Self-Assembly of Amphiphilic PDI and NDI Derivatives with Opposite Thermoresponsive Fluorescent Behaviors in Aqueous Solution.

This work presents a study of the thermally induced aggregation of perylene diimide (PDI) and naphthalene diimide (NDI) derivatives modified with oligo ethylene glycol (OEG) chains in aqueous solution. Water-soluble and flexible OEG side chains were introduced into the π-core of glutamate-modified NDI and PDI structures, and the aggregation process was modulated by heating or cooling in water. Interestingly, a rare opposite temperature response of fluorescent behavior from the two amphiphilic chromophores was revealed, in which the PDI exhibited fluorescent enhancement, while fluorescent quenching upon temperature increase was observed from the NDI assembly. The mechanism of thermally induced aggregation is clearly explained by studies with various spectroscopic techniques including UV-visible, fluorescence, 1H NMR, 2D NMR spectroscopy, and SEM observation as well as control experiments operated in DMSO solution. It is found that although similar J-aggregates were formed by both amphiphilic chromophores in aqueous solution, the temperature response of the aggregates to temperature was opposite. The degree of PDI aggregation decreased, while that of NDI increased upon temperature rising. This research paves a valuable way for understanding the complicated supramolecular behaviors of amphiphilic chromophores.

A Fluorescence Biosensor Based on Carbon Quantum Dots Prepared from Pomegranate Peel and T-Hg2+-T Mismatch for Hg2+ Detection.

Mercury ions (Hg2+) can cause damage to human health, and thus, the study of the detection of Hg2+ is extraordinarily important in daily life. This work reported a fluorescence biosensor for the detection of Hg2+. The key point of this strategy was that the fluorescence of carbon quantum dots made from pomegranate peel (P-CQDs) was quenched by hemin, and restored after G-quadruplex binding with hemin. The presence of Hg2+ caused thymine (T)-rich DNA fragments to form T-Hg2+-T mismatches, and this change allowed the release of G-quadruplex. G-quadruplex could change the fluorescence of hemin/P-CQDs. P-CQDs exhibited excellent properties through characterization analysis, such as transmission electron microscope, X-ray photoelectron spectroscopy and Fourier transform infrared. This proposed fluorescence detection strategy established the linear ranges of Hg2+ from 1 nM to 50 nM. In conclusion, this simple biosensor had the advantages of strong sensitivity, high selectivity, and low cost for Hg2+ detection in environmental water samples.

Boosting the Faraday Efficiency of Electrochemical Ammonia Synthesis via the Strain Effect Induced by Interfacial Hybrid Formation between BN and Carbon Nanotubes.

The electrochemical nitrogen reduction reaction (eNRR) is a highly promising alternative to the Haber-Bosch (H-B) process, but its commercial development is limited by the high bond energy of N2 molecules and the presence of the competitive hydrogen evolution reaction (HER). Here, a metal-free composite electrocatalyst of boron nitride (h-BNNs) and carbon nanotubes (CNTs) was explored through the interfacial hybridization of h-BNNs and CNTs, which showed a highly improved eNRR Faraday efficiency (FE) of 63.9% and an NH3 yield rate of 36.5 µg h-1 mgcat.-1 at -0.691 V (vs RHE). New chemical bonds of C-B and C-N were observed, indicating a strong interaction between CNTs and h-BNNs. According to the Raman spectra and the optimized model of h-BNNs/CNTs, an obvious strain effect between h-BNNs and CNTs was supposed to play a significant role in the highly improved FE, compared with the FE of h-BNNs alone (4.7%). Density functional theory (DFT) calculations further showed that h-BNNs/CNTs had lower energy barriers in eNRR, giving them higher N2 to NH3 selectivity, while h-BNNs have lower energy barriers in the HER. This work shows the important role of the strain effect in boosting the selectivity in the eNRR process.

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.