Search Results (25)

The enrichment of ⁶Li isotopes from a natural stage of 7.6% to above 59% is required for the development of next-generation green technologies capable of sustaining climate change mitigation and energy-mix targets. In this study, we developed two categories of custom laboratory-made organic membranes, membranes that were non-impregnated before electromigration (AI-1) and membranes impregnated with LiNTf₂ (AI-2), to evaluate their performance in lithium isotope separation. Both types of membranes were exposed in synthesis to ionic liquid and crown ether. The objective of the study was to test the performance of membranes in separating lithium isotopes from a lithium-loaded organic phase in an aqueous solution with variable potentials and time intervals. The results show that the impregnated AI-2 membranes increased the enrichment of ⁶Li in the early stages, and the effect decreased after 25 h. The efficiency of lithium isotope enrichment was positively related to the potential profile applied, migration time, and concentration of organic solution in the anode chamber. The 0.5 mol/L Bis-(trifluoromethane) sulfonimide lithium salt (Li[NTf₂]) with 0.1 M tetra butyl ammonium perchlorate (TBAP) in acetonitrile (CH₃CN) ionic solution significantly improved Li isotope separation compared with an aqueous environment with higher salt concentrations. The maximum isotopic separation coefficient (α) for AI-1.2 (15-crown-5 ether and 1 mol/L LiNTf₂ in TBAP solution after 48 h of electromigration) gradually increased to 1.0317. Our results demonstrated that in the laboratory-made setup described, the migration efficiency and Li isotope separation in the catholyte environment needed a minimum of 9 V and a migration time of 6 h, respectively; these values varied with the concentration of the organic solution in the anode chamber. The ability of laboratory-engineered membranes to impart isotope selectivity and enhance permselectivity or selectivity towards singly charged ions was demonstrated through the functionality of single-collector inductively coupled plasma mass spectrometry (ICP-MS). This technology is particularly valuable and commercially feasible for future lithium isotope research in nuclear technology. Full article

Four non-fluorinated sulfonimide polyamides (s-PAs) were successfully synthesized and a series of membranes were prepared by blending s-PA with polyvinylidene fluoride (PVDF) to achieve high-methanol-permeation resistivity for direct methanol fuel cell (DMFC) applications. Four membranes were fabricated by blending 50 wt% PVDF with s-PA, named BPD-101, BPD-102, BPD-111 and BPD-211, respectively. The s-PA/PVDF membranes exhibit high methanol resistivity, especially for the BPD-111 membrane with methanol resistivity of 8.13 × 10⁻⁷ cm²/s, which is one order of magnitude smaller than that of the Nafion 117 membrane. The tensile strength of the BPD-111 membrane is 15 MPa, comparable to that of the Nafion 117 membrane. Moreover, the four membranes also show good thermal stability up to 230 °C. The BPD-x membrane exhibits good oxidative stability, and the measured residual weights of the BPD-111 membrane are 97% and 93% after treating in Fenton’s reagent (80 °C) for 1 h and 24 h, respectively. By considering the mechanical, thermal and dimensional properties, the polyamide proton-exchange membrane exhibits promising application potential for direct methanol fuel cells. Full article

This work introduces the synthesis of hybrid polymer electrolytes based on polyethylene oxide (PEO) and electrolyte solution bis(trifluoromethane)sulfonimide lithium salt/ionic liquid 1-ethyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide (LiTFSI/EMIMTFSI) with in situ produced and dispersed silica particles by the sol–gel method. Conventional preparation of solid polymer electrolytes was followed by desolvation of lithium salt in a polymer matrix of PEO, which, in some cases, additionally contains plasticizers. This one-pot synthesis is an alternative route for fabricating a solid polymer electrolyte for solid-state batteries. The presence of TFSI- reduces the crystallinity of the PEO matrix (plasticizing effect), increases the dissociation and solubility of LiTFSI in the PEO matrix because of a highly delocalized charge distribution, and reveals excellent thermal, chemical, and electrochemical stability. Tetraethylorthosilicate (TEOS) was chosen due to the slow reaction rate, with the addition of (3-glycidyoxypropyl)trimethoxysilane (GLYMO), which contributes to the formation of a silica network. FTIR studies confirmed the interactions between the silica, the polymer salt, and EMIMTFSI. Impedance spectroscopy measurements were performed in a wide range of temperatures from 25 to 70 °C. The electrochemical performance was explored by assembling electrolytes in LiCoO₂ (LCO), NMC(811), and LiFePO₄ (LFP) coin half-cells. The HPEf15 shows a discharge capacity of 143 mA/g for NMC(811) at 0.1 C, 134 mA/g for LCO, and 139 mA/g for LFP half-cells at 0.1 C and 55 °C. The LFP half-cell with a discharge capacity of 135 mA/g at 0.1 C (safety potential range of 2.8 to 3.8) obtained a cyclability of 97.5% at 55 °C after 100 cycles. Such a type of electrolyte with high safety and good electrochemical performance provides a potential approach for developing a safer lithium-ion battery. Full article

The cold sintering process (CSP) for synthesizing oxide-based electrolytes, which uses water transient solvents and uniaxial pressure, is a promising alternative to the conventional high temperature sintering process due to its low temperature (<200 °C) and short processing time (<2 h). However, the formation of amorphous secondary phases in the intergranular regions, which results in poor ionic conductivity (σ), remains a challenge. In this study, we introduced high-boiling solvents of dimethylformamide (DMF, b.p.: 153 °C) and dimethyl sulfoxide (DMSO, b.p.: 189 °C) as transient solvents to develop composite electrolytes of Li₁.₅Al₀.₅Ge₁.₅(PO₄)₃ (LAGP) with bis(trifluoromethane)sulfonimide lithium salt (LiTFSI). Our results show that composite electrolytes processed with the DMF/water mixture (CSP LAGP-LiTFSI DMF/H₂O) yield a high σ of 10⁻⁴ S cm⁻¹ at room temperature and high relative densities of >87%. Furthermore, the composite electrolytes exhibit good thermal stability; the σ maintains its initial value after heat treatment. In contrast, the composite electrolytes processed with the DMSO/water mixture and water alone show thermal degradation. The CSP LAGP-LiTFSI DMF/H₂O composite electrolytes exhibit long-term stability, showing no signs of short circuiting after 350 h at 0.1 mAh cm⁻² in Li symmetric cells. Our work highlights the importance of selecting appropriate transient solvents for producing efficient and stable composite electrolytes using CSP. Full article

The NF-E2-related factor 2 transcription factor (Nrf2) orchestrates the basal and stress-inducible activation of a vast array of antioxidant genes. A high amount of reactive oxygen species (ROS) promotes carcinogenesis in cells with defective redox-sensitive signaling factors such as Nrf2. In breast cancer (BC), emerging evidence indicates that increased Nrf2 activity enhances cell metastatic potential. An interconnection between peroxisome proliferator-activated receptors (PPARs) and Nrf2 pathways in cancer has been shown. In this light, newly synthesized PPARα antagonists, namely IB42, IB44, and IB66, were tested in the BC cell line MCF7 in parallel with GW6471 as the reference compound. Our results show that the most promising compound of this phenylsulfonimide series (IB66) is able to decrease MCF7 proliferation by blocking cells at the G2/M checkpoint. The underlying mechanism has been investigated, disclosing a caspase 3/Akt-dependent apoptotic/pyroptotic pathway induced by the increased generation of oxidative stress. Moreover, the involvement of Nrf2 and COX2 in IB66-treated MCF7 cell response has been highlighted. The reported data lay the groundwork for the development of alternative targeted therapy involving the Nrf2/PPARα molecular axis, able to overcome BC cell chemoresistance and cause better clinical outcomes, promoting other forms of programmed cell death, such as pyroptosis. Full article

(1R,2S,5R)-2-isopropyl-5-methylcyclohexyl (R)-4-methylbenzenesulfonimidate was synthesized via the stereoselective NH-transfer to (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl (S)-4-methylbenzenesulfinate. The reaction employed diacetoxyiodobenzene (DIB) and ammonium carbamate, and occurred in acetonitrile at room temperature. The imidation of sulfur proceeded with complete stereocontrol, and the reaction afforded the desired product as a single diastereoisomer and with high enantiocontrol (e.r. = 97:3) in 70% yield. The product was characterized by ¹H-NMR, ¹³C-NMR, COSY, HSQC, IR spectroscopy, HRMS, and the enantiomeric ratio was established by HPLC analysis at the chiral stationary phase. Full article

A solid-state polymer electrolyte membrane is formed by blending poly(vinylidene fluoride-co-hexafluoropropylene) with the synthesized copolymer of poly(methyl methacrylate-co-1-vinyl-3-butyl-imidazolium bis(trifluoromethanesulfonyl)imide, in which lithium bis(trifluoromethane)sulfonimide molecules are applied as the source of lithium ions. The accordingly formed membrane that contains 14 wt.% of P(MMA-co-VBIm-TFSI), 56 wt.% of PVDF-HFP, and 30 wt.% of LiTFSI manifests the best electrochemical properties, achieving an ionic conductivity of 1.11 × 10⁻⁴ S·cm⁻¹ at 30 °C and 4.26 × 10⁻⁴ S·cm⁻¹ at 80 °C, a Li-ion transference number of 0.36, and a wide electrochemical stability window of 4.7 V (vs. Li/Li⁺). The thus-assembled all-solid-state lithium-ion battery of LiFePO₄/SPE/Li delivers a discharge specific capacity of 148 mAh·g⁻¹ in the initial charge–discharge cycle at 0.1 C under 60 °C. The capacity retention of the cell is 95.2% after 50 cycles at 0.1 C and the Coulombic efficiency remains close to 100% during the cycling process. Full article

Structure, and consequently properties, of ionic liquids can be easily tailored by changing cation/anion combinations and/or attaching functional groups. By grafting enantiopure moieties to the framework of ionic liquid it is possible to prepare bioinspired chiral molecules that can serve as a reaction medium, additive or even asymmetric catalyst. In this context, new chiral ionic liquids (CILs), based on biomolecules, such as aminoacids (l-Cysteine derivatives), have been synthesised and tested in asymmetric aldol condensation of aldehydes and ketones. The best results were obtained for CILs composed of S-methyl-l-cysteine cation and bis(trifluoromethane)sulfonimide anion, in the reaction of 2- or 4-nitrobenzaldehyde with acetone or cyclohexanone, giving the aldol product in moderate yields 70–76% and high ee values (up to 96%). Full article

The synthesis and characterization of a new class of 1,2,4-oxadiazolylpyridinium as a cationic scaffold for fluorinated ionic liquid crystals is herein described. A series of 12 fluorinated heterocyclic salts based on a 1,2,4-oxadiazole moiety, connected through its C(5) or C(3) to an N-alkylpyridinium unit and a perfluoroheptyl chain, differing in the length of the alkyl chain and counterions, has been synthesized. As counterions iodide, bromide and bis(trifluoromethane)sulfonimide have been considered. The synthesis, structure, and liquid crystalline properties of these compounds are discussed on the basis of the tuned structural variables. The thermotropic properties of this series of salts have been investigated by differential scanning calorimetry and polarized optical microscopy. The results showed the existence of an enantiotropic mesomorphic smectic liquid crystalline phase for six bis(trifluoromethane)sulfonimide salts. Full article

Polymerized ionic liquids (PILs) are interesting new materials in sustainable technologies for energy storage and for gas sensor devices, and they provide high ion conductivity as solid polymer electrolytes in batteries. We introduce here the effect of polar protic (aqueous) and polar aprotic (propylene carbonate, PC) electrolytes, with the same concentration of lithium bis(trifluoromethane) sulfonimide (LiTFSI) on hydrophobic PIL films. Cyclic voltammetry, scanning ionic conductance microscopy and square wave voltammetry were performed, revealing that the PIL films had better electroactivity in the aqueous electrolyte and three times higher ion conductivity was obtained from electrochemical impedance spectroscopy measurements. Their energy storage capability was investigated with chronopotentiometric measurements, and it revealed 1.6 times higher specific capacitance in the aqueous electrolyte as well as novel sensor properties regarding the applied solvents. The PIL films were characterized with scanning electron microscopy, energy dispersive X-ray, FTIR and solid state nuclear magnetic resonance spectroscopy. Full article

Improved proton conductivity and high durability are now a high concern for proton exchange membranes (PEMs). Therefore, highly proton conductive PEMs have been synthesized from branched sulfonimide-based poly(phenylenebenzophenone) (SI-branched PPBP) with excellent thermal and chemical stability. The branched polyphenylene-based carbon-carbon backbones of the SI-branched PPBP membranes were attained from the 1,4-dichloro-2,5-diphenylenebenzophenone (PBP) monomer using 1,3,5-trichlorobenzene as a branching agent (0.1%) via the Ni-Zn catalyzed C-C coupling reaction. The as-synthesized SI-branched PPBP membranes showed 1.00~1.86 meq./g ion exchange capacity (IEC) with unique dimensional stability. The sulfonimide groups of the SI-branched PPBP membranes had improved proton conductivity (75.9–121.88 mS/cm) compared to Nafion 117 (84.74 mS/cm). Oxidation stability by thermogravimetric analysis (TGA) and Fenton’s test study confirmed the significant properties of the SI-branched PPBP membranes. Additionally, a very distinct microphase separation between the hydrophobic and hydrophilic moieties was observed using atomic force microscopic (AFM) analysis. The properties of the synthesized SI-branched PPBP membranes demonstrate their viability as an alternative PEM material. Full article

There are more than 50 families of dendrimers, and some of which, such as polyamidoamine PAMAM, are well studied, and some are just starting to attract the attention of researchers. One promising type of dendrimers is sulfonimide-based dendrimers (SBDs). To date, SBDs are used in organic synthesis as starting reagents for the convergent synthesis of higher generations dendrimers, in materials science as alternative electrolyte solutions for fuel cells, and in medicinal chemistry as potential substances for drug transfer procedures. Despite the fact that most dendrimers are amorphous substances among the SBDs, several structures are distinguished that are prone to the formation of crystalline solids with melting points in the range of 120–250 °C. Similar to those of other dendrimers, the chemical and physical properties of SBDs depend on their outer shell, which is formed by functional groups. To date, SBDs decorated with end groups such as naphthyl, nitro, methyl, and methoxy have been successfully synthesized, and each of these groups gives the dendrimers specific properties. Analysis of the structure of SBD, their synthesis methods, and applications currently available in the literature reveals that these dendrimers have not yet been fully explored. Full article

In this work, we investigate the effect of the cation structure on the structure and dynamics of the electrode–electrolyte interface using molecular dynamics simulations. A constant potential method is used to capture the behaviour of 1-ethyl-3-methylimidazolium bis (trifluoromethane)sulfonimide ([C${}_2$mim][NTf${}_2$]) and butyltrimethylammonium bis(trifluoromethane) sulfonimide ([N${}_{4,1,1,1}$][NTf${}_2$]) ionic liquids at varying potential differences applied across the supercapacitor. We find that the details of the structure in the electric double layer and the dynamics differ significantly, yet the charge profile and capacitance do not vary greatly. For the systems considered, charging results in the rearrangement and reorientation of ions within ∼1 nm of the electrode rather than the diffusion of ions to/from the bulk region. This occurs on timescales of $\mathcal{O}$(10 ns) for the ionic liquids considered, and depends on the viscosity of the fluid. Full article

This study presents the synthesis of a novel asymmetric 1,3-di(alkoxy)imidazolium based room temperature ionic liquid, more precisely 1-butoxy-3-ethoxy-2-ethyl-imidazolium bis(trifluoromethane)sulfonimide, and its application as an extraction solvent in liquid-phase microextraction of cannabidiol from natural cosmetics. Quantification was implemented, using a high performance liquid chromatography system coupled to ultraviolet detection. Molecular structure elucidation was performed by nuclear magnetic resonance spectroscopy. The extraction procedure was optimized by means of two different design of experiments. Additionally, a full validation was executed. The established calibration model, ranging from 0.6 to 6.0 mg g⁻¹, was linear with a coefficient of determination of 0.9993. Accuracy and precision were demonstrated on four consecutive days with a bias within −2.6 to 2.3% and a maximum relative standard deviation value of 2.5%. Recoveries, tested for low and high concentration within the calibration range, were 80%. Stability of extracted cannabidiol was proven for three days at room temperature and fourteen days at 4 °C and −20 °C. An autosampler stability for 24 h was validated. Liquid-phase microextraction of cannabidiol from different formulated cream based cosmetics was performed, including four ointments and four creams. The results show that a significantly higher selectivity could be achieved compared to a conventional extraction methods with methanol. Full article

Iodonium salts are well established photoacid generators, cationic photoinitiators, as well as additives commonly used in photoredox catalytic cycles. However, as a strong limitation, iodonium salts are characterized by low light absorption properties for λ > 300 nm so that these latter cannot be activated with cheap, safe, and eco-friendly near UV or even visible light emitting diodes (LEDs). To overcome this drawback, the covalent linkage of an iodonium salt to a chromophore absorbing at longer wavelength is actively researched. With aim at red-shifting the absorption spectrum of the iodonium salt, the synthesis of new compounds combining within a unique chemical structure both the chromophore (here the naphthalimide scaffold) and the iodonium salt is presented. By mean of this strategy, a polymerization could be initiated at 365 nm with the modified iodonium salts whereas no polymerization could be induced with the benchmark iodonium salt i.e., Speedcure 938 at this specific wavelength. To examine the effect of the counter-anion on the photoinitiating ability of these different salts, five different counter-anions were used. Comparison between the different anions revealed the bis(trifluoromethane)sulfonimide salt to exhibit the best photoinitiating ability in both the free radical polymerization of acrylates and the cationic polymerization of epoxides. To support the experimental results, molecular orbital calculations have been carried out. By theoretical calculations, the initiating species resulting from the photocleavage of the iodonium salts could be determined. The cleavage selectivity and the photochemical reactivity of the new iodoniums are also discussed. Full article