Fluorescence Emission Mechanism Research Articles

Pyrene carbaldehyde derived carbon dots for detecting water in alcohol and security printing

This study focuses on preparing Carbon dots (CDs) from Pyrene-1-carbaldehyde (PCA) using a solvothermal method and further purification using column chromatography. The aggregation-induced emission (AIE) of CDs was systematically investigated in a THF/water medium. The CDs showed red shifts in their photoluminescence (PL) spectra upon increase in water content. Scanning electron microscopic (SEM) images revealed the formation of aggregates, while X-ray diffraction (XRD) confirmed that the d-spacing values remains unchanged. The NMR spectrum of the CDs displayed peaks corresponding to aromatic carbon, which disappeared upon addition of water due to π-π stacking, indicating aggregate formation. Based on the aggregation-induced fluorescence emission mechanism, detection of water content in alcohol is demonstrated. Moreover, the synthesized CDs were used as fluorescent colorant in screen inks along with polyvinyl alcohol (PVA) and hydroxyethyl cellulose (HEC) as binders. The print proofs obtained on UV-dull paper using PVA-based screen ink exhibited fluorescence emission at longer wavelengths and showcased desirable photostability under prolonged UV exposure compared to the prints obtained using HEC-based ink. Moreover, though the PVA based print appeared blue or cyan fluorescent, the actual yellow emissions from the CDs can be visualised using UV block filter. Such features, masked to the forger, but known to the user can be utilised in checking the authenticity of the print.

Investigations of fluorescence emission Mechanism: Formation of ring-like structures by interactions influenced by hydroxyl group and deprotonation

As one of the gaseous signaling molecules in biological systems, hydrogen sulfide(H2S) is involved in numerous physiological processes and diseases. Therefore, rapid, effective, and real-time detection of H2S is of great importance. Based on its excellent optical properties, dicyanoisophorone has attracted much attention in recent years, and a large number of corresponding probes have been developed to detect H2S in biological systems. In this paper, the fluorescence mechanisms of three dicyanoisophorone-based fluorescent probes are investigated and the near-infrared (NIR) fluorescence attribution of the products is discussed by density-functional theory and time-dependent density-functional theory methods. Frontier molecular orbital analysis shows that the non-fluorescence of the probes is attributed to the photo-induced electron transfer process. Structural change and reduced density gradient analyses indicate that the position of the hydroxyl group and the deprotonation have a non-negligible influence on the interactions within the products. The five- or six-membered ring-like structures formed by interactions make the molecule stain as a planar and the fluorescence emission, while the twist exists the fluorescence quenching. In addition, spectral information shows that the emission of NIR fluorescence originates from the deprotonated form of the product.

One- and Two-Photon Photophysical Properties, Ultrafast Dynamics, and DFT Study of Three Modified Zinc Phthalocyanines.

As two-photon absorption (TPA) materials, phthalocyanine molecules have promising application prospects due to their large TPA absorption cross-section, high third-order nonlinear optical susceptibility, and ultrafast response characteristics. In this work, optical properties and the ultrafast response of three modified zinc phthalocyanine molecules (P-HPcZn, Pc-P-Pc, and (DR1)4PcZn) were analyzed. No obvious side-shoulder absorption peaks in the Q-band can be observed from the steady-state absorption spectra of the three molecules, confirming the lack of aggregation products in the solutions of our measurement. Open-aperture Z-scan results show relatively large TPA cross-section values of 136.4 and 55.3 GM for Pc-P-Pc and (DR1)4PcZn, respectively. The nonlinear optical results show that the absorption process observed under the excitation of femtosecond pulses is a reverse saturable absorption (RSA) mechanism. Up-conversion fluorescence spectra of (DR1)4PcZn in THF solution indicate that the fluorescence emission mechanism is TPA. In the study of ultrafast dynamics, the transient absorption spectra were investigated and the decay lifetime of the dynamic traces corresponding to some representative probe wavelengths was obtained through data fitting with a multi-exponential function. Finally, the charge transfer and excited state properties of the modified zinc phthalocyanine molecules were discussed in depth by the DFT method. The energy gaps of P-HPcZn, Pc-P-Pc, and (DR1)4PcZn are 2.16, 1.39, and 2.13 eV, respectively. The results indicate that the Pc-P-Pc of donor-acceptor-donor (D-A-D) structure has the smallest energy gap as well as the best charge transfer properties.

Rare-earth-free up and down-conversion dual-emission carbon dots for Cu2+ sensing

In this work, up- and down-conversion dual-emission CDs without rare-earth (UD D-CDs) were synthesized using RhB and 1,4-Diaminoanthraquinone as precursors. The synthesized UD D-CDs exhibited dual emissions at 496 and 580 nm under 260 and 865 nm excitation, respectively. The fluorescence emission mechanism, including contributions from carbon nuclei, surface states, molecular states, and internal defect states, was discussed through the separation and purification of UD D-CDs. Based on the interaction between UD D-CDs and copper ions (Cu2+), a dual-mode ratio fluorescence probe was developed to detect and quantify Cu2+. The up-conversion ratio fluorescent probe shows a linear range of 0.0500–15.0 μM, with a detection limit as low as 2.76 nM. This method has been successfully applied to detecting Cu2+ in human serum and has potential applications in biochemical analysis and biological imaging. The successful preparation of up-conversion fluorescent carbon dots without rare earth elements and the ability to perform low-damage detection in high-background biological samples provide a new approach to constructing non-rare earth up-conversion probes.

The Delayed Box: Biphenyl Bisimide Cyclophane, a Supramolecular Nano-environment for the Efficient Generation of Delayed Fluorescence.

Activating delayed fluorescence emission in a dilute solution via a non-covalent approach is a formidable challenge. In this report, we propose a strategy for efficient delayed fluorescence generation in dilute solution using a non-covalent approach via supramolecularly engineered cyclophane-based nanoenvironments that provide sufficient binding strength to π-conjugated guests and that can stabilize triplet excitons by reducing vibrational dissipation and lowering the singlet-triplet energy gap for efficient delayed fluorescence emission. Toward this goal, a novel biphenyl bisimide-derived cyclophane is introduced as an electron-deficient and efficient triplet-generating host. Upon encapsulation of various carbazole-derived guests inside the nanocavity of this cyclophane, emissive charge transfer (CT) states close to the triplet energy level of the biphenyl bisimide are generated. The experimental results of host-guest studies manifest high association constants up to 104 M-1 as the prerequisite for inclusion complex formation, the generation of emissive CT states, and triplet-state stabilization in a diluted solution state. By means of different carbazole guest molecules, we could realize tunable delayed fluorescence emission in this carbazole-encapsulated biphenyl bisimide cyclophane in methylcyclohexane/carbon tetrachloride solutions with a quantum yield (QY) of up to 15.6%. Crystal structure analyses and solid-state photophysical studies validate the conclusions from our solution studies and provide insights into the delayed fluorescence emission mechanism.

Unraveling two yellow fluorescence emission mechanisms and color-changing afterglow characteristics of Dy-doped Mg2SnO4 luminescent materials

In this work, Dy ion doped Mg2SnO4 (Mg2SnO4:Dy3+) with monochromatic yellow fluorescence and color-changing long afterglow properties are prepared by the high-temperature solid-phase method. Mg2SnO4:Dy3+ shows the best luminescence performance under the preparation conditions of 1550 °C and 0.02 Dy3+ concentration. The samples are able to achieve yellow fluorescence emission (λem = 575 nm) under 350 nm and 291 nm excitation, and the emission intensity of the samples under 350 nm excitation is much higher than that of 291 nm excitation. Under 254 nm excitation, the sample not only emits bright white fluorescence but also has the ability of obvious afterglow after excitation. Moreover, the afterglow also has the color change function of transition from bright white to yellow. The luminescence mechanism study shows that Mg2SnO4:Dy3+ contains two emission centers, Dy3+ and lattice defects. Combining the results of spectroscopic measurements with the Dy3+ energy level distribution data, two different fluorescence emission processes under 291 and 350 nm excitation as well as the afterglow discoloration mechanism due to 254 nm excitation are discussed in detail.

Photophysical Properties of (E)-1-(4-(Diethyla-mino)-2-hydroxybenzylidene)-4,4-dimethylthiosemicarbazide Compound and Its Triple Fluorescence Emission Mechanism: A Theoretical Perspective.

In view of the application prospects in biomedicine of (E)-1-(4-(diethyla-mino)-2-hydroxybenzylidene)-4,4-dimethylthiosemicarbazide (DAHTS), the behavior of excited-state dynamics and photophysical properties were studied using the density functional theory/time-dependent density functional theory method. A series of studies indicated that the intramolecular hydrogen-bond (IHB) intensity of DAHTS was enhanced after photoexcitation. This was conducive to promoting the excited-state intramolecular proton-transfer (ESIPT) process. Combining the analysis of the IHB and hole-electron, it revealed that the molecule underwent both the ESIPT process and the twisted charge-transfer (TICT) process. Relying on exploration of the potential energy surface, it was proposed that the different competitive mechanisms between the ESIPT and TICT processes were regulated by solvent polarity. In acetonitrile (ACN) solvent, the ESIPT process occurred first, and the TICT process occurred later. In contrast, in the CYH solvent, the molecule first underwent the TICT process and then the ESIPT process. Furthermore, we raised the possibility that the TICT behavior was the cause of weak fluorescence emission for the DAHTS in CYH and ACN solvents. By the dimer correlation analysis, the corresponding components of triple fluorescence emission were clearly assigned, corresponding to the monomer, dimer, and ESIPT isomer in turn. Our work precisely elucidated the photophysical mechanism of DAHTS and the attribution of the triple fluorescence emission components, which provided valuable guidance for the development and regulation of bioactive fluorescence probes with multiband and multicolor emission characteristics.

Luminescent carbon dots versus quantum dots and gold nanoclusters as sensors.

Ultra-small nanoparticles, including quantum dots, gold nanoclusters (AuNCs) and carbon dots (CDs), have emerged as a promising class of fluorescent material because of their molecular-like properties and widespread applications in sensing and imaging. However, the fluorescence properties of ultra-small gold nanoparticles (i.e., AuNCs) and CDs are more complicated and well distinguished from conventional quantum dots or organic dye molecules. At this frontier, we highlight recent developments in the fundamental understanding of the fluorescence emission mechanism of these ultra-small nanoparticles. Moreover, this review carefully analyses the underlying principles of ultra-small nanoparticle sensors. We expect that this information on ultra-small nanoparticles will fuel research aimed at achieving precise control over their fluorescence properties and the broadening of their applications.

Study on the Tunable Fluorescence Emission Mechanism of Nitrogen-Doped Carbon Dots and Ion Sensing Potential Applications

Study on the Tunable Fluorescence Emission Mechanism of Nitrogen-Doped Carbon Dots and Ion Sensing Potential Applications

Nitrogen fluorescence emission induced by femtosecond vortex beams in air

Fluorescence emission is a typical nonlinear phenomenon occurring during the femtosecond laser filamentation in air. The characteristics of nitrogen fluorescence emission induced by femtosecond vortex beams in air are experimentally studied. It is found that the topological charge has a great influence on the nitrogen fluorescence emission induced by a femtosecond filament: the fluorescence signals from nitrogen molecules (e.g., 337, 357 and 380 nm spectral lines) and molecular nitrogen ions (e.g., 391 and 428 nm spectral lines) differ much in the intensity distribution along the propagation direction. The discrepancy is explained by revisiting the generation mechanisms for nitrogen fluorescence, and it is found that the intersystem crossing scheme can account for it, indicating that the intersystem crossing scheme plays the main role in the formation of This work is helpful to the understanding of the physical mechanism of fluorescence emission induced by the filamentation of femtosecond vortex beams in air.

Exploring the highly selective Fe(III) and Al(III) triggered “OFF-ON” ellagic acid based fluorescent sensor: Spectroscopic, structural elucidations and dual-response mechanism

Owing to the favorable efficiency and low cost, dual-response fluorescent sensors play critical roles in the development of fluorescence assay systems. In this paper, the dual-response fluorescent of ellagic acid was reported both turn-off to Fe3+ and turn-on to Al3+, as well as the effects of pH by UV–vis absorption and fluorescence emission spectroscopy. The addition of Fe3+ changed the color of the ellagic acid solution from colorless to grey-green, and the fluorescence emission was quenched. In contrast, the addition of Al3+ changed the colorless solution to light yellow, and the fluorescence emission was significantly enhanced. The coordination constants of EA to Fe3+ and Al3+ were determined to be 3.42 × 104 M−1 and 2.83 × 105 M−1, respectively, according to Job's plot. By comparing the reaction with urolithin and its derivatives, the fluorescence emission mechanism of the ellagic acid reaction with Fe3+ and Al3+ was elucidated. The detection limits of EA for Fe3+ and Al3+ were 9.80 × 10−7 and 1.90 × 10−7 M, respectively.

β-Cyclodextrin derived full-spectrum fluorescent carbon dots: The formation process investigation and biological applications

Carbon dots (CDs), a new building unit, have been revolutionizing the fields of biomedicine, bioimaging, and optoelectronics with their excellent physical, chemical, and biological properties. However, the difficulty of preparing excitation-dependent full-spectrum fluorescent CDs has seriously hindered their further research in fluorescence emission mechanisms and biomedicine. Here, we report full-spectrum fluorescent CDs that exhibit controlled emission changes from purple (380 nm) to red (613 nm) at room temperature by changing the excitation wavelength, and the excitation dependence was closely related to the regulation of sp2 and sp3 hybrid carbon structures by β-cyclodextrin-related groups. In addition, by regulating the content of β-cyclodextrin, the optimal quantum yields of full-spectrum fluorescent CDs were 8.97%, 8.35%, 7.90%, 9.69% and 17.4% at the excitation wavelengths of 340, 350, 390, 410 and 540 nm, respectively. Due to their excellent biocompatibility and color tunability, full-spectrum fluorescent CDs emitted bright and steady purple, blue, green, yellow, and red fluorescence in MCF-7 cells. Moreover, we optimized the imaging conditions of CDs and mitochondrial-specific dyes; and realized the mitochondrial-targeted co-localization imaging of purple, blue and green fluorescence. After that, we also explored the effect of full-spectrum fluorescent CDs in vivo fluorescence imaging through the intratumorally, subcutaneously, and caudal vein, and found that full-spectrum fluorescent CDs had good fluorescence imaging ability in vivo.

A novel phenanthroline[9,10-d] imidazole-based fluorescent sensor for Hg2+ with “turn-on” fluorescence response

Herein, a phenanthro[9,10-d] imidazole Schiff based “turn-on” fluorescence sensor (compound 1) was synthesized by 4-hydroxy-3-nitrobenzaldehyde and 9,10-phenanthrenequinone. In DMF/PBS buffer solution (1:4, v/v, pH 7.4), compound 1 responsed to Hg2+ with high sensitivity (detection limit was 45.76 nM) and rapid response (completed within 5 s), accompanied by the fluorescence change from null to blue. The binding ratio of compound 1 to Hg2+ was 1:1, and the binding constant was 2.933 × 106 M−1. Through detailed analysis of 1H–1H COSY and 1H–13C HSQC spectra, we proposed the possible fluorescence emission mechanism of compound 1 and Hg2+, and verified the recognition mechanism of compound 1 through density functional theory (DFT) calculation. Compound 1 was successfully used to detect Hg2+ in actual water samples, the recovery was 91 %–106 %, and the relative standard deviation (R.S.D.) was less than 2.5 %, which provided possibility for compound 1 to be used as a sensor in environmental research.

Design of ZnO/Ag dimer/porous silicon sandwich structures and theoretical investigation on its fluorescence emission mechanism

Design of ZnO/Ag dimer/porous silicon sandwich structures and theoretical investigation on its fluorescence emission mechanism

Smart probes for optical imaging of T cells and screening of anti-cancer immunotherapies.

T cells are an essential part of the immune system with crucial roles in adaptive response and the maintenance of tissue homeostasis. Depending on their microenvironment, T cells can be differentiated into multiple states with distinct functions. This myriad of cellular activities have prompted the development of numerous smart probes, ranging from small molecule fluorophores to nanoconstructs with variable molecular architectures and fluorescence emission mechanisms. In this Tutorial Review, we summarize recent efforts in the design, synthesis and application of smart probes for imaging T cells in tumors and inflammation sites by targeting metabolic and enzymatic biomarkers as well as specific surface receptors. Finally, we briefly review current strategies for how smart probes are employed to monitor the response of T cells to anti-cancer immunotherapies. We hope that this Review may help chemists, biologists and immunologists to design the next generation of molecular imaging probes for T cells and anti-cancer immunotherapies.

Fluorescence Behavior and Emission Mechanisms of Poly(ethylene succinamide) and Its Applications in Fe3+ Detection and Data Encryption

Fluorescence Behavior and Emission Mechanisms of Poly(ethylene succinamide) and Its Applications in Fe3+ Detection and Data Encryption

Efficient Exciton Dislocation and Ultrafast Charge Extraction in CsPbI3 Perovskite Quantum Dots by Using Fullerene Derivative as Semiconductor Ligand.

CsPbI3 quantum dots (QDs) are of great interest in new-generation photovoltaics (PVs) due to their excellent optoelectronic properties. The long and insulative ligands protect their phase stability and enable superior photoluminescence quantum yield, however, limiting charge transportation and extraction in PV devices. In this work, we use a fullerene derivative with the carboxylic anchor group ([SAM]C60) as the semiconductor ligand and build the type II heterojunction system of CsPbI3 QDs and [SAM]C60 molecules. We find their combination enables obvious exciton dislocation and highly efficient photogenerated charge extraction. After the introduction of [SAM]C60, the exciton-binding energy of CsPbI3 decreases from 30 meV to 7 meV and the fluorescence emission mechanism also exhibits obvious changes. Transient absorption spectroscopy visualizes a ~5 ps electron extraction rate in this system. The findings gained here may guide the development of perovskite QD devices.

The crosstalk fluorescence spectroscopy analysis principle and an accurate fluorescence quantitative method for multi-composition fluorescence substances

Fluorescence quantitative analysis methods are extensively used in biomedicine inspection, petrochemical industry, environmental monitoring, and many other fields in the past decades. When the analyte is composed of multiple compositions, the accuracy of the conventional method declines significantly due to the fluorescence spectral crosstalk. In this research, the interactions between the light and the multiple compositions are comprehensively analyzed. The concepts of the quenching due to mutual absorption and the fluorescence overlapping are considered, and the mechanism of multi-composition fluorescence emission under single-wavelength excitation light is analyzed theoretically. The mixture experiment and the dilution experiment are designed to illustrate that the quenching due to mutual absorption has a significant nonlinear impact on fluorescence quantitative analysis and the mechanism of fluorescence spectral crosstalk gives a good explanation for these experiments. Through the in-depth theoretical analysis, the computer simulation, and the experiments, a novel principle named the Crosstalk Fluorescence Spectroscopy Analysis (CFSA) is proposed and verified, which has much higher quantitative analysis accuracy (R2>0.99 and RMSE≤0.2) than the conventional methods when analyzing the multi-composition samples. Unlike many correction approaches to fluorescence spectroscopy, the novel CFSA can serve as a complete analysis method rather than a correction method. These concepts and the principle are expected to be applied in many practical analysis fields.

One-pot alkali cutting-assisted synthesis of fluorescence tunable amino-functionalized graphene quantum dots as a multifunctional nanosensor for sensing of pH and tannic acid

Herein, a one-pot alkali cutting-assisted synthesis approach has been developed to gain fluorescence (FL) tunable amino functionalized GQDs (NH2-GQDs), which exhibit concentration- and excitation-dependent FL behaviors, due to the self-assembled J-type aggregation effect and different electronic transitions governed by graphene basal plane and functional groups. While NH2-GQDs possess brighter FL emission than pristine GQDs, owning to the functionalization of amino groups with strong electron withdrawing ability. Particularly, the pH-dependent FL behavior of NH2-GQDs further reflects the FL emission mechanism originated from the intrinsic zigzag sites and introduced amino and carboxylic groups, which is available for pH sensing. Moreover, the NH2-GQDs also show a FL quenching upon reaction with tannic acid (TA), resulting in the construction of a FL turn-off TA sensing platform. A good linear relationship is obtained between logarithm of FL intensity (log F) and TA concentration in a linear dynamic range of 1–40 μM and a limit of detection of 43.3 nM (3σ/s, n = 9) is achieved, with a precision of 0.08% RSD at a concentration level of 5 μM (n = 9). This work features a simple and direct approach to acquire multifunctional nanosensor, providing great potential for further applications in chem/biosensing.

Structural Features of a Family of Coumarin-Enamine Fluorescent Chemodosimeters for Ion Pairs.

A family of coumarin-enamine chemodosimeters is evaluated for their potential use as fluorescent molecular probes for multiple analytes [cadmium(II), cobalt(II), copper(II), iron(II), nickel(II), lead(II), and zinc(II)], as their chloride and acetate salts. These fluorophores displayed excellent optical spectroscopic modulation when exposed to ion pairs with different Lewis acidic and basic properties in dimethyl sulfoxide (DMSO). The chemodosimeters were designed to undergo excited-state intramolecular proton transfer (ESIPT), which leads to significant Stokes shifts (ca. 225 nm) and lower-energy fluorescence emission (ca. 575 nm). A more basic anion, e.g., acetate, inhibited the ESIPT mechanism by deprotonation of the enol, producing a binding pocket (N^O- chelate) that can coordinate to an appropriate metal ion. Coordination of the metal ions enhances the fluorescent intensity via the chelation-enhanced fluorescence emission mechanism. Subjecting the spectroscopic data to linear discriminant analysis provided insights into the source of these systems' markedly different behavior toward ion pairs, despite the subtle structural differences in the organic framework. These compounds are examples of versatile, low-molecular-weight, dual-channel fluorescent sensors for ion-pair recognition. This study paves the way for using these probes as practical components of a sensing array for different metal ions and their respective anions.