Inspired by the enhanced photoluminescence of Au nanoclusters (AuNCs)with arigid shell, the formation of rigid host-guest assemblies on AuNC surfaces was employed to screen novel electrochemiluminophores with 6-aza-2thiothymine(ATT)-protected AuNCs (ATT-AuNCs) and larginine (ARG) as models for the first time.T he rigid hostguest assemblies formed between ARG and ATTont he ATT-AuNC surface enabled aqueous-soluble ARG/ATT-AuNCs with ad ramatically enhanced electrochemiluminescence (ECL) compared to ATT-AuNCs.T his includes one cathodic ECL process (À1.30 V) and three anodic ECL processes (+ 0.78, 0.90, and 1.05 V) in as o-called half-scan experiment without aco-reactant, as well as a70-fold enhanced oxidativereduction ECL at + 0.78 Vw ith tri-n-propylamine as ac oreactant. Importantly,t he ECL of the ARG/ATT-AuNCs is highly monochromatic with an emission maximum around 532 nm and afull width at half-maximum of 36 nm, whichisof great interest for color-selective ECL assays.
Screening a novel
electrochemiluminescence (ECL) system is crucial
to ECL evolution. Herein, an efficient ECL system with less interference
and environmental concern under physiological condition is developed
via a unique internal Cu(I)/Cu(II) couple cycling amplified strategy
by employing the glutathione- and citrate-capped copper indium sulfide
(CIS)/ZnS nanocrystals (NCs) as electrochemiluminophore and
N2H4·H2O as co-reactant. CIS/ZnS
NCs can be electrochemically injected with valence band (VB) hole
at 0.46 and 0.87 V (vs Ag/AgCl), and then achieve the same hole-injected
states by relocalizing VB holes with the Cu(I) species inside of CIS/ZnS
NCs to form internal Cu(II) defects, while each N2H4·H2O molecule can be successively oxidized
to two more reducing species N2H3
• and N2H2 around 0.10 V, and inject conduction
band (CB) electron onto CIS/ZnS NCs for triple times. The internal
Cu(I)/Cu(II) couple cycling involved radiative-charge recombination
between these VB hole and CB electron eventually enables two efficient
near-infrared ECL processes (around 731 nm) at 0.55 and 0.87 V, in
which each single nanocrystal may participate in multiple ECL reaction
cycles to produce multiple photons for amplified ECL, similar to the
tris(bipyridyl)ruthenium(III) based ECL system. The low-triggering-potential
ECL process at 0.55 V can be utilized to selectively determine Cu(II)
with a wide linear range from 10 and 1500 nM and a limit of detection
of 5 nM (S/N = 3). This work presents
a NCs engineering and co-reactant selecting combined strategy for
further ECL evolution.
Electrochemiluminescence
(ECL) with high electrode compatibility
and less electrochemical interference has conventionally been envisioned
by lowering the oxidative potential of luminophores and/or screening
luminophores with a low oxidative potential. Herein, an alternative
was developed by employing the environmental-friendly carbohydrazide
as a coreactant, which enabled serial luminophores with oxidative-reduction
ECL at one similar low triggering potential around 0.55 V versus
Ag/AgCl, including Ru(bpy)3
2+ as well as CdTe,
CdSe, CuInS2/ZnS, and Au nanocrystals. Because the eight-electron
releasing process of carbohydrazide was electrochemically triggered
at ∼0.25 V versus Ag/AgCl, the radicals generated via electrochemical
oxidation of carbohydrazide could reduce the luminophores at a much
lower potential than those of traditional coreactants. All the luminophore/carbohydrazide
systems exhibited one ECL process around 0.55 V, which was about 0.65
V lower than that of a traditional Ru(bpy)3
2+/tri-n-propylamine system (typically around +1.2
V), and even lower than the oxidative potential of some luminophores.
The ECL of the luminophore/carbohydrazide system was spectrally close
to that of the corresponding luminophore/tri-n-propylamine
system; the maximum emission wavelength of the low triggering potential
ECL could shift from 540 to 783 nm via the selection of luminophores
in this case. The coreactant screening strategy would be a favorable
addition to the expected luminophore screening strategy for achieving
enhanced ECL performance. This work created an avenue toward a deeper
understanding of the ECL mechanism.
Screening toxic-element-free and biocompatible electrochemiluminophores was crucial for electrochemiluminescence (ECL) evolution. Herein, L-glutathione (GSH)-capped Ag−Ga−In−S (AGIS) nanocrystals (NCs) were prepared by doping Ag−In−S (AIS) NCs in a doping-in-growth way and utilized as a model for both ECL modulating and developing multinary NC-based electrochemiluminophores with enhanced ECL performance than trinary NCs. AGIS NCs not only primarily preserved the morphology, size, phase structure, and water monodisperse characteristics of AIS NCs with broadened band gap but also demonstrated obviously enhanced oxidative-reduction ECL than AIS NCs. Importantly, ECL of AGIS NCs was located at the nearinfrared region with a maximum emission wavelength of 744 nm and could be utilized for an ECL immunoassay with human prostate-specific antigen (PSA) as a model, which exhibited a linearity range from 0.05 pg/mL to 1.0 ng/mL and a low limit of detection of 0.01 pg/mL (S/N = 3). This work provided a promising alternative to the traditional binary NCs for developing toxicelement-free and biocompatible electrochemiluminophores with efficient near-infrared ECL.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.