- Anticancer Activity of Polyoxometalate-Bisphosphonate Complexes: Synthesis, Characterization, in Vitro and in Vivo Results
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We synthesized a series of polyoxometalate-bisphosphonate complexes containing MoVIO6 octahedra, zoledronate, or an N-alkyl (n-C6 or n-C8) zoledronate analogue, and in two cases, Mn as a heterometal. Mo6L2 (L = Zol, ZolC6, ZolC8) and Mo4L2Mn (L = Zol, ZolC8) were characterized by using single-crystal X-ray crystallography and/or IR spectroscopy, elemental and energy dispersive X-ray analysis and 31P NMR. We found promising activity against human nonsmall cell lung cancer (NCI-H460) cells with IC50 values for growth inhibition of ～5 μM per bisphosphonate ligand. The effects of bisphosphonate complexation on IC50 decreased with increasing bisphosphonate chain length: C0 ≈ 6.1×, C6 ≈ 3.4×, and C8 ≈ 1.1×. We then determined the activity of one of the most potent compounds in the series, Mo4Zol2Mn(III), against SK-ES-1 sarcoma cells in a mouse xenograft system finding a ～5× decrease in tumor volume than found with the parent compound zoledronate at the same compound dosing (5 μg/mouse). Overall, the results are of interest since we show for the first time that heteropolyoxomolybdate-bisphosphonate hybrids kill tumor cells in vitro and significantly decrease tumor growth, in vivo, opening up new possibilities for targeting both Ras as well as epidermal growth factor receptor driven cancers.
- Boulmier, Amandine,Feng, Xinxin,Oms, Olivier,Mialane, Pierre,Rivière, Eric,Shin, Christopher J.,Yao, Jiaqi,Kubo, Tadahiko,Furuta, Taisuke,Oldfield, Eric,Dolbecq, Anne
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- Novel alkylimidazolium ionic liquids as an antibacterial alternative to pathogens of the skin and soft tissue infections
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Keeping in mind the concept of green chemistry, this research aims to synthesize and characterize new ionic liquids (ILs) derived from N-cinnamyl imidazole with different sizes of alkyl chains (1, 6, 8, and 10 carbon atoms), and evaluate their antibacterial activity against Skin and soft tissue infections (SSTIs) causative bacteria. The antibacterial screening was carried out by agar well diffusion and the Minimum Inhibitory Concentration (MIC) and Half Maximum Inhibitory Concentration (IC50) of the different ILs were determined by microdilution in broth, also Molecular dynamics simulations were performed to study the interaction mechanism between ILs and membranes. The MIC value in Gram-positive bacteria showed that as the hydrocarbon chain increases, the MIC value decreases with a dose-dependent effect. Furthermore, Gram-negative bacteria showed high MIC values, which were also evidenced in the antibacterial screening. The molecular dynamics showed an incorporation of the ILs with the longer chain (10 C), corresponding to a passive diffusion towards the membrane surface, for its part, the ILs with the shorter chain due to its lack of hydrophobicity was not incorporated into the bilayer. Finally, the new ILs synthesized could be an alternative for the treatment of Gram-positive bacteria causative of SSTIs.
- Doria, Oscar Forero,Castro, Ricardo,Gutierrez, Margarita,Valenzuela, Diego Gonzalez,Santos, Leonardo,Ramirez, David,Guzman, Luis
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- Alkylation of imidazole by solid-liquid phase transfer catalysis in the absence of solvent
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Phase Transfer Catalysis in the absence of solvent is described as a useful and general method for the selective N-alkylation of imidazole. In all cases high yields are obtained while quaternization is avoided.
- Diez-Barra,De La Hoz,Sanchez-Migallon,Tejeda
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- Chemical Tuning of Zwitterionic Ionic Liquids for Variable Thermophysical Behaviours, Nanostructured Aggregates and Dual-Stimuli Responsiveness
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The design and synthesis of a series of zwitterionic ionic liquids (ZILs) to understand the structure–property relationship towards an increase of the thermal stability, a variation of the glass transition temperature, the shape-tuning of nanostructured aggregates and the tuning of the stimuli responsiveness are demonstrated. The substitution reaction of imidazole with various aliphatic and aromatic bromides followed by the reaction of the corresponding substituted imidazoles with bromoalkyl carboxylic acids of varying spacer length produces the ZILs. In aqueous solution, a ZIL molecule either exist in its ionic liquid (substituted imidazolium bromide) form or its zwitterionic (substituted imidazolium alkyl carboxylate) form with an isoelectric point (pI) depending on the pH value of the solution. Upon changing the pH to near or above the pI, the aqueous ZIL solution undergoes transition from a transparent to a turbid phase due to the formation of insoluble hierarchical nanostructured aggregates of various morphologies, such as spheres, tripods, tetrapods, fern-like, flower-like, dendrites etc. depending on the pH of the solution and the nature of the alkyl/vinyl/aryl substituents. Upon heating the solution a phase transition occurs from turbid to transparent, exhibiting a distinct reversible upper critical solution temperature (UCST)-type cloud point (Tcp). It is observed that the cloud point varies with the nature of the substituent, an increase of the concentration of the ZIL as well as with changes of the pH of the solution.
- Biswas, Yajnaseni,Ghosh, Pratyush,Mandal, Tarun K.
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- Inhibition of bacterial growth and galactosyltransferase activity of WbwC by α, ω-bis(3-alkyl-1H-imidazolium)alkane salts: Effect of varying carbon content
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A series of compounds was designed and synthesized having two imidazolium rings separated by a polymethylene spacer and having alkyl substituents on each of the imidazolium rings. The compounds were assayed for their effects on the activity of galactosyltransferase WbwC, and also on the growth of Gram-negative and Gram-positive bacteria, as well as human cells. The inhibition observed on enzyme activities and cell growth was dependent on the total number of carbons in the spacer and the alkyl substituents on the imidazolium rings. These readily synthesized, achiral compounds have potential as antimicrobial and antiseptic agents.
- Brockhausen, Inka,Kocev, Alexander,Kong, Xianqi,Melamed, Jacob,Szarek, Walter A.,Vlahakis, Jason Z.,Wang, Shuo,Xu, Yaozu
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- Synthesis, structure and photophysical properties of complexes [1-(9-anthracylmethyl)-3-alkylimidazol-2-ylidene]2Pt(C≡CPh) 2
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1-(9-Anthracenylmethyl)-3-octylimidazolium chloride (1a) or 1-(9-anthracenylmethyl)-3-ethylimidazolium iodide (1b) was treated with (cod)Pt(CCPh)2 to afford the luminescent complexes [1-(9-anthracylmethyl)-3-alkylimidazol-2-ylidene]2
- Liu, Qing-Xiang,Xu, Feng-Bo,Li, Qing-Shan,Song, Hai-Bin,Zhang, Zheng-Zhi
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- Fluoroalkylated N-heterocyclic carbene complexes of palladium
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Fluoroalkylated N-heterocyclic carbene complexes of palladium have been synthesized from imidazolium salts and Pd(OAc)2. The analogous carbene complexes bearing long alkyl chains have also been prepared. The formation of these carbene complexes proceeds via an intermediate binuclear species, which has been isolated. Complexes such as these may find applications in catalysis in supercritical CO2 (scCO2).
- Xu, Lijin,Chen, Weiping,Bickley, Jamie F.,Steiner, Alexander,Xiao, Jianliang
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- CO2/N2 triggered Switchable surfactants with imidazole group
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In order to overcome the hydrolysis of 2-alkyl-1-hydroxyethyl imidazoline and its unsatisfactory emulsification-demulsification switchability to water-alkane, the long-chain N-alkylimidazole compounds were synthesized by n-octyl bromide, n-decyl bromide, n-dodecyl bromide, n-tetradecyl bromide and n-hexadecyl bromide with imidazole, respectively and characterized by MS, 1H NMR and FTIR. The long-chain N-alkylimidazole compounds can be reversibly transformed into charged surfactants by exposure to CO2. Surface tension values indicated that N-alkylimidazolium bicarbonates had excellent surface activity compared with corresponding conventional surfactants with a lower γ CMC. The surface behaviors of the five surfactants can be illustrated by A min. Five conductivity cycles by bubbling CO2 and N2 alternately indicated that these surfactants could be switched by CO2 reversibly and repeatedly. Emulsions were repeatedly stabilized for five cycles by N-alkylimidazolium bicarbonate and broken by bubbling N2 through the solutions to reverses the reaction, releasing CO2.
- Chai, Mingfeng,Zheng, Zhibo,Bao, Lei,Qiao, Weihong
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- A Comprehensive Study on the Synthesis and Micellization of Disymmetric Gemini Imidazolium Surfactants
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Two groups of disymmetric Gemini imidazolium surfactants, [C14C4Cmim]Br2 (m?=?10, 12, 14) and [CmC4Cnim]Br2 (m?+?n?=?24, m?=?12, 14, 16, 18) surfactants, were synthesized and their structures were confirmed by 1H NMR and ESI–MS spectroscopy. Their adsorption at the air/water interface, thermodynamic parameters and aggregation behavior were explored by means of surface tension, electrical conductivity and steady-state fluorescence. A series of surface activity parameters, including cmc, γcmc, πcmc, pC20, cmc/C20, Γmax and Amin, were obtained from surface tension measurements. The results revealed that the overall hydrophobic chain length (Nc) for [C14C4Cmim]Br2 and the disymmetry (m/n) for [CmC4Cnim]Br2 had a significant effect on the surface activity. The cmc values decreased with an increase of Nc or m/n. The thermodynamic parameters of micellization (ΔGm θ, ΔHm θ, ΔSm θ) derived from the electrical conductivity indicated that the micellization process of [C14C4Cmim]Br2 and [CmC4Cnim]Br2 was entropy-driven at different temperatures, but the contribution of ΔHm θ to ΔGm θ was enhanced by increasing Nc or m/n. The micropolarity and micellar aggregation number (Nagg) were estimated by steady-state fluorescence measurements. The results showed that the surfactant with higher Nc or m/n can form larger micelles, due to a tighter micellar structure.
- Zhao, Xiaohui,An, Dong,Ye, Zhiwen
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- Aggregation of double-tailed ionic liquid 1,3-dioctylimidazolium bromide and the interaction with triblock copolymer F127
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The aggregation of ionic liquid-based double-tailed surfactant, 1,3-dioctylimidazolium bromide ([Doim]Br) and its interaction with pluronic copolymer F127 were systematically investigated by nuclear magnetic resonance (NMR), surface tension, dynamic light scattering (DLS), and isothermal titration calorimetry (ITC). It was found that the [Doim]Br aggregates are composed with the alkyl chains embedded in the micellar core and with the imidazolium rings parallel and staggered on the hydrophilic layer of micelles, which was generally different from the single-tailed IL [omim]Br. The hydrogen bonding between protons attached to the imidazolium rings and anion Br- was enhanced upon the aggregation of [Doim]Br. The aggregation of F127 was promoted by addition of [Doim]Br, which was more efficient than the single-tailed surfactant. At lower [Doim]Br content, [Doim]Br monomers embedded deeply into F127 micelle core. At higher [Doim]Br concentrations, the F127 micelles were disassociated, and then F127 chains penetrated into [Doim]Br micelle. In addition, the microstructure of F127/[Doim]Br complex can also be tuned by temperature. ? 2013 American Chemical Society.
- Ge, Lingling,Wang, Qi,Wei, Duo,Zhang, Xiaohong,Guo, Rong
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- Symmetrical 1, 3-Dialkylimidazolium Based Ionic Liquid Crystals
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The synthesis and characterization for a series of symmetrical 1, 3-dialkylimidazolium salts with different chain lengths and counter anions together with their 1-alkylimidazole precursors are described. Liquid crystal (LC) properties of these salts are studied. Images under polarizing optical microscopy show focal conic texture together with homeotropic domains. A smectic A mesophase, typical for rod-like imida-zolium salts, is assigned. Studies from powder X-ray diffraction suggest a lamellar structure with non-interdigitated monolayer arrangement for the LC salts in the mesophase. In addition, a short note on the structure and property relationship for rod-like, discor fan-like, and dendritic shaped imidazolium ionic liquid crystals (ImILCs) forming smectic, columnar, and cubic phase is briefly summarized. Acomparison of minimum alkyl chain length needed for 1-alkyl-3-methyl and symmetrical 1, 3-dialkyl ImILCs to exhibit LC behavior is addressed.
- Rohini, Rondla,Lee, Ching-Kuan,Lu, Jung-Tang,Lin, Ivan J.B.
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- Design and synthesis of piperazine-based task-specific ionic liquids for liquid-liquid extraction of CuII, NiII, and CoII from water
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The novel synthesis of task-specific ionic liquids (TSILs) introducing piperazine substructures was described. Piperazine functional groups were easily grafted onto an imidazolium cationic derivative via a simple four-step process starting from available materials such as imidazole, ethylene glycol, and 1-butylamine or 3-dimethylaminopropylamine. Effects of pH, temperature, and structure of functional groups on the performance of liquid-liquid extraction of Cu2+, Ni2+, and Co2+ from water were investigated. It was found that TSILs were efficient for removal of these metal ions in mild acid solutions. The TSIL with an extra nitrogen atom showed a higher capability to separate metal ions, especially for Cu2+. This may be ascribed to the intrinsic structure of the functional groups - the more coordination sites, the higher the affinity for the metal ions. Furthermore, the thermodynamics indicated that the extraction process was exothermic and spontaneous in nature.
- Xu, Weiyuan,Wang, Liang,Huang, Jianying,Ren, Gerui,Xu, Dandan,Tong, Haihe
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- Structured semifluorinated polymer ionic liquids for metal nanoparticle preparation and dispersion in fluorous compartments
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Structured semifluorinated polymer ionic liquids (FPILs) contain a flexible hyperbranched polyether core connected with a covalently attached shell of imidazolium cations and perfluorinated alkyl chains at their periphery. In a facile synthesis, alkylatio
- Schadt, Kristina,Kerscher, Benjamin,Thomann, Ralf,Muelhaupt, Rolf
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- Tris-imidazolium and benzimidazolium ionic liquids: A new class of biodegradable surfactants
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Based on imidazolium and benzimidazolium, two series of novel tris-cationic ionic liquid surfactants containing ester groups were synthesized simply from readily available starting materials in high yields. Biodegradability and surfactants properties of the tris-imidazolium and tris-benzimidazolium ionic liquids were investigated. Some compounds showed assembly behaviour in the pure form (i.e. absence of solvent) and in the presence of polar or nonpolar solvents. These surfactants are effectively reducing the surface tension of water in the range of 28-31 mN m-1. Through using the 'Closed-Bottle Test' OECD 301D, the incorporation of alkyl or phenyl side chains with ester groups in the same molecule significantly improved the biodegradation compared to sodium n-dodecyl sulphate (SDS) as a reference. The aliphatic alkyl side chain, i.e., butyl, hexyl, octyl, decyl and dodecyl, in both imidazolium and benzimidazolium ionic liquids have marked increasing biodegradation and phase behaviour results compared to aromatic side-chains.
- Al-Mohammed, Nassir N.,Duali Hussen, Rusnah Syahila,Alias, Yatimah,Abdullah, Zanariah
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- Exploring the cellular uptake and localisation of phosphorescent rhenium: Fac -tricarbonyl metallosurfactants as a function of lipophilicity
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A systematic study of the cellular uptake of emissive complexes as a function of their lipophilicity is presented. Here a series of amphiphilic rhenium fac-tricarbonyl bisimine complexes bearing axial substituted imidazole or thiazole ligands, [Re(bpy)(CO)3(ImCnHm)]+ {n = 1 m = 3 (1+), n = 4 m = 9 (2+), n = 8 m = 17 (3+), n = 12 m = 25 (4+), n = 16 m = 33 (5+), n = 2 m = 3 (6+); bpy = 2,2′-bipyridine, Im = imidazole} and [Re(bpy)(CO)3(L)]+ {L = 1-mesitylimidazole, ImMes (7+), 4,5-dimethylthiazole, dmt (8+) and 4-methyl-5-thiazole-ethanol, mte (9+)} is reported. The X-ray crystal structures of 2+, 8+ and 9+ confirm the geometry and expected distribution of ligands and indicated that the plane of the imidazole/thiazole ring is approximately parallel to the long axis of the bipy ligand. Luminescence studies revealed excellent properties for their use in cell imaging with visible excitation and broad emission profiles. Their uptake in two distinct species has been examined by fluorescence imaging of the diplomonad fish parasite Spironucleus vortens (S. vortens) and rod-shaped yeast Schizosaccharomyces pombe (Schiz. pombe) as a function of their lipophilicity. The uptake of the complexes was highest for the more lipophilic 2+-5+ in both S. vortens and Schiz. pombe in which the long alkyl chain aids in crossing bilipid membranes. However, the increased lipophilicity of longer chains also resulted in greater toxicity. Localisation over the whole cell varied with differing alkyl chain lengths with complex 2+ preferentially locating to the nucleus of S. vortens, 3+ showing enhanced nuclear partitioning in Schiz. pombe, and 4+ for the remaining cell wall bound in the case of S. vortens. Interestingly, complexes of intermediate lipophilicity such as 7+ and 8+ showed reasonable uptake, proved to be non-toxic, and were capable of crossing exterior cell walls and localising in the organelles of the cells.
- Hallett, Andrew J.,Placet, Emeline,Prieux, Roxane,McCafferty, Danielle,Platts, James A.,Lloyd, David,Isaacs, Marc,Hayes, Anthony J.,Coles, Simon J.,Pitak, Mateusz B.,Marchant, Sarah,Marriott, Stephen N.,Allemann, Rudolf K.,Dervisi, Athanasia,Fallis, Ian A.
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- Synthesis, In silico and in vitro studies of Silver (I)-N heterocyclic carbene complexes
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In the present study, four silver based NHC (N-heterocyclic carbene) complexes (1c-4c) were designed and synthesized from their precursor salts (1b-4b). The successful synthesis of salts and complexes was assured through spectroscopic techniques (UV-visible, FTIR, 1H NMR) as well as mass spectrometry. The in silico ADMET study and molecular docking calculations predicted the compounds are good drug candidates having therapeutic potential against multiple cancer targets including COX-1, VEGFA, HIF as well as VGF. Results of in vitro study conducted through MTT assay confirmed that all test compounds have concentration dependent potency but silver complexes (1c-4c) have far superior activity than precursor, salts (1b-4b) and slightly lower than standard drugs (carboplatin and cisplatin) against various cancer cell lines. Among the studied compounds, 3c showed lowest IC50 value of 0.981 ± 0.09, 1.10 ± 0.14 and 0.973 ± 0.12 μg/mL against MCF-7, HCT-116 and A549 respectively. The test compounds were found good antibacterial agents, when screened against bacterial strains (Staphylococcus aureus, Micrococcus luteus, Escherichia coli and S. typhimurium), as well as antioxidant agents when tested against DPPH free radicals.
- Sarfraz, Ayesha,Ashraf, Rizwan,Ali, Shaukat,Taskin-Tok, Tugba,Khalid, Zohra,Ullah, Sana,Kahlid, Talha,Mushtaq, Muhammad,El-Bahy, Salah M.,El-Bahy, Zeinhom M.
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- A Remarkable Fluorescence Quenching Based Amplification in ATP Detection through Signal Transduction in Self-Assembled Multivalent Aggregates
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Signal transduction is essential for the survival of living organisms, because it allows them to respond to the changes in external environments. In artificial systems, signal transduction has been exploited for the highly sensitive detection of analytes. Herein, a remarkable signal transduction, upon ATP binding, in the multivalent fibrillar nanoaggregates of anthracene conjugated imidazolium receptors is reported. The aggregates of one particular amphiphilic receptor sensed ATP in high pm concentrations with one ATP molecule essentially quenching the emission of thousands of receptors. A cooperative merging of the multivalent binding and signal transduction led to this superquenching and translated to an outstanding enhancement of more than a millionfold in the sensitivity of ATP detection by the nanoaggregates; in comparison to the “molecular” imidazolium receptors. Furthermore, an exceptional selectivity to ATP over other nucleotides was demonstrated.
- Biswas, Rakesh,Naskar, Sumit,Ghosh, Surya,Das, Mousumi,Banerjee, Supratim
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supporting information
p. 13595 - 13600
(2020/10/06)
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- MICROBICIDE AMMONIUM-IMIDAZOLIUM OLIGOMERS AND THEIR ANTI-FUNGAL COMPOSITIONS
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The present disclosure relates to compositions comprising an oligomer of Formula (I): having imidazolium and diammonium substituents; and an anti-fungal compound comprising at least one triazole group, e.g. fluconazole, itraconazole, or voriconazole. The compositions as described herein may be used as an anti-fungal composition for therapeutic and non-therapeutic applications.
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Page/Page column 27
(2020/04/25)
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- Cell Permeable Imidazole-Desferrioxamine Conjugates: Synthesis and in Vitro Evaluation
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Desferrioxamine (DFO), a clinically approved iron chelator used for iron overload, is unable to chelate labile plasma iron (LPI) because of its limited cell permeability. Herein, alkyl chain modified imidazolium cations with varied hydrophobicities have been conjugated with DFO. The iron binding abilities and the antioxidant properties of the conjugates were found to be similar to DFO. The degree of cellular internalization was much higher in the octyl-imidazolium-DFO conjugate (IV) compared with DFO, and IV was able to chelate LPI in vitro. This opens up a new avenue in using N-alkyl imidazolium salts as a delivery vector for hydrophilic cell-impermeable drugs.
- Pramanik, Shreya,Chakraborty, Saikat,Sivan, Malavika,Patro, Birija S.,Chatterjee, Sucheta,Goswami, Dibakar
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p. 841 - 852
(2019/03/07)
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- Molecular tunability of surface-functionalized metal nanocrystals for selective electrochemical CO2 reduction
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Organic ligands are used in homogeneous catalysis to tune the metal center reactivity; in contrast, clean surfaces are usually preferred in heterogeneous catalysis. Herein, we demonstrate the potential of a molecular chemistry approach to develop efficient and selective heterogeneous catalysts in the electrochemical CO2 reduction reaction (CO2RR). We have tailor-made imidazolium ligands to promote the CO2RR at the surface of hybrid organic/inorganic electrode materials. We used silver nanocrystals for the inorganic component to obtain fundamental insights into the delicate tuning of the surface chemistry offered by these ligands. We reveal that modifying the electronic properties of the metal surface with anchor groups along with the solid/liquid interface with tail groups is crucial in obtaining selectivities (above 90% FE for CO), which are higher than the non-functionalized Ag nanocrystals. We also show that there is a unique dependency of the CO2RR selectivity on the length of the hydrocarbon tail of these ligands, offering a new way to tune the interactions between the metal surface with the electrolyte and reactants.
- Pankhurst, James R.,Guntern, Yannick T.,Mensi, Mounir,Buonsanti, Raffaella
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p. 10356 - 10365
(2019/11/20)
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- IMIDAZOLIUM COMPOUNDS, METHODS OF SYNTHESIS AND USES THEREOF
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The present invention generally relates to a non-linear imidazolium compound of Formula (I), comprising a planar or stereo core structure. In addition, the present invention relates to the method of preparing the imidazolium compound as disclosed herein.
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Page/Page column 32
(2018/04/20)
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- Tungstate supported mesoporous silica SBA-15 with imidazolium framework as a hybrid nanocatalyst for selective oxidation of sulfides in the presence of hydrogen peroxide
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In this work, a new heterogeneous catalyst (SBA-15/Im/WO4 2?) was prepared, and then its performance in the oxidation of organic sulfides was studied (using 30% H2O2 as green oxidant under neutral reaction conditions). This organic–inorganic hybrid mesoporous material was characterized by various techniques, such as FT-IR, inductively coupled plasma, X-ray powder diffraction, high-resolution-transmission electron microscopy, N2 adsorption–desorption and thermogravimetric analysis. The catalyst was also applied to the selective oxidation of various sulfides. The hybrid catalyst was easily recovered, and was very stable and retained good activity for at least five successive runs without any additional activation. Moreover, there was no remarkable decrease in the activity and selectivity of the catalyst. The products could be easily isolated by just removing the solvent after filtering the catalyst. The yields of the catalytic productions through this catalyst were in the range from 75% to 97%.
- Sedrpoushan, Alireza,Hosseini-Eshbala, Fereshteh,Mohanazadeh, Farajollah,Heydari, Masoud
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- Metal Ion Complex-Modified Layered Silicates
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A layered silicate modified with a metal ion N-heterocyclic complex is provided. The N-heterocyclic ligand of the metal ion N-heterocyclic complex is N-alkyl substituted or alkylated at positions 2-, 4- or 5- of the N-heterocyclic ring. The modified layered silicate is useful in treating water to disinfect the water.
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Paragraph 0047; 0048; 0065
(2018/10/04)
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- Br?nsted acidic ionic liquids for cellulose hydrolysis in an aqueous medium: Structural effects on acidity and glucose yield
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The conversion of cellulose into valuable chemicals has attracted much attention, due to the concern about depletion of fossil fuels. The hydrolysis of cellulose is a key step in this conversion, for which Br?nsted acidic ionic liquids (BAILs) have been considered promising acid catalysts. In this study, using BAILs with various structures, their acidic catalytic activity for cellulose hydrolysis assisted by microwave irradiation was assessed using the Hammett acidity function (H0) and theoretical calculations. The glucose yields exceeded 10% when the H0 values of the BAIL aqueous solutions were below 1.5. The highest glucose yield was about 36% in 1-(1-octyl-3-imidazolio)propane-3-sulfonate (Oimps)/sulfuric acid (H2SO4) aqueous solution. A long alkyl side chain on the imidazolium cation, which increased the hydrophobicity of the BAILs, enhanced the glucose yield.
- Suzuki, Shiori,Takeoka, Yuko,Rikukawa, Masahiro,Yoshizawa-Fujita, Masahiro
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p. 14623 - 14632
(2018/04/26)
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- Synthesis of Imidazolium Oligomers with Planar and Stereo Cores and Their Antimicrobial Applications
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A series of imidazolium oligomers with novel planar and stereo core structures were designed and synthesized. These compounds have symmetric structures with different cores, tails, and linkers. These new imidazolium oligomers demonstrated a desirable set
- Yuan, Yuan,Zhang, Yugen
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supporting information
p. 835 - 840
(2017/06/13)
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- Tungstate ions (WO4 =) supported on imidazolium framework as novel and recyclable catalyst for rapid and selective oxidation of benzyl alcohols in the presence of hydrogen peroxide
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Tungstate salt with imidazolium framework is found to be a recoverable and heterogeneous system favouring the highly selective oxidation of primary benzylic alcohols to corresponding aldehydes with 30% H2O2 as a green oxidant under neutral aqueous reaction conditions. Furthermore, in order to demonstrate the recyclability of the catalyst, it was recovered and efficiently reused in seven succeeding reaction cycles without any significant loss. The use of green solvent, very short reaction time with excellent yields and recyclability of the catalyst make this protocol highly advantageous.
- Hosseini Eshbala, Fereshteh,Mohanazadeh, Farajollah,Sedrpoushan, Alireza
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- 1,1 the [...] -di-alkyl -3,3 the [...] -(2-phosphate ester -1,3-propyl) imidazole in the process for the preparation of salt compound
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The invention relates to a 1,1'-dialkyl-3,3'-(2-phosphate-1,3-propylidene)imidazolium compound and a preparation method thereof. The structural formula of the 1,1'-dialkyl-3,3'-(2-phosphate-1,3-propylidene)imidazolium compound is shown in the specification, wherein n is 6, 8, 10, 12 and 14, and the alkyl imidazole can be replaced with alkyl benzimidazole. The 1,1'-dialkyl-3,3'-(2-phosphate-1,3-propylidene)imidazolium is a amphoteric dimeric surfactant, and a concrete synthesis method comprises the following steps: synthesizing 1, 3-dichloro-2-propanol, synthesizing N-alkyl imidazole, synthesizing 1,1'-dialkyl-3,3'-(2-hydroxyl-1,3-propylidene)imidazole hydrochloride, and synthesizing 1,1'-dialkyl-3,3'-(2-phosphate-1,3-propylidene)imidazolium. The 1,1'-dialkyl-3,3'-(2-phosphate-1,3-propylidene)imidazolium compound and the preparation method are easily available in raw materials, the reaction technology conditions are easy to control, operation is simple, the product is easy to purify, and yield is high. The compound has low critical micelle concentration, and can be used as a wetting agent, an emulsifier, a foaming agent and a foam stabilizer. A molecular structure has macrocyclic cefpimizole group and phosphate ester, and thus the compound has good thermal stability, solubility, salinity resistance, temperature resistance and acid and base resistance.
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Paragraph 0039; 0040
(2016/12/07)
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- Catalytic asymmetric cycloaddition of CO2 to epoxides via chiral bifunctional ionic liquids
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A series of new chiral ionic liquid catalysts composed of the N,N'-bis(salicyclidene) cyclohexene diaminatocobalt and an imidazolium salt were designed, prepared and applied for the chiral cyclic carbonate synthesis from racemic epoxides and carbon dioxide. All reactions exhibit good enantioselectivity for the chiral cyclic carbonate without polycarbonate and other by-products. The order of The order of catalytic activity toward the axial anions is OAc- > CF3CO2- > CCl3CO2- > OTs- and the order of enantioselectivity is OTs- > OAc- > CCl3CO2- > CF3CO2-.
- Duan, Shuhui,Jing, Xinyao,Li, Dandan,Jing, Huanwang
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- Alkyl-imidazolium glycosides: Non-ionic - Cationic hybrid surfactants from renewable resources
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A series of surfactants combining carbohydrate and imidazolium head groups were prepared and investigated on their assembly behavior. The presence of the imidazolium group dominated the interactions of the surfactants, leading to high CMCs and large molecular surface areas, reflected in curved rather than lamellar surfactant assemblies. The carbohydrate, on the other hand, stabilized molecular assemblies slightly and reduced the surface tension of surfactant solutions considerably. A comparative emulsion study discourages the use of pure alkyl imidazolium glycosides owing to reduced assembly stabilities compared with APGs. However, the surfactants are believed to have potential as component in carbohydrate based surfactant mixtures.
- Salman, Abbas Abdulameer,Tabandeh, Mojtaba,Heidelberg, Thorsten,Hussen, Rusnah Syahila Duali,Ali, Hapipah Mohd
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supporting information
p. 28 - 33
(2015/05/27)
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- Synthesis of polyoxymethylene dimethyl ethers from methylal and trioxane catalyzed by Br?nsted acid ionic liquids with different alkyl groups
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Br?nsted acid ionic liquids with different alkyl group carbon chain lengths and an alkane sulfonic acid group were synthesized through bromoalkane, imidazole and 1,4-butane sultone as raw materials. The structures and properties of the ionic liquids were experimentally characterized. Catalytic reaction of methylal (DMM) with trioxane (TOX) for preparation of polyoxymethylene dimethyl ethers (PODMEn, CH3O(CH2O)nCH3, where n > 1) was investigated in various Br?nsted acid ionic liquids with different carbon chain length of alkyl groups. The carbon chain length of alkyl groups and activity correlation for the ionic liquids was studied. It was found that the structures of ionic liquids were consistent with the designed structure and their purities were high. They possessed high thermal stability and wide liquid range. The hydrophobicity of ionic liquids became stronger with the increase of carbon chain length. With increasing the carbon chain length of ionic liquids, the selectivity of PODME3-8 is increased at first and then decreased. Among all the ionic liquids, [C6ImBS][HSO4] shows the best catalytic performance and the selectivity of PODME3-8 is 57.85%.
- Wu, Qin,Li, Weijiao,Wang, Min,Hao, Yu,Chu, Tonghua,Shang, Jiqing,Li, Hansheng,Zhao, Yun,Jiao, Qingze
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p. 57968 - 57974
(2015/07/20)
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- Tetrakis-imidazolium and benzimidazolium ionic liquids: A new class of biodegradable surfactants
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Novel series of tetra-cationic ionic liquids containing alkyl or phenyl side chains and ester groups within the same molecule were successfully prepared. Based on imidazolium and benzimidazolium, these ionic liquids were synthesized from readily available starting materials in high yield. Surfactant properties including liquid crystalline behaviour and surface properties as well as their biodegradability were investigated. Tetrakis-imidazolium ionic liquid compounds showed assembly behaviour in the pure form (i.e. spontaneously) and in the presence of polar or nonpolar solvents, while both imidazolium and benzimidazolium ionic liquids effectively reduced the surface tension of water in the range of 29-34 mN m-1. The incorporation of tetra alkyl or phenyl side chains into imidazolium and benzimidazolium ionic liquids with tetra-ester groups, significantly improved the biodegradation. 'Closed-Bottle Test' OECD 301D and sodium n-dodecyl sulphate (SDS) as a reference were used for evaluation. The linear alkyl side chains (i.e. butyl, hexyl, octyl, decyl and dodecyl) in both tetrakis-imidazolium and benzimidazolium ionic liquids promote the increasing in biodegradation and phase behaviour results comparing to aromatic side-chains.
- Al-Mohammed, Nassir N.,Duali Hussen, Rusnah Syahila,Ali, Tammar Hussein,Alias, Yatimah,Abdullah, Zanariah
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p. 21865 - 21876
(2015/11/27)
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- Synthesis of methylal from methanol and formaldehyde catalyzed by Br?nsted acid ionic liquids with different alkyl groups
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The catalytic reaction of methanol with formaldehyde for the preparation of methylal was investigated in various Br?nsted acid ionic liquids with different carbon chain length of alkyl groups. The structures, acidities, and properties of ionic liquids were experimentally characterized and theoretically analyzed. The Br?nsted acidity-viscosity-activity correlation for the ionic liquids was studied. Among all these ionic liquids, [C6ImBS][HSO4] exhibited the best catalytic performance, which was ascribed to its strong Br?nsted acidity and low viscosity. The catalytic activity of the ionic liquid was near that of concentrated sulfuric acid. The influences of ionic liquid dosage, reaction temperature and molar ratio of methanol to formaldehyde were explored using [C6ImBS]HSO4 as the catalyst. Under the optimal conditions of n(methanol):n(formaldehyde):n(ILs) = 2.5:1:0.0258, 60 °C, and 4 h, the conversion of formaldehyde can reach 63.37%. The ionic liquid [C6ImBS]HSO4 could be reused.
- Sun, Jiahan,Li, Hansheng,Song, Haoran,Wu, Qin,Zhao, Yun,Jiao, Qingze
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p. 87200 - 87205
(2015/11/09)
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- Antimicrobial activity and SAR study of new gemini imidazolium-based chlorides
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A series of 70 new 3,3′(α,ω-dioxaalkyl)bis(1- alkylimidazolium) chlorides were synthesized. They were characterized with respect to surface active properties and antimicrobial activity against the following pathogens: Staphylococcus aureus, Enterococcus faecalis, Acinetobacter baumannii, Escherichia coli, Klebsiella pneumoniae, Enterobacter cloacae, Pseudomonas aeruginosa, Candida krusei, and Candida albicans. In this article, besides description of the synthesis, we characterize a set of features of these compounds, concerning their structure (described by the length of the dioxaalkan spacer and the length of the alkyl substituent in the aromatic ring) and surface active properties (critical micelle concentration, value of surface tension at critical micelle concentration, value of surface excess, molecular area of a single particle, and free energy of adsorption of molecule). Then, we present a SAR study for Staphylococcus aureus, as one of the most widespread pathogenic strains, conducted with the help of the Dominance-based Rough Set Approach (DRSA), that involves identification of relevant features and relevant combinations of features being in strong relationship with a high antimicrobial activity of the compounds. The SAR study shows, moreover, that the antimicrobial activity is dependent on the type of substituents and their position at the chloride moiety, as well as on the surface active properties of the compounds.
- Pa?kowski, ?ukasz,B?aszczyński, Jerzy,Skrzypczak, Andrzej,B?aszczak, Jan,Kozakowska, Karolina,Wróblewska, Joanna,Kozuszko, Sylwia,Gospodarek, Eugenia,Krysiński, Jerzy,S?owiński, Roman
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p. 278 - 288
(2014/03/21)
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- Peroxopolyoxotungsten-based ionic hybrid as a highly efficient recyclable catalyst for epoxidation of vegetable oil with H2O2
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A peroxopolyoxotungsten-based ionic hybrid was synthesized by anion-change of peroxopolyoxometalate (POM) PW4O243- with dicationic long-chain alkyl imidazolium ionic liquids. The characterization was conducted by FT-IR, TGA, 1H-NMR and CHN Elemental analyses. Its catalytic performance was evaluated by the epoxidation of soybean oil with H2O2 under solvent-free condition, including testing of organic cations influence, catalytic reusability and reaction conditions. The catalyst was proved to be a highly efficient recyclable catalyst for epoxidation of various vegetable oils with H2O2, showing high H 2O2 utilization efficiency, high catalytic activity, convenient recovery and good reuse ability.
- Wu, Jianghao,Jiang, Pingping,Qin, Xiaojie,Ye, Yuanyuan,Leng, Yan
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p. 1675 - 1680
(2014/07/07)
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- Chemo-immunotherapeutic antimalarials targeting isoprenoid biosynthesis
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We synthesized 30 lipophilic bisphosphonates and tested them in malaria parasite killing (targeting parasite geranylgeranyl diphosphate synthase, GGPPS) and human γδ T cell activation (targeting human farnesyl diphosphate synthase, FPPS). Similar patterns of activity were seen in inhibiting human FPPS and Plasmodium GGPPS, with short to medium chain-length species having most activity. In cells, shorter chain-length species had low activity, due to poor membrane permeability, and longer chain length species were poor enzyme inhibitors. Optimal activity was thus seen with ～C 10 side-chains, which have the best combination of enzyme inhibition and cell penetration. We also solved the crystal structure of one potent inhibitor, bound to FPPS. The results are of interest since they suggest the possibility of a combined chemo/immuno-therapeutic approach to antimalarial development in which both direct parasite killing and γδ T cell activation can be achieved with a single compound.
- Zhang, Yonghui,Zhu, Wei,Liu, Yi-Liang,Wang, Hong,Wang, Ke,Li, Kai,No, Joo Hwan,Ayong, Lawrence,Gulati, Anmol,Pang, Ran,Freitas-Junior, Lucio,Morita, Craig T.,Oldfield, Eric
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supporting information
p. 423 - 427
(2013/06/05)
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- β-Carotene: A green, inexpensive, and convenient solvatochromic probe for the determination of solvent polarizability
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Solvent polarizability has been previously determined by using the solvatochromic probe 3,20-di-tert-butyl-2,2,21,21-tetramethyl-3,5,7,9,11,13,15, 17,19-docosanonaene whose synthesis involves 15 steps. We show here that the natural dye β-carotene, 1,1′-(3,7,12,16-tetramethyl-1,3,5,7,9,11,13, 15,17-octadecanonaene-1,18-diyl)bis[2,6,6-trimethylcyclohexene], can be conveniently employed for the accurate determination of the same solvent property. This conclusion is based on both theoretical calculations and experimental data. The former includes free energies of solvation, and the wavenumber of the longest wavelength (i.e., the solvatochromic) transition. Both quantities for β-carotene correlate linearly with the corresponding values of the docosanonaene, with slopes and correlation coefficients of practically unity. The plot of experimentally calculated solvent polarizability of β-carotene versus that of the docosanonaene was found to be linear for 68 solvents. Previously unknown solvent polarizability values are reported for eight ROCH2CH2OH (R = C1 to C10) and four 1-allyl-3-R-imidazolium chloride ionic liquids (R = C6 to C10). The dependence of solvent polarizability on the number of carbon atoms in the hydrocarbon chains of several classes of solvents is calculated, it shows the importance of van der Waals interactions in ionic liquids.
- Loffredo, Carina,Pires, Paulo Augusto R.,Imran, Muhammad,El Seoud, Omar A.
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p. 16 - 24,9
(2020/07/31)
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- Anisotropic ionic conductivity in fluorinated ionic liquid crystals suitable for optoelectronic applications
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In this work, we report a library of thirteen fluorinated ionic liquids consisting of iodide salts of 1-alkyl-3-polyfluoroalkyl-imidazolium cations. By changing the length of the alkyl and polyfluoroalkyl pendants, we discovered that particular combinations of these result in compounds showing a mesophase. The nature and the molecular arrangement of the mesophase are characterised by polarised optical microscopy and powder X-ray diffraction analysis, among others. We demonstrate that, after the addition of I2 to generate the I-/I3- redox couple, anisotropic ionic conductivity takes place along preferential pathways in the lamellar structure of the mesophase. Notably, the addition of I2 does not suppress the mesophase temperature range, contrary to previously reported systems. Furthermore, the tendency of these materials to supercool allows the molecular arrangement in the mesophase to be retained in a solid film at ambient temperatures. Finally, we demonstrate their applicability as a quasi-solid electrolyte by preparing dye-sensitised solar cells with power conversion efficiencies comparable to the previous reports.
- Abate, Antonio,Petrozza, Annamaria,Cavallo, Gabriella,Lanzani, Guglielmo,Matteucci, Francesco,Bruce, Duncan W.,Houbenov, Nikolay,Metrangolo, Pierangelo,Resnati, Giuseppe
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p. 6572 - 6578
(2013/07/26)
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- 1,2-Bis[N-(N′-alkylimidazolium)]ethane salts: A new class of organic ionic plastic crystals
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A new class of organic ionic plastic crystals was discovered. A series of alkylene 1,2-bis[N-(N′-alkylimidazolium)] salts with Br- and PF6- anions was prepared and most of the ethylene (C 2) linked compounds undergo multiple solid-solid phase transitions as determined by differential scanning calorimetry (DSC). The salts with longer spacers (C3 or C4) between the imidazolium units do not display any solid-solid transitions. The PF6- salts with terminal C10 and C12n-alkyl moieties are "classical" organic ionic plastic crystals by Timmermans' definition; they have low ΔSf (11 J K-1 mol-1 for C10 and 12 J K-1 mol-1 for C12). Additionally, the C2 linked bis-imidazolium salts with n-butyl, n-hexyl, n-heptyl and n-octyl termini all undergo two, three or four solid state transitions and exhibit ΔSf values in the range of 36-49 J K-1 mol-1, which are similar to those of other known ionic plastic crystalline materials. These materials were additionally characterized via ionic conductivity and solid state NMR. These ionic plastic crystals are presumably single-ion conductors, but the ionic conductivities appear to be too low for practical applications. The activation energy for conduction decreases as these compounds are heated through each solid-solid transition. The lack of any change in solid state 2H NMR spectra with temperature indicates that there is no change in phenyl ring flipping, suggesting no change in the imidazolium local environment. A resolution of this apparent dichotomy is perhaps that the counterions reside with the ethylene spacers between imidazolium moieties.
- Lee, Minjae,Choi, U Hyeok,Wi, Sungsool,Slebodnick, Carla,Colby, Ralph H.,Gibson, Harry W.
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supporting information; experimental part
p. 12280 - 12287
(2011/12/21)
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- Artificial enzymes with thiazolium and imidazolium coenzyme mimics
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Hydrophobic thiazolium and imidazolium coenzyme mimics in the presence of modified-polyethylenimine enzyme mimics catalyze the benzoin condensation 2300-3300 times faster than the coenzyme mimics alone. Polycationic enzyme mimics provide not only a hydrophobic binding domain for coenzyme and substrate, but also electrostatic stabilization of anionic species that arise along the reaction pathway of the benzoin condensation. Copyright
- Zhao, Huanyu,Foss Jr., Frank W.,Breslow, Ronald
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supporting information; experimental part
p. 12590 - 12591
(2009/04/10)
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- Synthesis and properties of chiral imidazolium ionic liquids with a (1R,2S,5R)-(-)-menthoxymethyl substituent
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A series of 1-[(1R,2S,5R)-(-)-menthoxymethyl]-3-alkylimidazolium salts have been synthesized, producing both hydrophilic and hydrophobic chiral imidazolium ionic liquids. Their physicochemical properties, single-crystal X-ray structures, antimicrobial activities, and antielectrostatic effects were determined and these compounds have proven to represent not only potential new solvents in asymmetric synthesis, but also effective, disinfectants with antielectrostatic activity. Given the number and diversities of the possible conformations and interionic interactions, coupled with the chiral nature of the cations, it should come as no surprise that these salts exhibit ionic liquid behavior and are so difficult to crystallize. The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.
- Pernak, Juliusz,Feder-Kubis, Joanna,Cieniecka-Ros?onkiewicz, Anna,Fischmeister, Cedric,Griffin, Scott T.,Rogers, Robin D.
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p. 879 - 892
(2008/02/12)
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- Thermodynamic properties of mixtures containing ionic liquids: Activity coefficients at infinite dilution of organic compounds in 1-propyl boronic acid-3-alkylimidazolium bromide and 1-propenyl-3-alkylimidazolium bromide using inverse gas chromatography
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Activity coefficients at infinite dilution γ∞ of 28 organic compounds in eight room-temperature ionic liquids of the family of 1-propyl boronic acid-3-alkylimidazolium bromide and 1-propenyl-3-alkylimidazolium bromide (with alkyl = methyl, octyl, decyl, or dodecyl) were determined at 323.15 K using inverse gas chromatography. Using all the available γ∞ data, the selectivities at infinite dilution S12 ∞ were determined. Indeed, such values are extremely useful for the design and the optimization of separation processes.
- Mutelet, Fabrice,Jaubert, Jean-Noel,Rogalski, Marek,Boukherissa, Malika,Dicko, Amadou
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p. 1274 - 1279
(2007/10/03)
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- Self-assembled N-alkylimidazolium perfluorooctanesulfonates
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Thermostability of a smectic A phase composed of N-alkyl-imidazolium heptadecafluorooctanesulfonate was improved by the formation of nonpolar layer composed of mixed perfluoroalkyl and aliphatic chains. Copyright
- Mukai, Tomohiro,Yoshio, Masafumi,Kato, Takashi,Ohno, Hiroyuki
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p. 442 - 443
(2007/10/03)
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- Synthesis of N-alkylated derivatives of imidazole as antibacterial agents
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N-Alkylation of imidazole, 2-methylimidazole and 2-methyl-4-nitroimidazole have been carried out to achieve effective antibacterial agents. The products were then investigated for antibacterial activity against Escherichia coil, Staphylococcus aureus and Pseudomonas aeruginosa. Antibacterial effects of 1-alkylimidazole derivatives increase as the number of carbons in alkyl chain increases up to nine carbons. Also substitution of 2-methyl and 2-methyl-4-nitro groups on imidazole ring increases the antibacterial activity.
- Khabnadideh,Rezaei,Khalafi-Nezhad,Bahrinajafi,Mohamadi,Farrokhroz
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p. 2863 - 2865
(2007/10/03)
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- Synthesis and surface activity of some imidazole, 1,2,4-triazole, and tetrazole derivatives
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Imidazole, 1,2,4-triazole, and tetrazole derivatives containing large alkyl substituents are prepared, and their surface activity is studied.
- Abramzon,Pevzner,Kofman,Alam
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p. 1841 - 1848
(2007/10/03)
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- Synthese et proprietes antibacteriennes et antifongiques d'une serie de 1-alkylimidazoles
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A homologous series of 1-alkylimidazoles (pentyl to octadecyl) has been obtained with a good yield (75-95percent) by the phase transfer catalyzed reaction of imidazole with the appropriate alkyl halides.The antifungal and antibacterial activities of these compounds were tested.A poor activity was observed towards the Gram-negative (Gram-) microorganisms, whereas the aerobic and anaerobic Gram-positive (Gram+) microorganisms and some yeasts (Pityrosporum ovale) were inhibited.We found that the inhibitory potency of such compounds increased with increasing chain length,passing through a maximum with chain length C10-C13 and decreased for the higher homologs.An explanation is suggested in relation to the ability of these compounds to bind with the active sites of the microorganisms and to adopt a conformation able to promote the migration through the biological membranes.
- Savignac, A. de,Roques, C.,Hinedi, M.,Michel, G.,Lattes, A.
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p. 449 - 454
(2007/10/02)
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- Preparation of 1-substituted imidazoles
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A process for the preparation of 1-substituted imidazoles by reacting an α-dicarbonyl compound with ammonia, an aldehyde and a primary amine in an aqueous medium, in a single stage, at 20°-150° C.
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- An improved and convenient procedure for the synthesis of 1-substituted imidazoles
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1-Protected imidazoles, such as 1-acetyl- and 1-benzoylimidazoles, react with various halides, such as benzyl, allyl, α-keto, and alkyl halides, to give 1-protected-3-substituted imidazolium salts in high yields. The resultant imidazolium salts are easily deprotected by treatment with water or alcohols to give the corresponding 1-substituted imidazoles in excellent yields. In this reaction the yields of 1-substituted imidazoles vary with the kinds of halides used and/or with the protecting groups, and the yields increase in the following order: benzyl halides≥allyl halides~α-keto halides>alkyl halides, and acetyl≥benzoyl>ethoxycarbonyl>diethoxymethyl>trimethylsilyl>tosyl.
- Kamijo,Yamamoto,Harada,Iizuka
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p. 1213 - 1221
(2007/10/02)
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