High Fluorescence Quantum Yield Research Articles

Synergistic Modulation of Excited State Ingredients and Chiroptical Activity for High‐Performance Pure‐Green Circularly Polarized Electroluminescence

Synergistic Modulation of Excited State Ingredients and Chiroptical Activity for High‐Performance Pure‐Green Circularly Polarized Electroluminescence

Cyclic Azahelicene Dimers ShowingBright Circularly Polarized Luminescence and Selective Fluoride Recognition.

Although helicenes are promising molecules, the synthetic difficulty and tediousness have often been problems, and only small amounts of optically pure helicenes have been obtained by using chiral HPLC in most cases. Herein, aza[7]helicenes or closed-aza[7]helicenes with(1R)-menthyl substituents were selectively synthesized via the intramolecular Scholl reaction, and the diastereomeric pairs were separated by silica gel column chromatography. The optically pure helicenes were further transformed into the corresponding cyclic dimers, and the chiroptical properties were investigated. The rigidp-frameworks of the dimers led to the high molar extinction coefficients and fluorescence quantum yields, while the twisted helicene moieties induced clear Cotton effects and CPLin the visible region,and thehighCPL brightness (BCPL) was achieved. Furthermore, the cyclic dimers were found to have the macrocyclic cavity with the two NH groups suitable for the selective binding of a fluoride anion, which induced significantly redshifted fluorescence and CPL in the red region.

Cyclic Azahelicene Dimers Showing Bright Circularly Polarized Luminescence and Selective Fluoride Recognition

Although helicenes are promising molecules, the synthetic difficulty and tediousness have often been problems, and only small amounts of optically pure helicenes have been obtained by using chiral HPLC in most cases. Herein, aza[7]helicenes or closed‐aza[7]helicenes with (1R)‐menthyl substituents were selectively synthesized via the intramolecular Scholl reaction, and the diastereomeric pairs were separated by silica gel column chromatography. The optically pure helicenes were further transformed into the corresponding cyclic dimers, and the chiroptical properties were investigated. The rigid p‐frameworks of the dimers led to the high molar extinction coefficients and fluorescence quantum yields, while the twisted helicene moieties induced clear Cotton effects and CPL in the visible region, and the high CPL brightness (BCPL) was achieved. Furthermore, the cyclic dimers were found to have the macrocyclic cavity with the two NH groups suitable for the selective binding of a fluoride anion, which induced significantly redshifted fluorescence and CPL in the red region.

Emission behaviors from ZnO microwire pumped CsPbBr3 perovskite microwire.

Perovskite semiconductor materials have attracted significant attention in the fields of photovoltaics and luminescence due to their excellent photoelectric properties, such as high carrier mobility, high absorption coefficient, and high fluorescence quantum yield. In particular, low-dimensional metal-halide perovskite microcrystalline materials have been reported to exhibit low-dimensional lasing phenomena and laser devices due to their high gain and widely tunable bandgap. In this Letter, one-dimensional (1-D) ZnO microwires with their ultraviolet lasing emissions are utilized as an excitation source to pump CsPbBr3 microwire on hybrid ZnO-CsPbBr3 microscale structures. At higher excitation, the amplified spontaneous emission (ASE) behaviors from CsPbBr3 microwire are realized with ultralow threshold by indirect pumping from the ZnO lasing emission for the first time, to the best of our knowledge. In comparison, the ASE behaviors from the CsPbBr3 microwire directly pumped by Nd:YAG Q-switched laser and continuous wave laser are also performed at room temperature. There are also no multimode lasing behaviors observed. The paper provides a new method to achieve a low threshold on-chip microlaser by a high-quality perovskite micro-nano structure.

Responsive Organic Fluorescent Aggregates Based on Ion‐π Interactions Away from Fluorescent Conjugated Groups

Responsive organic luminescent aggregates have a wide range of application fields, but currently there is still a lack of reasonable molecular design strategies. Introducing ion‐π interactions into molecules can effectively alter their luminescent properties. However, current research typically focuses on ion localization at luminescent conjugated groups with the strong interaction forces. In this work, we introduce the flexible alkoxy chain spacers between fluorescent conjugated groups and ion‐π interaction sites, and then adjust the fluorescence performance of the molecule by changing the strength of ion‐π interactions. Bromine ion‐based molecules with strong ion‐π interactions exhibit high and stable fluorescence quantum yields in crystals and amorphous powders under the external stimuli. Hexafluorophosphate ion‐based molecules with weak ion‐π interactions have the high fluorescence quantum yield in crystals and very low fluorescence quantum yield in amorphous powders, showing variable fluorescence intensities under external stimuli. This demonstrates a new class of responsive organic luminescent solid‐state materials.

Responsive Organic Fluorescent Aggregates Based on Ion-π Interactions Away from Fluorescent Conjugated Groups.

Responsive organic luminescent aggregates have a wide range of application fields, but currently there is still a lack of reasonable molecular design strategies. Introducing ion-π interactions into molecules can effectively alter their luminescent properties. However, current research typically focuses on ion localization at luminescent conjugated groups with the strong interaction forces. In this work, we introduce the flexible alkoxy chain spacers between fluorescent conjugated groups and ion-π interaction sites, and then adjust the fluorescence performance of the molecule by changing the strength of ion-π interactions. Bromine ion-based molecules with strong ion-π interactions exhibit high and stable fluorescence quantum yields in crystals and amorphous powders under the external stimuli. Hexafluorophosphate ion-based molecules with weak ion-π interactions have the high fluorescence quantum yield in crystals and very low fluorescence quantum yield in amorphous powders, showing variable fluorescence intensities under external stimuli. This demonstrates a new class of responsive organic luminescent solid-state materials.

Bright luminescent Zn2GeO4:Mn NP/MXene hydrogel-based ECL biosensor for glioblastoma diagnosis

In this work, miRNA-10b in the glioblastoma (GBM) tumor tissues has been detected by a novel electrochemiluminescence (ECL) biosensor. Firstly, a new kind of bright luminescent Zn2GeO4:Mn NPs were prepared as ECL nanoprobe, which possessed high fluorescence quantum yield and ECL quantum efficiency. Secondly, Ti3C2 MXene hydrogel (MXG) have been developed as the sensing interface. The MXG retained the inherent biocompatibility and mechanical features of hydrogel. Furthermore, the uniform distribution of metallic Ti3C2 MXene in the hydrogel microstructure provided the good conductivity and multiple binding sites for biomolecules. MXene also can promote the separation of the electrons and holes to accelerate the electron-transfer rate and improve ECL efficiency. Due to these synergistic effects, the screen printed electrode was successfully modified with MXG as sensing platform to enhance the ECL intensity of Zn2GeO4:Mn NP, which greatly improved the detection efficiency and facilitated the high-throughput analysis. Finally, the toehold mediated strand displacement (TMSD) strategy was employed with then biosensor to detect miRNA-10b with the range of 10 fM to 1 nM. The limit of detection was 5 fM. This ECL biosensor has been used to analyze miRNA-10b expression in GBM tumor tissues, which possessed the great potential value for clinical diagnosis.

A facile green synthesis of photoluminescent carbon dots using Pumpkin seeds for ultra-sensitive Cu2+ and Fe3+ ions detection in living cells

A facile and efficient green synthesis of photoluminescent carbon dots (CDs) was achieved using pumpkin seeds (PS) through the hydrothermal-carbonization method. Pumpkin seeds, well-known for their nutrient-rich composition, offer potential health benefits, including heightened fertility, enhanced heart health, and improved blood sugar regulation. The as-synthesized PS-CDs characterization through UV–vis, photoluminescence (PL), FTIR, XRD, and HR(TEM) analysis. The PL PS-CDs exhibited an excitation-dependent behavior, with the peak shifting from 410 nm to 475 nm under excitation wavelengths ranging from 270 nm to 400 nm. Notably, the synthesized PS-CDs displayed outstanding advantages, such as a high fluorescent quantum yield of 12.7 % with bright blue emissions when exposed to UV light at 365 nm. High-resolution TEM images revealed an average size of approximately 4.0 ± 0.2 nm for the synthesized PS-CDs, ranging from 2 to 7 nm with interlayer distance of 0.21 nm. PL spectra of PS-CDs solution, with an excitation wavelength of 338 nm and emission wavelength of 420 nm, were examined in the presence of various metal ions (50 μM). The fluorescence lifetime of the PS-CDs showed an exponential curve, with an average lifetime (τav) of 8.47 ns for Cu2+and 3.61 ns for Fe3+ ions, respectively, which is strongly indicates that quenching occurs through a static mechanism. The PS-CDs exhibited high sensitivity and selectivity towards Cu2+ and Fe3+ ions, with a linear relationship observed up to a concentration of 50 μM and detection limits of 0.43 and 0.11 μM (S/N = 3), respectively. Moreover, the low-toxicity and strongly fluorescent PS-CDs were successfully applied for cell imaging. The practical utility of the developed sensor was determined through the analysis of Cu2+ and Fe3+ ions in spiked water samples, highlighting its considerable analytical and bioanalytical applications.

Carbohydrate-Functionalized Anthracene Carboximides as Multivalent Ligands and Bio-Imaging Agents.

Anthracene carboximides (ACIs) conjugated with gluco-, galacto- and mannopyranosides are synthesized, by glycosylation of N-hydroxyethylanthracene carboximide acceptor with glycosyl donors. Glycoconjugation of anthracene carboximide increases the aq. solubility by more than 3-fold. The glycoconjugates display red-shifted absorption and emission, as compared to anthracene. Large Stokes shift (λabs/ λem = 445/525 nm) and high fluorescence quantum yields (Ф) of 0.86 and 0.5 occur in THF and water, respectively. The ACI-glycosides undergo facile photodimerization in aqueous solutions, leading to the formation of the head-to-tail dimer, as a mixture of syn and anti-isomers. Solution phase and solid-state characterizations by dynamic light scattering (DLS), microscopic imaging by atomic force (AFM) and transmission electron (TEM) microscopies reveal self-assembled vesicle structures of ACI glycosides. These self-assembled structures act as multivalent glycoclusters for ligand-specific lectin binding, as evidenced by the binding of Man-ACI to Con A, by fluorescence and turbidity assays. The conjugates do not show cellular cytotoxicity (IC50) till concentrations of 50 μM with HeLa and HepG2 cell lines and are cell-permeable, showing strong fluorescence inside the cells. These properties enable the glycoconjugates to be used in cell imaging. The non-selective cellular uptake of the glycoconjugates suggests a passive diffusion through the membrane.

Engineering Cyanine- and Hemicyanine-Based Probes for Optical Imaging of Kidney Diseases.

Molecular optical probes paly pivotal roles in in vivo imaging of biomarkers associated to kidney diseases. Relying on structural tunability and high fluorescence quantum yields, versatile optical probes have been constructed on cyanine or hemicyanine-based scaffold in recent years. This review summaries the recent progress on the development of optical probes for imaging of kidney diseases, particularly through near-infrared fluorescence, chemiluminescence and photoacoustic imaging modalities. The chemical design and sensing mechanisms are discussed along with applications in the detection of renal cell carcinoma and acute kidney injury. This progress provides insights and directions for the development of next generation kidney-targeted probes and for pushing their further applications in preclinical and clinical research.

Conjugated molecularly imprinted polymers based on covalent organic frameworks: Fluorescent sensing platform for specific capture of urea and elimination of ethyl carbamate

This study described the preparation of an azide covalent organic framework-embedded molecularly imprinted polymers (COFs(azide)@MIPs) platform for urea adsorption and indirect ethyl carbamate (EC) removal from Chinese yellow rice wine (Huangjiu). By modifying the pore surface of COFs using the copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction, COFs(azide) with a high fluorescence quantum yield and particular recognition ability were inventively produced. In order to selectively trap urea, the COFs(azide) were encased in an imprinted shell layer via imprinting technology. With a detection limit (LOD) of 0.016 μg L-1 (R2 = 0.9874), the COFs(azides)@MIPs demonstrated a good linear relationship with urea in the linear range of 0–5 μg L-1. Using real Huangjiu samples, the spiking recovery trials showed the viability of this sensing platform with recoveries ranging from 88.44 % to 109.26 % and an RSD of less than 3.40 %. The Huangjiu processing model system achieved 38.93 % EC reduction by COFs(azides)@MIPs. This research will open up new avenues for the treatment of health problems associated with fermented alcoholic beverages, particularly Huangjiu, while also capturing and removing hazards coming from food.

Aggregation-Induced Modulation of Ground and Excited State Photophysics of 5-(tert-Butyl)-2-Hydroxy-1,3-Isophthalaldehyde (5-tBHI).

5-(tert-Butyl)-2-hydroxy-1,3-isophthalaldehyde (5-tBHI) is a photochromic material susceptible to either excited state proton transfer or excited state intramolecular proton transfer, depending upon the solvent. However, it has also been found to aggregate in the presence of sodium dodecyl sulfate. In this current study, based on the steady-state and time-resolved spectroscopy, supported by crystallography, quantum chemical density functional theory calculation, and molecular dynamics (MD) simulation, we report on the aggregation of this potential single benzene-based emitter (SBBE) in neat solvents as well as solid phase to modulate its photophysics. It has been found that 5-tBHI forms mixed aggregates of different orders, owing to the presence of both enolic and tautomeric forms, to yield tunable emission, although the emission intensity is quenched. These findings suggest that the intramolecular hydrogen bonding of 5-tBHI not only limits intermolecular interactions but also promotes nonradiative deactivation pathways. Hence, designing and structural engineering, with a focus to suppressing intramolecular hydrogen bonding as well as increasing through space conjugation by replacing the aldehydic moieties with bulky aliphatic or aromatic ketonic groups, can be a plausible approach to yielding improved probes with tunable emission and higher fluorescence quantum yields.

Doubly Spiro-Conjugated Chiral Carbocycles Exhibiting SOMO-HOMO Inversion in Persistent Radical Cations.

Persistent chiral organic open-shell systems have captured growing interest due to their potential applications in organic spintronic and optoelectronic devices. Nevertheless, the integration of configurationally stable chirality into an organic open-shell system continues to pose challenges in molecular design. The π-extended skeleton incorporated in spiro-conjugated carbocycles can provide robust chiroptical properties and a significant stabilization of the excited and ionic radical states. However, this approach has been relatively less explored in the design of persistent organic open-shell systems. We report here the (S,S)-, (R,R)-, and meso-isomers of doubly spiro-conjugated carbocycles featuring flat and rigid carbon-bridged para-phenylenevinylene (CPV) of different conjugation lengths connected by two spiro-carbon centers, which we denote D-spiro-CPV for its quasi-dimeric structure. Our synthetic method based on a double lithiation cyclization approach enables facile production of D-spiro-CPV. D-spiro-CPVs exhibit circularly polarized luminescence (CPL) with high fluorescence quantum yields (ΦFL) resulting in a high CPL brightness of 21 M-1 cm-1 and also exhibit high thermal and photostability. The monoradical cation of D-spiro-CPV absorbing near-infrared light is notably persistent, exhibiting a half-life of 570 h under ambient conditions due to doubly spiro-conjugative stabilization. Theoretical and electrochemical studies indicate the radical cation of D-spiro-CPVs presents a non-Aufbau electron filling, exhibiting inversion of the energy level of the singly occupied molecular orbital (SOMO) and the highest (doubly) occupied molecular orbitals with the SOMO level even below the HOMO-1 level (double SHI effect). Our discoveries provide valuable insights into non-Aufbau molecules and the development of configurationally stable, optically active persistent radicals.

Carbon quantum dots derived from agro waste biomass for pioneering bioanalysis and in vivo bioimaging

Waste to Wealth’s mission aims to develop valuable products for choice of environmental and biological purposes, especially from agricultural wastes. A vast variety of organic and inorganic elements that are left over from agricultural activities like crop cultivation or livestock raising are referred to as agricultural waste, for example, pista shell (PS) and groundnut shell (GNS). These agricultural waste materials can be effectively utilized for preparing wealth materials depending on materials and their composition. Owing to the presence of high carbon content in these waste materials, preparing carbon-based nanostructured wealth materials for environmental and biological applications is significant, interestingly, it also fulfills the sustainable approach along with a cost-effective strategy. This hypothesis led us to prepare one such type of carbon-based nanostructured material, carbon quantum dots (CQDs), from PS and GNS agro-wastes. These agro-wastes derived CQDs were formulated by hydrothermal method and their distinct structural, morphological, functional, optical, and bioactive properties were determined. The XRD data divulges the amorphous nature of CQDs with interlayer spacing (∼0.30 nm) similar to graphite. HRTEM images express spherical morphology with a particle size of ca. 5 nm and ca. 12 nm for PSE and GNSE CQDs, respectively. Raman spectra divulge a doublet D band (1335 and 1447 cm−1) with ID/IG ratio of 1.6 and 1.2 for PSE and GNS CQDs, respectively. Using UV–Vis and photoluminescence (PL) spectroscopy data reveals that PSE and GNS CQDs show excitation at 370 and 309 nm, and emission at 456 and 440 nm, respectively. Further, high fluorescence quantum yield (9.5 % for PSE and 9.0 % for GNS), virtuous cell viability (90 % for both CQDs), high hemocompatibility (0.3 for PSE and 0.1 % for GNS), accelerated anti-bacterial activity, protein denaturation, bacteria interaction, and growth factors (IGF-1, Col-1) expression levels enable these CQDs to function as a probe for live quantitative bioimaging in Zebrafish.

Intelligent Biogenic Missile for Two-Photon Fluorescence Imaging-Guided Combined Photodynamic Therapy and Chemotherapy in Tumors.

Photodynamic therapy (PDT) is a significant noninvasive therapeutic modality, but it is often limited in its application due to the restricted tissue penetration depth caused by the wavelength limitations of the light source. Two-photon (TP) fluorescence techniques are capable of having an excitation wavelength in the NIR region by absorbing two NIR photons simultaneously, which offers the potential to achieve higher spatial resolution for deep tissue imaging. Thus, the adoption of TP fluorescence techniques affords several discernible benefits for photodynamic therapy. Organic TP dyes possess a high fluorescence quantum yield. However, the biocompatibility of organic TP dyes is poor, and the method of coating organic TP dyes with silica can effectively overcome the limitations. Herein, based on the TP silica nanoparticles, a functionalized intelligent biogenic missile TP-SiNPs-G4(TMPyP4)-dsDNA(DOX)-Aptamer (TGTDDA) was developed for effective TP bioimaging and synergistic targeted photodynamic therapy and chemotherapy in tumors. First, the Sgc8 aptamer was used to target the PTK7 receptor on the surface of tumor cells. Under two-photon light irradiation, the intelligent biogenic missile can be activated for TP fluorescence imaging to identify tumor cells and the photosensitizer assembled on the nanoparticle surface can be activated for photodynamic therapy. Additionally, this intelligent biogenic missile enables the controlled release of doxorubicin (DOX). The innovative strategy substantially enhances the targeted therapeutic effectiveness of cancer cells. The intelligent biogenic missile provides an effective method for the early detection and treatment of tumors, which has a good application prospect in the real-time high-sensitivity diagnosis and treatment of tumors.

Plasmon-emitter coupling in cytosine-rich hairpin DNA-templated silver nanoclusters: Thermal reversibility, white light emission, and dynamics inside live cells.

Bio-templated luminescent noble metal nanoclusters (NCs) have attracted great attention for their intriguing physicochemical properties. Continuous efforts are being made to prepare NCs with high fluorescence quantum yield (QY), good biocompatibility, and tunable emission properties for their widespread practical applications as new-generation environment-friendly photoluminescent materials in materials chemistry and biological systems. Herein, we explored the unique photophysical properties of silver nanoclusters (AgNCs) templated by cytosine-rich customized hairpin DNA. Our results indicate that a 36-nucleotide containing hairpin DNA with 20 cytosine (C20) in the loop can encapsulate photostable red-emitting AgNCs with an absolute QY of ∼24%. The luminescent properties in these DNA-templated AgNCs were found to be linked to the coupling between the surface plasmon and the emitter. These AgNCs exhibited excellent thermal sensitivity and were employed to produce high-quality white light emission with an impressive color rendering index of 90 in the presence of dansyl chloride. In addition, the as-prepared luminescent AgNCs possessing excellent biocompatibility can effectively mark the nuclear region of HeLa cells and can be employed as a luminescent probe to monitor the cellular dynamics at a single molecular resolution.

Nitrogen-doped carbon quantum dots as dual mode fluorescence sensors for the determination of food colorant quinoline yellow

Quinoline yellow (QY), as a food coloring agent, will consume a large number of detoxifying substances in the body after being ingested by the human body, interfering with the normal metabolic functions of the human body, and may cause allergies, diarrhea and other symptoms, as well as a certain degree of carcinogenicity, posing a great threat to human health. As a result, it is critical to develop a fast, sensitive, and effective approach to determining quinoline yellow in food. In this study, carbon dots (N-CQDs) with high fluorescence quantum yield were prepared and used to determine the QY content using the dual mode of internal filtering effect and fluorescence emission shift detection. Both methods showed good linearity in the range of QY concentration of 0.3–3.2 μM, and the detection limits were classified as 2.6 nM and 0.18 μM. In addition, in order to achieve visual detection of QY, fluorescent test strips were constructed using the carbon dots and non-fluorescent qualitative filter paper to make the detection of QY more convenient. This probe presents a novel way for detecting quinoline yellow in food analysis.

Synthesis of Naphthalimide Azocarboxylates Showing Turn-On Fluorescence by Substitution Reaction with Sulfinates.

The synthesis and characterization of sulfinate addition-responsive fluorescent molecules are described. We found that addition reaction of sulfinates to naphthalimide-substituted azocarboxylates afforded the corresponding sulfonyl hydrazides with high fluorescence quantum yields (up to 0.91 in THF and 0.54 in methanol), which exhibited a large Stokes shift (105 nm) in protic methanol solvent, while the unsubstituted hydrazide and the sulfonyl-position isomer showed no fluorescence in polar solvents.

Supra-Fluorophores: Ultrabright Fluorescent Supramolecular Assemblies Derived from Conventional Fluorophores in Water.

Fluorescent organic nanoparticles (NPs) with exceptional brightness hold significant promise for demanding fluorescence bioimaging applications. Although considerable efforts are invested in developing novel organic dyes with enhanced performance, augmenting the brightness of conventional fluorophores is still one of the biggest challenges to overcome. This study presents a supramolecular strategy for constructing ultrabright fluorescent nanoparticles in aqueous media (referred to as "Supra-fluorophores") derived from conventional fluorophores. To achieve this, this course has employed a cylindrical nanoparticle with a hydrophobic microdomain, assembled by a cyclic peptide-diblock copolymer conjugate in water, as a supramolecular scaffold. The noncovalent dispersion of fluorophore moieties within the hydrophobic microdomain of the scaffold effectively mitigates the undesired aggregation-caused quenching and fluorescence quenching by water, resulting in fluorescent NPs with high brightness. This strategy is applicable to a broad spectrum of fluorophore families, covering polyaromatic hydrocarbons, coumarins, boron-dipyrromethenes, cyanines, xanthenes, and squaraines. The resulting fluorescent NPs demonstrate high fluorescence quantum yield (>30%) and brightness per volume (as high as 12060 m-1 cm-1 nm-3). Moreover, high-performance NPs with emission in the NIR region are constructed, showcasing up to 20-fold increase in both brightness and photostability. This Supra-fluorophore strategy offers a versatile and effective method for transforming existing fluorophores into ultrabright fluorescent NPs in aqueous environments, for applications such as bioimaging.

Single-crystal strategy towards enhanced carrier mobility of fluorescent molecules for high-efficiency blue OLEDs

The organic single crystal, due to its long-range ordered molecular arrangement, high quality, low defect state density, and excellent luminescent properties, plays an irreplaceable role in the field of optoelectronics and organic light-emitting diodes. By employing strategies for constructing organic single crystals, it is possible to significantly enhance the carrier mobility and stability of devices, leading to superior optoelectronic properties. In particular, in organic light-emitting diode (OLED) devices, the introduction of an organic single crystal luminescent layer can unlock the potential of luminescent materials, extend their operational lifetimes, and enable them to withstand higher current densities. Here, we have grown high fluorescence quantum yield (PLQY) blue-emitting 1,4-bis (2-methylstyryl) benzene (BMSB) molecules in single crystal form. The average mobility has been improved from non-existent in thin films to 0.188 cm2/(V·s) in crystal devices. Additionally, through the rational design of device structures and the enhancement of electrical properties, we have achieved a transition from non-functional thin film devices to stable blue-emitting crystal devices, achieving a current density of 853.60 mA/cm2.