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Synthetic transmembrane channels: Functional characterization using solubility calculations, transport studies, and substituent effects

Dibenzyldiaza- 18-crown-6 (PhCH2CH2Ph, 1), di(dodecyldiaza-18- crown-6(C12H25C12H25, 2), HOOC(CH2)11(CH2)11COOH (3), <18N>(CH2)12(CH2)12 (4), (CH2)12(CH2)12 (5), C12H25(CH2)12(CH2)12C12H25 (6), PhCH2(CH2)12(CH2)12CH2Ph(7), 4-(p- MeOC6H4CH2C12)2 (8), (p-NO2C6H4CH2C12)2 (9), and [chol-O-(CH2)2C12]2(N18N) (10) were studied. Octanol- water partition coefficients were determined for 1, 6, 7, 8, 10, and 3- cholestanyl-OCOCH2(CH2)12(CH2)12COCH2O-3- cholestanyl (11). All were found to favor octanol, and by implication the phospholipid bilayer membrane, by at least 104-fold. Transport of Na+ was assessed in both a phospholipid bilayer and in a bulk CHCl3 membrane phase. Addition of ionophores to the latter was found in some cases to strongly enhance CHCl3 phase hydration. An attempt to correlate transport rates determined in the two systems failed, suggesting that the carrier mechanism, required in the CHCl3 phase, does not apply to the tris(macrocyclic) compounds in the bilayer. Sodium transport rates were also assessed for these compounds by using the bilayer clamp technique. Although Na+ flux rates thus determined for 7-9 in the phospholipid bilayer did not correlate with results obtained by the 23Na-NMR technique, the traces are similar to those obtained with protein channels, further supporting the function of tris(macrocycle)s as channel formers.

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Solid-state 23Na nuclear magnetic resonance of sodium complexes with crown ethers, cryptands, and naturally occurring antibiotic ionophores: A direct probe to the sodium-binding sites

We report a systematic solid-state 23Na nuclear magnetic resonance study of sodium complexes with crown ethers, cryptands, and naturally occurring antibiotic ionophores. Precise information about 23Na quadrupole coupling constants and chemical shifts was determined from analysis of 23Na magic-angle spinning (MAS) NMR spectra. We found that the experimental 23Na chemical shifts can be related to an empirical parameter that is a function of the atomic valence of the donor ligand, the Na+-ligand distance, and the coordination number (CN) around the Na+ ion of interest. A reasonably good correlation was also observed between the 23Na quadrupole parameters measured in CDCl3 solution and those measured in the solid state, indicating that the cation exchange is slow in CDCl3. In MeOH solution, however, neither 23Na quadrupole parameters nor chemical shifts of the Na-ionophore complexes show correlation with the corresponding solid-state data. Finally, we report the 23Na chemical shift tensor in Na(12C4)2ClO4: delta11 = delta22 = -1 ppm and delta33 = -15 ppm.

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Oxonium ions from aqua regia: Isolation by hydrogen bonding to crown ethers

The preparation and structures of a variety of oxonium ion tetrachloroaurate(III) salts isolated from aqua regia are reported. The new compounds are [(H5O2)2(12-crown-4)2] [AuCl4]2 (1), [(H7O3)(15-crown-5)][AuCl4] (2), [(H5O2)(benzo-15-crown-5)2] [AuCl4] (3), [(H3O)(18-crown-6)][AuCl4] (4), [(H5O2)(dibenzo-24-crown-8)][AuCl4] (5), [(H5O2)(4-nitrobenzo-15-crown-5)2] [AuCl4] (6), [(H3O)(4-nitrobenzo-18-crown-6)][AuCl4] (7), [(H11O5)-(tetrachlorodibenzo-18-crown-6)2] [AuCl4] (8), and [(H7O3)(dinitrodibenzo-30-crown-10)][AuCl4] (9). A significant correlation between the degree of proton hydration and crown ether size is observed. Aryl crown ethers are nitrated in concentrated aqua regia, but nonnitrated products may be obtained in a dilute solution of aqua regia by reaction with aqueous HAuCl4.

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Synthesis and crystal structure of the monomeric in-cavity complex [smi3(dibenzo-18-crown-6)]

Red crystals of [SmI3(dibenzo-18-crown-6)] are obtained by reaction of SmI3 with dibenzo-18-crown-6-ether in acetonitrile. The crystal structure (tetragonal, P4321, Z = 4; a = 962.7(1) pm, c = 2690.0(3) pm; R1 = 0.041; wR2 = 0.101) contains the neutral molecules [SmI3(dibenzo-18-crown-6)]. Distorted triangular SmI3 units are surrounded perpendicularly by one molecule of the crown ether so that a coordination number of 9 results for Sm3+ (three iodide ions and the six oxygen atoms of the crown ether).

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Novel dibenzo-18-crown-6 ether functionalized bis-benzimidazole derivatives: Synthesis and antifungal evaluation

A series of novel 18-crown-6 ether functionalized bis-benzimidazole derivatives (3a-g) have been synthesized by reacting various substituted ortho-phenylene diamines and pyridine diamines with 4,4?-diformyl dibenzo-18-crown-6 ether (1). The required starting material 4,4?-diformyl dibenzo-18-crown-6 ether (1) was prepared by Duff formylation method. All synthesized novel molecules have been identified on the basis of infrared (IR), 1H nuclear magnetic resonance (NMR), 13C NMR, mass spectroscopy (MS), and elemental analyses. The title compounds (3a-g) were tested for antifungal activity against Aspergillus Niger, Trichothecium sp., Rhizopus sp., and Sclerotium rolfsii fungi species using agar well diffusion method, showing mild to good results. Graphical abstract: [Figure not available: see fulltext.]

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Resorcinarene bis-thiacrowns: Prospective host molecules for silver encapsulation

Mixed-donor atom tetramethoxy resorcinarene bis-thiacrown hosts, in which the crown unit contains both hard oxygen and soft sulfur donor atoms, were synthesized for soft metal cation binding. The binding properties were investigated both in solution and in the solid state by NMR spectroscopy and X-ray crystallography. It was found that the resorcinarene bis-thiacrowns were able to complex silver cations with remarkable affinity forming readily 1:2 host-guest complexes in solution. The solid state structures also revealed that the bis-thiacrowns form silver complexes in an unanticipated endo- and exo-cavity fashion within the same host molecule. Both the solution and solid state studies indicated the sulfur atoms to be the major contributing donor atoms in forming the binding interactions with silver cations.

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Solvent extraction separation of vanadium with dibenzo-18-crown-6

A novel method is described for the simultaneous extraction and direct spectrophotometric determination of vanadium with dibenzo-18-crown-6 from 1.0 mol dm-3 potasium thiocyanate containing 3.0 mol dm-3 hydrochloric acid solution.The effect of concentrations of hydrochloric acid, potassium thiocyanate, crown ethers and role of diluents has been studied.Vanadium has been separated from many mixtures, containing, lead, cadmium, chromium, thallium, cerium, thorium and yttrium which are generally associated in ores, alloys and in steel samples.The proposed method is simple, sensitive, rapid, selective and permits extractive separation and direct spectrophotometric determination in one single operation.

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Interaction of ferrocenecarbaldehyde with zinc tetrahydroborate and its derivatives

Ferrocenecarbaldehyde was reduced to methylferrocene upon interaction with zinc tetrahydroborate in THF. The reactions proceeded rapidly (5-10 min) in high yields (ca. 90%). Analogous results were obtained when a mechanically activated mixture of zinc chloride and sodium tetrahydroborate or the complex of zinc tetrahydroborate with dibenzo-18-crown-6, 2Zn(BH4)2 ¡¤ DB-18-C-6, was used in the reaction.

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New macrocyclic derivatives containing chiral and linear lateral amino-acid moieties

We report the preparation of a new series of functionalized derivatives of dibenzo-18-crown-6, containing in second sphere of coordination lateral arms of different linear and chiral L-amino acids: glycine, beta-alanine, 11-aminoundecanoic acid, L-cysteine, L-aspartic acid, L-phenylalanine, L-tryptophan, L-histidine. All these new derivatives were characterized by elemental analysis, IR and 1H-NMR spectroscopy, and these data were in agreement with proposed molecular structures.

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The “picrate effect” on extraction selectivities of aromatic group-containing crown ethers for alkali metal cations

As evaluated with 15 crown ethers which contain varying numbers of benzo substituents, the magnitude of the extraction selectivities (and in one case, the selectivity order) of aromatic group-containing ionophores for alkali metal picrates may vary significantly from those for alkali metal salts with inorganic anions as a result of pi-pi interactions between picrate ion and an aromatic unit of the ionophore. The importance of the “picrate effect” increases as the number of benzo groups in the crown ether is enhanced and varies with their location in the macrocycle. To verify the involvement of picrate-crown ether pi-stacking in complexation, crown ether-alkali metal picrate complexes were examined in solution by 1H NMR spectroscopy and solid-state structures for nine complexes were determined by X-ray diffraction. Dependence of the chemical shift for the picrate proton singlet in the NMR spectrum on the metal cation and/or macrocycle identity in the metal picrate-crown ether complex was found to be a convenient tool for studying anion-ligand pi-pi interactions in solution.

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