High Fluorescence Quantum Yield Research Articles

Fast detection of hypobromous acid in cells and the water environment using a lysosome-targeted fluorescent probe.

A new fluorescent probe SWJT-23 with lysosomal targeting ability for detection of hypobromous acid (HBrO) was synthesised based on the naphthalimide skeleton. This probe exhibited a fast response (within 3s), a low detection limit (1.24 nM), excellent selectivity and a high fluorescence quantum yield (Φ = 0.490). Moreover, SWJT-23 not only realized the sensitive detection of HBrO in cells and water samples, but also was fabricated as a paper-based sensor. In consequence, SWJT-23 is expected to be an efficient and powerful tool for monitoring HBrO in organisms and the environment in realistic scenarios.

One-step solvothermal synthesis of full-color fluorescent carbon dots for information encryption and anti-counterfeiting applications.

Multicolor fluorescent carbon dots (CDs) have received extensive attention due to their excellent fluorescence tunable performance. In this study, multicolor CDs with color tunable and high fluorescence quantum yields (QYs) were successfully prepared under the same conditions by a one-step solvothermal method using 2-aminoterephthalic acid (ATA) and Nile Blue A (NBA) as reaction reagents, achieving a wide color field coverage. Detailed studies on the relevant mechanisms have been carried out for blue, green and red CDs, indicating that the regulating mechanism of multicolor luminescence is determined by the size of the sp2 conjugated domains, which is due to the increase of particle size that causes an increase in the size of the sp2 conjugated domains, resulting in the narrowing of the band gap and the red-shift of the emission wavelength. It was found that the CDs have the advantages of simple preparation, high photostability and high quantum yield. They were used as fluorescent ink and mixed with polyvinyl alcohol (PVA) to form CD/PVA composites, which were successfully applied in the field of information encryption and anti-counterfeiting. This work provides a new strategy for the synthesis of panchromatic tunable fluorescent CDs and their application in the field of information encryption and anti-counterfeiting.

Yellow emissive and high fluorescence quantum yield carbon dots from perylene-3,4,9,10-tetracarboxylic dianhydride for anticounterfeiting applications.

Forged products are widespread in the market and there is an immediate need to counter this growing menace. Anti-counterfeit techniques using fluorescent materials with covert features that appear hidden under daylight and display characteristic fluorescence upon specific source irradiation have gained popularity. Carbon dots (CDs) that can be prepared through facile synthesis from various raw materials are a class of fluorescent materials that provide tremendous opportunities to combat counterfeiting. This work focuses on the fabrication of perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) derived CDs via the solvothermal approach and their subsequent purification using column chromatography. The fifth fraction obtained exhibited remarkable yellow emission (λem = 540 nm) with a high fluorescence quantum yield of 53.22% and a lifetime of 4 ns. The CDs appeared quasi-spherical during TEM imaging with an average diameter of 1-3 nm and appeared polycrystalline from the SAED pattern. The XPS and TEM-EDS results suggested carbon as the major element along with oxygen and nitrogen as the other heteroatoms. The water-based ecofriendly ink formulated using the CDs was printed on UV dull paper using the flexography technique. The print-proof paper samples appeared pale pink under daylight and fluorescent yellow upon 365 nm UV illumination. Moreover, the stability of the print was confirmed upon exposure to strong UV radiation cycles and abrasion resistance. Besides, the fluorescence emission remained unaltered even after 5 months of storage under room temperature conditions. The ink was used to print on PVC sheets and FBB boards with good stability against scuffing, suggesting its applicability in the packaging industry. The CDs could also serve as fluorescent markers for identifying post-consumer plastic packaging for a circular economy.

Planar-structured thiadiazoloquinoxaline-based NIR-II dye for tumor phototheranostics.

Second near-infrared (NIR-II) fluorescence imaging shows huge application prospects in clinical disease diagnosis and surgical navigation, while it is still a big challenge to exploit high performance NIR-II dyes with long-wavelength absorption and high fluorescence quantum yield. Herein, based on planar π-conjugated donor-acceptor-donor systems, three NIR-II dyes (TP-DBBT, TP-TQ1, and TP-TQ2) were synthesized with bulk steric hindrance, and the influence of acceptor engineering on absorption/emission wavelengths, fluorescence efficiency and photothermal properties was systematically investigated. Compared with TP-DBBT and TP-TQ2, the TP-TQ1 based on 6,7-diphenyl-[1,2,5]thiadiazoloquinoxaline can well balance absorption/emission wavelengths, NIR-II fluorescence brightness and photothermal effects. And the TP-TQ1 nanoparticles (NPs) possess high absorption ability at a peak absorption of 877 nm, with a high relative quantum yield of 0.69% for large steric hindrance hampering the close π-π stacking interactions. Furthermore, the TP-TQ1 NPs show a desirable photothermal conversion efficiency of 48% and good compatibility. In vivo experiments demonstrate that the TP-TQ1 NPs can serve as a versatile theranostic agent for NIR-II fluorescence/photoacoustic imaging-guided tumor phototherapy. The molecular planarization strategy provides an approach for designing efficient NIR-II fluorophores with extending absorption/emission wavelength, high fluorescence brightness, and outstanding phototheranostic performance.

Protein aggregation monitoring in cells under oxidative stress: a novel fluorescent probe based on a 7-azaindole-BODIPY derivative.

The development of new fluorescent probes as molecular sensors is a critical step for the understanding of molecular mechanisms. BODIPY-based probes offer versatility due to their high fluorescence quantum yields, photostability, and tunable absorption/emission wavelengths. Here, we report the synthesis and evaluation of a novel 7-azaindole-BODIPY derivative to probe hydrophobic proteins as well as protein misfolding and aggregation. In organic solvents, this compound shows two efficiently interconverting emissive excited states. In aqueous environments, it forms molecular aggregates with unique photophysical properties. The complex photophysics of the 7-azaindole-BODIPY derivative was explored for sensing applications. In the presence of albumin, the compound is stabilized in hydrophobic protein regions, significantly increasing its fluorescence emission intensity and lifetime. Similar effects occur in the presence of protein aggregates but not with other macromolecules like pepsin, DNA, Ficoll 40, and coconut oil. Fluorescence lifetime imaging microscopy (FLIM) and two-photon fluorescence microscopy on breast (MCF-7) and lung (A549) cancer cells incubated with this compound display longer fluorescence lifetimes and higher emission intensity under oxidative stress. Synchrotron FTIR micro spectroscopy confirmed that the photophysical changes observed were due to protein misfolding and aggregation caused by the oxidative stress. These findings demonstrate that this compound can serve as a fluorescent probe to monitor protein misfolding and aggregation triggered by oxidative stress.

Design, synthesis, and biological application of A-D-A-type boranil fluorescent dyes.

For the first time, three acceptor-donor-acceptor (A-D-A)-type boranil fluorescent dyes, CSU-BF-R (R = H, CH3, and OCH3), featuring phenothiazine as the donor, were designed and synthesized. CSU-BF-R exhibited remarkable photophysical characteristics, including large Stokes shifts (>150 nm), high fluorescence quantum yields (up to 40%), long-wavelength emissions, and strong red solid-state fluorescence. Moreover, these CSU-BF-R fluorescent dyes were demonstrated to function as highly selective and sensitive ratiometric fluorescent probes for detecting hypochlorous acid (HClO). The preliminary biological applications of CSU-BF-OCH3 for sensing intracellular HClO in living cells and zebrafish were demonstrated. Therefore, CSU-BF-R possess the potential to further explore the physiological and pathological functions associated with HClO and provide valuable insights into the design of high-performance A-D-A-type fluorescent dyes.

Fluorescent Nitrogen‐Doped Carbon Dots as Nanosensors for the Detection of Fe3+ Ions

Fluorescent nitrogen‐doped carbon dots (N‐CDs) are obtained by a straightforward hydrothermal method, and tartaric acid and L‐histidine hydrochloride are used as precursors. The obtained N‐CDs exhibit nanoscale structure, good water solubility, photostability, and excellent fluorescence (FL) properties with a high FL quantum yield of 19%. The designed N‐CDs are used as fluorescent probes for detecting Fe3+ with the FL “on‐off” strategy. Two good linear relationships can be observed for the concentration of Fe3+ from 0 to 80 μm and from 80 to 600 μm, and the calculated detection limit for Fe3+ is 0.88 μm (3σ/slope). Moreover, the N‐CDs‐based FL probe can also be used for detecting Fe3+ in tap water and possesses great potential application in the field of anti‐fake information encryption.

Substituent and Solvent Effects on the Spectral Properties of 3-Substituted Derivatives of 4-Hydroxycoumarin

Solvent and substitution effects on the UV/Vis spectroscopic and fluorescence behaviour of seven synthesized 3-substituted 4-hydroxycoumarin derivatives were tested. The tested compounds were dissolved in ethyl acetate, acetonitrile, and dimethyl sulfoxide. Absorption and emission spectra were recorded in the range of 200–800 nm. All tested 4-hydroxycoumarin derivatives showed good absorption in a wide range of 200–550 nm, depending on the properties of the substituents on the benzene ring of the cinnamoyl moiety and the type of solvent. In comparison to the unsubstituted analogue, compounds with an electron-donating group exhibited bathochromically shifted UV/Vis absorption and emission spectra. The highest fluorescence quantum yield was observed for compounds with dimethylamino and acetamido groups as substituents at the benzene ring. Considering that both substitution and solvent affect the absorption and emission spectra of the tested compounds, it can be concluded that judiciously selecting these parameters can improve their absorption and fluorescence properties, making them suitable for various analytical uses.

Green synthesis of carbon dots from fish scales for selective turn off-on detection of glutathione.

Carbon dots as fluorescent probes were fabricated using readily available grass carp fish scales as the carbon source via one-step synthesis based on a pyrolytic reaction. The as-prepared grass carp fish scale carbon dots (GF-CDs) exhibited good biocompatibility and excellent optical properties with a high fluorescence quantum yield of 23.8%. Glutathione (GSH) is an essential small tri-peptide molecule present in every body cell and plays a crucial role in vivo and performs a wide range of biological functions. Ag+ can effectively quench the fluorescence of GF-CDs because of the electron transfer between GF-CDs and Ag+; however, the addition of GSH can significantly increase GF-CD-Ag+ fluorescence. Because of their combination with Ag+ and GSH, GF-CDs show selective fluorescence recovery. GF-CDs can serve as fluorescent probes for GSH detection. This detection method covered a wide linear range (1.6-36.0 μg mL-1) with the lowest detection limit of 0.77 μg mL-1 and manifested great advantages such as a short analysis time, good stability, repeatability, and ease of operation.

Silicon distyryl-BODIPY hybrid photodiode: moving a step ahead from organic interface layer to type II band alignment

Organic-inorganic heterojunctions are becoming an attractive topic of research for their applications in hybrid photodetectors, solar cells, resistive switching memory devices etc. The easy chemical synthesis and low-cost fabrication for organic thin films come with the benefit of high light absorptivity, high fluorescence quantum yield and band gap tunability along with high charge carrier lifetime that could be combined with the existing silicon-based technology. In this aspect, various organic dyes utilised as an interfacial layer with silicon Schottky junction are reported earlier. However, the photo responses are quite limited. Here, in this report, a Type II Silicon/Distyryl-BODIPY p-n junction has been proposed as an organic-inorganic hybrid photodetector which has not been explored extensively yet. The transformation from a mere organic interfacial layer to band aligned junction enhances the charge carrier separation providing higher photo-responsive behaviour. With the simple spin-coating technique, the Distyryl-BODIPY derivative with phenolic functionalities is coated to fabricate the p-n junction diode. To further improve the performance, pyramidal surface texturization on silicon is deployed using wet chemical etching that supplements the light absorption with internal reflections. Both the devices have been investigated for their photo-response characteristic where a high photo-responsivity of 4353 A W−1 is attained for the textured device as compared to 118 A W−1 for the planar silicon device at a − 3 V bias with an ultra-high specific detectivity of 1012 Jones and 1010 Jones respectively. The behaviours of interfacial states have been demonstrated using the capacitance (C), conductance (G) and series resistance (RS) vs voltage (V) curves at different frequencies. Further calculations of interfacial state density revealed the existence of 1000 times higher interfacial states in planar device leading to lower performance as compared to pyramidal device. The findings in this report suggest that dye-based organic-inorganic heterostructures find potential applications in photodetectors and other optoelectronic devices.

Effect of aggregation configuration of molecular fluorophore CZA on photoluminescence properties of carbon dots

The effect of aggregation configuration of molecular fluorophore citrazinic acid (CZA) on the photoluminescence (PL) properties of carbon dots (CDs) has been investigated using first-principles method. The structural stability of all aggregates has been analyzed, and the results show that the most stable structures are J-type CZA aggregates with head-to-tail configurations and the CZA/CD aggregates are bonded by replacing H atoms on the CD edges with de-OH from the pyridine ring of CZA. The luminescent properties of CZA/CD aggregates are mainly affected by the binding modes and binding sites. When the sites belong to electron-donating groups, electron-withdrawing groups or sp2 domain, the PL spectra of CDs are shifted and the luminescent intensities are significantly enhanced. The results suggest that covalently bonded CZA/CD aggregates are responsible for the high fluorescence quantum yield of CD. Moreover, the distance between the centers of the two pyridine rings in H-type CZA dimers less than 3.5 Å is prone to π-π stacking, leading to fluorescence quenching of aggregates. The present work is helpful in understanding the effect of molecular fluorophores on the PL properties of CDs and provides theoretical guidance for the controllable synthesis of CDs.

The Synthesis and Properties of Ladder-Type π-Conjugated Compounds with Pyrrole and Phosphole Rings.

The phosphole ring is known as a useful building block for constructing π-conjugated organic materials. Here, we report ladder-type benzophospholo[3,2-b]indole (BPI) derivatives where the phosphole and the pyrrole rings are directly fused. Compounds 8a-8d with different aryl groups on the phosphorous center were successfully synthesized, and the solid-state structure of 8a was confirmed using X-ray crystallographic analysis. The BPIs exhibit relatively high fluorescence quantum yield (Φ 0.50-0.72) and demonstrate a larger Stokes shift compared with a series of benzophospholo[3,2-b]benzoheteroles. The benzophospholo[3,2-b]carbazole derivative 9, which possesses a benzene ring between the phosphole and the pyrrole rings of the BPI, was also synthesized, and its solid-state structure was confirmed using X-ray crystallographic analysis. Compound 9 was found to show a smaller Stokes shift compared with the BPI.

Design and synthesis of triphenylphosphine-based donor-π-acceptor fluorophores with strong aggregation-induced emission and enantiomer-paired flower-like stacking

Triphenylphosphine (TPP) shows stereo pyramidal configuration and has been considered as a poor electron-donor and fluorophore. Here, seven TPP-based compounds (o-TPPs 3a–3e and p-TPPs 3f/g) introducing simple non-aromatic electron-withdrawing (EW) groups at the ortho- and para-position of P atom have been synthesized to understand the inherent optical properties of TPP. All TPPs show aggregation-induced emission (AIE): non-emissive in solutions but emissive upon aggregation. Unexpectedly, lower conjugative o-TPPs possess much higher fluorescence quantum yields (43 and 65 %) than those (1 and 29 %) of their corresponding position isomers, p-TPPs; these achiral pyramidal TPPs in crystals exist as racemic M- and P-enantiomers, with all o-TPPs showing unique MP-paired flower-like arrangements; and the pyramidal TPP moiety could form an excellent electron delocalization system via through-space conjugation. This work proves that TPP could act as an excellent electron-donor and AIEgen by reasonable design, opens a new window to the application of pyramidal TPPs or other pyramidal compounds and affords a new strategy to design strong AIE fluorophores.

Luminescent Mono‐, Di‐ and Trisubstituted 2,4,6‐Triphenylpyridine‐Based Molecules: Synthesis and Properties

AbstractThe chromophores based on a pyridine central acceptor and one/two/three peripheral substituents of different electronic and spatial nature have been designed and synthesized. The structure‐property relationship was studied using differential scanning calorimetry, cyclic voltammetry, UV‐Vis and emission spectroscopy. A study of the thermal properties of the synthesized compounds showed that the presence of a 3,6‐bis(tert‐butyl)carbazole fragment leads to a significant increase in the glass transition temperature of the compounds. Photophysical studies have revealed that N,N‐diphenylamine‐containing pyridines are characterized by a high fluorescence quantum yield. In this regard, the expediency of the simultaneous presence in the structure of chromophores of electron‐donating groups of different natures has been proven, since this approach makes it possible to obtain compounds with high fluorescence quantum yield and molar absorption coefficient, as well as a narrow band gap and a deep level of the highest occupied molecular orbital.

The fabrication of fluorescent sensor for Fe3+ detection and configurable logic gate operation based on N-doped carbon dots

Herein, fluorescent N-doped carbon dots (N-CDs) were obtained using hydrothermal treatment of polyethyleneimine and melamine. The N-CDs exhibit nanoscale structure, good water solubility, photostability and excellent fluorescence property with a high fluorescence quantum yield of 26 %. The as-prepared N-CDs were selected for the detection of Fe3+ with a fluorescence “OFF-ON” strategy by the mechanism of internal filtration effect (IFE). A good linear relationship can be observed for the concentration of Fe3+ from 0 to 500 μM, and the calculated detection limit (LOD) for Fe3+ was 0.88 μM (3σ/slope). Meanwhile, the N-CDs based sensor can be utilized for tracing Fe3+ in real water samples. In addition, the quenched fluorescence can be recovered with the treatment of l-cysteine, and thus can be designed for quantitative determination of l-cysteine with a fluorescent “ON-OFF-ON” switch. Moreover, a set of resettable, multireadout logic gate operations including OR and AND have been realized for the N-CDs.

Carbonyl- and Nitrogen-Embedded Multi-Resonance Emitter with Ultra-Pure Green Emission and High Electroluminescence Efficiencies.

Multi-resonance thermally activated delayed fluorescence (MR-TADF) emitters with narrow emission spectra have garnered significant attention in future organic light-emitting diode (OLED) displays. However, current C=O/N-embedded MR-TADF systems still lack satisfactory performance in terms of electroluminescence bandwidths and external quantum efficiencies (EQEs). In this study, a C=O/N-embedded green MR-TADF emitter, featuring two acridone units incorporated in a sterically protected 11-ring fused core skeleton, is successfully synthesized through finely controlling the reaction selectivity. The superior combination of multiple intramolecular fusion and steric wrapping strategies in the design of the emitter not only imparts an extremely narrow emission spectrum and a high fluorescence quantum yield to the emitter but also mitigates aggregation-induced spectral broadening and fluorescence quenching. Therefore, the emitter exhibits leading green OLED performance among C=O/N-based MR-TADF systems, achieving an EQE of up to 37.2 %, a full width at half maximum of merely 0.11 eV (24 nm), and a Commission Internationale de l'Éclairage coordinate of (0.20, 0.73). This study marks a significant advance in the realization of ideal C=O/N-based MR-TADF emitters and holds profound implications for the design and synthesis of other MR-TADF systems.

Carbonyl‐ and Nitrogen‐Embedded Multi‐Resonance Emitter with Ultra‐Pure Green Emission and High Electroluminescence Efficiencies

AbstractMulti‐resonance thermally activated delayed fluorescence (MR‐TADF) emitters with narrow emission spectra have garnered significant attention in future organic light‐emitting diode (OLED) displays. However, current C=O/N‐embedded MR‐TADF systems still lack satisfactory performance in terms of electroluminescence bandwidths and external quantum efficiencies (EQEs). In this study, a C=O/N‐embedded green MR‐TADF emitter, featuring two acridone units incorporated in a sterically protected 11‐ring fused core skeleton, is successfully synthesized through finely controlling the reaction selectivity. The superior combination of multiple intramolecular fusion and steric wrapping strategies in the design of the emitter not only imparts an extremely narrow emission spectrum and a high fluorescence quantum yield to the emitter but also mitigates aggregation‐induced spectral broadening and fluorescence quenching. Therefore, the emitter exhibits leading green OLED performance among C=O/N‐based MR‐TADF systems, achieving an EQE of up to 37.2 %, a full width at half maximum of merely 0.11 eV (24 nm), and a Commission Internationale de l′Éclairage coordinate of (0.20, 0.73). This study marks a significant advance in the realization of ideal C=O/N‐based MR‐TADF emitters and holds profound implications for the design and synthesis of other MR‐TADF systems.

4,7-(bis(octyloxy)-3-(quinoline-2-ylmethylene)isoindoline-1-one and its boronflouride complex. synthesis and spectral-luminescent properties

4,7-Bis(octyloxy)isoindoline-1,3-dione was obtained by reacting 3,6-bis(octyloxy)phthalonitrile with sodium butoxide in butanol, followed by treatment with hydrochloric acid. Its condensation with quinaldine in the presence of zinc oxide leads to the formation of ( E , Z )-4,7-bis(octyloxy)-3-(quinolin-2-ylmethylene)isoindolin-1-one, which was treated with BF3۰Et2O in the presence of triethylamine in toluene to give a new unsymmetrical analogue of BODIPY - ( Z )-2-(difluoroboryl)-4,7-bis(octyloxy)-3-(quinolin-2-ylmethylene)isoindolin-1-one. The complex exhibits a Stokes shift of 25 nm and a high relative fluorescence quantum yield (0.68). To support the experimental data, DFT and TD-DFT calculations were performed.

Anion-directed cationic supramolecular dyes with reversible mechanochromism and fabric staining

It is vital to create supramolecular dyes with excellent photo-luminescence properties based on host-gust interaction. In this study, we present three novel self-assembled cationic supramolecular dyes driven by host-guest electrostatic interaction and with ultrasmall cavities. These cationic dyes were developed and synthesized using pyridine-substituted phenanthrene, triphenylamine (TPA), and tetraphenyl ethylene (TPE) as chromophores through the pyridine quaternary ammonium salt reaction. These anion-trapped supramolecular dyes exhibit outstanding aggregation-induced emission (AIE) characteristics as well as reversible mechanochromism behavior and high solid-state fluorescence quantum yields (∼60.87 %). Furthermore, the cationic supramolecular dyes directly stain cotton fibers with 50 % dyeing rate in water-methanol solutions, in which the deprotonated glucose-O- guest possibly interacts with the cationic dye through host-guest encapsulation. Additionally, we characterized the dyeing process through IR spectroscopy, UV–vis spectroscopy, fluorescence spectroscopy, and energy-dispersive X-ray spectroscopy (EDS). Due to the reversible, tractable, and high-contrast mechanochromism of the dyes, they can make up a color-changing flower pattern. Thus, we anticipate that these dyes will have potential applications in information security storage and anti-counterfeiting.

Facile synthesis of fluorescent carboxymethyl cellulose polymer dots and multi-purpose applications in pH and glucose sensing

Herein, fluorescent carboxymethyl cellulose polymer dots (B-PDs) were synthesized by a straightforward route under mild conditions using ethylenediamine-modified carboxymethyl cellulose (CMC-NH2) and phenylboronic acid as precursors. The B-PDs exhibit a uniform nanoscale size distribution, good water solubility, photostability and excellent fluorescence emission with a high fluorescence quantum yield of 21.6 %. The B-PDs display a reversible fluorescence response with blue emission in acidic solution and green emission in alkaline solution. Moreover, the B-PDs can be designed as an excellent fluorescent sensor for glucose detection. After the addition of glucose, the FL intensity at λex = 388 nm can be enhanced due to the assembly of glucose on the B-PDs based on the reversible reaction between boronic acid and cis-diols through the aggregation-induced enhancement effect (AIE). Two good linear relationships can be obtained between (F-F0)/F0 and the glucose amount ranging from 0 ∼ 0.005 M (R2 = 0.9971) and 0.01 ∼ 1.2 M (R2 = 0.9984), and the detection limit (LOD) was calculated to be 52 μM (3σ/slope). Meanwhile, the proposed probe was successfully utilized to analyze glucose in human urine samples (recovery: 97.9–104.1 %, RSD: 2.64–4.23 %) by the standard addition method, indicating good feasibility as a practical platform for sensing.