Multi-functional ratiometric detection based on dual-emitting N-doped carbon dots.

Ratiometric fluorescence probes based on multi-emission carbon dots improve accuracy and sensitivity on detecting various environment issues. Herein, a novel dual-emitting N-doped carbon dots (N-CDs) was synthesized from citric acid and urea via a solvothermal method in N,N-dimethylformamide (DMF). The blue and orange emissions of N-CDs in water were modulated, and pure white light-emitting with Commission Internationale de L'Eclairage (CIE) coordinates of (0.33, 0.33) was achieved. The two PL centers behaved differently for Fe3+, Cu2+ and Ag+ ions, with the limit of detection (LOD) of ppm as fluorescence probes. Additionally, N-CDs displayed unique solvatochromism phenomenon. A new green emission appeared in organic solvents and gradually quenched with the increase of solvent polarity. The ratiometric PL displayed an excellent linear response for detecting water, and the LOD was between 0.003 % and 0.3 % in DMF, ethanol, isopropanol and N-methylpyrrolidone. Furthermore, N-CDs exhibited pH-sensitive response in the range of 4.0-7.0 and temperature-dependent response during heating-cooling cycles between 15 and 70 °C. A simple, efficient and reliable multi-functional ratiometric probe for detecting metal ions, water content, pH and temperature simultaneously was realized. However, there is a need for future application research to overcome the limitation imposed by the excitation wavelength of 330 nm.

A Novel Ion Species- and Ion Concentration-Dependent Anti-Counterfeiting Based on Ratiometric Fluorescence Sensing of CDs@MOF-Nanofibrous Films.

Traditional fluorescent anti-counterfeiting labels based on "on-off" fluorescence can be easily cloned. It is important to explore advanced anti-counterfeiting fluorescent labels with high-level security. Here, a pioneering ion species- and ion concentration-dependent anti-counterfeiting technique is developed. By successive loading Cu2+ -sensitive yellow emitted carbon dots (Y-CDs) and Cu2+ non-sensitive blue emitted carbon dots (B-CDs) into metal-organic frameworks (MOFs) and followed by electrospinning, the B&Y-CDs@MOF-nanofibrous films are prepared. The results show that the use of MOF not only avoids the fluorescence quenching of CDs but also improves the fluorescence stability. The fluorescence Cu2+ -sensitivity of the CDs@MOF-nanofibrous films can be regulated by polymer coating or lamination. The fluorescent label consisting of different Cu2+ -sensitivity films will show Cu2+ concentration-dependent decryption information. Only at a specific ion species and concentration (Cu2+ solution of 40-90 µm), the true information can be read out. Less or more concentration (<40 or >90 µm) will lead to false information. The identification of the real information depends on both the species and the concentration. After Cu2+ treatment, the fluorescence of the label can be recovered by ethylenediaminetetraacetic acid disodium (EDTA-2Na) for further recycling. This work will open up a new door for designing high-level fluorescent anti-counterfeiting labels.

Heating-free synthesis of red emissive carbon dots through separated processes of polymerization and carbonization.

Polymerization and carbonization are believed as two basic processes for the bottom-up synthesis of carbon dots (CDs). Since these two processes usually occur simultaneously due to the high reaction temperature and fast reaction rate, it is still a challenge to separate and control these two processes. In the present work, we reported a new room temperature method, which achieved the separated and controlled polymerization and carbonization processes. The polymerization process is realized by dissolving o-phenylenediamine (OPD) in ethanol at room temperature, and finally obtained polymer dots (PDs) without any lattice with a sphere size of 29.6 nm. The carbonization process begins in a manual way by adding concentrated sulfuric acid. After carbonization, CDs (noted as CPDs in this work) with a size of 3.6 nm and a clear lattice can be obtained. Importantly, the separated polymerization and carbonization make us possible to adjust the composition or interactions of intermediate products during the synthesis process. As a prototype, we added acetic acid (AA) additives into OPD precursors during the polymerization stage. Due to the crosslink enhanced emission (CEE) effect via hydrogen bonds which are produced by the amide groups from AA reaction products with H in the -NH3+ or aromatic ring, the resulted CPDs show improved PLQY from an initial 6.87% (without AA) to 16.47%. The current work realized the separated and controllable polymerization and carbonization processes, opening up the door for tuning the composition and interactions of intermediate products before carbonization.

Post-synthetic regulation of the fluorescence of CDs: insights into the fluorescence mechanism.

Exploring the origin of emission is fundamental in the field of carbon dots (CDs). Due to the lack of suitable in situ probing techniques, it is necessary to explore effective alternative methods that can accurately reflect the relationship between the emission and the composition of the functional groups of CDs. Herein, we propose a new method of post-synthetic treatment of CDs by photo-oxidation to investigate the origin of emission for CDs. After the addition of a photo-oxidant into pre-prepared CDs under UV irradiation, the fluorescence of CDs can be regulated from the original orange emission to the final green emission due to the damage of original functional groups and the formation of new functional groups on CDs during the post-treatment process. The abundant dynamic information about the functional groups and emissions of CDs during the visible and ready-to-monitor post-treatment process makes it possible to quantitatively analyze the origin of the emission of CDs. Our results suggest that the emission sub-peaks at 560 nm and 600 nm relate to the CD surface-state-associated -NH3+ groups, while the emission sub-peak at 537 nm or 494 nm is associated with the CD surface-state-associated -OH groups or the CD surface-state-associated carbonyl groups (CO). Under UV irradiation, the CD surface-state-associated -NH3+ groups can be continuously converted into the CD surface-state-associated -OH groups and the CD surface-state-associated carbonyl groups (CO), leading to the changed emission color of CDs.

Solvent stimuli-responsive off-on fluorescence induced by synergistic effect of doping and phase transformation for Te4+ doped indium halide perovskite: Giving printable and colorless ink for information encryption and decryption.

Since traditional fluorescent materials are too easily observed by the eyes just under the UV light, off-on fluorescent materials are explored as the new generation of fluorescent labels. In the "off" state, such off-on fluorescent labels cannot be observed by naked eyes under either natural light or UV light. Only after a specific decryption treatment to make the fluorescent materials turning into the "on" state, the fluorescent labels can be observed under the UV light. Up to now, it is still a challenge to prepare fluorescent inks with aforementioned ideal properties by using halide perovskite materials. Herein, we reported the first example of Te4+ doped indium halide perovskite inks with both off-on fluorescence under solvent stimuli and invisible ink color by the naked eyes. The synergistic effect of doping/undoping of Te4+ together with the reversible phase transformation between Cs2InCl5(H2O) and Cs3InCl6 under solvent stimuli is key for the off-on fluorescence of crystals. Under acid solvent, the substitutional doping of Te4+ during the process of phase transformation from Cs3InCl6 to Cs2InCl5(H2O):Te4+ gives rise to "turning-on" orange emission from Te-induced self-trap emission (STE). Under the stimuli of methanol, the dissolution of Te4+ from the crystals destroys the structure of Te4+ in ligand-field and results in "turning-off" Te-induced emission during the process of phase transformation from Cs2InCl5(H2O):Te4+ to Cs3InCl6. On the basis of the Te4+ doped indium halide perovskite, printable and colorless ink can be prepared for the confidential information encryption and decryption. Since the mixture of Cs3InCl6 crystals and TeCl4 have no absorption in visible light scope, the printed encrypted information by such off-state fluorescent ink is colorless and invisible by the naked eyes under either ambient light or UV light. After decryption by acid solvent stimuli, the resulted Cs2InCl5(H2O):Te4+ doping crystals have a large Stokes shift with absorption below 450 nm from the excitation of Te4+ in ligand-field and emission around 570 nm from Te-induced STE. It makes the decryption information still colorless and invisible by the naked eyes under the ambient light but visible and readable under the UV light. In comparison to traditional undoped CsPbBr3/CsPb2Br5 perovskites with small Stokes shift and eye-visible ink color, the current colorless Te4+doped indium halide perovskites are no doubt providing better security level for both encrypted and decrypted information.