High Fluorescence Efficiency Research Articles

Fabrication of a novel mixed-valent copper-based coordination polymer as a fluorescent sensor for selective and efficient detection of multiple analytes

A novel three-dimensional fluorescent mixed-valent copper-based coordination polymer (CP), namely {[CuICuII4(triazol)6(bpta)2]Cl}n (Cu-CP), was synthesized hydrothermally in the presence of Cu(II) ion, 2,4,6-tri(1H-1,2,4-triazol-1-yl)-1,3,5-triazine (TTT), and 2,2′,4,4′-biphenyltetracarboxylic acid (H4bpta). The structure of the Cu-CP was studied using single-crystal X-ray diffraction (SCXRD) and powder X-ray diffraction (PXRD). Interestingly, the crystallographic data revealed that a part of Cu(II) ions were reduced in situ to Cu(I) ions as well as the nitrogen-containing ligand TTT was converted to triazol, which possessed excellent fluorescence characteristics as a transition metal ion with a d10 electronic configuration, prompting further investigation into the fluorescence sensing properties of Cu-CP. The results confirmed that Cu-CP exhibited excellent fluorescence performance which an outstanding candidate as a fluorescence sensor for Fe3+, Cr2O72−, CrO42−, MnO4− and nitrobenzene (NB), with a low limit of detection. For ethylene glycol (EG) detection, Cu-CP showed high-efficiency fluorescence enhancement across a range of temperatures. The underlying mechanism of fluorescence enhancement was investigated through comprehensive experimental studies.

Organoboron Polymorphs with Different Molecular Packing Modes for Optical Waveguides.

Organoboron compounds offer a new strategy to design optoelectronic materials with high fluorescence efficiency. In this paper, the organoboron compound B-BNBP with double B←N bridged bipyridine bearing four fluorine atoms as core unit is facilely synthesized and exhibits a narrowband emission spectrum and a high photoluminescence quantum yield (PLQY) of 86.53 % in solution. Its polymorphic crystals were controllable prepared by different solution self-assembly methods. Two microcrystals possess different molecular packing modes, one-dimensional microstrips (1D-MSs) for H-aggregation and two-dimensional microdisks (2D-MDs) for J-aggregation, owing to abundant intermolecular interactions of four fluorine atoms sticking out conjugated plane. Their structure-property relationships were investigated by crystallographic analysis and theoretical calculation. Strong emission spectra with the full width at half maximum (FWHM) of less than 30 nm can also be observed in thin film and 2D-MDs. 1D-MSs possess thermally activated delayed fluorescence (TADF) property and exhibit superior optical waveguide performance with an optical loss of 0.061 dB/μm. This work enriches the diversity of polymorphic microcrystals and further reveals the structure-property relationship in organoboron micro/nano-crystals.

A novel rhodamine B fluorescence probe for rapid identification of different amino acids by high efficiency fluorescence spectrum-mass spectrometry.

Rapid detection of amino acids plays an important role in the field of medical diagnosis. By combining Rhodamine B with triphenylamine, a novel double-response fluorescence probe (E)-4-((4-(((3',6'-bis(diethylamino)-3-oxospiro[isoindoline-1,9'-xanthen]-2-yl)imino)methyl)phenyl)(phenyl)amino)benzaldehyde (RBTPA) was prepared for rapid identification of different amino acids. Under daylight and 365 nm irradiation, it was found that the color change was most bright at pH = 3, and changed to dim at pH = 4. When pH = 3 and pH = 4, the photophysical properties of the two strong acids are very different. The maximum redshift of UV absorption light is 110nm, and the maximum fluorescence emission intensity is 4 times different. In order to further observe their binding structure analysis with different amino acids, qualitative analysis of each response structure was determined by mass spectrometry according to different molecular weights. The fluorescence probe RBTPA has two different isomers for recognition response in aldehyde group and imine group, respectively.

Substituent effects on the mechanochromic behaviour of pyrene-based AIEgens

It is extremely significant and desirable to integrate the fascinating properties of mechanochromism and aggregation-induced emission (AIE) in one simple molecule. Herein, pyrene-based aggregation-induced emission luminogens (AIEgens) with mechanofluorochromic (MFC) properties solve the traditionally existing aggregation-caused quenching (ACQ) challenge. Three cyanoethylene-functionalized pyrene-based derivatives were designed and synthesized. All compounds exhibit remarkable aggregation-enhanced emission (AEE) activity by a 3–20 times enhancement in mixed H2O/THF solutions. More importantly, high fluorescence efficiency was recorded in the solid state, especially for the luminogen 2c, with more than 200 times observed increased efficiency from 0.3% in solution to 69.8% in the solid state. Meanwhile, excellent mechanochromism properties and reversibility against the grinding treatment was systematically investigated. The excellent fatigue resistance properties are a necessity for potential applications in the field of anti-counterfeiting fluorescent inks and for the encryption of security information.

Bidirectional hybridized hairpin DNA fluorescent aptasensor based on Au-Pd NPs and CDs for ratiometric detection of AFB1.

Anovel and simple ratiometric fluorescent aptasensor was developed for the sensitive detection of aflatoxin B1 (AFB1). A hairpin DNA (h-DNA) was independently synthesized as the basic skeleton, and the bidirectional hybridization of h-DNA can increase the load of aptamer and signal probes, thereby realizing signal amplification. The high-efficiency fluorescence resonance energy transfer interaction between gold-palladium nanoparticles (Au-Pd NPs) and the self-synthesized fluorescent probe carbon dots (CDs) was utilized. Moreover, the label-free probe SYBR Green I (SG I) dye was introduced to form a double-signal probe with CDs, and a ratiometric sensor with FCDs/FSG I as a response signal was constructed. The ratio strategy can eliminate the fluctuation of external factors, thus improving the accuracy and reliability of the sensor. The quenching effect of Au-Pd NPs on CDs was 1.4 times that of AuNPs and 3.4 times that of Pd NPs, respectively. In the range 1-100ng/mL, FCDs/FSG I showed a good linear relationship with the logarithm of the concentration of AFB1, and the limit of detection was as low as 0.07ng/mL. The sensor was used to detect AFB1 in spiked peanuts and wine samples, and the recovery was between 91 and 115%, indicating that the sensor has high application potential in real sample analysis.

Facile synthesis of sulfur quantum dots with red light emission: Implications for electrochemiluminescence analysis application

Sulfur quantum dots (SQDs) have been reported as a potential candidate due to their low toxicity and high luminescent performance. Here, SQDs with red light fluorescence (FL) emission were synthesized by a one-step hydrothermal method using Na2CO3 as an etching agent, using sublimed sulfur powder as a sulfur source, and using bovine serum albumin (BSA) as a stabilizer. The choice of etching agent (NaOH or Na2CO3) realized the tuning of SQDs’ FL emission with blue and red light. The synthesized SQDs showed good FL stability and high FL efficiency, with a quantum yield of 1.03 % in an aqueous solution at 575 nm. In addition, stable and efficient electrochemiluminescence (ECL) emission was achieved by employing SQDs as ECL emitters with K2S2O8 as the co-reactant. The resorcinol (RS) can enhance the ECL intensity of the SQDs-K2S2O8 system, and the ECL intensity had a good linear relationship with the concentration of RS in a range from 2.5 nM to 25 nM with a detection limit of 0.61 nM. This work provides an emerging red-light luminescent SQDs, which would open up a way for the development of new types of luminophor in FL or ECL analysis. It also provides convenience for bio-labeling of live cells, in vivo imaging and provide new materials for photoelectric devices.

Application of hyperbranched polysiloxanes in biomedical materials based on AIE polymer properties

Application of hyperbranched polysiloxanes in biomedical materials based on AIE polymer properties

Theoretical Insights into the Photophysical Properties of 4CzIPN Doped in Different Hosts: A Multiscale Study.

As a typical thermally activated delayed fluorescence (TADF) emitter with green emission, 4CzIPN has attracted much attention recently. Most studies indicated that 4CzIPN doped in different hosts presented different performances; thus, the hosts should have an obvious influence on its photophysical properties. Herein, the influence of four kinds of hosts, including m-CzPym, m-CzTrz, p-CzPym, and p-CzTrz, on the photophysical properties of 4CzIPN is investigated. Molecular dynamics simulations were performed to simulate the host-guest conformations, and the photophysical properties were studied using the combined quantum mechanics/molecular mechanics method coupled with the thermal-vibration correlation function method. It is found that 4CzIPN in doped films has larger transition dipole moments and spin-orbital coupling constants compared to that in nondoped films. Faster radiative decay, intersystem crossing rates, and higher fluorescence efficiency could be obtained in doped films. Our work helps to better understand the photophysical properties of 4CzIPN in doped films and may favor the design of new hosts.

Color-tunable circularly polarized luminescence from liquid crystalline polymer networks

Chiroptical materials with circularly polarized luminescence (CPL) activities have attracted increasing interest because of their promising applications in optoelectronics, biosensing and imaging. Nevertheless, the construction of CPL-active materials with large luminescence dissymmetry (glum) factors and high emission efficiency is still challenging. Herein, a series of liquid crystalline polymer network films have been prepared by photopolymerization of cholesteric liquid-crystalline mixtures doped with aggregation-induced emission-active luminogens, TPE-TA and BDABFN. Through adjustment of the mass ratio of the two luminogens, the resultant films exhibit multicolour CPL from blue to red to white with absolute glum values up to 0.71 and fluorescence quantum yields up to 44 %. This work provides a strategy for fabricating polymeric film materials with color-tunable CPL properties and high fluorescence efficiency.

Integration of jackfruit seed-derived carbon dots and electronic nose for a sensitive detection of formaldehyde vapor

The preparation of carbon dots from jackfruit seeds through a pyrolysis method at 280℃ and their use for the detection of formaldehyde were reported. The as-prepared carbon dots showed a high fluorescence efficiency with a quantum yield of 12.7% and excellent photostability and dispersibility in aqueous solution with a zeta potential of ‒62.5 mV. The integration of carbon dot thin film and a home-made optical electronic nose system possessed sensitivity towards formaldehyde vapor with a detection limit of 24.7%v/v across a linear range of 25%v/v to 100%v/v. Furthermore, the sensor showed the highest sensitivity towards formaldehyde against other volatile organic compounds through a strong interaction between the carbonyl groups and the carbon dots. Additionally, principal component analysis (PCA) was conducted to achieve quantitative measurements of formaldehyde content in different formaldehyde volume ratios with substantial variance. Due to the significance of methanol as a typical chemical precursor for the industrial manufacturing of formaldehyde, the quantitative analytical method is essential to determining formaldehyde or methanol concentration. The sensing ability of carbon dot film-integrated electronic nose towards formaldehyde in formaldehyde/methanol mixtures was measured to be 10.74%v/v in a linear range of 25%v/v to 100%v/v. The PCA showed orderly linear combinations of the data set, which can be potentially utilized to analyze formaldehyde and methanol content in industrial processes. The results indicate the significant potential of carbon dots and optical electronic nose system as an effective formaldehyde sensing platform. Potential applications include the quantification of formaldehyde from methanol conversion and determination of methanol contaminant in formaldehyde.

Fluorescent polymer as a biosensing tool for the diagnosis of microbial pathogens

Diseases and diagnoses are predominant in the human population. Early diagnosis of etiological agents plays a vital role in the treatment of bacterial infections. Existing standard diagnostic platforms are laborious, time-consuming, and require trained personnel and cost-effective procedure, though they are producing promising results. These shortcomings have led to a thirst for rapid diagnostic procedures. Fluorescence-based diagnosis is one of the efficient rapid diagnostic methods that rely on specific and sensitive bacterial detection. Emerging bio-sensing studies on conducting polymers (CPs) are gaining popularity in medical diagnostics due to their promising properties of high fluorescence efficiency, good light stability, and low cytotoxicity. Poly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV), is the first identified soluble polymer and model material for understanding the fundamental photophysics of conventional CPs. In this present study, MEH-PPV is used as a fluorescent dye for direct pathogen detection applications by interacting with the microbial cell surface. An optimized concentration of MEH-PPV solution used to confirm the presence of selective bacterial structures. The present study endeavours towards bacterial detection based on the emission from bacteria due to interfacial interaction between polymer and bacterial surface.

Energy landscape of perylenediimide chromophoric aggregates.

Understanding the self-assembly of conjugated organic materials at the molecular level is crucial in their potential applications as active components in electronic and optoelectronic devices. The type of aggregation significantly influences the intriguing electronic and optical characteristics differing from their constituent molecules. Perylenediimides (PDIs), electron-deficient molecules exhibiting remarkable n-type semiconducting properties, are among the most explored organic fluorescent materials due to their high fluorescence efficiency, photostability, and optoelectronic properties. PDI derivatives are reported to form well-tailored supramolecular architectures: cofacial with minor slip (H-aggregates), staggered with major slip (J-aggregates), magic angle stacking (M-aggregates), rotated (X-aggregates), rotated orthogonal ((+)-aggregates), etc. H*-aggregates are defined here as an ideal case of H-aggregate with an eclipsed configuration. Although numerous reports regarding the formation and optical properties of various PDI aggregates are known, the key driving force within the PDI units guiding the self-assembly to form distinct aggregate systems remains elusive. To unravel the molecular-level mechanisms behind the self-assembly of PDI units by probing the intermolecular interactions, symmetry-adapted perturbation theory-based energy decomposition, potential energy surface scans, and non-covalent interaction index analyses were employed on PDI dimer models. Quantum theory of atoms in molecules and frontier molecular orbital analyses were implemented on the dimer models to comprehend the effect of heteroatoms and orbital interactions in stabilising the X-aggregates over the other PDI aggregate systems. Competition between the attractive and repulsive non-covalent interactions dictates a stability order of X > H > J > M > (+) > H* for the PDI aggregate system, while in the parent perylene system, the stability order was found to be X > (+) > H > M > J > H*.

Efficient solution-processed fluorescent OLEDs realized by removing charge trapping emission loss of BODIPY fluorochrome.

The thermally activated delayed fluorescence (TADF)-sensitized fluorescent (TSF) dye strategy has been used successfully in thermally evaporated organic light-emitting diodes (eOLEDs), but the development of solution-processed TSF-OLEDs (TSF-sOLEDs) is still very limited to date. Previously, the introduction of electronically inert shielding terminal groups for TADF sensitizer and/or fluorescent dyes was commonly used in TSF-sOLEDs, which aimed to achieve sufficient Förster energy transfer (FET) while restraining notorious Dexter energy transfer (DET) at a high doping concentration of fluorescent dyes. However, this approach has not yet enabled efficient TSF-sOLEDs owing to severe charge trapping emission (CTE) for triplet loss. In this study, by simply utilizing highly efficient boron-dipyrromethene derivatives (BODIPYs) that simultaneously feature high fluorescent quantum efficiency and narrow-band emission spectra, we developed highly efficient and super color-purity TSF-sOLEDs using a 0.1 wt% ultralow doping strategy. As confirmed, the resultant ultralow doping TSF-sOLEDs achieved sufficient FET from sensitizer to fluorochrome without noticeable CTE issues. The device achieves record maximum external quantum efficiency (EQEmax) and current efficiency (CEmax) of 21.5% and 78.8 cd A-1, respectively, and an ultrapure green emission with Commission International de l'Eclairage (CIE) coordinates of (0.28, 0.65). This study validates the new device architecture of ultralow doping TSF-sOLEDs, which paves the way for future development of high-resolution TSF-sOLED displays via a simple solution-processed manufacturing approach.

High-efficiency multicolor fluorescent indoleninonaphthooxazole derivatives with adjustable excitation

Solvatochromic fluorophores are one of the most investigated dyes because they exhibit multi-color luminescence properties as the polarity of the solvent changes. It remains a challenge to regulate solvatochromism with a large emission shift and maintain high fluorescence efficiency from apolar to polar solvents. Herein, we report a new type of solvatochromic fluorophore that exhibits both multicolor solvatochromism and stable high fluorescence efficiency in polar solvents. The unique solvatochromic properties of indoleninonaphthooxazole derivatives are realized by constructing a single carbon-bond-linked coplanar scaffold containing indolenine and naphthooxazole components with different substituents. We propose a possible mechanism to explain the unique solvatochromism. Excited USTS-3 and USTS-4 exhibit LE state in non-polar solvent and different HLCT states in polar solvents with both high luminescence efficiency. And the excitation of USTS-3 and USTS-4 is determined by aggregation states of molecular USTS-3 and USTS-4 under different concentrations, which exhibits different relaxations but share the same luminescence decay pathway. Benefitting from the unique luminescence properties of indoleninonaphthooxazole derivatives, they exhibit potential applications in solvent polarity detection, bioimaging, anticounterfeiting, electroluminescence, and lighting in different matrix. Our results also provide a new perspective on designing novel fluorophores based on indolenine and naphthoxazole moieties.

Stable two-dimensional tin-based perovskites for warm-white light emitters

Two-dimensional (2D) Sn-based organic-inorganic hybrid perovskites are useful materials for white light emitters due to their super high fluorescence efficiency and higher stability when compared to their three-dimensional (3D) counterparts. Herein, 2D Ruddlesden-Popper (RP) perovskites (BA)2Sn(Br1-x Ix)4 (BA = n-butylammonium, x: 0–1) were prepared and regulated using halogen doping. As iodine content increased, the band gap of (BA)2Sn(Br1-xIx)4 was finely regulated from 2.35 eV to 2.0 eV, thereby tuning the photoluminescence from yellow to red with relatively high PLQY exceeding 40 %. The use of small amounts of Pb2+ to stabilize Sn2+ through the addition of PbO in the precursor solution resulted in high air- and photo stable (BA)2Pb0.1Sn0.9(Br–I)4 phosphors with bright yellow to red light. The mixture with (BA)2PbBr4 (blue light phosphor) followed by excitement by UV LED chips (285 nm) resulted in cold and warm white Sn–Br–I perovskite LEDs. The CIE coordinates and correlated color temperature (CCT) indicated Br0.4I0.6 LED as an ideal warm-white emitter with suitable CIE (0.352, 0.330) and CCT (4376.3 K). The prepared white LEDs showed high photo and air stability without significant luminescence decay (<5 % relative) under continuous UV light excitation over 200 min and exposure to air for 3 months.

A Mitochondria‐Targeted Fluorescent and Colorimetric Probe for Sulfur Dioxide Derivatives and Hydrogen Peroxide in Live Cells

AbstractThe abnormal fluctuations of sulfur dioxide (SO2) and its derivatives are closely associated with various physiological and pathological progresses in biological systems. Herein, we have developed two fluorescent and colorimetric probes based on a hemicyanine dye for the detection of SO2 derivatives and hydrogen peroxide (H2O2) in vitro and live cells. The response mechanisms involve an SO2‐derivative‐mediated nucleophilic addition reaction to the double bond and subsequent H2O2‐promoted elimination of bisulfite. As well as having excellent photophysical properties, the probe with higher fluorescence efficiency is further applied for live cell imaging, and it is found that it can solely accumulate in mitochondria and track SO2 derivatives and H2O2 in live cells.

Thermal lens Z-scan measurements: theoretical and experimental uncertainties for lowand high fluorescence quantum yields.

The single-beam Z-scan thermal lens technique is conducted to evaluate the fluorescence quantum yield of various solutions in the case of high-moderate absorption, considering both scenarios: solutions with substantial fluorescence and solutions with high thermal efficiency but low fluorescence. An analytical calculation is performed to determine the uncertainties associated with the random errors introduced by optical detectors. The results reveal that solutions with low fluorescence lead to a significant error, whereas higher fluorescence can help in decreasing the uncertainty. Additionally, the issue of random errors arising when multiple measurements are needed to accurately estimate the fluorescence of a solution will be discussed in different situations.

Two new CdII/ZnII coordination polymers as high-efficiency fluorescence sensors for identifying biomarker 3-nitrotyrosine

3-Nitrotyrosine (3-NT), as a stable biomarker in the human body, is closely related to a variety of diseases. Therefore, the detection of 3-NT is of important significance for human disease monitoring. In addition, under the same dimension, the influence of CPs with different metals on 3-NT detection still has important research value. Herein, we successfully synthesized two new 2D coordination polymers (CPs), namely [M(L)(BTEC)0.5]·H2O (M = Cd for CP 1, M = Zn for CP 2), by using the bis(pyridyl)-bis(amide) ligand L [(E)-4,4′-(ethene-1,2-diyl)bis[(N-pyridin-3-yl)benzamide] as the main ligand and 1,2,4,5-benzenetetracarboxylic acid (H4BTEC) as the auxiliary ligand under hydrothermal conditions. CPs 1–2 can be used as fluorescent sensors to effectively detect 3-NT, and have the advantages of excellent stability, anti-interference, recyclability and low limits of detection (LODs). The influence of the different metals in the CPs on the fluorescence sensing 3-NT was discussed, and the difference of sensing mechanism and performance of CPs 1–2 on 3-NT were studied in detail, which provided a reference for the design of CPs and the influencing factors of 3-NT detection.

Quantifying the Energy Loss of Triplet Excitons on High‐Lying Triplet States to Develop High Efficiency Blue Fluorescence OLEDs Based on AIE Emitter

Abstract“Hot exciton” molecules that allow the transition of excitons from a high‐lying triplet state (Tn, n≥ 2) to singlet states (Sm, m≥1) by a reverse intersystem crossing (hRISC) process have become an effective strategy to achieve high efficiency fluorescence organic light emitting diodes (OLEDs). However, the understanding of the dynamic behavior of the “hot exciton” process is still very lacking. Herein, the exciton dynamics of an aggregation‐induced emission (AIE) molecule TPA‐An‐mPhCz with the “hot exciton” property are deeply investigated, and the proportion between hRISC and internal inversion (IC) of excitons on Tn is successfully quantified by in situ transient electroluminescent measurements and theoretical calculation. It is found that the IC process increases severe energy loss of Tn excitons. By introducing a triplet–triplet annihilation up‐conversion layer in the emissive layer to efficiently recapture the IC excitons and further doping a blue fluorescent emitter in the TPA‐An‐mPhCz layer to achieve high photoluminescence quantum yield (PLQY), the resulting OLED achieves a maximum external quantum efficiency of 12.5% with negligible efficiency roll‐off. More impressively, the operational lifetime LT75 (lifetime to 75% of the initial luminance) of the device with efficient triplets utilization performs a remarkable 116 h under 1000 cd m−2. This work provides the fundamentals for the design of hot exciton materials with efficient exciton utilization to develop efficient blue fluorescence OLEDs.

Organic Nanoparticles with Aggregation-Induced Emission and Two-Photon Excitation for Fluorescence Imaging of Living Cells/Tissues.

Aggregation-induced emission (AIE) nanoparticles (NPs) have been applied in bioimaging for cancer diagnosis due to high fluorescence efficiency. However, the poor cell permeability as well as autofluorescence of biological cells/tissues caused by ultraviolet (UV) irradiation is still the key problem of AIE luminophores for biological imaging. Here, we report green-emitting organic AIE luminophores for fluorescence imaging of living cells/tissues, which possess high fluorescence quantum yields and strong AIE under two-photon excitation with near-infrared light beyond 800 nm. These AIE luminophores can bind with bovine serum albumin (BSA) to form biocompatible BSA/AIE-NPs due to their terminal aldehyde groups providing specific anchor sites with the receptor groups in BSA. Furthermore, one/two-photon fluorescence bioimaging for Hela cancer cells has been successfully carried out with BSA/AIE-NPs as the fluorescent probe, and BSA/AIE-NPs show excellent stain properties with a fast permeability of only 5 min, high cellular uptakes, and strong fluorescence. The results demonstrate the great advantages of BSA/AIE-NPs in fast fluorescence biological imaging as well as further cancer diagnosis and therapy.