l-Cysteine-Tuned the Hierarchical Structure Based on Benzimidazole: Synthesis, Characterization, and Application in Ratiometric Electrochemiluminescence Immunoassay.

Efficient and robust electrochemiluminescence (ECL) emitters are crucial for enhancing the ECL immunosensor sensitivity. This study introduces a novel ECL emitter, CoBIM/Cys, featuring a hierarchical core-shell structure. The core of the structure is created through the swift coordination between the sulfhydryl and carboxyl groups of l-cysteine (l-Cys) and cobalt ions (Co2+), while the shell is constructed by sequentially coordinating benzimidazole (BIM) with Co2+. This design yields a greater specific surface area and a more intricate porous structure compared to CoBIM, markedly enhancing mass transfer and luminophore accessibility. Moreover, the l-Cys and Co2+ core introduces Co-S and Co-O catalytic sites, which improve the catalytic decomposition of H2O2, leading to an increased production of hydroperoxyl radicals (OOH•). This mechanism substantially amplifies the ECL performance. Leveraging the competitive interaction between isoluminol and BIM for OOH• during ECL emission, we developed a ratiometric immunosensor for cardiac troponin I (cTnI) detection. This immunosensor demonstrates a remarkably broad detection range (1 pg mL-1 to 10 ng mL-1), a low detection limit (0.4 pg mL-1), and exceptional reproducibility and specificity.

[Foliar Application of L-Cysteine: Effects on the Concentration of Cd and Mineral Elements in Rice].

To evaluate the feasibility of applying L-cysteine (L-Cys) as a foliar conditioner for Cd reduction in rice, a field experiment was conducted to investigate the concentration of Cd and mineral elements in rice after the foliar application of L-Cys. The variation in Cd distribution and morphology in key rice organs was examined to study the Cd reduction mechanisms of spraying L-Cys on rice. The results showed that foliar application of L-Cys at the rice-flowering stage significantly decreased Cd concentration in grains, in a concentration dependent manner, without inhibiting the accumulation of mineral elements Ca, Mg, K, Mn, and Zn. With a 10 mmol ·L-1 L-Cys application, Cd concentration in rice grains decreased by 59.2%, to below 0.2 mg ·kg-1, which is the maximum safety limit in China. Foliar application of L-Cys also inhibited Cd accumulation in rice vegetative organs, including rachises, first nodes, neck-panicles, flag leaves, second internodes, second nodes, second leaves, stalks, and roots (58.3%, 56.0%, 62.7%, 67.0%, 59.3%, 61.5%, 60.2%, 54.9%, and 50.3%, respectively). After transfer factor calculation, first nodes were found to be the key organ for Cd blocking in rice. The application of L-Cys increased Cd transfer from flag leaves and second internodes to first nodes (105.4% and 45.8%, respectively), but decreased Cd transfer from first nodes up to neck-panicles (27.5%). In rice first nodes, the concentrations of Cd in the inorganic, water soluble, and residue states were all lower following L-Cys application, and the proportion of residual Cd increased to 94.4%. Therefore, foliar application of L-Cys significantly inhibited Cd transport and accumulation in rice grains, by decreasing the Cd concentrations of various vegetative organs and improving Cd interception in the first nodes. This is a promising way to produce rice with lower Cd concentrations and normal mineral element concentrations in Cd-contaminated paddy fields.

Fluorescence turn-on sensing of L-cysteine based on FRET between Au-Ag nanoclusters and Au nanorods.

The applications of metallic nanoclusters and nanoparticles in biological sensing have attracted special attention owing to their optical interaction based on fluorescence and surface plasmon resonance (SPR). In this work, we designed a fluorescent nanoprobe for the determination of L-cysteine (L-Cys) based on fluorescence resonance energy transfer (FRET) from gold­silver bimetallic nanoclusters (Au-Ag NCs) to gold nanorods (AuNRs). Firstly, the negatively charged Au-Ag NCs protected by bovine serum albumin (BSA) are directly adsorbed on the surface of the positively charged AuNRs through electrostatic interaction, and the FRET effect leads to distinct fluorescence quenching of Au-Ag NCs at 615nm. The SPR wavelength of AuNRs is dependent on the aspect ratio, so the SPR of AuNRs could be tuned to have a better spectral overlap with fluorescence of Au-Ag NCs, which enhances the fluorescence quenching effect. Because the SH group of L-Cys has an affinity with gold, the addition of L-Cys can result in the release of Au-Ag NCs from the surface of AuNRs via forming AuS bonds. Thus, the introduction of L-Cys could effectively restore the fluorescence emission of the AuNRs/Au-Ag NCs system because of the restraint of FRET effect. Under the optimized conditions, the fluorescence recovery of AuNRs/Au-Ag NCs probe exhibits a linear response to L-Cys concentration ranging from 5 to 100µM, and the corresponding theoretical detection limit (LOD) is 1.73µM. Meanwhile, this method displays excellent sensitivity and selectivity for L-Cys over other amino acids, and it has been successfully applied to detect L-Cys in real samples.