Materials for electrochemiluminescence : TADF, hydrogen-bonding, and aggregation- and crystallization-induced emission luminophores

Authors thank the Natural Sciences and Engineering Research Council Canada (NSERC, DG RGPIN-2018- 06556, DG RGPIN-2023-05337 and SPG STPGP-2016-493924), New Frontiers in Research Fund (NFRFR-2021-00272), Canada Foundation of Innovation/Ontario Innovation Trust (CFI/OIT, 9040) and The University of Western Ontario for the support to this research. KC is an Ontario Graduate Scholar.Electrochemiluminescence (ECL) is a rapidly growing discipline with many analytical applications from immunoassays to single-molecule detection. At the forefront of ECL research is materials chemistry, which looks at engineering new materials and compounds exhibiting enhanced ECL efficiencies compared to conventional fluorescent materials. In this review, we summarize recent molecular design strategies that lead to high efficiency ECL. In particular, we feature recent advances in the use of thermally activated delayed fluorescence (TADF) emitters to produce enhanced electrochemiluminescence. We also document how hydrogen bonding, aggregation, and crystallization can each be recruited in the design of materials showing enhanced electrochemiluminescence.Publisher PDFPeer reviewe

Enhanced electrochemiluminescence from a stoichiometric ruthenium(II)-iridium(III) complex soft salt

The authors thank NSERC, CFI, FQRNT, PREA, and The University of Western Ontario for generous financial support to this research.Electrochemiluminescence (ECL) and electrochemistry are reported for a heterometallic soft salt, [Ru(dtbubpy)3][Ir(ppy)2(CN)2]2 ([Ir][Ru][Ir]), consisting of a 2:1 ratio of complementary charged Ru and Ir complexes possessing two different emission colors. The [Ru]2+ and [Ir]− moieties in the [Ir][Ru][Ir] greatly reduce the energy required to produce ECL. Though ECL intensity in the annihilation path was enhanced 18× relative to that of [Ru(bpy)3]2+, ECL in the co-reactant path with tri-n-propylamine was enhanced a further 4×. Spooling spectroscopy gives insight into ECL mechanisms: the unique light emission at 634 nm is due to the [Ru]2+* excited state and no [Ir]−* was generated in either route. Overall, the soft salt system is anticipated to be attractive and suitable for the development of efficient and low-energy-cost ECL detection systems.PostprintPeer reviewe

Simple and Fast Fabrication Methodology for Platinum and Carbon Ultramicroelectrodes (UME) in Scanning Electrochemical Microscopy (SECM)

Scanning electrochemical microscopy (SECM) is a highly versatile method for measuring and imaging a wide range of systems. When paired with an intricately made ultramicroelectrode (UME) probe, SECM becomes an even more powerful tool for imaging microscale features in a system. However, purchasing these UME’s comes at a high cost with less ability for modification. Having high quality UME’s expands the ability of SECM and enables precise measuring and imaging in a wide range of applications such as solar cells in Dr. Ding’s lab, and corroding metals in Dr. Gateman’s lab. To combat this issue of high cost and set specifications, a simple and fast methodology for preparing UME’s was developed

Learning Granularity-Unified Representations for Text-to-Image Person Re-identification

Text-to-image person re-identification (ReID) aims to search for pedestrian images of an interested identity via textual descriptions. It is challenging due to both rich intra-modal variations and significant inter-modal gaps. Existing works usually ignore the difference in feature granularity between the two modalities, i.e., the visual features are usually fine-grained while textual features are coarse, which is mainly responsible for the large inter-modal gaps. In this paper, we propose an end-to-end framework based on transformers to learn granularity-unified representations for both modalities, denoted as LGUR. LGUR framework contains two modules: a Dictionary-based Granularity Alignment (DGA) module and a Prototype-based Granularity Unification (PGU) module. In DGA, in order to align the granularities of two modalities, we introduce a Multi-modality Shared Dictionary (MSD) to reconstruct both visual and textual features. Besides, DGA has two important factors, i.e., the cross-modality guidance and the foreground-centric reconstruction, to facilitate the optimization of MSD. In PGU, we adopt a set of shared and learnable prototypes as the queries to extract diverse and semantically aligned features for both modalities in the granularity-unified feature space, which further promotes the ReID performance. Comprehensive experiments show that our LGUR consistently outperforms state-of-the-arts by large margins on both CUHK-PEDES and ICFG-PEDES datasets. Code will be released at https://github.com/ZhiyinShao-H/LGUR.Comment: Accepted by ACM Multimedia 202

Near-Infrared Photoluminescence and Electrochemiluminescence from an Exceptionally Simple Boron Difluoride Formazanate Dye

Electrochemiluminescence involves the generation of light via electrochemical reactions and has recently shown utility for single-cell imaging. To further develop this novel imaging platform, it is necessary to produce readily available dyes that photoluminesce and electrochemiluminesce in the near-infrared region to limit absorption by biological tissue. To address this need, we prepared a boron difluoride formazanate dye that exhibits near-infrared photoluminescence and electrochemiluminescence in two straightforward synthetic steps. Examination of its solid-state structure suggests that the N-aryl substituents have significant quinoidal character, which narrows the S1-S0 energy gap and leads to near-infrared absorption and photoluminescence. Electrochemical properties were probed using cyclic voltammetry and revealed four electrochemically reversible waves. Electrochemiluminescence properties were examined in the presence of tri-n-propylamine, leading to maximum intensity at 910 nm, at least 85 nm (1132 cm‒1) red-shifted compared to all other organic dyes. This work sets the stage for the development of future generations of dyes for emerging applications, including single-cell imaging, that require near-infrared photoluminescence and electrochemiluminescence

Effect of dexmedetomidine on miR-144-3p expression and epithelial mesenchymal transition in gastric cancer cells

Purpose: To investigate the effect of dexmedetomidine (DEX) on epithelial mesenchymal transition (EMT) in gastric cancer cells, and the role of microRNA-144-3p (miR-144-3p) in the process.Methods: The effect of DEX on miRNA expression profile was analyzed using GEO database(https://www.ncbi.nlm.nih.gov/gds/). Human gastric cancer cells were cultured in vitro, and one group of cells was treated with saline for 48 h (control group). Cells treated with DEX at doses of 0.01, 0.1 and 1.0 μmol/L for 48 h were marked as low-, medium- and high-DEX concentration groups. The mRNA expression levels of miR-144-3p, ZEB1, E-cadherin and vimentin were determined using real-time quantitative polymerase chain reaction (RT-PCR), while the protein expressions of ZEB1, E-cadherin and vimentin were assayed with Western blotting. Cell proliferation was determined with CCK-8 assay, while metastasis was measured using Transwell assay.Results: The GEO database demonstrated that the expression of miR-144-3p in rat cardiomyocytes was significantly decreased after DEX treatment (p < 0.05). The expression of miR-144-3p was decreased in all groups, when compared to the control group, but the expressions of ZEB1 and vimentin were increased, while that of E-cadherin was down-regulated (p < 0.05). Cell proliferation in the high-DEX concentration group was decreased (p < 0.05). The degrees of cell invasion and migration were increased in the medium- and high-DEX concentration groups (p < 0.05).Conclusion: DEX promotes the metastasis of gastric cancer cells by regulation of epithelialmesenchymal transition (EMT) and the expression of miR-144-3p. This finding provides a new insight into the treatment of gastric cancer

Insights into enhanced electrochemiluminescence of a multiresonance thermally activated delayed fluorescence molecule

Funding: Walloon Region, Grant/Award Number:n1117545; Leverhulme Trust, Grant/Award Numbers: RPG‐2016047,SRF\R1\201089; Natural Sciences and Engineering Research Council Canada, Grant/Award Numbers: DG RGPIN‐2018‐06556, SPG STPGP‐2016‐493924; Fonds dela Recherche Scientifiques de Belgique, Grant/Award Numbers: 2.5020.11,F.4534.21; Engineering and Physical Sciences Research Council, Grant/Award Number: EP/P010482/1.The electrochemiluminescence (ECL) behavior of a multiresonance thermally activated delayed fluorescence molecule has been investigated for the first time by means of ECL-voltage curves, newly designed ECL-time observatory, and ECL spectroscopy. The compound, Mes3DiKTa, shows complex ECL behavior, including a delayed onset time of 5 ms for ECL generation in both the annihilation pathway and the coreactant route, which we attribute to organic long-persistent ECL (OLECL). Triplet-triplet annihilation, thermally activated delayed fluorescence and uncompensated solution resistance cannot be ruled out as contributing mechanisms to the ECL. A very long ECL emission decay was attributed to OLECL as well. The absolute ECL efficiencies of Mes3DiKTa were enhanced and reached 0.0013% in annihilation route and 1.1% for the coreactant system, which are superior to those of most other organic ECL materials. It is plausible that ECL materials with comparable behavior as Mes3DiKTa are desirable in applications such as ECL sensing, imaging, and light-emitting devices.Publisher PDFPeer reviewe

Electrochemical assessment of water|ionic liquid biphasic systems towards cesium extraction from nuclear waste

A room temperature ionic liquid (IL) composed of a quaternary alkylphosphonium (trihexyltetradecylphosphonium, P66614(+)) and tetrakis(pentafluorophenyl) borate anion (TB) was employed within a water| P66614TB (w|P66614TB or w|IL) biphasic system to evaluate cesium ion extraction in comparison to that with a traditional water|organic solvent (w|o) combination. Cs-137 is a major contributor to the radioactivity of spent nuclear fuel as it leaves the reactor, and its extraction efficiency is therefore of considerable importance. The extraction was facilitated by the ligand octyl(phenyl)-N, N'-diisobutylcarbamoylphosphine oxide (CMPO) used in TRans- Uranium EXtraction processes and investigated through well established liquid| liquid electrochemistry. This study gave access to the metal ion to ligand (1: n) stoichiometry and overall complexation constant, beta, of the interfacial complexation reaction which were determined to be 1: 3 and 1.6 x 10(11) at the w| P66614TB interface while the study at w|o elicited an n equal to 1 with beta equal to 86.5. Through a straightforward relationship, these complexation constant values were converted to distribution coefficients, da, with the ligand concentrations studied for comparison to other studies present in the literature; the w|o and w|IL systems gave delta(alpha) of 2 and 8.2 x 10(7), respectively, indicating a higher overall extraction efficiency for the latter. For the w|o system, the metal ion-ligand stoichiometries were confirmed through isotopic distribution analysis of mass spectra obtained by the direct injection of an emulsified water-organic solvent mixture into an electron spray ionization mass spectrometer. (c) 2014 Elsevier B.V. All rights reserved

Aluminum Complexes of N2O23‒ Formazanate Ligands Supported by Phosphine Oxide Donors

The synthesis and characterization of a new family of phosphine-oxide-supported aluminum formazanate complexes (7a, 7b, 8a, 9a) are reported. X-ray diffraction studies revealed that the aluminum atoms in the complexes adopt an octahedral geometry in the solid state. The equatorial positions are occupied by an N2O23‒ formazanate ligand, and the axial positions are occupied by L-type phosphine oxide donors. UV-vis absorption spectroscopy revealed that the complexes were strongly absorbing (ε ~ 30,000 M‒1 cm‒1) between 500 and 700 nm. The absorption maxima in this region were simulated using time-dependent density-functional theory. With the exception of 3-cyano substituted complex 7b, which showed maximum luminescence intensity in the presence of excess phosphine oxide, the title complexes are non-emissive in solution and the solid state. The electrochemical properties of the complexes were probed using cyclic voltammetry. Each complex underwent sequential one-electron oxidations in potential ranges of ‒0.12 to 0.29 V and 0.62 to 0.97 V, relative to the ferrocene/ferrocenium redox couple. Electrochemical reduction events were observed at potentials between ‒1.34 and ‒1.75 V. When combined with tri-n-propylamine as a coreactant, complex 7b acted as an electrochemiluminescence emitter with a maximum electrochemiluminescence intensity at a wavelength of 735 nm, red-shifted relative to the photoluminescence maximum of the same compound