Facile Oxidation of Ce(III) to Ce(IV) Using Cu(I) Salts.

The synthesis, luminescence, and electrochemical properties of the Ce(III) compound, [(C5Me5)2(2,6-iPr2C6H3O)Ce(THF)], 1, were investigated. Based on the electrochemical data, treatment of 1 with CuX (X = Cl, Br, I) results in the formation of the corresponding Ce(IV) complexes, [(C5Me5)2(2,6-iPr2C6H3O)Ce(X)]. Each complex has been characterized using NMR, IR, and UV-vis spectroscopy as well as structurally determined using X-ray crystallography. Additionally, the treatment of [(C5Me5)2(2,6-iPr2C6H3O)Ce(Br)] with AgF results in the formation of the putative [(C5Me5)2(2,6-iPr2C6H3O)Ce(F)]. The electronic structure of these Ce(IV)-X complexes was investigated by bond analyses and the Ce(IV)-F moiety using quantum chemistry NMR calculations.

Progress in the application of ionic liquids and deep eutectic solvents for the separation and quantification of per- and polyfluoroalkyl substances.

Per- and polyfluoroalkyl substances (PFASs), often labeled as "forever chemicals," earned this moniker due to their widespread presence in the environment, bioaccumulative tendencies, and resistance to remediation efforts. Employed for decades in various applications, spanning from stain-resistant fabrics to grease-proof food containers and fire-fighting foams, PFASs have evolved into an anthropogenic nightmare. Their adverse impact on human health, including immune dysfunction, infertility, and a spectrum of cancers, is alarming. Conventional water treatment methods, notably in the case of short-chain congeners, struggle to effectively eliminate PFASs, underscoring the pressing need for enhanced adsorbents. In recent years, there has been a prominent surge in the exploration of innovative techniques centered around ionic liquids (ILs) and deep eutectic solvents (DESs) for the removal of PFASs from various sources, including food samples like cooking oil, as well as environmental waters. In this Review, we delve into key advancements and discoveries related to the utilization of ILs and DESs as media for the liquid-liquid extraction of PFASs, as well as their applications as sorbents on solid-state or nanoscale supports. Our exploration encompasses groundbreaking approaches, including the utilization of dicationic ILs for ultra-sensitive mass spectrometric PFAS detection, alongside the innovative application of fluorinated ILs and hydrophobic DESs, enabling highly efficient PFAS sequestration. The landscape of existing PFAS extraction methods is riddled with formidable challenges, including limited selectivity, matrix interferences, subpar extraction efficiency, exorbitant costs, laborious procedures, ecological consequences, and a lack of standardization. Given these challenges, our review unequivocally asserts the pivotal role ILs and DESs will play in shaping the next generation of PFAS remediation strategies. Rigorous characterization of water solubility, toxicity, and biodegradation, along with improved recyclability and thorough techno-economic analyses, are essential for further progress. Future focus must also extend to addressing short-chain PFASs (such as PFBS) and PFAS alternatives (including ADONA, GenX, F-53B), which often pose higher toxicity risks than the compounds they aim to replace. A forward-thinking approach will integrate cutting-edge data-driven techniques, such as machine learning, to enhance our understanding and response to PFAS-related issues. Finally, we advocate seamless integration of PFAS separation with advanced treatment, efficiently isolating and destroying these compounds for a lasting solution to contamination challenges.

The Huge Role of Tiny Impurities in Nanoscale Synthesis.

Nanotechnology is vital to many current industries, including electronics, energy, textiles, agriculture, and theranostics. Understanding the chemical mechanisms of nanomaterial synthesis has contributed to the tunability of their unique properties, although studies frequently overlook the potential impact of impurities. Impurities can show adverse effects, clouding the interpretation of results or limiting the practical utility of the nanomaterial. On the other hand, as successful doping has demonstrated, the intentional introduction of impurities can be a powerful tool for enhancing the properties of a nanomaterial. This Review examines the complex role of impurities, unintentionally or intentionally added, during nanoscale synthesis and their effects on the performance and usefulness of the most common classes of nanomaterials: nanocarbons, noble metal and metal oxide nanoparticles, semiconductor quantum dots, thermoelectrics, and perovskites.

Structure-Dependence and Mechanistic Insights into the Piezoelectric Effect in Ionic Liquids.

We reported recently that two imidazolium room-temperature ionic liquids (RTILs) exhibit the direct piezoelectric effect (J. Phys. Chem. Lett., 2023, 14, 2731-2735). We have subsequently investigated several other RTILs with pyrrolidinium and imidazolium cations and tetrafluoroborate and bis(trifluoromethylsulfonyl)imide anions in an effort to gain insight into the generality and mechanism of the effect. All the RTILs studied exhibit the direct piezoelectric effect, with a magnitude (d33) and threshold force that depend on the structures of both the cation and anion. The structure-dependence and existence of a threshold force for the piezoelectric effect are consistent with a pressure-induced liquid-to-crystalline solid phase transition in the RTILs, and this is consistent with experimental X-ray diffraction data.

Imidazolium-based zwitterionic liquid-modified PEG-PLGA nanoparticles as a potential intravenous drug delivery carrier.

Zwitterionic-based systems offer promise as next-generation drug delivery biomaterials capable of enhancing nanoparticle (NP) stimuli-responsiveness, biorecognition, and biocompatibility. Further, imidazole-functionalized amphiphilic zwitterions are able to readily bind to various biological macromolecules, enabling antifouling properties for enhanced drug delivery efficacy and bio-targeting. Herein, we describe structurally tuned zwitterionic imidazole-based ionic liquid (ZIL)-coated PEG-PLGA nanoparticles made with sonicated nanoprecipitation. Upon ZIL surface modification, the hydrodynamic radius increased by nearly 20 nm, and the surface charge significantly shifted closer to neutral. 1H NMR spectra suggests that the amount of ZIL on the nanoparticle surface is controlled by the structure of the ZIL and that the assembly occurs as a result of non-covalent interactions of ZIL-coated nanoparticle with the polymer surface. These nanoparticle-zwitterionic liquid (ZIL) constructs demonstrate selective affinity towards red blood cells in whole mouse blood and show relatively low human hemolysis at ∼5%. Additionally, we observe higher nanoparticle accumulation of ZIL-NPs compared with unmodified NP controls in human triple-negative breast cancer cells (MDA-MB-231). Furthermore, although the ZIL shows similar protein adsorption by SDS-PAGE, LC-MS/MS protein analysis data demonstrate a difference in the relative abundance and depletion of proteins in mouse and human serum. Hence, we show that ZIL-coated nanoparticles provide a new potential platform to enhance RBC-based drug delivery systems for cancer treatments.

Isotopic biographies reveal horse rearing and trading networks in medieval London.

This paper reports a high-resolution isotopic study of medieval horse mobility, revealing their origins and in-life mobility both regionally and internationally. The animals were found in an unusual horse cemetery site found within the City of Westminster, London, England. Enamel strontium, oxygen, and carbon isotope analysis of 15 individuals provides information about likely place of birth, diet, and mobility during the first approximately 5 years of life. Results show that at least seven horses originated outside of Britain in relatively cold climates, potentially in Scandinavia or the Western Alps. Ancient DNA sexing data indicate no consistent sex-specific mobility patterning, although three of the five females came from exceptionally highly radiogenic regions. Another female with low mobility is suggested to be a sedentary broodmare. Our results provide direct and unprecedented evidence for a variety of horse movement and trading practices in the Middle Ages and highlight the importance of international trade in securing high-quality horses for medieval London elites.