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.

Purposefully Designed Surfactants for Facile and Controllable Gold Colloidal Nanocrystal Synthesis.

Three new cationic surfactants-N-cetyl-bis(2-dimethylaminoethyl)ether bromide (CBDEB), N-dodecyl-bis(2-dimethylaminoethyl)ether bromide (DBDEB), and N-hexyl-bis(2-dimethylaminoethyl)ether bromide (HBDEB)-have been designed herein using a simple and tailorable synthesis route. CBDEB and DBDEB, the 16- and 12-carbon chain surfactants, demonstrate facile, rapid, and controllable aqueous syntheses of gold nanoparticles (AuNPs) as dual-action reducing and capping agents. The synthesis strategy, using only surfactant and HAuCl4 salt, and 4 min of heating at 80 °C, results in spherical AuNPs (average diameters of 13.4 ± 3.8 nm for CBDEB and 12.0 ± 3.8 nm for DBDEB). Microwave irradiation was also investigated as a heating method and produces AuNPs in as little as 30 s. Control over the size and shape of AuNPs was proven to be feasible (toward populations of Euclidean shapes) by appropriately tuning reaction parameters, such as the molar ratio of surfactant to Au3+, temperature, incorporation of a time delay before heating, or shape control agents, such as Cu2+. Frustratingly, the cytotoxicity of CBDEB is similar to that of cetyltrimethylammonium bromide (CTAB), a popular 16-carbon chain cationic surfactant. Notably, while the shorter HBDEB (6-carbon chain) does not produce AuNPs under the applied conditions, it does appear to improve cell viability upon cytotoxicity evaluation and may be favorable as a new biological surfactant.

Nanocapsules of unprecedented internal volume seamed by calcium ions.

The inception of an unprecedented class of voluminous Platonic solids displaying hierarchical geometry based on pyrogallol[4]arene moieties seamed by divalent calcium ion is described. Single-crystal X-ray structural determination has established the highly conserved geometry of two original Ca2+-seamed nanocapsules to be essentially cubic in shape with C-ethylpyrogallol[4]arene units located along the twelve edges of the cube which are then bridged by metallic polyatomic cations ([Ca4Cl]7+ or [Ca(HCO2)Na4]5+) at the six cube faces. The accessible volume of the nanocapsules is ca. 3500 Å3 and 2500 Å3 and is completely isolated from the exterior of the capsules. These remarkable nanocapsule discoveries cast a spotlight on a marginalized area of synthetic materials chemistry and encourage future exploration of diversiform supramolecular assemblies, networks, and capsules built on calcium, with clear benefits deriving from the intrinsic biocompatibility of calcium. Finally, a proof-of-concept is demonstrated for fluorescent reporter encapsulation and sustained release from the calcium-seamed nanocapsules, suggesting their potential as delivery vehicles for drugs, nutrients, preservatives, or antioxidants.