Rational design and synthesis of yellow-light emitting triazole fluorophores with AIE and mechanochromic properties.
ABSTRACT: Previously, we reported that N-2-aryl triazoles (NATs) exhibited good fluorescence activity in the UV/blue light range. In an effort to achieve biocompetitive NAT fluorophores with green/yellow emission, a new class of 4-keto-2-(4'-N,N-diphenyl)-phenyl triazoles were designed and synthesized. Herein, we present our study on these novel fluorophores which demonstrated excellent luminescence emission both in solution (? up to 96%) and in the solid state (? up to 43%). Furthermore, these new compounds showed aggregation-induced emission (AIE) properties and reversible mechanochromic luminescence properties, which suggested their potential applications in chemical and materials science.
Project description:Organic solid fluorophores with a tunable emission color have been widely applied in multiple areas. However, rational design and efficient crafting of these fluorophores from a simple core skeleton is still a formidable challenge because of the undesirable concentration quenching emission effect. Herein, we present the development of two series of organic solid fluorophores based on a backbone of p-bis(2,2-dicyanovinyl)benzene. Notably, the introduction of either non-aromatic or aromatic substituents provides fluorophores with a tunable emission color. Moreover, the fluorophores with aromatic substituents exhibit additional unique optical phenomena, such as aggregation-induced emission, polymorphism-dependent emission, and reversible mechanochromic luminescence.
Project description:Supramolecular self-assembly is an excellent tool for controlling the optical and electronic properties of chromophore-based molecular systems. Herein, we demonstrate how differential self-assembly affects mechanoresponsive luminescence of fluorene-benzothiadiazole-based fluorophores. We have synthesized two donor-acceptor-donor-type conjugated oligomers consisting of fluorene as the donor and benzothiadiazole as the acceptor. For facile self-assembly, both molecules are end-functionalized with hydrogen-bonding amide groups. Differential self-assembly was induced by attaching alkyl chains of different lengths onto the fluorene moiety: hexyl (FB-C6) and dodecyl (FB-C12). The molecules self-assemble to form well-defined nanostructures in nonpolar solvents and solvent mixtures. Although their optical properties in solution are not affected by the alkyl chain length, significant effects were observed in the self-assembled state, particularly in the excitation energy migration properties. As a result, remarkable differences were observed in the mechanochromic luminescence properties of the molecules. A precise structure-property correlation is made using UV-visible absorption and fluorescence spectroscopy, time-correlated single-photon counting analysis, scanning electron microscopy, and X-ray diffraction spectroscopy.
Project description:In neuroscience, fluorescence labeled two-photon microscopy is a promising tool to visualize ex vivo and in vivo tissue morphology, and track dynamic neural activities. Specific and highly photostable fluorescent probes are required in this technology. However, most fluorescent proteins and organic fluorophores suffer from photobleaching, so they are not suitable for long-term imaging and observation. To overcome this problem, we utilize tetraphenylethene-triphenylphosphonium (TPE-TPP), which possesses aggregation-induced emission (AIE) and two-photon fluorescence characteristics, for neuroimaging. The unique AIE feature of TPE-TPP makes its nanoaggregates resistant to photobleaching, which is useful to track neural cells and brain-microglia for a long period of time. Two-photon fluorescence of TPE-TPP facilitates its application in deep in vivo neuroimaging, as demonstrated in the present paper.
Project description:A new class of donor-acceptor type luminescent bis(alkynyl)gold(iii) N?C complexes has been synthesized and characterized. These gold(iii) complexes not only exhibit high photoluminescence quantum yields of up to 0.81, but also interesting mechanochromic luminescence behaviors that are reversible. Upon grinding, a dramatic luminescence color change from green to red can be observed in solid samples of the gold(iii) complexes, and the mechanochromic luminescence can be readily tuned via a judicious selection of substituents on the pyridine ring. In addition, solution-processable OLEDs based on this class of complexes with EQE values of up to 4.0% have been realized, representing the first demonstration of bis(alkynyl)gold(iii) N?C complexes as emissive materials in solution-processable OLEDs.
Project description:Two new series of aggregation-induced emission (AIE) fluorophore-containing amphiphilic copolymers possessing the segments of a monomeric AIE fluorophore, N-(2-hydroxypropyl)methacrylamide (HPMA), [2-(methacryloyloxy)ethyl]trimethylammonium chloride (MATMA), and/or 2,2,2-trifluoroethyl methacrylate (TFEMA) were synthesized. Photophysical properties were investigated using UV-Vis absorbance and fluorescence spectrofluorometry. The increases of molar fractions of the hydrophobic AIE fluorophores and/or the trifluoroethyl moieties result in the higher quantum yields of the AIE fluorophores in the polymers. Using 1-mol% of AIE fluorophores with the tuning of molar fractions of TFEMA, 40% quantum yield was achieved, whereas only less than 10% quantum yield was obtained for the polymers without the TFEMA segments. The quantum yield difference indicates the importance of the fluorine segments for getting high quantum yields of the AIE fluorophores. These polymers were explored for fluorescent bioimaging using human brain glioblastoma U87MG and human esophagus premalignant CP-A cell lines. All the polymers are cell permeable and located in the cellular cytoplasma area. Cellular uptake was demonstrated to be through endocytosis, which is time and energy dependent. The polymers are non-cytotoxic to the two cell lines. Because the polymers contain (19)F segments, we studied the spin-lattice relaxation time (T1) and spin-spin relaxation time (T2) of these polymers. T1 and T2 are the two important parameters for the evaluations of the capacity of these polymers for further applications in (19)F magnetic resonance imaging ((19)F MRI). Structure influence on T1 and T2, especially for T2, was observed. These new multifunctional materials are the first series of fluorinated polymers with AIE fluorophores for bioapplications.
Project description:Difluoroboron ?-diketonate (BF2bdk) compounds show environment-sensitive optical properties in solution, aggregation-induced emission (AIE) and multi-stimuli responsive fluorescence switching in the solid state. Here, a series of 4-azepane-substituted ?-diketone (bdk) ligands (L-H, L-OMe, L-Br) and their corresponding difluoroboron dyes (D-H, D-OMe, D-Br) were synthesized, and various responsive fluorescence properties of the compounds were studied, including solvatochromism, viscochromism, AIE, mechanochromic luminescence (ML) and halochromism. Compared to the ?-diketones, the boron complexes exhibited higher extinction coefficients but lower quantum yields, and red-shifted absorption and emission in CH2Cl2. Computational studies showed that intramolecular charge transfer (ICT) dominated rather than ?-?* transitions in all the compounds regardless of boron coordination. In solution, all the bdk ligands and boron dyes showed red-shifted emission in more polar solvents and increased fluorescence intensity in more viscous media. Upon aggregation, the emission of the ?-diketones was quenched, however, the boronated dyes showed increased emission, indicative of AIE. Solid-state emission properties, ML and halochromism, were investigated on spin cast films. For ML, smearing caused a bathochromic emission shift for L-Br, and powder X-ray diffraction (XRD) patterns showed that the "as spun" and thermally annealed states were more crystalline and the smeared state was amorphous. No obvious ML emission shift was observed for L-H or L-OMe, and the boronated dyes were not mechano-active. Trifluoroacetic acid (TFA) and triethylamine (TEA) vapors were used to study halochromism. Large hypsochromic emission shifts were observed for all the compounds after TFA vapor was applied, and reversible fluorescence switching was achieved using the acid/base pair.
Project description:Multiphoton microscopy is an exciting tool for biomedical research because it can be used to image single cells <i>in vivo</i> due to its greater penetration depth, lower phototoxicity and higher resolution when compared to confocal laser scanning microscopy. This helps researchers understand how certain cells change over time and evaluate the efficacy of different therapies. Herein, we report a new AIE luminogen (AIEgen), abbreviated as TPE-TETRAD, with a favorable absorption and efficient deep-red emission in the solid state. TPE-TETRAD possesses a high two-photon absorption cross-section (313 MG at 830 nm) and a rich array of non-linear optical properties including aggregation-induced three-photon luminescence. Biotinylated TPE-TETRAD nanoparticles are also fabricated and applied to stain mitochondria in live cancer cells with high specificity. The purpose of this study is to characterize a novel deep-red AIEgen and fabricate biotinylated nanoparticles for applications as (1) biocompatible and photostable AIE probes for specific mitochondria imaging and (2) multiphoton imaging probes suitable for two/three-photon fluorescence microscopy.
Project description:Two probes, AIE-1 and AIE-2, were synthesized to investigate the effect of substitutional functional group on aggregation (aggregation-caused quenching (ACQ) or aggregation-induced emission (AIE)) and intramolecular charge transfer (ICT) behavior as well as on the cell imaging aspect. The yellow-color non-substituted probe AIE-1 showed weak charge-transfer absorption and an emission band at 377 nm and 432 nm, whereas the yellowish-orange color substituted probe AIE-2 showed a strong charge-transfer absorption and an emission band at 424 nm and 477 nm in THF solvent. The UV-Vis studies of AIE-1 and AIE-2 in THF and THF with different water fractions showed huge absorption changes in AIE-2 with high water fractions due to its strong aggregation behavior, but no such noticeable absorption changes were observed for AIE-1. Interestingly, the fluorescence intensity of AIE-1 at 432 nm gradually decreased with increasing water fractions and became almost non-emissive at 90% water. However, the monomer-type emission of AIE-2 at 477 nm was shifted to 584 nm with a 6-fold increase in fluorescence intensity in THF-H2O (1:9, v/v) solvent mixtures due to the restriction of intramolecular rotation on aggregation in high water fractions. This result indicates that the probe AIE-1 shows ACQ and probe AIE-2 shows AIE behaviors in THF-H2O solvent mixtures. Furthermore, the emission spectra of AIE-1 and AIE-2 were carried out in different solvent and with different concentrations to see the solvent- or concentration-dependent aggregation behavior. Scanning electron microscope (SEM) and dynamic light scattering (DLS) experiments were also conducted to assess the morphology and particle size of two probes before and after aggregation. Both of the probes, AIE-1 and AIE-2, showed less toxicity on HeLa cells and were suitable for cell imaging studies. Density functional theory (DFT) calculation was also carried out to confirm the ICT process from an electron-rich indole moiety to an electron-deficient cyano-phenyl ring of AIE-1 or AIE-2.
Project description:Bioimaging systems with cytocompatibility, photostability, red fluorescence, and optical nonlinearity are in great demand. Herein we report such a bioimaging system. Integration of tetraphenylethene (T), triphenylamine (T), and fumaronitrile (F) units yielded adduct TTF with aggregation-induced emission (AIE). Nanodots of the AIE fluorogen with efficient red emission were fabricated by encapsulating TTF with phospholipid. The AIE dots enabled three-dimensional dynamic imaging with high resolution in blood vessels of mouse brain under two-photon excitation.
Project description:Semiconducting polymer (SP)-based afterglow luminogens are showing increasing potential for in vivo imaging because of their long-life luminescence and the associated benefits (e.g., zero-autofluorescence background and high signal-to-noise ratio). However, such organic afterglow luminescence agents are still rare and their application is usually limited by their relatively low afterglow intensity and short afterglow duration. Herein, we report an aggregation-induced emission (AIE) dye-powered SP afterglow luminogen by leveraging on the unique characteristics of an AIE dye to circumvent the concentration-quenching effect, enhance afterglow intensity and prolong afterglow duration. The underlying working mechanism is investigated by a series of experiments and it is found that the AIE dye provides sufficient 1O2 to excite SPs and form massive amounts of high-energy intermediates, and then the SP intermediates emit photons that can activate the AIE dye to generate 1O2 and simultaneously trigger the energy transfer process between the SPs and AIE dye, resulting in a deep-red emission. It is this closed-loop of "photon-1O2-SP intermediates-photon" that provides the afterglow emission even after the cessation of the excitation light. The as-prepared luminogen shows good performance in in vivo tumour imaging. This study demonstrates the advantages of AIE-facilitated afterglow luminescence and discloses its mechanism, and hopefully it could inspire the development of other innovative designs for cancer theranostics.