ABSTRACT
This work presents an innovative approach to obtain a multifunctional hybrid material operating via combined anti-Stokes (upconversion) and Stokes (downshifting) emissions for oxygen gas sensing and related functionalities. The material is based on a Cu(I) complex exhibiting thermally activated delayed fluorescence emission (TADF) and infrared-to-visible upconverting Tm3+/Yb3+-doped NaYF4 nanoparticles supported in a polystyrene (PS) matrix. Excitation of the hybrid material at 980 nm leads to efficient transfer of Tm3+ emission in the ultraviolet/blue region to the Cu(I) complex and consequently intense green emission (560 nm) of the latter. Additionally, the green emission of the complex can also be directly generated with excitation at 360 nm. Independently of the excitation wavelength, the emission intensity is efficiently suppressed by the presence of molecular oxygen and the quenching rate is properly characterized by the Stern-Volmer plots. The results indicate that the biocompatible hybrid material can be applied as an efficient O2 sensor operating via near-infrared or ultraviolet excitation, unlike most optical oxygen sensors currently available which only work in downshifting mode.
ABSTRACT
Upconversion nanoparticles (UCNPs) have emerged as promising luminescent nanomaterials due to their unique features that allow the overcoming of several problems associated with conventional fluorescent probes. Although UCNPs have been used in a broad range of applications, it is probably in the field of sensing where they best evidence their potential. UCNP-based sensors have been designed with high sensitivity and selectivity, for detection and quantification of multiple analytes ranging from metal ions to biomolecules. In this review, we deeply explore the use of UCNPs in sensing systems emphasizing the most relevant and recent studies on the topic and explaining how these platforms are constructed. Before diving into UCNP-based sensing platforms it is important to understand the unique characteristics of these nanoparticles, why they are attracting so much attention, and the most significant interactions occurring between UCNPs and additional probes. These points are covered over the first two sections of the article and then we explore the types of fluorescent responses, the possible analytes, and the UCNPs' integration with various material types such as gold nanostructures, quantum dots and dyes. All the topics are supported by analysis of recently reported sensors, focusing on how they are built, the materials' interactions, the involved synthesis and functionalization mechanisms, and the conjugation strategies. Finally, we explore the use of UCNPs in paper-based sensors and how these platforms are paving the way for the development of new point-of-care devices.
ABSTRACT
Chiral pesticides have been used in agriculture, including (±)-lambda-cyhalothrin ((±)-LC), which is a pyrethroid insecticide widely employed on crops for protection against different types of insects. However, enantioselectivity is poorly studied in biodegradation processes. Therefore, the (±)-LC enantioselective biodegradation by bacteria from Brazilian savannah was reported in this study with a validated analytical method. All bacterial strains biodegraded (±)-LC with different efficiencies. Residual concentrations of LC (3.7-43.1% of biodegradation) and its enantiomeric excesses (0-27% ee) were determined. Additionally, the formation of the main biodegradation metabolite 3-phenoxybenzoic acid was also quantified. A Bacillus consortium composed of the three most efficient strains biodegraded more LC than any isolated strain solely employed in this work, showing that the use of a consortium is an interesting approach. In addition, 13 metabolites were identified and a biodegradation pathway with biochemical reactions of hydrolysis, reduction, esterification, amidation, elimination and group transfer were proposed, confirming the bioremediation potential of these strains. The LC stereoisomer with the highest insecticidal activity (1R,3R,αS-enantiomer, also known as gamma-cyhalothrin) was preferentially biodegraded by the studied bacteria. Therefore, crops protection with gamma-cyhalothrin, which can be applied in lower concentrations than (±)-LC because it is a more effective product against insects, may also be biodegraded faster than the racemic mixture in the environment, decreasing the toxic effects on non-target organisms.
