Low Vapor Pressure Solvents for Single-Molecule Junction Measurements.

Nonpolar solvents commonly used in scanning tunneling microscope-based break junction measurements exhibit hazards and relatively low boiling points (bp) that limit the scope of solution experiments at elevated temperatures. Here we show that low toxicity, ultrahigh bp solvents such as bis(2-ethylhexyl) adipate (bp = 417 °C) and squalane (457 °C) can be used to probe molecular junctions at ≥100 °C. With these, we extend solvent- and temperature-dependent conductance trends for junction components such as 4,4'-bipyridine and thiomethyl-terminated oligophenylenes and reveal the gold snapback distance is larger at 100 °C due to increased surface atom mobility. We further show the rate of surface transmetalation and homocoupling reactions using phenylboronic acids increases at 100 °C, while junctions comprising anticipated boroxine condensation products form only at room temperature in an anhydrous glovebox atmosphere. Overall, this work demonstrates the utility of low vapor pressure solvents for the comprehensive characterization of junction properties and chemical reactivity at the single-molecule limit.

Soft-sphere continuum solvation models for nonaqueous solvents.

Solvation effects profoundly influence the characteristics and behavior of chemical systems in liquid solutions. The interaction between solute and solvent molecules intricately impacts solubility, reactivity, stability, and various chemical processes. Continuum solvation models gained prominence in quantum chemistry by implicitly capturing these interactions and enabling efficient investigations of diverse chemical systems in solution. In comparison, continuum solvation models in condensed matter simulation are very recent. Among these, the self-consistent continuum solvation (SCCS) and the soft-sphere continuum solvation models (SSCS) have been among the first to be successfully parameterized and extended to model periodic systems in aqueous solutions and electrolytes. As most continuum approaches, these models depend on a number of parameters that are linked to experimental or theoretical properties of the solvent, or that can be tuned based on reference data. Here, we present a systematic parameterization of the SSCS model for over 100 nonaqueous solvents. We validate the model's efficacy across diverse solvent environments by leveraging experimental solvation-free energies and partition coefficients from comprehensive databases. The average root means square error over all the solvents was calculated as 0.85 kcal/mol which is below the chemical accuracy (1 kcal/mol). Similarly to what has been reported by Hille et al. (J. Chem. Phys. 2019, 150, 041710.) for the SCCS model, a single-parameter model accurately reproduces experimental solvation energies, showcasing the transferability and predictive power of these continuum approaches. Our findings underscore the potential for a unified approach to predict solvation properties, paving the way for enhanced computational studies across various chemical environments.

Emerging Processes for Sustainable Li-Ion Battery Cathode Recycling.

The colossal growth in the use of Li-ion batteries (LiBs) has raised serious concerns over the supply chain of strategic minerals, e.g., Co, Ni, and Li, that make up the cathode active materials (CAM). Recycling spent LiBs is an important step toward sustainability that can establish a circular economy by effectively tackling large amounts of e-waste while ensuring an unhindered supply of critical minerals. Among the various methods of LiB recycling available, pyro- and hydrometallurgy have been utilized in the industry owing to their ease of operation and high efficiency, although they are associated with significant environmental concerns. Direct recycling, a more recent concept that aims to relithiate spent LiBs without disrupting the lattice structure of the CAMs, has been realized only in the laboratory scale so far and further optimization is required before it can be extended to the bulk scale. Additionally, significant progress has been made in the areas of hydrometallurgy in terms of using ecofriendly green lixiviants and alternate sources of energy, e.g., microwave and electrochemical, that makes the recycling processes more efficient and sustainable. In this review, the latest developments in LiB recycling are discussed that have focused on environmental and economic viability, as well as process intensification. These include deep eutectic solvent based recycling, electrochemical and microwave-assisted recycling, and various types of direct recycling.

Wearable Device with High Thermoelectric Performance and Long-Lasting Usability Based on Gel-Thermocells for Body Heat Harvesting.

Utilizing the thermogalvanic effect, flexible thermoelectric materials present a compelling avenue for converting heat into electricity, especially in the context of wearable electronics. However, prolonged usage is hampered by the limitation imposed on the thermoelectric device's operational time due to the evaporation of moisture. Deep eutectic solvents (DESs) offer a promising solution for low-moisture gel fabrication. In this study, a bacterial cellulose (BC)/polyacrylic acid (PAA)/guanidinium chloride (GdmCl) gel is synthesized by incorporating BC into the DES. High-performance n-type and p-type thermocells (TECs) are developed by introducing Fe(ClO4)2/3 and K3/4Fe(CN)6, respectively. BC enhances the mechanical properties through the construction of an interpenetrating network structure. The coordination of carboxyl groups on PAA with Fe3+ and the crystallization induced by Gdm+ with [Fe(CN)6]4- remarkably improve the thermoelectric performance, achieving a Seebeck coefficient (S) of 2.4 mV K-1 and ion conductivity (σ) of 1.4 S m-1 for the n-type TEC, and ‒2.8 mV K-1 and 1.9 S m-1 for the p-type TEC. A flexible wearable thermoelectric device is fabricated with a S of 82 mV K-1 and it maintains a stable output over one month. This research broadens the application scope of DESs in the thermoelectric field and offers promising strategies for long-lasting wearable energy solutions.

Asymmetric Alkyl Chain Engineering for Efficient and Eco-Friendly Organic Photovoltaic Cells.

Recent advancements in organic photovoltaic (OPV) cells have resulted in power conversion efficiencies (PCEs) surpassing 20%. However, the use of halogen solvents in the fabrication of OPV cells raises concerns due to their potential environmental and health impacts. In this work, a novel non-fullerene small molecule acceptor BO-AM-4F, featuring an asymmetric alkyl chain design that includes a 2-butyloctyl and a unique 6-(hexylamino)-6-oxohexyl chain is synthesized. This design significantly improves molecular packing, crystallinity, and electrostatic potential distribution compared to the controlled acceptor DBO-4F, which possesses symmetric 2-butyloctyl chains. When combined with the polymer donor PBDB-TF and processed using the non-halogen solvent o-xylene, the BO-AM-4F-based OPV cell achieves an impressive PCE of 18.0%, surpassing the 16.6% PCE observed in the PBDB-TF:DBO-4F device. Furthermore, the PBDB-TF:BO-AM-4F system demonstrates enhanced photostability and thermal stability compared to its DBO-4F counterpart. These findings emphasize asymmetric alkyl chain engineering as an effective strategy for developing high-performance, environmentally friendly OPV materials. This represents a significant step towards sustainable OPV technology.

2D NiFe2O4/Ni(OH)2 Heterostructure-Based Self-Supporting Electrode With Synergistic Surface/Interfacial Engineering for Efficient Water Electrooxidation.

To meet the industrial demand for overall water splitting, oxygen evolution reaction (OER) electrocatalysts with low-cost, highly effective, and durable properties are urgently required. Herein, a facile confined strategy is utilized to construct 2D NiFe2O4/Ni(OH)2 heterostructures-based self-supporting electrode with surface-interfacial coengineering, in which abundant and ultrastable interfaces are developed. Under the high molar ratio of Ni/Fe, both spinel oxide and hydroxides phases are formed simultaneously to obtain 2D NiFe2O4/Ni(OH)2 heterostructure. The in-depth analysis indicates that the NiFe2O4/Ni(OH)2 interface displays strong electronic interactions and triggers the formation of crystalline-amorphous coexisting catalytic active NiOOH. Meanwhile, the stable catalyst-collector interface favors the electron transfer and oxygen molecules transport. The resultant 2D NiFe2O4/Ni(OH)2@CP electrode exhibits superior OER performance, including a low overpotential of 389 mV and a long operating time of 12 h at 1 A cm-2. This work paves a novel method for fabricating efficient and low-cost electrocatalysts for electrochemical conversation devices.

Fluorinated Co-Solvents Enable Excellent Performances of Practical Cells Comprising LixSiO-Graphite Composite Anodes and LiNi0.89Co0.05Mn0.05Al0.01O2 (NCMA) Cathodes.

Li-ion batteries based on high specific capacity LixSiO-Graphite anodes and LiNi0.89Co0.05 Mn0.05Al0.01O2 (NCMA) cathodes may have numerous practical applications owing to high energy density without a necessary compromise on safety. SiO, which is an attractive Li insertion anode material, offers more cycling stability than Si and a higher capacity than graphite. Therefore, a new trend has emerged for developing composite C-Si anodes, possessing the excellent cyclability of graphite coupled with high capacity SiO. The composite structure described herein prevents the volume expansion of SiO and maintains the structural integrity during prolonged cycling. However, graphite electrodes suffer from exfoliation in propylene carbonate (PC) based electrolyte solutions, which avoids well known safety benefits related to a possible use of PC based electrolyte solutions in all kinds of Li batteries. Herein, it is reported that trifluoro propylene carbonate (TFPC) is compatible with graphite anodes. New electrolyte formulations are developed and tested containing fluorinated co-solvents and compared the performance of several electrolyte solutions, including conventional alkyl carbonates-based solutions in full Li-ion cells, which included LixSiO-Graphite anodes and LiNi0.89Co0.05Mn0.05Al0.01O2 (NCMA) cathodes. Cells with new electrolyte solutions developed herein demonstrated nearly twice capacity retention in prolonged cycling experiments compared to similar reference cells containing conventional electrolyte solutions.

Enantiomeric separation of nefopam and cathinone derivatives using a supramolecular deep eutectic solvent as a chiral selector in capillary electrophoresis.

The present study investigates the utilization of a supramolecular deep eutectic solvent (SUPRADES), consisting of sulfated-ß-cyclodextrin (S-ß-CD) and citric acid (CA), as a chiral selector (CS) in capillary electrophoresis for the enantiomeric separation of nefopam (NEF) and five cathinone derivatives (3-methylmethcathinone [3-MMC], 4-methylmethcathinone [4-MMC], 3,4-dimethylmethcathinone [3,4-DMMC], 4-methylethcathinone [4-MEC], and 3,4-methylendioxycathinone [MDMC]). A significant improvement in enantiomeric separation of the target analytes was observed upon the addition of S-ß-CD-CA to the background electrolyte (BGE), leading to a baseline separation of all analytes. In particular, the optimum percentage of S-ß-CD-CA, added to the BGE, was determined to be 0.075% v/v for NEF (Rs = 1.5) and 0.050% v/v for three out of five cathinone derivatives (Rs = 1.5, 1.6, and 2.4 for 3-MMC, 4-MEC, and 3,4-DMMC, respectively). In the case of 4-MMC and MDMC, a higher percentage of the CS, equal to 0.075% and 0.10% v/v, respectively, was required to achieve baseline separation (Rs = 1.5, 1.9 for MDMC and 4-MMC, respectively). The outcomes of the present study highlight the potential effectiveness of using SUPRADES as a CS in electrophoretic enantioseparations.

Switchable Deep Eutectic Solvents for Sustainable Sulfonamide Synthesis.

A sustainable and scalable protocol for synthesizing variously functionalized sulfonamides, from amines and sulfonyl chlorides, has been developed using environmentally responsible and reusable choline chloride (ChCl)-based deep eutectic solvents (DESs). In ChCl/glycerol (1 : 2 mol mol-1) and ChCl/urea (1 : 2 mol mol-1), these reactions yield up to 97 % under aerobic conditions at ambient temperature within 2-12 h. The practicality of the method is exemplified by the sustainable synthesis of an FFA4 agonist and a key building block en route to anti-Alzheimer drug BMS-299897. A subtle interplay of electronic effects and the solubility characteristics of the starting materials in the aforementioned DESs seem to be responsible for driving the reaction successfully over the hydrolysis of sulfonyl chlorides. The procedure's eco-friendliness is validated by quantitative metrics like the E-factor and the EcoScale, with products isolated by extraction or filtration after decantation.

Sustainable Electrolytes: Design Principles and Recent Advances.

Today, rechargeable batteries are omnipresent and essential for our existence. In order to improve the electrochemical performance of electric fields, the introduction of electrolytes with fluorine (F)-based inorganic elemental compositions is a direction of exploration. However, most fluorocarbons have a high global warming potential and ozone depletion potential, which do not meet the sustainability requirements of the battery industry. Therefore, developing sustainable electrolytes is a viable option for future battery development. Although researchers have made much progress in electrolyte optimization, little attention has been paid to developing low-toxic and safe electrolytes. This review aims to elucidate the design principles and recent advances in this direction for solvents and salts. It concludes with a summary and outlook on future research directions for the molecular design of green electrolytes for practical high-voltage rechargeable batteries.

Glycerol as Reaction Medium for Sonogashira Couplings: A Green Approach for the Synthesis of New Triarylamine-Based Materials with Potential Application in Optoelectronics.

This study focuses on the design, eco-friendly synthesis, and characterization of several novel three-legged triphenylamine derivatives. By performing Sonogashira couplings of functionalized aryl iodides with tris(4-ethynylphenyl)amine in glycerol, a readily available bio-derived solvent, we achieved the synthesis of target products in short times and high yields, up to 94 %, with consistently lower E-factors and reduced costs compared to standard conditions using toluene as the reaction medium. The target molecules possess a D-(π-A)3 or D-(π-D)3 structure, where an electron-donating core connects to three electron-donating (D) or electron-accepting (A) peripheral aromatic subunits through an acetylene spacer. Their main optical and electronic properties have been determined experimentally and by DFT simulations and suggest a possible implementation in energy conversion technologies such as luminescent solar concentrators (LSCs) and perovskite solar cells (PSCs).

Wittig Reaction in Deep Eutectic Solvents: Expanding the DES Toolbox in Synthesis.

Wittig reaction between substituted phosphonium salts and (hetero)aromatic and alkyl carbonyl compounds in Deep Eutectic Solvents has been developed under a scalable and friendly protocol. Highly efficient reactions were successfully run with a wide range of bases including organic (DBU, LiTMP, t-BuOK) and inorganic (NaOH, K2CO3) ones in ChCl/Gly 1 : 2 (mol/mol) as solvent under mild conditions, at room temperature and under air. The proposed protocol was applied to a wide range of substrates, including (hetero)aromatic aldehydes with substituents as halogens (I, Br, Cl), EDG (alkoxy, methyl), EWG (NO2, CF3) or reactive groups as CN, esters, and ketones. Vinylic, alkynyl and cycloalkyl, alicyclic and α,ß-unsaturated aldehydes can also be used. Highly electrophilic ketones gave good yields. The diastereoselectivity of the reaction is in complete agreement with the E/Z ratio predictable under traditional conditions. We demonstrated that the protocol is scalable to 2 g (5 mmol) of phosphonium salt, furthermore the proposed workup protocol allows to remove TPPO without need of additional chromatographic purification.

Binary and Ternary Deep Eutectic Solvents for Methylene Green Electropolymerization on Multiwalled Carbon Nanotubes: Optimization, Characterization and Application.

Choline chloride (ChCl) based binary and ternary deep eutectic solvents (DES) were evaluated for methylene green electropolymerization with oxalic acid (OA) and ethylene glycol (EG) as hydrogen bond donors. Binary DES ChCl : OA in molar ratios 1 : 1 and 2 : 1 and ChCl : EG 1 : 2 and ternary DES (tDES) in different molar ratios and percentages of water were evaluated. The highest polymer growth was in ChCl : OA : EG-tDES with 13% added water, that had a lower viscosity and higher ionic conductivity when associated with HCl as dopant. This enhanced the formation of more cation radicals and, consequently, more polymer formation. The PMG/MWCNT/GCE-tDES sensor was successfully applied to the simultaneous determination of 5-aminosalicylic acid (5-ASA) and acetaminophen (APAP) by differential pulse voltammetry in the concentration range 1 µM-200 µM, with detection limits of 0.37 µM and 0.49 µM for 5-ASA and APAP, respectively. The sensor demonstrated good repeatability, reproducibility and stability, and was successfully applied in pharmaceutical formulations.

On the solvation properties of menthol-thymol mixtures. A Molecular Dynamics Investigation.

Using classical molecular dynamics, we have investigated the solvation of catechol, resorcinol, hydroquinone and 1,4-benzoquinone at infinite dilution, in a series of menthol - thymol mixtures in which the molar fraction of thymol (xTHY) has been increased by steps of 0.1, from 0 (pure menthol) to 1 (pure thymol). The evolution of the solvation shell around the solutes reveals that when xTHY is increased, the average number of hydrogen bonds (HB) where the solute acts as HB acceptor (HBA) and the solvent as HB donor (HBD) increases, while the amount of HB, in which the solute acts as HBD and the solvent as HBA, decreases. Overall, the total number of HBs between the different benzenediols and the solvent decreases with an increase of xTHY, while for benzoquinone the total number of HB increases. This points to the fact that "acidic" or HBD molecules are better solvated in mixtures with high menthol proportion, while "basic" or HBA molecules, are better solvated in thymol rich mixtures. The results reported herein follow the same trends as experimentally reported Kamlet-Taft parameters and present insights on how the composition of these "deep eutectic" mixtures maybe tweaked in order to optimize their solvation properties.

Exploring Unconventional σ-Hole Interactions: Computational Insights into the Interaction of XeO3 with Non-Aromatic Coordinating Solvents.

In order to control the explosiveness and shock sensitivity of XeO3 , we have investigated its plausible interaction with various non-aromatic coordinating solvents, serving as potential Lewis base donors, through density functional theory (DFT) calculations. Out of twenty six such solvents, the top ten were thus identified and then thoroughly examined by employing various computational tools such as the mapping of the electrostatic potential surface (MESP), Wiberg bond indices (WBIs), non-covalent interaction (NCI) plots, Bader's theory of atoms-in-molecules (AIM), natural bond orbital (NBO) analysis, and the energy decomposition analysis (EDA). The amphoteric nature of XeO3 was also explored by investigating the extent of back donation from the lone pair of Xe to the antibonding orbital of the donating atom/group of the solvent molecules. The C-H…O interactions were also found to be a contributing factor in the stabilization of these adducts. Although these aerogen-bonding interactions were found to be predominantly electrostatic, significant contributions from the orbital contributions, as well as dispersion interactions, were observed. The top three non-aromatic solvents (among the twenty six studied) which form the strongest adducts with XeO3 are proposed to be hexamethylphosphoramide (HMPA), N,N'-dimethylpropyleneurea (DMPU) and tetramethylethylenediamine (TMEDA).

The Effect of Salts on the CO2 Reduction Product Distribution in an Aprotic Electrolyte.

Electrochemical CO2 reduction in non-aqueous solvents is promising due to the increased CO2 solubility of organic-based electrolytes compared to aqueous electrolytes. Here the effect of nine different salts in propylene carbonate (PC) on the CO2 reduction product distribution of polycrystalline Cu is investigated. Three different cations (tetraethylammonium (TEA), tetrabutylammonium (TBA), and tetrahexylammonium (THA)) and three different anions (chloride (Cl), tetrafluoroborate (BF4), and hexafluorophosphate (PF6)) were used. Chronoamperometry and in-situ FTIR measurements show that the size of the cation has a crucial role in the selectivity. A more hydrophobic surface is obtained when employing a larger cation with a weaker hydration shell. This stabilizes the CO2-· radical and promotes the formation of ethylene. CO2 reduction in 0.7 M THACl/PC shows the highest hydrocarbon formation. Lastly, we hypothesize that the hydrocarbon formation pathway is not through C-C coupling, as the CO solubility in PC is very high, but through the dimerization of the COH intermediate.

Tunable Properties of Non-Volatile Magnetic Mixtures on Different Surfaces.

In this work, the surface nature-dependent behaviors of magnetic deep eutectic solvents (MDESs) and magnetic low-transition-temperature non-volatile mixtures (MLTTMs) are reported for the first time. It has been observed that the surface of the material where the MDES or the MLTTM is placed could considerably affect the dispersion and the magnetic and structural properties of these magnetic mixtures. Different techniques and analyses have been carried out to highlight the differences observed in the properties depending on the material on which these magnetic mixtures are placed. To that end, differential scanning calorimetry (DSC), surface tension, contact angle and scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX) measurements have been performed. As a result, it has been shown that the MDESs or MLTTMs are retained and adhered to glass surfaces, resulting in a loss of magnetism of the mixture in addition to a loss in the performance of synthesis carried out on the closeness of glass materials as the interaction between the glass and the mixture modify the composition and therefore the properties. As a preliminary result, when using these magnetic mixtures as extractant solvents in dispersive liquid-liquid microextraction, the MDES or MLTTM is retained on the walls of the glass tubes reducing the extraction efficiency, repeatability and the extraction recovery using an external magnetic field. For all these reasons, polypropylene materials should be recommended when handling magnetic deep eutectic solvents and non-volatile MLTTMs.

Genomic insights into clostridia in bioenergy production: Comparison of metabolic capabilities and evolutionary relationships.

Bacteria from diverse genera, including Acetivibrio, Bacillus, Cellulosilyticum, Clostridium, Desulfotomaculum, Lachnoclostridium, Moorella, Ruminiclostridium, and Thermoanaerobacterium, have attracted significant attention due to their versatile metabolic capabilities encompassing acetogenic, cellulolytic, and C1-metabolic properties, and acetone-butanol-ethanol fermentation. Despite their biotechnological significance, a comprehensive understanding of clostridial physiology and evolution has remained elusive. This study reports an extensive comparative genomic analysis of 48 fully sequenced bacterial genomes from these genera. Our investigation, encompassing pan-genomic analysis, central carbon metabolism comparison, exploration of general genome features, and in-depth scrutiny of Cluster of Orthologous Groups genes, has established a holistic whole-genome-based phylogenetic framework. We have classified these strains into acetogenic, butanol-producing, cellulolytic, CO2-fixating, chemo(litho/organo)trophic, and heterotrophic categories, often exhibiting overlaps. Key outcomes include the identification of misclassified species and the revelation of insights into metabolic features, energy conservation, substrate utilization, stress responses, and regulatory mechanisms. These findings can provide guidance for the development of efficient microbial systems for sustainable bioenergy production. Furthermore, by addressing fundamental questions regarding genetic relationships, conserved genomic features, pivotal enzymes, and essential genes, this study has also contributed to our comprehension of clostridial biology, evolution, and their shared metabolic potential.

Menthol-Based (Deep) Eutectic Solvents: A Review on Properties and Application in Extraction.

In the last 10 years the interest in deep eutectic solvents (DESs) as a new class of green solvents has considerably increased. The emergence of numerous of hydrophobic DESs has stimulated intensive research into their application in extraction technologies, including sample preparation. As the properties of such systems are highly dependent on the properties of their components (hydrogen bond donors and acceptors) and can be finely tuned, DESs can be successfully used for the extraction of both metal ions and organic substances, including biomolecules. Despite the rapidly increasing number of publications on the use of DESs as an extraction medium, including review articles, information on the extraction properties of DESs in terms of their chemical composition has not yet been summarized. This review covers available literature data on the physicochemical properties of menthol-based eutectic solvents and the results of their practical application as an extraction medium. Also, the appropriateness of using the term "DES" for all mixtures with melting points lower than the melting points of their components is discussed.

Role of Nitrogenous Functional Group Identity in Accelerating 1,2,3-Trichloropropane Degradation by Pyrogenic Carbonaceous Matter (PCM) and Sulfide Using PCM-like Polymers.

Groundwater contamination by 1,2,3-trichloropropane (TCP) poses a unique challenge due to its human toxicity and recalcitrance to degradation. Previous work suggests that nitrogenous functional groups of pyrogenic carbonaceous matter (PCM), such as biochar, are important in accelerating contaminant dechlorination by sulfide. However, the reaction mechanism is unclear due, in part, to PCM's structural complexity. Herein, PCM-like polymers (PLPs) with controlled placement of nitrogenous functional groups [i.e., quaternary ammonium (QA), pyridine, and pyridinium cations (py+)] were employed as model systems to investigate PCM-enhanced TCP degradation by sulfide. Our results suggest that both PLP-QA and PLP-py+ were highly effective in facilitating TCP dechlorination by sulfide with half-lives of 16.91 ± 1.17 and 0.98 ± 0.15 days, respectively, and the reactivity increased with surface nitrogenous group density. A two-step process was proposed for TCP dechlorination, which is initiated by reductive ß-elimination, followed by nucleophilic substitution by surface-bound sulfur nucleophiles. The TCP degradation kinetics were not significantly affected by cocontaminants (i.e., 1,1,1-trichloroethane or trichloroethylene), but were slowed by natural organic matter. Our results show that PLPs containing certain nitrogen functional groups can facilitate the rapid and complete degradation of TCP by sulfide, suggesting that similarly functionalized PCM might form the basis for a novel process for the remediation of TCP-contaminated groundwater.