One-pot synthesis of carbon dots co-doped with N and S: high quantum yield governed by molecular state and fluorescence detection of Ag+

Fluorescent carbon-based nanoparticles, called chronically as carbon dots (CDs), were synthesised from citric acid (CA) and 2-Aminothiophenol (2AT) via an N and S co-doped hydrothermal method. After a series of micro-structural characterisation, N and S elements could be sufficiently doped by means of the heteroatom in the CDs solution. The as-prepared CDs solution showed blue colour fluorescence with the highest QY of 78.6%, and study on the UV–visible and PL spectra further revealed that the outstanding fluorescence of as-prepared CDs mainly originates from the generated molecular fluorophores instead of the surface state. Owing to the strong fluorescence, the as-prepared CDs can be used as a sensing probe for the detection of Ag⁺ with high sensitivity and selectivity. However, the changes of fluorescence intensity exhibited the complex nature of the quenching mechanism due to the –SH and –NH₂ groups on the fringes of carbonaceous cores or molecular fluorophores to aggregate into another fluorescent cores with the assistance of Ag⁺ ions, which promises a new approach for efficient detection of Ag⁺ for the application in industrial pollutants.

This figure shows citric acid (CA) and 2-Aminothiophenol (2AT) via an N and S co-doped hydrothermal method to prepare CDs with blue colour fluorescence and the highest QY of 78.6%. Owing to the excellent fluorescence, the as-prepared CDs can be used as a sensing probe for the detection of Ag⁺ with high sensitivity and selectivity, and the changes of fluorescence intensity exhibited the complex nature of the quenching mechanism due to the –SH and –NH₂ groups on the fringes of carbonaceous cores or molecular fluorophores to aggregate into another fluorescent cores with the assistance of Ag⁺ ions, which promises a new approach for efficient detection of Ag⁺ for the application in industrial pollutants.     

A FRET Fluorescent Sensor for Ratiometric and Visual Detection of Sulfide Based on Carbon Dots and Silver Nanoclusters

In this work, the fluorescent sensor based on fluorescence resonance energy transfer (FRET) and electrostatic interaction (EI) was prepared for the ratiometric and visual detecting S^2–. The FRET fluorescent sensor consists of two fluorophores, with carbon dots (CDs) as energy donors and silver nanoclusters (Ag NCs) as acceptors. At 390 nm excitation, CDs and Ag NCs showed two well-separated peaks at 445 nm and 660 nm, separately. The existence of S^2– caused the red fluorescence at 660 nm to be quenched, whereas the blue fluorescence at 445 nm was restored, and the fluorescence color of the ratiometric sensor changed from pink to blue. It could be employed in ratiometric and visual detecting S^2–. The linear range of quantitative detection S^2– was 0.5–100 μM, and its detection limit was 0.35 μM. CDs-Ag NCs could be used for detecting S^2– in mineral water and tap water. The results showed that the FRET ratiometric fluorescent sensor exhibits good anti-interference and high selectivity for detecting S^2– in environmental water samples.

     

Gold‐Cluster‐Based Dual‐Emission Nanocomposite Film as Ratiometric Fluorescent Sensing Paper for Specific Metal Ion

A dual‐emission ratiometric fluorescent sensing film for metal ion detection is designed. This dual‐emission film is successfully prepared from chitosan, graphitic carbon nitride (g‐C₃N₄), and gold nanoclusters (Au NCs). Here, it is shown that the g‐C₃N₄ not only serves as the fluorescence emission source, but also enhances the mechanical and thermal stability of the film. Meanwhile, the Au NCs are adsorbed on the surface of chitosan film by the electrostatic interaction. The as‐prepared dual‐emission film can selectively detect Cu²⁺, leading to the quench of red fluorescence of Au NCs, whereas the blue fluorescence from g‐C₃N₄ persists. The ratio of the two fluorescence intensities depends on the Cu²⁺ concentration and the fluorescence color changes from orange red to yellow, cyan, and finally to blue with increasing Cu²⁺ concentration. Thus, the as‐prepared dual‐emission film can be worked as ratiometric sensing paper for Cu²⁺ detection. Furthermore, the film shows high sensitivity and selectivity, with low limit of detection (LOD) (10 ppb). It is observed that this novel gold‐cluster‐based dual‐emission ratiometric fluorescent sensing paper is an easy and convenient way for detecting metal ions. It is believed that this research work have created another avenue for the detection of metal ions in the environment.     

高激子利用率的蓝光荧光材料及其激发态性质

制备了具有高激子利用率的A-π-D-π-A结构的蓝光荧光材料CzPAF-CP,并通过紫外-可见吸收光谱和荧光光谱以及理论计算等方法对化合物的光物理性质及激发态性质进行了研究。该化合物表现出显著的溶剂化效应,溶剂化红移高达116 nm。根据Lippert-Mataga关系以及瞬态光谱测试证明CzPAF-CP具有局域电荷转移杂化态,这一点从理论计算结果也可以得到证明。由于CzPAF-CP具有扭曲A-π-D-π-A结构,在水含量高达90%的水和四氢呋喃混合溶液中荧光没有被猝灭,具有聚集诱导发光性质。以CzPAF-CP为发光材料制备的OLED器件发射蓝光,其电致发光光谱最大发射峰在452 nm,半峰宽54 nm,色坐标为（0.150,0.117）。最大外量子效率达到6.3%,激子利用率达到71.6%,超出25%的上限,这是由于CzPAF-CP局域电荷转移杂化态导致高能级单线态和三线态激子发生反系间窜越导致的。     

Coal Pitch Derived Yellow-Emissive Carbon Dots and Their Application in Luminescent Solar Concentrators

Using coal pitch as the carbon source to synthesize carbon dots (CDs), one of the most promising photoluminescence (PL) materials, can play an important role in the global demand for carbon neutralization. However, the reported CDs derived from coal pitch are mainly limited blue emission. Here, a new route to synthesize yellow-emissive CDs from coal pitch is developed by extracting the lightweight aromatic compounds from coal pitch and solvothermally treating the extracts in dichloromethane in the presence of a small amount of nitric acid and sulfuric acid. Notably, the obtained CDs exhibit excitation independent yellow emission, large Stokes shift and good photostability. The application of the CDs for luminescent solar concentrators (LSCs) is evaluated. It is found that the CDs can be well dispersed in polymethyl methacrylate (PMMA) matrix and fabricated transparent LSCs. The synthesized LSC (4 × 4 × 0.2 cm³) with the optimal CDs concentration exhibits an optical conversion efficiency (η_opt) of 3.31% and power conversion efficiency (η_PCE) of 1.95% under simulated sun light illumination (100 mW cm⁻²). This research offers a new strategy to synthesize new kind of CDs with desired performance by exploiting the native chemistries of coal pitch.     

Synthesis of Novel Fluorescent Cyclohexenone Derivatives and their Partitioning Study in Ionic Micellar Media

An approach is demonstrated toward the synthesis of four novel cyclohexenone derivatives (CDs) via a convenient route of Michael addition of ethyl acetoacetate. The molecular structures of CDs were confirmed by means of FT-IR, ¹H NMR, EIMS, UV and also by X-ray single crystal structure analysis. CDs are strongly fluorescent compounds and their fluorescent spectra exhibits intense violet fluorescence. To model the binding to biological membranes the behavior of CDs in micellar solutions of a cationic surfactant, cetyltrimethylammonium bromide (CTAB) and an anionic surfactant, sodium dodecylsulfate (SDS) has also been examined. The characteristics of partition and binding interactions of CDs with CTAB and SDS were investigated by UV-Visible and fluorescence spectroscopic techniques. Higher values of all mentioned interactions in case of CTAB, compared to SDS, indicate that there are greater interactions between the CDs and CTAB than with SDS.     

The optical properties and energy transition process in nanocomposite of polyvinyl-pyrrolidone polymer and Mn-doped ZnS

This study has been carried out on the optical properties of polyvinyl-pyrrolidone (PVP), the energy transition process in nanocomposite of PVP capped ZnS:Mn nanocrystalline and the influence of the PVP concentration on the optical properties of the PVP capped ZnS:Mn nanocrystalline thin films synthesized by the wet chemical method. The microstructures of the samples were investigated by X-ray diffraction, the atomic absorption spectroscopy, and transmission electron microscopy. The results showed that the prepared samples belonged to the sphalerite structure with the average particle size of about 2–3 nm. The optical properties of samples are studied by measuring absorption, photoluminescence (PL) spectra and time-resolved PL spectra in the wavelength range from 200 to 700 nm at 300 K. From data of the absorption spectra, the absorption edge of PVP polymer was found about of 230 nm. The absorption edge of PVP capped ZnS:Mn nanoparticles shifted from 322 to 305 nm when the PVP concentration increases. The luminescence spectra of PVP showed a blue emission with peak maximum at 394 nm. The luminescence spectra of ZnS:Mn–PVP exhibits a blue emission with peak maximum at 437 nm and an orange–yellow emission of ion Mn²⁺ with peak maximum at 600 nm. While the PVP coating did not affect the microstructure of ZnS:Mn nanomaterial, the PL spectra of the PVP capped ZnS:Mn samples were found to be affected strongly by the PVP concentration.     

Fluorescence Properties and Dipole Moments of Novel Fused Thienobenzofurans. Solvent and Structural Effects

The electronic absorption, fluorescence excitation and emission spectra, and fluorescence quantum yields of novel fused thienobenzofurans, including thieno[3,2-b][1]benzofuran (1), [1]benzothieno[3,2-b]furan (2), and [1]benzothieno[3,2-b][1]benzofuran (3), were recorded in fourteen solvents of different polarities at room temperature. Compound 2 was not fluorescent. Experimental ground-state dipole moments of compounds 1–3 were measured in benzene at 298 K and compared with the corresponding theoretical dipole moment values. The solvent effects on the electronic absorption and fluorescence spectra of these thienobenzofurans were quantitatively investigated by means of solvatochromic correlations based on the Kawski-Chamma-Viallet and McRae equations. A weak negative solvatochromic behavior was found for these compounds, showing that their dipole moments are slightly lower in the excited singlet-state than in the ground-state. Kamlet-Abboud-Taft multiparameter relationships were also established for electronic absorption and fluorescence wavenumbers, and fluorescence quantum yields in most solvents, demonstrating the occurrence of specific solute-solvent interactions.     

A Coumarin-Based Fluorescent Chemosensor for Zn<Superscript>2+</Superscript> in Aqueous Ethanol Media

A coumarin-based fluorescent chemosensor 1 for Zn²⁺ was designed and synthesized. Compound 1 exhibits lower background fluorescence due to intramolecular photoinduced electron transfer. However, upon mixing with Zn²⁺ in 30% (v/v) aqueous ethanol, a “turn-on” fluorescence emission is observed. The fluorescence emission increases linearly with Zn²⁺ concentration in the range 0.5–10 μmol L⁻¹ with a detection limit of 0.29 μmol L⁻¹. No remarkable emission enhancement was, however, observed for other metal ions. The proposed chemosensor was applied to the determination of Zn²⁺ in water samples with satisfactory results.     

Nitrogen-doped carbon dots embedded in a SiO<Subscript>2</Subscript> monolith for solid-state fluorescent detection of Cu<Superscript>2+</Superscript> ions

We describe the simple fabrication of SiO₂ sol-gel monoliths embedding highly luminescent carbon nanodots (CDs) sensitive to metal ions. The pristine CDs we synthesize display an intense dual emission consisting in two fluorescence bands in the green and violet region, and we demonstrate that this photoluminescence is substantially unchanged when the dots are incorporated in the SiO₂ matrix. The emission of these CDs is quenched by interactions with Cu²⁺ ions, which can be used to detect these ions with a detection limit of 1 μM. The chromophores remain accessible to diffusing Cu²⁺ ions even after embedding CDs in the sol-gel monolith, where their detection capabilities are preserved. Such a result provides the proof-of-principle of a new sensing scheme, where CDs are exploited as active sensing centers of metal transition ions within a solid-state device. The different interaction mechanisms of CDs with copper, in liquid and solid phase, are analyzed in detail and discussed in terms of different accessibility of their chromophores when the dots are incorporated in the SiO₂ matrix.     

Energy transfer between activators at different crystallographic sites in Sr3SiO5:Eu

A yellow phosphor, Sr₃SiO₅:Eu²⁺, was synthesized by a high temperature solid-state method. Sr₃SiO₅:Eu²⁺ exhibits a single yellow emission under the blue radiation excitation. However, Sr₃SiO₅:Eu²⁺ shows a two-peak emission under the ultraviolet radiation excitation when Eu²⁺ doping content is less than 0.01 mol. Moreover, the blue emission disappears and the yellow emission reaches the peak value when Eu²⁺ doping content is 0.01 mol. Namely, the energy transfer takes place between the Eu²⁺ activators, which is located at two different crystallographic sites in the Sr₃SiO₅. And the energy transfer mechanism is the dipole-dipole interaction.     

Enhanced Device Performances of Blue‐Emitting PLEDs Coupled with Silver‐Nanoicosahedrons

Silver‐nanoicosahedron particles (AgNIPs) are produced by chemical reduction and photochemical methods and doped into the hole transport layer (HTL) or emissive layer (EML) of blue‐emitting polymer light‐emitting diodes (PLEDs) to improve their luminous efficiency. The optimal distributed‐densities of the AgNIPs are determined from current density–voltage–luminance measurements at different doping concentrations. The AgNIP dopant doses that maximize the average luminous efficiency of the proposed PLED are 6.71 µg cm^?2 in EML (achieving 3.48 cd A^?1) and 6.88 µg cm^?2 in HTL (achieving 3.35 cd A^?1). Although the luminous efficiencies of the blue‐emitting PLEDs fabricated by both doping methods are not significantly different, the maximum plasmonic enhancement (around 30‐fold) of the blue‐emitting PLED with AgNIPs in EML is red‐shifted to the green region (≈530 nm in the electroluminescence spectrum), seriously degrading the luminescent monochromaticity of the blue‐emitting PLED. The maximum plasmonic enhancement (around 33‐fold) of blue‐emitting PLED with AgNIPs in HTL occurred at 430 nm, overlapping the localized surface‐plasmon resonance extinctions of the AgNIPs in HTL (425 nm), thus favoring the enhancement of fluorescence emission. Therefore, to enhance the large‐area emission of blue‐emitting PLEDs, the AgNIPs should be doped in the HTL rather than the EML.     

Testing Fluorescence Lifetime Standards using Two-Photon Excitation and Time-Domain Instrumentation: Rhodamine B,Coumarin 6 and Lucifer Yellow

Having good information about fluorescence lifetime standards is essential for anyone performing lifetime experiments. Using lifetime standards in fluorescence spectroscopy is often regarded as a straightforward process, however, many earlier reports are limited in terms of lifetime concentration dependency, solvents and other technical aspects. We have investigated the suitability of the fluorescent dyes rhodamine B, coumarin 6, and lucifer yellow as lifetime standards, especially to be used with two-photon excitation measurements in the time-domain. We measured absorption and emission spectra for the fluorophores to determine which wavelengths we should use for the excitation and an appropriate detector range. We also measured lifetimes for different concentrations, ranging from 10^?2– 10^?6 M, in both water, ethanol and methanol solutions. We observed that rhodamine B lifetimes depend strongly on concentration. Coumarin 6 provided the most stable lifetimes, with a negligible dependency on concentration and solvent. Lucifer yellow lifetimes were also found to depend little with concentration. Finally, we found that a mix of two fluorophores (rhodamine B/coumarin 6, rhodamine B/lucifer yellow, and coumarin 6/lucifer yellow) all yielded very similar lifetimes from a double-exponential decay as the separate lifetimes measured from a single-exponential decay. All lifetime measurements were made using two-photon excitation and obtaining lifetime data in the time-domain using time-correlated single-photon counting.     

One step synthesis of ultra-high quantum yield fluorescent carbon dots for “on-off-on” detection of Hg2+ and biothiols

In this paper, the carbon dots (CDs) with strong blue fluorescence were synthesized through hydrothermal method, which using folic acid, ammonium citrate and ethylenediamine as precursors. The prepared CDs with a high absolute quantum yield of 81.94% and showed excellent stability in high concentration salt solution and different pH conditions. With the addition of Hg²⁺, the signal of CDs was selectively quenched. At the same time, the CDs-Hg²⁺ system could be recovered after the introduction of biothiols. Moreover, the fluorescence of CDs showed a good linear relationship with Hg²⁺ (1–15 µM), and the detection limit as low as 0.08 µM. In addition, the prepared CDs with low toxicity could be used to detect Hg²⁺ in living cells and actual water samples.

     

Practical Use of Corrected Fluorescence Excitation and Emission Spectra of Fluorescent Proteins in Förster Resonance Energy Transfer (FRET) Studies

Corrected fluorescence excitation and emission spectra have been obtained from several enhanced variants of the green fluorescent protein (EGFP) isolated from the jellyfish Aequorea victoria, blue fluorescence protein (EBFP), cyan fluorescent protein (ECFP), EGFP and yellow fluorescent protein (EYFP–citrine) and from the red fluorescent protein (DsRed) isolated from the coral species Discosoma. The spectra are stored in a database. This report describes how the spectra can be used as templates to derive the critical transfer distance for any pair of fluorescent proteins.     

Optical characterization of ZnO nanoparticles capped with various surfactants

The presence of surfactants (Hexamine, tetraethylammonium bromide (TEAB), cetyltrimethylammonium bromide (CTAB), tetraoctylammonium bromide (TOAB) and PVP) on the surface of zinc oxide (ZnO) nanoparticles resulted variation in their optical properties. The optical properties of each surfactant-capped zinc oxide nanoparticles were investigated using UV-visible absorption and fluorescence techniques. The particle size of these nanoparticles were calculated from their absorption edge, and found to be in the quantum confinement range. The absorption spectra and fluorescent emission spectra showed a significant blue shift compared to that of the bulk zinc oxide. Large reduction in the intensity of visible emission of zinc oxide/surfactant was observed and these emissions were vanished more quickly, with the decrease in excitation energy, for the smaller nanoparticles. Out of the four surfactants (other than PVP), CTAB-capped zinc oxide has smallest particle size of 2.4 nm, as calculated from the absorption spectrum. Thus the presence of surfactant on the surface of zinc oxide plays a significant role in reducing defect emissions. Furthermore, ZnO/PVP nanoparticles showed no separate UV emission peak; however, the excitonic UV emission and the visible emission at 420 nm overlap to form a single broad band around 420 nm.     

Nitrogen-Doped and Surface Functionalized CDs: Fluorescent Probe for Cellular Imaging and Environmental Sensing of ClO–

A novel nitrogen doped and surface functionalized fluorescent CDs (T1) was synthesized by one-step and green hydrothermal method, which exhibits a satisfactory fluorescence quantum yield and a series of admirable features such as good aqueous solubility, narrow particle size distribution, resistance to photobleaching as well as excitation-dependent behavior. Benefitting from above merits, T1 can be employed to serve as an outstanding sensing platform for sensitive and accurate detection of ClO^– by remarkable fluorescence “on–off” process with rapid and anti-interference. More notably, the good biocompatibility and photostability can ensure enormous bioimaging potential and successful application of T1 in monitoring of exogenous ClO^– in MG-63 cells. Meanwhile, T1 can also be regarded as a filter paper sensor providing a convenient and efficient analyzing technology for monitoring of free residual chlorine in practical environmental samples. All these results demonstrate that there exists promising possibility for practical applications of T1 in bioimaging systems and environmental monitoring.

Graphical abstract

     

Solvatochromic Studies of Fluorescent Azo Dyes: Kamlet-Taft (π*, α and β) and Catalan (Spp, SA and SB) Solvent Scales Approach

A new metal ion-responsive azo-based fluorescent probes have been synthesized and characterized by NMR spectral techniques. Steady-state fluorometric study has been used to analyze the spectroscopic and photophysical characteristics of dye derivatives in various solvents. The fluorescence properties of these dyes are strongly solvent dependent, the wavelength of maximum fluorescence emission shifts to the red. The Kamlet-Taft and Catalan’s solvent scales were found to be the most suitable for describing the solvatochromic shifts of the absorption and fluorescence emission. The hydroxy substituted azo dye formed complexes with several metal ions (Co²⁺, Hg²⁺, Ni²⁺ and Cu²⁺) and fluorescence quenching with metal ions reveal that it can be used as a new fluorescence sensor to detect the Cu²⁺ ion.     

Synthesis and Investigation of Derivatives of 1,8-Naphthalimide with a Red Emission via an Aromatic Nucleophilic Substitution Reaction

1,8-Napthalimides (NIs) have been widely used as fluorescent molecules in biological, chemical, and medical fields because NIs shows high stability and various fluorescence properties under different conditions. However, NIs typically display a fluorescence emission wavelength in the range of 350 – 550 nm which can be notably interfered with by autofluorescence in living cells, significantly limiting their bio-applications. Moreover, low solubility in aqueous media is another major limitation for NIs. In this project, four derivatives of NIs (1–4) have been synthesized via an aromatic nucleophilic substitution reaction and their photophysical properties have been investigated in various media (water, MeOH, MeCN, DMSO, EtOAc, and THF). All of these derivatives (1–4) show a long emission wavelength around 600 nm and high solubility in polar solvents. Particularly molecules (1–4) show the longest emission (624–629 nm) in water and the fluorescence intensity is not significantly varied in the range of pH 4–11. These unique features, long emission wavelength, high solubility, and high stability in difference pH media, will allow these derivative (1–4) to be used as excellent labeling reagents in the biological system.

     

Near infrared to red and yellow to blue upconversion emissions from Pr: ZrF4-BaF2-LaF3-YF3-AlF3-NaF glasses

This paper describes the development and a detailed analysis carried out on the luminescence characteristics of Pr³⁺ doped ZrF₄-BaF₂-LaF₃-YF₃-AlF₃-NaF glasses. In the present work our objectives are to elucidate the possible mechanisms that are responsible for NIR to red upconversion process and yellow to blue upconversion emission in terms of energy level schemes from the praseodymium containing fibre optical glass composition. We have studied their different physical and optical properties. Besides our investigation on the upconversion emission of these glasses, normal fluorescence studies have also been undertaken in explaining the mechanisms in demonstrating bright red and blue emissions upon excitations at visible and UV wavelengths. Besides these measurements works, a bright blue colour emission was observed under an UV source and upconverted prominent red emissions were observed with a laser diode (LD of ). Similarly under a yellow light source, a blue colour emission was observed from these praseodymium glasses studied.