Search Results (211)

We hypothesized that compounds containing ether linkages within their backbone structures, when exposed to hydroxyl radicals (•OH), can generate ultra-weak photon emission (UPE) as a result of the formation of triplet excited carbonyl species (³R=O*). To evaluate this hypothesis, we investigated the UPE of four compounds, each at a final concentration of 185.2 µmol/L: EGTA (ethylene glycol-bis(β-aminoethyl ether)-N,N,N′,N′-tetraacetic acid), a potent chelator of divalent cations, and three crown ethers—12-crown-4, 15-crown-5, and 18-crown-6—containing two, four, five, and six ether bonds, respectively. •OH was generated using a modified Fenton reagent—92.6 µmol/L Fe²⁺ and 2.6 mmol/L H₂O₂. The highest UPE was recorded for the Fe²⁺–EGTA–H₂O₂ (2863 ± 158 RLU; relative light units), followed by 18-crown-6, 15-crown-5, and 12-crown-4 (1161 ± 78, 615± 86, and 579 ± 109 RLU, respectively; p < 0.05), corresponding to the number of ether groups present. Controls lacking either H₂O₂ or Fe²⁺ exhibited no significant light emission compared to the buffer medium. These findings support the hypothesis that ether bonds, when oxidatively attacked by •OH, undergo chemical transformations resulting in the formation of ³R=O* species, the decay of which is associated with UPE. In crown ethers exposed to Fe²⁺-H₂O₂, the intensity of UPE was correlated with the number of ether bonds in their structure. Full article

This review surveys recent advances and emerging prospects in phase-transfer catalysis (PTC) for fuel desulfurization. In response to increasingly stringent environmental regulations, the removal of sulfur from transportation fuels has become imperative for curbing SO_x emissions. Conventional hydrodesulfurization (HDS) operates under severe temperature–pressure conditions and displays limited efficacy toward sterically hindered thiophenic compounds, motivating the exploration of non-hydrogen routes such as oxidative desulfurization (ODS). Within ODS, PTC offers distinctive benefits by shuttling reactants across immiscible phases, thereby enhancing reaction rates and selectivity. In particular, PTC enables efficient migration of organosulfur substrates from the hydrocarbon matrix into an aqueous phase where they are oxidized and subsequently extracted. The review first summarizes the deployment of classic PTC systems—quaternary ammonium salts, crown ethers, and related agents—in ODS operations and then delineates the underlying phase-transfer mechanisms, encompassing reaction-controlled, thermally triggered, photo-responsive, and pH-sensitive cycles. Attention is next directed to a new generation of catalysts, including quaternary-ammonium polyoxometalates, imidazolium-substituted polyoxometalates, and ionic-liquid-based hybrids. Their tailored architectures, catalytic performance, and mechanistic attributes are analyzed comprehensively. By incorporating multifunctional supports or rational structural modifications, these systems deliver superior desulfurization efficiency, product selectivity, and recyclability. Despite such progress, commercial deployment is hindered by the following outstanding issues: long-term catalyst durability, continuous-flow reactor design, and full life-cycle cost optimization. Future research should, therefore, focus on elucidating structure–performance relationships, translating batch protocols into robust continuous processes, and performing rigorous environmental and techno-economic assessments to accelerate the industrial adoption of PTC-enabled desulfurization. Full article

Aza-crown ether structures have been proven to be effective in constructing fluorescent biosensors for selectively detecting and imaging alkali metal ions in biological environments. However, choosing the right aza-crown ether for a specific alkali metal ion remains challenging for synthetic chemists because theoretical guidance on the chelating activities between aza-crown ethers and alkali metal ions has not been available up to now. Predicting the physical properties of the chelator–metal complexations poses a greater challenge due to the numerous quantum mechanical functionals and basis sets to be used in any theoretical investigation. In this study, we report a theoretical investigation of different aza-crown ether structures and their selectivities to alkali metal ions via a novel relationship between the binding energy and charge transfer calculated using twelve different quantum mechanical methods, using a myriad of bases, within the Jacob’s Ladder of Chemical Accuracies. Furthermore, this report represents a guide for the synthetic chemist in the selection of aza-crown ethers in the capturing of specific alkali metal ions, primary objectives, while benchmarking different quantum mechanical calculations, as a secondary objective. Full article

The growing energy demand has emphasized the importance of developing nuclear technologies and high-purity lithium isotopes (⁶Li and ⁷Li) as raw materials. This study investigates how voltage and migration time affect two types of low-density polyethylene membranes—one impregnated with ionic liquids and the other non-impregnated—for lithium isotope separation via electromigration from a lithium-loaded organic phase to an aqueous solution. We developed a laboratory-made setup for high-precision lithium isotope measurements (2RSD = ±0.30‰) of natural carbonate samples (LSVEC) and an optimized protocol for isotope ratio measurements using quadrupole ICP-MS with the sample-standard bracketing method (SSB). The results document that both impregnated and non-impregnated membranes can achieve promising ⁶Li enrichment under different environmental conditions, including ionic liquids and organic solutions in the cathode chamber. Lithium-ion mobility is influenced by voltage in an environment assisted by 0.1 mol/L tetrabutylammonium perchlorate and increases quasi-linearly from 5 to 15 V. Between 20 and 25 h, the lithium-ion concentration had the maximum value, after which the trend declined. In the BayesGLM model, we incorporated all data and systematically eliminated those with a low enrichment factor, either individually or in groups. Our findings indicated that the model was not significantly affected by the exclusion of measurements with low α. This suggests that voltage and migration time are crucial, and achieving a better enrichment factor depends on applying the optimal ratio of ionic liquids, crown ethers, and organic solvents. Ionic liquids used for impregnation sustain enrichment in the first hours, particularly for ⁷Li; however, after 25 h, ⁶Li demonstrated a higher enrichment capacity. The maximum single-stage separation factor for ⁶Li/⁷Li was achieved at 24 and 48 h for an impregnated membrane M2 (α = 1.021/1.029) and a non-impregnated membrane M5 (α = 1.031/1.038). Full article

This study demonstrates an eco-friendly synthesis of trifluoromethanesulfonyl fluoride (TFSF) as a sustainable SF₆ alternative. Optimized halogen exchange reactions using CF₃SO₂Cl/KF (3:1 ratio) with crown ether catalysis at low temperatures achieved 65% TFSF yield (97.9% purity). Scale-up trials in pressurized reactors showed >50% conversion and >90% selectivity. Acute inhalation tests (OECD standards) on Sprague-Dawley rats revealed transient toxicity at 20,000 ppm (4 h exposure), with survival rates >66% and LC₅₀ exceeding 22,600 ppm—significantly safer than SF₆. These findings confirm TFSF’s technical viability and low toxicity, positioning it as a practical insulating medium to curb SF₆ emissions. The methodology highlights precision halogen exchange control and systematic safety validation, offering actionable solutions for industrial adoption. Full article

Crown ethers have gained importance in the field of medicine because of their resemblance to natural ionophores like valinomycin. With the goal of developing new pharmacologically important crown ethers, a novel series of crown ethers linked with Fusidic acid butyl ester 10a–d were synthesized and characterized by means of their ¹H NMR, ¹³C NMR DEPT-135, FT-IR, and mass spectrometry. In vitro antioxidant and α-glucosidase inhibition activities of all crown ethers along with the precursor Fusidic acid butyl ester were examined and compared to the standard butylated hydroxyanisole and acarbose, respectively. Compounds (FABE-16-crown-4) 10b and (FABE-19-crown-5) 10c showed high antioxidant potential with the IC₅₀ = 22.5 ± 0.2 μM and 32.1 ± 0.3 μM, respectively, when compared to the standard BHA (IC₅₀ = 44.2 ± 0.34 μM). To understand the binding mode of the compounds, molecular docking investigations were performed using human antioxidant protein, peroxiredoxin 5. Molecular docking studies revealed higher docking scores (−6.5 and −6.7 kcal/mol) for the highly active compounds 10c and 10b, respectively, than standard BHA (−5.3 kcal/mol). Synthesized crown ethers exhibited moderate α-glucosidase inhibition with (IC₅₀ = 23.5 ± 0.2 to 76.5 ± 0.1 μM) when compared to acarbose as standard (IC₅₀ = 5.2 ± 0.8 μM). The in silico ADMET predictions indicated that the prepared compounds obeyed (bRO5) and Veber’s rule for the acceptance as orally administered drugs and indicated that all the prepared crown ethers exhibited calculated values of drug likeness parameters in acceptable ranges that showed good potential of these molecules for further drug development investigations. Full article

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

We study the structures of 24-crown-8/H⁺/diaminopropanol (CR/DAPH⁺) and 24-crown-8/CsF/H⁺/diaminopropanol (CR/CsF/DAPH⁺) non-covalent host–guest complexes in both the gas phase and aqueous solution using the density functional theory (DFT) method. We examine the environment (complexation with CR vs. solvation) around the guest functional groups (ammoium, hydroxyl, and amino) in the CR/DAPH⁺ and CR/CsF/DAPH⁺ complexes. We find that the gas-phase configurations with the ‘naked’ hydroxyl/amino devoid of H-bonding with CR or CR/CsF are structurally correlated with the lowest Gibbs free energy conformers in aqueous solution in which the functional groups are solvated off the CR or CR/CsF host. We predict that the latter thermodynamically disadvantageous host–guest configurations would be identified in the gas phase by infrared multiphoton dissociation (IRMPD) spectroscopy, originating from the complexes in aqueous solution. This predicted ‘thermodynamic reversal’ and ‘structural correlation’ of the host–guest configurations in the gas phase vs. in solution are discussed in relation to the possibility of obtaining information on host–guest–solvent interactions in the solution phase from the gas-phase host–guest configurations. Full article

Herein, we present hybrid crown ether ligands with siloxane and ethylene oxide units and their coordination with the cations Li⁺, Na⁺, Mg²⁺ and Ca²⁺. The compounds prepared are (SiMe₂O)₂(C₂H₄O)₃ (1, TrEGDS = Triethylenglycoldisiloxane) and (SiMe₂O)₂(C₂H₄O)₄ (2, TeEGDS = Tetraethylenglycoldisiloxane)), as well as the metal complexes [Li(TrEGDS][GaI₄] (3), [Na(TeEGDS)][GaI₄] (4), [Mg(TrEGDS)][GaI₄]₂ (5) and [Ca(TeEGDS)][GaI₄]₂ (6). Single-crystal X-ray diffraction was used to study the prepared complexes and coordination modes in the solid state. Full article

Background/Objectives: Crown ethers have received increasing interest owing to their ability to form stable complexes with cations. This molecular feature has been successfully exploited in the development of biologically relevant ionophores. Methods: In order to obtain innovative crown ethers derivatives, a Morita–Baylis–Hillman adduct (MBHA) acetate (4) bearing a phenylacetylene moiety was dimerized via the click-chemistry CuAAC reaction with oligo(ethylene glycol) diazide derivatives to build-up a small series of dimeric MBHA derivatives (5a-d). These dimeric MBHA derivatives were reacted with n-butylamine to afford tunable macrocyclic crown ether-paracyclophane hybrid architectures (6a-d). Results: Compounds (E,Z)-6a, (E,E)-6a, 6b-d showed, in human breast cancer MDA-MB-231 and human melanoma A375 cells, IC₅₀ values comparable with those of reference anticancer agent Doxorubicin. Conclusions: This exploration approach provides original new macrocyclic architectures potentially useful as anticancer agents. Full article

Several D-amino acid residue-containing peptides (DAACPs) with antimicrobial, cardio-excitatory, and neuronal activities have been identified in various species. The L-Asn-D-Trp-L-Phe-NH₂ (N(dW)F) tripeptide, derived from Aplysia kurodai, exhibits cardiac activity in invertebrates. The chirality of the tryptophan residue at the second position in N(dW)F influences its conformation and biological characteristics. We demonstrated the chiral separation of N(dW)F and its diastereomer NWF using (S)-3,3′-diphenyl-1,1′-binaphthyl-20-crown-6-ether columns (CR-I(+)). A reduction in the ratio of acetonitrile and methanol in the mobile phase allowed the complete separation of N(dW)F and its diastereomer, improving the separation factor (α) from 0.96 to 6.28. Molecular dynamics simulations revealed that the interaction of N(dW)F with CR-I(−) was more favorable than with CR-I(+). These findings indicate that the structure of the CR-I column stereoselectively recognizes peptides and facilitates the separation of naturally occurring D-amino acid residue-containing tripeptides. Full article

The large-scale application of aromatic polyamide (PA) thin-film composite (TFC) membranes for reverse osmosis has provided an effective way to address worldwide water scarcity. However, the water permeability and salt rejection capabilities of the PA membrane remain limited. In this work, cyclic micropores based on crown ether were introduced into the PA layer using a layer-by-layer interfacial polymerization (LbL-IP) method. After interfacial polymerization between m-phenylenediamine (MPD) and trimesoyl chloride (TMC), the di(aminobenzo)-18-crown-6 (DAB18C6) solution in methanol was poured on the membrane to react with the residual TMC. The cyclic micropores of DAB18C6 provided the membrane with rapid water transport channels and improved ion rejection due to its hydrophilicity and size sieving effect. The membranes were characterized by FTIR, XPS, SEM, and AFM. Compared to unmodified membranes, the water contact angle decreased from 54.1° to 31.6° indicating better hydrophilicity. Moreover, the crown ether-modified membrane exhibited both higher permeability and enhanced rejection performance. The permeability of the crown ether-modified membrane was more than ten times higher than unmodified membranes with a rejection above 95% for Na₂SO₄, MgSO₄, MgCl_2, and NaCl solution. These results highlight the potential of this straightforward surface grafting strategy and the modified membranes for advanced water treatment technologies, particularly in addressing seawater desalination challenges. Full article

A new Na⁺ ionophore with two 12-crown-4 moieties on silicon atoms and hydrophobic hydrocarbon groups on silicon atoms has been synthesized. The silicon-bridged bis(12-crown-4)s were easily obtained in high yield by simply mixing dichlorodiorganosilane and 2-hydroxymethyl-12-crown-4 under room temperature and nitrogen atmosphere. Seven compounds with different hydrocarbon substituents were synthesized. To investigate their properties as ionophores, PVC membrane-type ion-selective electrodes incorporating them were prepared, and the ion selectivity coefficients were determined. The typical selectivity sequence is Na⁺ > K⁺ > Rb⁺ > Cs⁺ > NH₄⁺ > Li⁺ > Ca²⁺ > Mg²⁺ > H⁺. The magnitude of selectivity depends on the structures of hydrocarbon substituents on the silicon atoms. The compound with two 2-ethylhexyl groups has particularly good Na⁺ selectivity, and the performance of the electrode is equal to or better than that of an electrode using a commercially available Na⁺ ionophore, malonate-bridged bis(12-crown-4). The electrode also showed better-aging stability than that of another known Na⁺ ionophore, tetraethyl 4-tert-butylcalix[4]arene-O,O′,O″,O‴-tetraacetate, indicating high utility. Full article

Enriched lithium isotopes (⁶Li and ⁷Li) are essential in the nuclear energy industry, where ⁶Li is bombarded with neutrons to produce tritium for fusion reactions, while ⁷Li is used as a core coolant and pH regulator. Separation of ⁶Li and ⁷Li by electromigration is a promising method for producing enriched lithium isotopes that fulfill industrial needs. In this work, based on a previously proposed biphasic system electromigration routine, a three-stage system of ‘LiCl aqueous solution (anolyte)|B12C4-[EMIm][NTf₂] organic solution|NH₄Cl aqueous solution (catholyte)’ was constructed and the rules of lithium isotope separation and lithium-ion migration investigated. It was shown that the isotope enrichment effect of the catholyte was greatly affected by the experimental conditions, while that of the organic solution was less affected. As the B12C4 concentration increased, enhancement of ⁷Li enrichment in the catholyte and ⁶Li enrichment in the organic solution was observed, and α(C/O) and α(O/A) reached 0.975 and 1.018 at B12C4 of 0.5 mol/L. With the increase in current, migration time, and LiCl concentration, the isotope that was enriched in the catholyte trended from ⁷Li to ⁶Li (about 6 mA, 12 h or LiCl of 5 mol/L). Taking lithium-ion transport efficiency and lithium isotope separation effect into consideration together, a current of at least 6 mA, duration of at least 12 h, LiCl concentration of at least 1 mol/L and B12C4 concentration of 0.2 mol/L are suggested for the electromigration process. The work provides an important reference for system construction and experimental design of a biphasic electromigration separation method, which is expected to be an industrial alternative because of its environmental protection and high efficiency. Full article

The detection of adrenaline (Adr) is essential for monitoring physiological and clinical conditions, including stress response, cardiovascular health, and neurological disorders. We present a novel glass-nanopipet electrode sensor based on a non-redox ion-transfer approach using ion transfer across two immiscible electrolyte solutions (ITIES). Two ionophores, dibenzo-24-crown-8 ether (DB24C8) and dibenzo-18-crown-6 ether (DB18C6), were evaluated for their ability to facilitate Adr transfer across aqueous/dichloroethane interfaces. Among these, DB24C8 demonstrated superior stability, attributed to its larger ring size and stronger complexation with Adr. We systematically studied Adr transfer in various media, including KCl, DI water, Millipore DI water, and Tris buffer, and constructed calibration curves based on peak potential shifts that follow a power-law relationship with Adr concentration. The sensor achieved a detection limit of 5 pM in Tris buffer using DB24C8 and 50 pM with DB18C6, both significantly lower than the physiological concentration of Adr. Furthermore, the effects of pH and ionic strength on the peak shifts were analyzed, revealing that pH changes had a more substantial impact compared to ionic strength variations. Importantly, while DB24C8 and DB18C6 are known to facilitate the transfer of other cations, such as potassium and calcium, our findings confirm that these cation transfers do not interfere with Adr detection. This innovative ITIES-based sensing platform offers ease of fabrication, robustness, and excellent potential for real-time, in vivo applications. It represents a significant advancement in electrochemical detection technologies, paving the way for practical applications in clinical and physiological settings. Full article