o-phenylenediamine Derived Fluorescent Carbon Quantum dots for Detection of Hg(II) in Environmental Water.

With the expansion of human activities, the consequent influx of mercury (Hg) into the food chain and the environment is seriously threatening human life. Herein, nitrogen and sulfur co-doped fluorescent carbon quantum dots (yCQDs) were prepared via a hydrothermal method using o-phenylenediamine (OPD) and taurine as precursors. The morphological characteristics as well as spectral features of yCQDs indicated that the photoluminescence mechanism should be the molecular state fluorophores of 2, 3-diaminophenothiazine (oxOPD), which is the oxide of OPD. The as-synthesized yCQDs exhibited sensitive recognition of Hg2+. According to the investigation in combination of UV-Vis absorption spectra, time-resolved fluorescence spectra and quantum chemical calculations, the abundant functional groups on the surface of yCQDs allowed Hg2+ to bind with yCQDs through various interactions, and the formed complexes significantly inhibited the absorption of excitation light, resulting in the static fluorescence quenching of yCQDs. The proposed yCQDs was utilized for Hg2+ sensing with the limit of detection calculated to be 4.50 × 10- 8 M. Furthermore, the recognition ability of yCQDs for Hg2+ was estimated in tap water, lake water and bottled water, and the results indicated that yCQDs have potential applications in monitoring Hg2+.

Synthesis and photoluminescence properties of orange-red carbon dots from the paper tissues as the precursor.

In recent years, stable and photoluminescence (PL) tunable fluorescent materials known as carbon dots (CDs) have seen rapid development. Here, a simple, low-cost, and environmentally friendly approach has been developed to synthesize the orange-red CDs (OR-CDs) with paper tissues as the precursor in the presence of ethanol and concentrated sulfuric acid. The average diameter of the OR-CDs was measured at around 1.25 nm. The as-prepared OR-CDs are composed of carbon cores with the graphite structure distributed in the middle and wrapped or entangled by polymers for the outside. Moreover, the PL characteristics of the OR-CDs under the dilute solution state and the concentrated solution state, respectively, were explored. The former with the blue light showed prominent excitation-dependent characteristics in the range from 365 to 420 nm; the latter rendered the excitation-independent property with distinguished orange-red fluorescence emission. With an increase in the concentration, the emission fluorescence intensities gradually increased under the excitation wavelength of 540 nm, which can be attributed to the aggregation-induced emission property of the OR-CDs. By virtue of their excellent PL properties and low toxicity, we believe that the OR-CDs have potential applications in various optoelectronic areas, especially in white LED fields.

Effect of Zn2+ on emodin molecules studied by time-resolved fluorescence spectroscopy and quantum chemical calculations.

Emodin is a natural drug for treating neurodegenerative diseases and plays a vital role in the mitigation of nerve damage. Metal ions can modify the drug properties of emodin, where Zn2+ can synergize with the emodin molecule and enhance the drug effect of emodin. Besides, complex changes can be observed in the fluorescence intensity and fluorescence lifetime of the emodin molecule as the concentration of Zn2+ increases. Herein, the synergistic effects of ligand structural in Zn(II)-Emodin complexes and the electronic effects of metal elements on the antioxidant properties of the complexes are discussed in detail based on UV-vis absorption spectroscopy, fluorescence spectroscopy, time-correlated single photon counting (TCSPC) technique and quantum chemical calculations at the B3LYP/6-31G(d) level. The experimental results confirm that Zn2+ can coordinate with the hydroxyl groups on the emodin to make the molecule structure more rigid, thus inhibiting the non-radiative processes such as high-frequency vibrations of the emodin molecule in solution. The suppression of non-radiative processes leads to an increase in the average fluorescence lifetime of the emodin molecule, and finally results in the enhanced fluorescence intensity. The chemical softness of Zn(II)-Emodin is then confirmed to be higher than that of emodin by Gaussian calculations, indicating its higher chemical reactivity and lower stability. The stronger electron donating ability of Zn(II)-Emodin compared to emodin may explain the higher antioxidant activity of Zn(II)-Emodin, which gives it a stronger pharmacological activity. The results of this study show that emodin can well complex with Zn2+ to remove excess Zn2+ in human body and the resulting complex has better antioxidant properties, which helps to understand the role of Zn2+ in drug-metal coordination and provides guidance for the design of new drugs.

Al2O3@Ag composite structure as SERS substrate for sensitive detection of sodium thiocyanate.

Sodium thiocyanate (NaSCN) can be added to fresh milk to enhance the sterilization ability of the lactoperoxidase system (LP system) in milk, extending shelf life. However, excessive intake of NaSCN can be harmful to human health because it can prevent absorption of iodine leading to disease. Also NaSCN can be used as a marker to distinguish smokers from non-smokers. In this work, we successfully synthesized meatball-like Al2O3@Ag composite structures as surface-enhanced Raman scattering (SERS) substrates using a simple wet chemical method adapted to conventional laboratory conditions. The substrate exhibited strong SERS enhancement for NaSCN. Under the optimal experiment conditions, we obtained a detection limit of 0.28 µg L-1 and a quantification limit of 1 µg L-1, R2 = 0.992. Based on the analysis of the intensity of SERS characteristic peak, the substrate had good reproducibility and uniformity. In summary, the Al2O3@Ag composite structure achieved sensitive SERS detection of NaSCN. Combining the facile and low-cost methods, we believe that the SERS detection method developed in this work can be used as a potential candidate for biosensing applications in the future.

A fluorescent probe based on FRET effect between carbon nanodots and gold nanoparticles for sensitive detection of thiourea.

Illegal abuse results in the presence of thiourea (TU) in soil, wastewater, and even fruits, which is harmful for the environment and human health. It has urgent practical significance to design an efficient and reliable probe for TU detection. Herein, a sensitive fluorescent probe with off-on response for harmful TU was reported. The probe was designed with fluorescent carbon nanodots (CNDs) and gold nanoparticles (AuNPs) based on fluorescence resonance energy transfer (FRET) effect. Firstly, the CNDs were pre-combined with AuNPs and the fluorescence of CNDs was quenched due to the FRET effect. Upon addition of TU, the fluorescence of CNDs recovered due to the unbinding of CNDs and AuNPs, since the coordination interaction between TU and AuNPs is stronger than the electrostatic interaction among CNDs and AuNPs. Under the optimum parameters, a linear relationship was found between the relative fluorescence intensity of the probe and the concentration of TU in the range of 5.00 × 10-8-1.00 × 10-6 M (R2 = 0.9958), with the limit of detection (LOD) calculated to be 3.62 × 10-8 M. This proposed method is easy to operate and has excellent selectivity and sensitivity for TU, which can be effectively applied in environmental water and compound fruit-vegetable juice.

Sensitive determination of Norfloxacin in milk based on ß-cyclodextrin functionalized silver nanoparticles SERS substrate.

The norfloxacin (NFX) residue in milk will increase human resistance to drugs and pose a threat to public health. In this work, a highly sensitive method for detection of NFX was developed based on surface enhanced Raman spectroscopy (SERS) using ß-cyclodextrin functionalized silver nanoparticles (ß-CD-AgNPs) as substrate. The unique spatial size and hydrophilicity of ß-CD on the surface of AgNPs could selectively capture the target molecule (NFX) through some weak interactions, including hydrogen-bond interaction, electrostatic interaction, etc. The interactions were characterized by the UV-Vis absorption spectroscopy, fluorescence spectroscopy, Zeta potential and DLS. The Raman signal of NFX is largely enhanced when anchored by ß-CD on the surface of AgNPs due to SERS effect. Through a series of experiments and analysis, the limit of detection (LOD) in standard solution and spiked milk were calculated to be 3.214 pmol/L and 5.327 nmol/L. The correlation coefficients (R2) were 0.986 and 0.984, respectively. For milk sample determination of NFX, the recovery was 101.29% to 104.00% with the relative standard deviation (RSD) from 2.986% to 9.136%. To sum up, this developed SERS strategy is sensitive and specific to detect NFX in milk, it has practical application value and prospects.