Lanthanide Luminescence Modulation by Cation–π Interaction in a Bioinspired Scaffold: Selective Detection of Copper(I)

Abstract

A prototype luminescent turn‐on probe for Cu+ (and Ag+) is described, harnessing a selective binding site (log Kass=9.4 and 7.3 for Cu+ and Ag+, respectively) based on the coordinating environment of the bacterial metallo‐chaperone CusF, integrated with a terbium‐ion‐signaling moiety. Cation–π interactions were shown to enhance tryptophan triplet population, which subsequently sensitized, on the microsecond timescale, the long‐lived terbium emission, offering a novel approach in bioinspired chemosensor design.

Photo-responsive cyclodextrin/anthracene/Eu3+ supramolecular assembly for a tunable photochromic multicolor cell label and fluorescent ink

“… 21 However, after irradiating the aqueous solution of Eu 3+ ⊂γ-CD· 1 2 under N 2 for 16 min at 365 nm with an intensity of 50 W, the resultant solution presented four characteristic emissions ( Fig. 2d , red line) of Eu 3+ at 590 nm ( 5 D 0 → 7 F 1 ), 615 nm ( 5 D 0 → 7 F 2 ), 645 nm ( 5 D 0 → 7 F 3 ) and 680 nm ( 5 D 0 → 7 F 4 ), 13 which were quite similar to those of Eu 3+ ⊂ 2 3 (Fig. S12 † ).…”

“…Materials that respond to external photo-modulation, accompanied by changes in physicochemical properties have drawn much attention for extensive research because of their potential applications in various fields. Among all kinds of stimuli-responsive artificial devices, it is beneficial to design luminescent materials based on lanthanide ions due to their unique luminescence properties, such as long-lived excited states, visible-light emission and narrow emission bandwidths, which could be easy to distinguish from shorter-lived (ns-based) autofluorescence from biological materials 13. Although multicolor luminescence has been reported several times recently, studies on in situ techniques are still rare,7 c particularly photo-tuning single lanthanide ions for multicolor luminescence including white light in aqueous solution remains a challenge.…”

“…Among all kinds of stimuli-responsive artificial devices, it is beneficial to design luminescent materials based on lanthanide ions due to their unique luminescence properties, such as long-lived excited states, visible-light emission and narrow emission bandwidths, which could be easy to distinguish from shorter-lived (ns-based) autofluorescence from biological materials. 13 Although multicolor luminescence has been reported several times recently, studies on in situ techniques are still rare, 7 c particularly photo-tuning single lanthanide ions for multicolor luminescence including white light in aqueous solution remains a challenge. Herein, combining a photo-tunable luminescent lanthanide, 13 c photo-erasable fluorescent ink 14 and cell imaging 15 of our previous reports, we designed a light-sensitive rotaxane network in aqueous solution from γ-cyclodextrin (γ-CD), 4-(anthracen-2-yl)pyridine-2,6-dicarboxylic acid ( 1 ) and Eu( iii ) as shown in Fig.…”

Luminescent lanthanide complexes for reactive oxygen species biosensing and possible application in Alzheimer’s diseases

“…Right bottom: time-gated luminescence images of ONOO − in HepG2 cells incubated with Eu(hdph) 3 (dpbt) and then with (A) 0 eq., (B) 0.5 eq., and (C) 1 eq of SIN-1 (3morpholinosydnonimine), which decomposes to release equimolar amounts of NO and O ÁÀ 2 , leading to spontaneous sustained production of ONOO -(adapted from reference [106]). detection of Cu(I) can be achieved by using a structure inspired by the metal-binding site of the metallo-chaperone CusF and a Tb(III) complex [118].…”

A Luminescent NOTA-Based Terbium(III) “Turn-Off” Sensor for Copper

“…26,30 An area of growing interest is the design of copper sensing probes that employ lanthanides, namely Tb(III) and Eu(III), due to their highly attractive photophysical properties (e.g., millisecond luminescence lifetimes, large Stokes shift, emission in the visible and sharp distinct emission bands, high photostability and low phototoxicity). 32,33 Designs of lanthanide probes for copper sensing include small molecule probes, [17][18][19][20][21][22][23][24][25][26][27] peptide mimics of metallo-protein binding sites, 45 nanoparticles, 8 and polymer-based materials. [34][35][36][37][38][39][40][41][42][43][44] The most typical design for small molecule copper sensors based on lanthanides are compounds that contain sensitizer-receptor units, as for example seen in the sensor S1 reported by Gunnlaugsson et al (Figure 1).…”