIPAM coronas was induced by increasing the solution temperature
and the spatial distance between NBD and RhB moieties was therefore shortened
leading to an enhanced probing sensitivity.As a result
the organic/inorganic nanoparticle-based fluorescent probe could be employed as a highly selective ratiometric fluorescent sensor for Hg2+ in aqueous solution.
关键词
杂化纳米粒子荧光共振能量转移比率型荧光探针Hg2+离子温敏性
Keywords
Hybrid nanoparticlesFluorescence resonance energy transferRatiometricFluorescent sensorHg2+ ionsThermo-responsiveness