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.

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.

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.

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.

Do Ionic Liquids Slow Down in Stages?

High impact recent articles have reported on the existence of a liquid-liquid (L-L) phase transition as a function of both pressure and temperature in ionic liquids (ILs) containing the popular trihexyltetradecylphosphonium cation (P666,14+), sometimes referred to as the "universal liquifier". The work presented here reports on the structural-dynamic pathway from liquid to glass of the most well-studied IL comprising the P666,14+ cation. We present experimental and computational evidence that, on cooling, the path from the room-temperature liquid to the glass state is one of separate structural-dynamic changes. The first stage involves the slowdown of the charge network, while the apolar subcomponent is fully mobile. A second, separate stage entails the slowdown of the apolar domain. Whereas it is possible that these processes may be related to the liquid-liquid and glass transitions, more research is needed to establish this conclusively.

Hierarchical 2D honeycomb-like network from barium-seamed nanocapsules.

We report on a two-dimensional hexagonal "honeycomb" network comprising barium-seamed metal-organic nanocapsules involving a hexameric assembly of pyrogallol[4]arene ligands. The incorporated barium ions act as spacers to generate a solvent-accessible void, hierarchical self-assembly having an individual void volume near 13 000 Å3. This work illustrates the surprising chemistry that remains to be discovered by integrating large or classically non-reactive metal ions within supramolecular assemblies, networks, and organic nanocapsules.

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.

Functionalized Ionic Liquids for CO2 Capture under Ambient Pressure.

Ionic liquids (ILs) have been widely explored as alternative solvents for carbon dioxide (CO2) capture and utilization. However, most of these processes are under pressures significantly higher than atmospheric level, which not only levies additional equipment and operation costs, but also makes the large-scale CO2 capture and conversion less practical. In this study, we rationally designed glycol ether-functionalized imidazolium, phosphonium and ammonium ILs containing acetate (OAc-) or Tf2N- anions, and found these task-specific ILs could solubilize up to 0.55 mol CO2 per mole of IL (or 5.9 wt% CO2) at room temperature and atmospheric pressure. Although acetate anions enabled a better capture of CO2, Tf2N- anions are more compatible with alcohol dehydrogenase (ADH), which is a key enzyme involved in the cascade enzymatic conversion of CO2 to methanol. Our promising results indicate the possibility of CO2 capture under ambient pressure and its enzymatic conversion to valuable commodity.

Relating the Induced Free Charge Density Gradient in a Room-Temperature Ionic Liquid to Molecular-Scale Organization.

We report on dilution-dependent changes in the local environments of chromophores incorporated into room-temperature ionic liquid (RTIL)-molecular solvent binary systems where the ionic liquid cation and molecular solvent possess the same alkyl chain length. We have used the RTIL 1-decyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (DMPyrr+TFSI-) and the molecular solvent 1-decanol. Perylene was used as a non-polar probe, and cresyl violet (CV+) was used as a polar probe chromophore. We observe that in both regions there is a change in the chromophore local environments with increasing 1-decanol content. The changes in the nonpolar regions of the binary RTIL-molecular solvent system occur at a lower 1-decanol concentration than changes in the polar regions. Both chromophores reorient as oblate rotors in this binary system, allowing detailed information on the relative values of the Cartesian components of the rotational diffusion constants to be extracted from the experimental data. The induced free charge density gradient, ρf, known to exist in RTILs, persists to high 1-decanol content (1-decanol mole fraction of 0.75), with the structural details of the gradient being reflected in depth-dependent changes in the Cartesian components of the rotational diffusion constants of CV+. This is the first time that changes in molecular organization have been correlated with ρf.

Anticancer Agents as Design Archetypes: Insights into the Structure-Property Relationships of Ionic Liquids with a Triarylmethyl Moiety.

A fundamental challenge underlying the design principles of ionic liquids (ILs) entails a lack of understanding into how tailored properties arise from the molecular framework of the constituent ions. Herein, we present detailed analyses of novel functional ILs containing a triarylmethyl (trityl) motif. Combining an empirically driven molecular design, thermophysical analysis, X-ray crystallography, and computational modeling, we achieved an in-depth understanding of structure-property relationships, establishing a coherent correlation with distinct trends between the thermophysical properties and functional diversity of the compound library. We observe a coherent relationship between melting (T m) and glass transition (T g) temperatures and the location and type of chemical modification of the cation. Furthermore, there is an inverse correlation between the simulated dipole moment and the T m/T g of the salts. Specifically, chlorination of the ILs both reduces and reorients the dipole moment, a key property controlling intermolecular interactions, thus allowing for control over T m/T g values. The observed trends are particularly apparent when comparing the phase transitions and dipole moments, allowing for the development of predictive models. Ultimately, trends in structural features and characterized properties align with established studies in physicochemical relationships for ILs, underpinning the formation and stability of these new lipophilic, low-melting salts.

Plasmon-controlled shaping of gold nanostar photothermal therapy agents.

Tunable gold nanostars were synthesized through the reduction of gold salt by an aminosugar, N-methyl-D-glucamine, in a seed-less route. The nanoparticle morphology and size were facilely tuned through adjustments in reaction pH and LED light-mediated synthesis. The materials demonstrated low inherent cytotoxicity and high potential for photothermal therapy.

Cation structure-dependence of the induced free charge density gradient in imidazolium and pyrrolidinium ionic liquids.

We report on the structure-dependence and magnitude of the induced free charge density gradient (ρf) seen in room-temperature ionic liquids (RTILs) with imidazolium and pyrrolidinium cations. We characterize the spatially-resolved rotational diffusion dynamics of a trace-level cationic chromophore to characterize ρf in three different pyrrolidinium RTILs and two imidazolium RTILs. Our data show that the magnitude of ρf depends primarily on the alkyl chain length of RTIL cation and the persistence length of ρf is independent of RTILs' cation structure. These findings collectively suggest that mesoscopic structure in RTILs plays a significant role in allowing charge density gradients to form.

Cation structure-dependence of the Pockels effect in aprotic ionic liquids.

We report on the dependence of surface charge-induced birefringence (the Pockels effect) in room temperature ionic liquids (RTILs) with different cation constituents. The induced birefringence is related to the induced free charge density gradient (ρf) in the RTIL. The RTILs are confined in a lens-shaped cell and the surface charge density of the concave cell surface is controlled by the current passed through the surface ITO film. We find that, in all cases, the induced birefringence is proportional to the surface charge density and that the change in refractive index nearest the ITO surface can be on the order of 20%. Our findings indicate that the induced birefringence depends more sensitively on the cation aliphatic substituent length than on the identity of the charge-carrying headgroup.

Deep eutectic solvents comprising creatine and citric acid and their hydrated mixtures.

We report the phase diagram for the binary creatine-citric acid mixture which features a stable and broad eutectic region. Combinations containing 10-60 mol% creatine yield a deep eutectic solvent with a glass transition temperature at 270 K. Addition of up to 70 mol% water to the binary mixture affords retention of the eutectic nature and a handle to vary solvent viscosity and polarity.

Laser-induced sound pinging for the rapid determination of total sugar or sweetener content in commercial beverages.

We recently reported on fixed-path length laser-induced sound pinging (FPL-LISP) as a rapid photoacoustic technique employing an inexpensive benchtop tattoo-removal laser for reliably determining the speed of sound in low-volume fluids. In this contribution, we demonstrate the capacity of FPL-LISP to analyze representative commercial beverages for their natural or artificial sweetener contents. As a benchmark, the speed of sound was determined for solutions of sugars (glucose, fructose, sucrose), mock high fructose corn syrup (HFCS-55), and 12 household sweeteners (culinary sugars, syrups, honey, molasses) across the concentration range of 1-20% w/v in water, simulating the typical sweetener range found in commercial soft drinks. The setup was then employed to estimate sweetener contents of 26 popular commercial beverages using the HFCS-55 standard curve as a training data set. Our results are remarkably consistent with the label values for these representative commercial beverages, in spite of the fact that some beverages clearly employ a sweetener other than HFCS-55 or a proprietary blend, suggesting the excellent potential of the FPL-LISP setup as a quick screening tool well-suited to quality control and real-time assessment in the beverage and fermentation industrial sectors. The proposed approach represents a significant improvement over many existing methods on the basis of measurement time (down to 1 s, which can be considered real time for many applications), lenient sample requirements (tens of microliters to 1 mL), robust and user-friendly analysis, practical considerations (e.g., economical, minimal service and maintenance concerns), and prospects for advancing both online monitoring and fully portable versions of this instrumentation.

Evaluation of canonical choline chloride based deep eutectic solvents as dye-sensitized solar cell electrolytes.

Deep eutectic solvents (DESs) are beginning to attract interest as electrolyte alternatives to conventional organic solvents and ionic liquids within dye-sensitized solar cells (DSSCs). The precise roles played by DES components and whether they simply represent a benign medium for mobilizing charge carriers or present beneficial functionality that impacts device performance remain unclear. To begin to address this deficiency in understanding, we performed a comprehensive characterization of the three "canonical" choline chloride-based DESs (i.e., reline, ethaline, and glyceline) as DSSC electrolytes hosting the iodide-triiodide (I-/I3 -) redox couple. The measurement of electrolyte viscosities, determination of triiodide diffusion coefficients, and photovoltaic performances assessed for water contents up to 40 wt. % allow the emergence of several important insights. A comparison to the observed photovoltaic performance arising from the individual components aids in further clarifying the impact of DES chemistry and solution viscosity on photovoltaic and charge carrier diffusion characteristics. Finally, we introduce the DES guaniline-consisting of a 1:1 molar ratio mixture of choline chloride with guanidinium thiocyanate-demonstrating it to be a superior DSSC electrolyte over those formulated from the three most widely studied canonical DESs at all water contents investigated.

Assessing rotation and solvation dynamics in ethaline deep eutectic solvent and its solutions with methanol.

Steady-state and time-resolved fluorescence were used to investigate the solvation of coumarin 153 (C153) and coumarin 343 (C343) in methanol + ethaline binary solutions, a deep eutectic solvent composed of a 1:2 molar ratio choline chloride + ethylene glycol. In addition, time-resolved anisotropy decays were used to determine the solute's rotational reorientation time as a function of viscosity. Measurements were made in solutions covering the entire range of mole fraction. Viscosity measurements were used to characterize the bulk solvent properties, and as expected, addition of methanol resulted in an decreased viscosity, showing an exponential decrease with mole fraction, up to ∼50-fold at xMeOH = 1.0. Probe rotational reorientation times were found to be biexponential at xMeOH < 0.3 for C153 and xMeOH < 0.5 for C343 and monoexponential at richer methanol content. In proportion to viscosity, C153 and C343 average rotation times decreased ∼30-fold from xMeOH = 0 to 0.9 and showed a power law dependence of ∼η0.85. Rotation times approached the stick boundary limit on dilution with methanol. Time-resolved Stokes shifts quantified the solvation dynamics and were nearly single exponential for C153 but were clearly biexponential for C343. Solvation times also tracked with viscosity according to a power law dependence, with exponents of 0.3 and 0.4 for C153 and C343, respectively. The dilution effect of methanol was not linear in proportion to the viscosity change and alone cannot account for the change in solvation. Dilution also showed a different correlation to solvation than did temperature variations to govern the viscosity change.

Coordination Polymers Constructed from Pyrogallol[4]arene-Assembled Metal-Organic Nanocapsules.

Coordination polymers, commonly known as infinite crystalline lattices, are versatile networks and have diverse potential applications in the fields of gas storage, molecular separation, catalysis, optics, and drug delivery, among other areas. Secondary building blocks, mainly incorporating rigid polydentate organic linkers and metal ions or clusters, are commonly employed to construct coordination polymers. Recently, novel building blocks such as coordination polyhedra have been utilized as metal nodes to fabricate coordination polymers. Benefiting from the rigid porous structure of the coordination polyhedron, prefabricated designer "pores" can be incorporated in this type of coordinate polymer. In this Account, coordination polymers built by pyrogallol[4]arene-assembled metal-organic nanocapsules are summarized. This class of metal-organic nanocapsule possesses the following advantages that make them excellent candidates in the construction of coordination polymers: (i) Various geometrical shapes with different volumes of the inner cavities can be obtained from these capsules. Among them, the two main categories illustrated are dimeric and hexameric capsules, which comprise two and six pyrogallol[4]arenes units, respectively. (ii) A wide range of possible metal ions ranging from main group metals to transition metals and even lanthanides have been demonstrated to seam the capsules. Therefore, these coordination polymers can be endowed with fascinating functionalities such as magnetism, semiconductivity, luminescence, and radioactivity. (iii) Up to 24 metal ions have been successfully embedded on the surface of the nanocapsule, each a potential reaction site in the construction of coordination polymers, opening up pathways for the formation of multidimensional frameworks.In this Account, we focus primarily on the synthesis and the structural information on pyrogallol[4]arene-derived coordination polymers. Coordination polymers can be formed by introducing linkers with two coordination sites, using pyrogallol[4]arenes with coordination sites on the tail, or even via metal ions cross-linking with each other. Machine learning was recently developed to help us predict and screen the structures of the coordination polymers. With single crystal analysis in hand, detailed structural information provides a molecular-level perspective. Significantly, following the formation of coordination polymers, the overall shape and structure of the discrete metal-organic nanocapsules remains essentially unchanged, with full retention of the prefabricated pores. If a rigid linker is used to connect capsules, more than one lattice void with different volumes can be found within the framework. Thus, molecules with different sizes could potentially be encapsulated within these coordination polymers. In addition, flexible ligands can also be employed as linkers. For example, polymers have been employed as large linkers that transform the crystalline coordination polymers into polymer matrices, paving the way toward the synthesis of advanced functional materials. Overall, coordination polymers constructed with pyrogallol[4]arene-assembled metal-organic nanocapsules show wide diversity and tunability in structure and fascinating properties, as well as the promise of built-in functionality in the future.