Efficient Fluorophores Research Articles

Isomerization enhanced fluorescence brightness of benzobisthiadiazole-based NIR-II fluorophores for highly efficient fluorescence imaging: A theoretical perspective

As a cutting-edge technique, fluorescence imaging in the second near-infrared window (NIR-II) is vital for both biomedical research and clinical applications. However, its intravital imaging capacity has been restricted by the extremely limited brightness of NIR-II fluorophores. To address this challenge, we elucidated the inner mechanism of constructing high-performance NIR-II chromophores based on molecular isomer engineering from detailed computational investigations. Herein, three pairs of cis–trans isomers (cis-1, 2, 3 and trans-1, 2, 3) are designed by attaching amino, methoxyl and nitro moieties to different positions on the donor–acceptor-donor molecular skeleton with benzobisthiadiazole as the acceptor and triphenylamine as the donor. All the compounds feature efficient NIR-II emission ranging in 1000–1164 nm, and the photophysical characterizations are regulated by molecular isomer manipulation. Interestingly, fluorescence quantum yields of cis-isomers are higher than those of their trans-counterparts. These enhancements can be attributed to the significant reduction in non-radiative transition, as evidenced by the non-adiabatic excitation energy, non-adiabatic electron coupling and electron-vibration coupling. Meanwhile, fluorophores with nitro terminal group exhibit superior performance facilitated by the prominently intramolecular charge transfer. As a result, cis-3 achieves an optimal brightness maxima of 196.36 M−1 cm−1 at 632 nm. Notably, the energy gap and the hole-electron related H index are respectively identified as strongly relevant to the emission wavelength and brightness, making them capable of evaluating the feasibility of fluorophores as effective NIR-II candidates. These findings highlight the correlations between molecular geometry and luminescent properties, which will inspire more insights into the development of highly efficient NIR-II fluorophores through rational isomer engineering for biomedical applications.

Efficient Near-Infrared Fluorophores Based on Cyanostyrene Derivatives for Two-Photon Fluorescence Bioimaging.

Organic fluorescent materials with red/near-infrared (NIR) emission are highly promising for use in biotechnology due to their exceptional advantages. However, traditional red/NIR fluorophores often exhibit weak emission at high concentrations or in an aggregated state due to the aggregate-caused quenching effect, which severely limits their applicability in biological imaging. To address this challenge, we developed a series of cyanostyrene derivatives with aggregation-induced emission characteristics, including 2,3-Bis-(4-styryl-phenyl)-but-2-enedinitrile (DPB), 2,3-Bis-{4-[2-(4-methoxy- phenyl)-vinyl]-phenyl}-but-2-enedinitrile (DOB), 2,3-Bis-{4-[2-(4-diphenylamino- phenyl)-vinyl]-phenyl}-but-2-enedinitrile (DTB), and 2,3-Bis-[4-(2-{4-[phenyl- (4-triphenylvinyl-phenyl)-amino]-phenyl}-vinyl)- phenyl]-but-2-enedinitrile (DTTB). Notably, these compounds exhibited intense solid state fluorescence owing to AIE effect, especially DTTB shows NIR emission with high solid state quantum efficiency (712 nm, ΦF=14.2 %). Then we prepared DTTB@PS-PEG NPs nanoparticles by encapsulating DTTB with the amphiphilic polymer polystyrene-polyethylene glycol (PS-PEG). Importantly, DTTB@PS-PEG NPs exhibited highly efficient NIR luminescence (ΦF=28.7 %) and a large two-photon absorption cross-section (1900 GM) under 800 nm laser excitation. The bright two-photon fluorescence of DTTB@PS-PEG indicated that it can be a highly promising candidate for two-photon fluorescence probe. Therefore, this work provides valuable insights for the design of highly efficient and NIR-emitting two-photon fluorescent probes.

Conformational Isomerization Promotes Balanced Ambipolar Transport for Efficient Narrowband Near-Ultraviolet Fluorophore and Non-doped Device with Low Efficiency Roll-Off

Conformational Isomerization Promotes Balanced Ambipolar Transport for Efficient Narrowband Near-Ultraviolet Fluorophore and Non-doped Device with Low Efficiency Roll-Off

Exploring Efficient Dual-Phase Emissive Fluorophores with High Mobility by Integrating a Rigid Donor and Flexible Acceptor.

Developing luminogens with a high emission efficiency in both single-molecule and aggregate states, as well as high mobility, shows promise for advancing the iteration and update of organic optoelectronic materials. However, achieving a delicate balance between the plane configuration of luminophores and the strong exciton interactions of aggregates is a formidable task from the molecular design perspective. This dilemma was overcome by integrating a rigid donor and flexible acceptor to establish donor-acceptor (D-A) type emitters. The π-conjugate-extended donor ensures the substantial planarity of these molecules, allowing strong emission in solution with photoluminescence quantum yield values of 86% and 75%. Furthermore, the restricted molecular motion of the aggregation-induced emission moiety and the formation of J-aggregates reduce the quenching effect, leading to a high emissive efficiency of 85% and 91% in the aggregate state. The mildly distorted D-A geometry builds moderate electrostatic interaction, resulting in high mobility with μM,h of 7.12 × 10-5 and 3.27 × 10-4 cm2/V s. Additionally, an improved synthesized procedure for terminal E-configured acrylonitrile with metal-free and concise reaction conditions is presented. The successful application of the synthesized compounds in organic light-emitting diode devices demonstrates the practicability of the molecular design strategy with connecting a rigid donor and flexible acceptor.

Synthesis of Tough and Fluorescent Self-Healing Elastomers by Scandium-Catalyzed Terpolymerization of Pyrenylethenylstyrene, Ethylene, and Anisylpropylene.

The synthesis of fluorescent self-healing polymers by the incorporation of a fluorophore-containing olefin into a polyolefin backbone through catalyst-controlled multicomponent copolymerization is of fundamental interest and practical importance, but such an approach has remained unexplored to date. Herein, we report for the first time the synthesis of tough and fluorescent self-healing polymers by sequence-controlled terpolymerization of 4-[2-(1-pyrenyl)ethenyl]styrene (Pyr), ethylene (E), and anisylpropylene (AP) using a sterically demanding half-sandwich scandium catalyst. The resulting terpolymers consisted of relatively long alternating E-alt-AP sequences, isolated Pyr units, and short E-E blocks, which exhibited excellent tensile strength, remarkable self-healability, and high fluorescence quantum yield. The excellent mechanical and self-healing properties could be attributed to the nanophase separation of the crystalline E-E segments and the hard Pyr aggregates from a flexible E-alt-AP segment matrix, in which the Pyr units not only served as an efficient fluorophore but also played an important role in forming nanodomains and enhancing the polymer mobility. Furthermore, the styrenyl C═C bond of the Pyr unit in the terpolymers could undergo [2 + 2] cycloaddition under photoirradiation, which thus enabled the fabrication of a self-healable fluorescent two-dimensional image on a terpolymer film through photolithography. This work offers an unprecedented efficient protocol for the synthesis of a brand-new family of fluorescent self-healing materials, showcasing the high potential of catalyst-controlled sequence-regular copolymerization of different olefins for the creation of novel functional polymers.

An efficient and stable deep-blue oxygen-bridged triphenylborane-based fluorophore with hybridized local and charge-transfer states

A multifunctional deep-blue HLCT fluorophore with remarkable performance was developed by incorporating a boron/oxygen-based multi-resonance skeleton.

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.

A record-high EQE of 7.65%@3300 cd m-2 achieved in non-doped near-ultraviolet OLEDs based on novel D'-D-A type bipolar fluorophores upon molecular configuration engineering.

Developing a high-performance near-ultraviolet (NUV) material and its simple non-doped device with a small efficiency roll-off and good color purity is a promising but challenging task. Here, we proposed a novel donor'-donor-acceptor (D'-D-A) type molecular strategy to largely solve the intrinsic contradictions among wide-bandgap NUV emission, fluorescence efficiency, carrier injection and transport. An efficient NUV fluorophore, 3,6-mPPICNC3, exhibiting a hybridized local and charge-transfer state, is achieved through precise molecular configuration engineering, realizing similar hole and electron mobilities at both low and high electric fields. Moreover, the planarized intramolecular charge transfer excited state and steric hindrance effect endow 3,6-mPPICNC3 with a considerable luminous efficiency and good color purity in the aggregation state. Consequently, the non-doped device emitting stable NUV light with Commission Internationale de l'Eclairage (CIE) coordinates of (0.160, 0.032) and a narrow full width at half maximum of 44 nm exhibits a state-of-the-art external quantum efficiency (EQE) of 7.67% and negligible efficiency roll-off over a luminance range from 0 to 3300 cd m-2. This is a record-high efficiency among all the reported non-doped NUV devices. Amazingly, an EQE of 7.85% and CIE coordinates of (0.161, 0.025) are achieved in the doped device. This demonstrates that the D'-D-A-type molecular structure has great potential for developing high-performance organic light-emitting materials and their optoelectronic applications.

Naptha-phenanthroimidazole-based blue fluorophores (y

Organic light-emitting diodes are a promising new technology for next-generation displays and lighting applications, particularly in the quest for efficient deep blue fluorophores (y= < 0.05). Despite the receipt of several reports, it remains imperative to advance the development of a deep blue emitter that can address solubility, stability, color purity, and efficiency. Eye on these challenges, herein, four new blue phenanthroimidazole and naphthalene-based derivatives, 2-(naphthalen-1-yl)-1H-phenanthro[9,10-d]imidazole(Pq-NH-NA), 2-(naphthalen-1-yl)-1-phenyl-1H phenanthro [9,10-d]imidazole (Pq-An-NA), 2-(naphthalen-1-yl)-1-(3-(trifluoromethyl)phenyl)-1H-phenanthro[9,10-d]imidazole (Pq-mF-NA), and 2-(naphthalen-1-yl)-1-(4-(trifluoromethyl)phenyl)-1H-phenanthro[9,10-d]imidazole (Pq-pF-NA) were designed and synthesized. Further, the PI molecules were structurally characterized by spectroscopic analysis, and their thermal decomposition (Td) is found to be 203–309 °C. Substitution at the N1 position of imidazole provides a facile alternative role for photophysical and electronic properties. The PI fluorophores were further characterized in solution, thin-film, and solid where the solid results are enhanced in terms of intense color emission (x = 0.158, y = 0.037). It showed a good quantum yield of 14.28 % in solution and 19.33 % in solid, indicating that fluorinated molecules lead to better performance than the rest of them. Additionally, the InGaN LED fabricated with the fluorinated molecule Pq-pF-NA emitted 425 nm with a deep blue emission and yielding CIE color coordinates (x = 0.154, y = 0.048). The film study also revealed the deep blue emission with increasing concentration of emitter (2.5 %). The observed results apprise that the synthesized fluorophores are efficient to deep blue emitters and capable candidates for organic light-emitting diodes.

Fluorescence Spectroscopic Studies to Evaluate Binding Interaction between Hoechst 33258 and Bilirubin.

A detailed spectroscopic study (fluorescence, absorption, and lifetime) was conducted to gain insight into the nature of the binding interaction between fluorophore Hoechst33258 (H258) and jaundice marker Bilirubin (Br). The fluorescence emission of the H258 (Ex/Em = 340-502nm) showed a conc. dependent quenching in the presence of Br (1.25 M to 10 M). The Stern-Volmer constant demonstrated an upward curve depicting the occurrence of both static and dynamic quenching with an acquired value of K = 3.1x 10 M and biomolecular quenching rate constant K = 8.6 x 10 M S . The static quenching was evaluated using the sphere of action model and a sphere radius of 0.3nm indicated the presence of a static component in the quenching. The FRET analysis with overlap integral (J) = 1.4x10 M cm nm and Foster Radius(R ) = 26.82 Å with 59% efficiency suggested occurrence of dynamic quenching. Further studies with the time-resolved fluorescence also indicated the presence of dynamic quenching. The lifetime values of H258 reduced from 3.9ns to 0.5ns. Molecular docking studies further support both static and dynamic components in quenching. A non-covalent interaction of H258 with Br in the presence of HSA is predominantly characterized by H-bonding with residues Lys, Asn, Glu, Gln, and Br. The H258 and Br interaction was within the distance of 3.04 Å, which is in coherence with the sphere of action model (0.3nm) and Van-der-Waals along with hydrophobic interactions, which suggested both static and dynamic quenching. Thus, H258 can serve as an efficient fluorophore to monitor binding interactions and can be further exploited as a suitable probe for investigating conformational changes and detection of Br in subsequent studies.

Non‐Doped Blue AIEgen‐Based OLED with EQE Approaching 10.3 %

AbstractAggregation‐induced emission (AIE) luminogens (AIEgens) are attractive for the construction of non‐doped blue organic light‐emitting diodes (OLEDs) owning to their high emission efficiency in the film state. However, the large internal inversion rate (kIC(Tn)) between high‐lying triplet levels (Tn) and Tn‐1 causes a huge loss of triplet excitons, resulting in dissatisfied device performance of these AIEgens‐based non‐doped OLEDs. Herein, we designed and synthesized a blue luminogen of DPDPB‐AC by fusing an AIEgen of TPB‐AC and a DMPPP, which feature hot exciton and triplet‐triplet annihilation (TTA) up‐conversion process, respectively. DPDPB‐AC successfully inherits the AIE feature and excellent horizontal dipole orientation of TPB‐AC. Furthermore, it owes smaller kIC(Tn) than TPB‐AC. When DPDPB‐AC was applied in OLED as non‐doped emitting layer, an outstanding external quantum efficiency of 10.3 % and an exceptional brightness of 69311 cd m−2 were achieved. The transient electroluminescent measurements and steady‐state dynamic analysis confirm that both TTA and hot exciton processes contribute to such excellent device performance. This work provides a new insight into the design of efficient organic fluorophores by managing high‐lying triplet excitons.

Non-Doped Blue AIEgen-Based OLED with EQE Approaching 10.3 .

Aggregation-induced emission (AIE) luminogens (AIEgens) are attractive for the construction of non-doped blue organic light-emitting diodes (OLEDs) owning to their high emission efficiency in the film state. However, the large internal inversion rate (kIC (Tn) ) between high-lying triplet levels (Tn ) and Tn-1 causes a huge loss of triplet excitons, resulting in dissatisfied device performance of these AIEgens-based non-doped OLEDs. Herein, we designed and synthesized a blue luminogen of DPDPB-AC by fusing an AIEgen of TPB-AC and a DMPPP, which feature hot exciton and triplet-triplet annihilation (TTA) up-conversion process, respectively. DPDPB-AC successfully inherits the AIE feature and excellent horizontal dipole orientation of TPB-AC. Furthermore, it owes smaller kIC (Tn) than TPB-AC. When DPDPB-AC was applied in OLED as non-doped emitting layer, an outstanding external quantum efficiency of 10.3 % and an exceptional brightness of 69311 cd m-2 were achieved. The transient electroluminescent measurements and steady-state dynamic analysis confirm that both TTA and hot exciton processes contribute to such excellent device performance. This work provides a new insight into the design of efficient organic fluorophores by managing high-lying triplet excitons.

Synthesis of new efficient fluorophores of thieno[2,3-&lt;i&gt;b&lt;/i&gt;]pyridine series

The reaction of 4-amino-6-aryl-2-halopyridine-3,5-dicarbonitriles with thioglycolic acid ethyl ester was used to synthesize a series of new efficient fluorophores of thieno[2,3- b ]pyridine series. The long-wavelength absorption bands of DMSO solutions of the prepared compounds are at the boundary of the UV and visible regions of the spectrum (λabs 375-388 nm) and show an ambiguous influence of the substituent electronic effect, that was explained by quantum chemical calculations. The emission maxima are in the yellow-green region (λem 490- 510 nm) and they are blue-shifted in the presence of electron donor groups with slightly increasing intensity (Φem 37.8-60.6%). It was found that the nitro group presence causes a complete photoluminescence quenching both in solution and in the solid state. In addition, the position of the emission maximum (λem 473-505 nm) and its intensity (Φem 3.6-72.7%) strongly depend on the polarity and the basic properties of the medium, that was established using the Catalan empirical model.

Dual Monomeric Inorganic Units Constructed Bright Emissive Zero-Dimensional Antimony Chlorides with Solvent-Induced Reversible Structural Transition.

A5M2X11 and A3M2X9 families (A = monovalent organic cation; M = trivalent metal; X = halogen) are receiving increasing attention because of their combination of easy solution processability and superior ferroelectricity properties. However, synthesizing highly efficient A5M2X11 and A3M2X9-type fluorophores with multiple monomeric inorganic units and achieving their structural interconversion remains challenging. Here, we report two novel zero-dimensional (0D) antimony halides, (C10H16N)5Sb2Cl11·C2H3N (1) and (C10H16N)3Sb2Cl9 (2), which not only contain two distinct [SbXn]3-n units but also have excellent orange (590 nm) and yellow-green emission (540 nm) with high PLQY of 17.7% and 31.5%, respectively. Interestingly, a reversible structural conversion could be triggered by acetonitrile steam stimulation, accompanied by luminescence switching properties. This work not only enriches the structure of hybrid Sb-based halides but also provides the possibility of well-known A5M2X11 and A3M2X9 families as structural transformation materials.

An amphiphilic molecule with a single fluorophore exhibits multiple stimuli-responsive behavior

Fluorescent materials that respond to multiple stimuli have broad applications ranging from sensing and bioimaging to information encryption. Herein, we report the design and synthesis of a single-fluorophore-based amphiphile DCSO, which shows temperature-, solvent-, humidity-, and radiation-dependent fluorescence. DCSO consists of a dicyanostilbene (DCS) group as a rigid hydrophobic core with oligo(ethylene glycol) (OEG) chains at both ends as a flexible hydrophilic periphery. The DCS group acts as a highly efficient fluorophore, while the OEG chain endows the molecule with thermo-responsiveness. Fluorescent colors can vary from blue to green to yellow in response to external stimuli. On the basis of light radiation, we demonstrate that this system can be applied to time-dependent information encryption, in which the correct information can only be read at a specific time under irradiation. This work further demonstrates the usefulness and application of single-fluorophore-based luminescent materials with multiple stimuli-responsive functions.

Side-chain engineering of highly efficient solid-state red fluorophore based on diaminoterephthalate with steric ortho-substituents

A series of 2,5-diaminoterephthalate-based fluorophores (Me, Et, iPr, and tBu) with steric ortho-substituents were designed and synthesized. There is an optical changing tendency of the four crystals with distinct red-shifted emissions. The crystal characteristics suggest that the enhanced anti-aromaticity of the central benzene rings of four compounds in the ground state might be an important reason for achieving long-wavelength fluorescence emission, which matches well with the changing tendency of C–N bond lengths. Moreover, all compounds exhibit highly efficient solid-state emission with fluorescence quantum efficiency reaching up to 69%.

Mulberry Leaves (Morus rubra)-Derived Blue-Emissive Carbon Dots Fed to Silkworms to Produce Augmented Silk Applicable for the Ratiometric Detection of Dopamine.

Silk fibers (SF) reeled from silkworms are constituted by natural proteins, and their characteristic structural features render them applicable as materials for textiles and packaging. Modification of SF with functional materials can facilitate their applications in additional areas. In this work, we report the preparation of functional SF embedded with carbon dots (CD) through the direct feeding of a CD-modified diet to silkworms. We obtained fluorescent and mechanically robust SF from silkworms (Bombyx mori) that were fed on CDs synthesized from the Morus rubra variant of mulberry leaves (MB-CDs). MB-CDs were introduced to silkworms from the third instar onwards by spraying them on the silkworm feed, the mulberry leaves. MB-CDs were synthesized hydrothermally without adding surface passivating agents and were observed to have a quantum yield of 22%. With sizes of ∼4nm, MB-CDs exhibited blue fluorescence, and they can be used as efficient fluorophores to detect Dopamine (DA) up to the limit of 4.39nM. The nanostructures and physical characteristics of SF weren't altered when the SF were infused with MB-CDs. Also, we demonstrate a novel DA sensing application based on fluorescence with the MB-CD incorporated SF. The MB-CD-embedded SF thus open up intriguing prospects for fluorescent micro-devices and fabrics. This article is protected by copyright. All rights reserved.

Lactim or lactam? A theoretical study on the possibility of excited-state intramolecular proton transfer in hydroxyphenyl-imidazo-isoindoles

The interest in organic molecules exhibiting Excited State Intramolecular Proton Transfer (ESIPT) has steadily increased in the last decades, as the peculiar properties of these compounds make them useful for various applications. However, designing efficient ESIPT fluorophores may result a non-trivial matter. In this work we analyze the controversial case of a family of hydroxyphenyl-imidazo-isoindoles that has been recently proposed to experience ESIPT through an unusual four-membered hydrogen-bonding cycle. We demonstrate herein that such a process is unlikely to occur in excited state, and provide a simpler rationalization to the experimental observations.

Straightforward smartphone assay for quantifying tannic acid in beverages based on colour change of Eu3+/polyethyleneimine complex

Tannic acid (TA)—a natural product—is a polyphenol derivative that occurs in certain kinds of beverages. A large amount of TA could give rise to an unpleasant flavour and could negatively affect the human body by causing stomach irritation, abdominal pain, nausea, vomiting, and even death. Thus, the need exists for a simple TA detection procedure that meets specific criteria such as on-site analysis, portability, and affordability. Herein, we present a new TA assay, which is based on the fluorescent quenching effect of an efficient fluorophore, and which comprises a smartphone-integrated homemade reader system. The fluorescent polyethyleneimine-derivatised polymer (FP), a strong emitter at 510 nm, was synthesised with the aid of a facile sonication method. In the presence of Eu3+ ions, TA quenches the fluorescence of the FP via electrostatic interaction. A smartphone was used to capture an image of the FP undergoing fluorescence for conversion to RGB values. The blue channel was chosen for further analysis because it offered the highest R2-value compared to the red and green channels. We verified these results using a commercial spectrofluorometer and calculated the limit of detection of this assay as 87 nM and 20 nM for the homemade reader and spectrofluorometer, respectively. The detection range for TA with the proposed assay is 0.16–66.66 μM. The application of the proposed method to real beverage samples for TA detection demonstrates its analytical applicability.

Benzilbis(2-hydroxyanil) – highly efficient ligand for ferric ion (Fe3+) sensing

Benzilbis(2-hydroxyanil) was found to be an efficient and selective turn-on fluorophore for ferric ion (Fe3+) sensing.