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At least 19 recordsLinked to original sources
PubMed2003

Molecular recognition and conductance in crown ethers.

Crown ethers have the remarkable property of recognizing and binding specific metal cations in complex mixtures. We propose to combine molecular recognition with molecular electric conductance. The question we address is: can the event of binding a cation be sensed by a change in conductance? Specifically, we study a short molecular wire (MW) containing a crown-6 molecule connected via sulfur atoms to two gold atomic wires acting as metallic leads. Upon binding a cation, the density of states of the system is only slightly affected. This reflects the fact that the cation binding is largely electrostatic in nature and is accompanied by little electronic reorganization. Yet, the cationic binding does significantly lower conductance. We also identify strong interference affecting the conductance. A striking feature is the insensitivity of conductance to the type of ligand with the exception of the proton.

Journal Article↗
PubMed2006

Newly synthesized tetraoxa-diaza crown ether derivatives versus commercialized crown ethers in the separation of positional isomers with capillary electrophoresis.

Three new tetraoxa-diaza derivatives of 1,4,10,13-tetraoxa-7,16-diazacyclo-octadecane (R-1, R-2 and R-3) and three commercially available crown ethers, 18-crown-6 (18C6), (+)-18-crown-6-tetracarboxilic acid (18C6H4) and 1,4,10,13-tetraoxa-7,16-diazacyclo-octadecane, were investigated to separate the positional isomers of aminophenol, aminobenzoic acid and aminocresol. The running electrolyte, in which the crown ethers were dissolved, was a 50 mM Tris solution adjusted to pH 2.0 with hydrochloric acid. Using 50 mM H3PO4 buffer, whose pH was adjusted to 2.0 with Tris, or only hydrochloric acid solution with the same pH, did not allow good separations for the tested components. The effect of the crown ether concentration on the separation of the 11 positional isomers was studied in the concentration range of 10-50 mM. The best separations were achieved using the 18C6 and the 18C6H4 crown ethers: 9 isomers out of 11 could be separated within one run. The m- and p-aminophenol isomers could not be separated under the investigated experimental conditions. The newly synthesized tetraoxa-diaza crown ether derivatives were only found suitable for the separation of aminobenzoic acid positional isomers. The macrocyclic ring of the tetraoxa-diaza crown ethers was not able to form a stable inclusion complex with the tested positional isomers. Consequently, the aminophenol and aminocresol isomers were not separated, the isomers migrated with the same or very similar velocities.

Crown Ethers↗
PubMed2004

Field-dependent effect of crown ether (18-crown-6) on ionic conductance of alpha-hemolysin channels.

Closing linear poly(ethylene glycol) (PEG) into a circular "crown" dramatically changes its dynamics in the alpha-hemolysin channel. In the electrically neutral crown ether (C2H4O)6, six ethylene oxide monomers are linked into a circle that gives the molecule ion-complexing capacity and increases its rigidity. As with linear PEG, addition of the crown to the membrane-bathing solution decreases the ionic conductance of the channel and generates additional conductance noise. However, in contrast to linear PEG, both the conductance reduction (reporting on crown partitioning into the channel pore) and the noise (reporting on crown dynamics in the pore) now depend on voltage strongly and nonmonotonically. Within the whole frequency range accessible in channel reconstitution experiments, the noise power spectrum is "white", showing that crown exchange between the channel and the bulk solution is fast. Analyzing these data in the framework of a Markovian two-state model, we are able to characterize the process quantitatively. We show that the lifetime of the crown in the channel reaches its maximum (a few microseconds) at about the same voltage (approximately 100 mV, negative from the side of protein addition) where the crown's reduction of the channel conductance is most pronounced. Our interpretation is that, because of its rigidity, the crown feels an effective steric barrier in the narrowest part of the channel pore. This barrier together with crown-ion complexing and resultant interaction with the applied field leads to behavior usually associated with voltage-dependent binding in the channel pore.

Computer Simulation↗
PubMed2005

Dibenzotetraaza crown ethers: a new family of crown ethers based on o-phenylenediamine.

Dibenzotetraaza (DBTA) crown ethers possess two o-phenylenediamine moieties. They are homologues of dibenzo crown ether phase-transfer catalysts and were prepared from the condensation of benzimidazoles with oligo(ethyleneglycol) dichlorides and oligo(ethyleneglycol) ditosylates. Compounds with ring sizes ranging from 18-crown-6 to 42-crown-14 were prepared. In addition, various altered benzimidizoles were used to produce DBTA crown ethers with modified substituents and ether bridges, as well as benzimidazolidine crown ethers. The synthetic approach presented here proved to be a convenient route to a new family of crown ethers with overall yields of up to 48% based on the benzimidazole. Yields for the ring-closing step were generally high, ranging from 51% to 94%, without the need for high-dilution conditions. Reaction of the DBTA crown ethers with alkyl and benzyl halides was found to be a facile way to obtain the corresponding tetra(N-organyl) compounds. Picrate extraction studies were carried out to determine phase-transfer catalytic capabilities. Extraction efficiencies for alkali-metal ions were lower than those for dibenzo-18-crown-6. Efficiencies were higher for other metal ions, with some selectivity for Pb(2+). Tetra(N-methyl) DBTA-18-crown-6 generally exhibited higher extraction efficiencies than its N-H analogue, but the selectivity was lower.

Journal Article↗
PubMed2005

Inclusion of a Cu2+ ion by a large-cavity crown ether dibenzo-24-crown-8 through supramolecular interactions.

A supramolecular copper-aqua-crown ether complex, [Cu(II)(H2O)4(dibenzo-24-crown-8]2+ (1c) is stabilized with a Lindqvist-type polyoxometalate anion, [Mo(VI)6O19]2- (1a), in an ion-pair compound [Cu(II)(H2O)4(dibenzo-24-crown-8][Mo(VI6O19] identical with [1c][1a] identical with 1. In the crystal, 1c and 1a assemble to a chainlike structure in which each polyoxoanion 1a is sandwiched by two 1c cations. 1c is a structurally characterized dibenzo-24-crown-8 (a larger-cavity crown ether) supramolecular complex that shows encapsulation of a small cation at the center of its internal cavity, and compound 1 represents a unique example of a first-row transition metal-crown ether inclusion complex that interacts with a polyoxometalate anion.

Journal Article↗
PubMed1997

Synthesis, Reactivity, and Structure of [H(13)O(6)][PtCl(5)(H(4)O(2))].2(18-cr-6): A Crown Ether Complex of a Pentachloroaquaplatinic Acid with an [H(13)O(6)](+) Cation in a Cage of Three Crown Ether Molecules.

An aqueous solution of H(2)[PtCl(6)].6 H(2)O reacts with crown ether 18-crown-6 to give [H(13)O(6)][PtCl(5)(H(4)O(2))]. 2(18-cr-6)(1) (1) and (H(3)O)(2)[PtCl(6)].2(18-cr-6) (2a). In the presence of HCl, only 2a is formed; in an analogous manner, (H(3)O)(2)[PtCl(6)].2(15-cr-5).2 H(2)O (2b) and (H(3)O)(2)[PtCl(6)].2(DCH-18-cr-6)(1) (2c) were obtained. 1 is gradually decomposed in water to give [PtCl(4)(H(2)O)(2)].(18-cr-6).2H(2)O (3). 1-3 were characterized by microanalysis and IR and NMR spectroscopy ((1)H, (13)C, (195)Pt). The X-ray structure analysis of 1 (orange needles; space group P2(1)2(1)2(1), a = 7.938(1) Å, b = 15.691(2) Å, c = 34.861(4) Å; Z = 4) shows an anionic entity [PtCl(5)(H(4)O(2))](-) and a cationic entity [H(13)O(6)](+) which are separated by a crown ether molecule 18-cr-6. The [H(13)O(6)](+) cations exhibit the structure [H(3)O(H(4)O(2))(2)(H(2)O)](+) and are also separated by crown ether molecules in such a way that the crystal is threaded by chains built up of 18-cr-6/[H(13)O(6)](+) units at which the 18-cr-6/[PtCl(5)(H(4)O(2))](-) moieties are fixed as lateral branches. Thus, the cations [H(13)O(6)](+) are embedded in three crown ether molecules. All terminal hydrogens are involved in hydrogen bridges to oxygen atoms of the crown ether molecules. The O(w).O(cr) distances are distinctly longer in the mean than the O(w).O(w) distances within the [H(13)O(6)](+) moiety.

Journal Article↗
PubMedDate not supplied

The use of crown ethers in peptide chemistry-V. Solid-phase synthesis of peptides by the fragment condensation approach using crown ethers as non-covalent protecting groups.

We have previously described the conditions by which peptide synthesis by the solid-phase fragment condensation approach can be carried out using crown ethers as non-covalent protection for the N alpha-amino group. Here we demonstrate that the procedure can be extended to large, partially protected peptide fragments possessing free Lys and/or Arg residues. The first step was to ensure that complex formation on the side chain of amino acids was not detrimental to the methodology and exhibited the same solubility and coupling properties as N alpha-complexed peptides. Thus, a model hexapeptide was synthesized using Fmoc chemistry containing Lys and Arg residues, which, when complexed with 18-Crown-6, was readily soluble in DCM and coupled quantitatively to a resin-bound tetrapeptide. Two tripeptides were then prepared, one containing a free Ser residue, the other free Tyr, to examine the possible occurrence of side reactions. After coupling using standard conditions only the former tripeptide exhibited the formation of the O-acylation by-product (5%). Another model hexapeptide containing Lys, Tyr, Ser and Asp protected with a TFA-stable adamantyl group was complexed with 18-Crown-6 and coupled to the resin-bound tetrapeptide with near quantitative yield. Extending the length of the peptide to 21 and 40 residues, which represent sequences Gly52 to Leu72 (21-mer) and Pro33 to Leu72 (40-mer) from Rattus norvegicus chaperonin 10 protein, respectively, resulted in partially protected fragments that were readily soluble in water, thus enabling purification by RP-HPLC. Complexation with 18-Crown-6 gave two highly soluble products that coupled to resin-board tetramer with 68% and 50% coupling efficiencies for the 21-mer and 40-mer, respectively. Treatment with 1% DIEA solutions followed by acidolytic cleavage and purification of the major product confirmed that the correct product has been formed, when analysed by amino acid analysis and ESI-MS. These results served to extend the methodology of non-covalent protection of large partially protected peptide fragments for the stepwise fragment condensation of polypeptides.

Amino Acids↗
PubMed2005

Cytotoxicity and the levels of oxidative stress parameters in WI38 cells following 2 macrocyclic crown ethers treatment.

BACKGROUND: Crown ethers as macrocyclic polyethers possess a hydrophilic cavity surrounded by hydrophobic ring which enable them to diffuse cell membrane. We evaluated cytotoxicity effects of 15-crown-5 and 18-crown-6 and the role of oxidative stress in WI38 cells culture. METHODS: The effect of these ethers in a range of doses (0.1 to 2 mmol/l) on the activity of antioxidant enzymes; superoxide dismutase (SOD), glutathione peroxidase (GPX), catalase (CAT), and on some macromolecules oxidative damages end products; malondialdehyde (MDA) and dityrosine were assessed by spectrometry and HPLC methods. RESULTS: Both compounds markedly inhibited the viability of cells with respect to control particularly at doses >0.5 mmol/l after 24- or 48 h incubation. The survivals of cells were measured using MTT assay. They lowered cell's viability and significantly promoted ROS generation, increased enzyme activities and enhanced oxidative damages in which 18-crown-6 was more effective. Treating cells with 30 microm of alpha-tocopherol in addition to 2 mmol/l of crown ethers showed significant decrease on the levels of ROS, enzyme activities, MDA and dityrosine. CONCLUSION: We document the oxidative radicals forming ability of the studied crown ethers and further strengthens the documentation of their cytotoxicity effects through lipid and proteins oxidation damages.

Antioxidants↗
PubMed2001

Methoxy-ether and crown-ether derivatives of tetrahomodioxa- and octahomotetraoxacalix[4]arenes.

Three methoxy-ether and one methoxy-ether/crown-ether derivatives of p-tert-butyltetrahomodioxa- and p-R-octahomotetraoxacalix[4]arenes (R = methyl, tert-butyl, H) have been investigated. The first three compounds, 7,15,21,27-tetra-tert-butyl-29,30,31,32-tetramethoxy-3,11-dioxapentacyclo[23.3.1.1(5,9).1(13,17).1(19,23)]ditriaconta-1(29),5,7,9(30),13,15,-17(31),19,21,23(32),25,27-dodecaene, C(50)H(68)O(6), 33,34,35,36-tetramethoxy-7,15,23,31-tetramethyl-3,11,19,27-tetraoxapentacyclo[27.3.1.1(5,9).1(13,17).1(21,25)]hexatriaconta-1(33),5,7,9(34),13,15,17(35),21,23,25(36),29,31-dodecaene, C(40)H(48)O(8), and 7,23-di-tert-butyl-33,34,35,36-tetramethoxy-3,11,19,27-tetraoxapentacyclo[27.3.1.1(5,9).1(13,17).1(21,25)]hexatriaconta-1(33),5,7,9(34),13,15,17(35),- 21,23,25(36),29,31-dodecaene, C(44)H(56)O(8), in the partial-cone or 1,2-alternate conformations, present the common feature of methoxy-ether self-inclusion, while the fourth, 42,43-dimethoxy-7,15,23,31-tetramethyl-3,11,19,27,34,37,40-heptaoxahexacyclo[15.15.9.1(5,9).1(21,25).0(13,41).0(29,33)]tritetraconta-5(42),6,8,13(41),14,16,21(43),22,24,29(33),30,32-dodecaene, C(42)H(50)O(9), adopts the 1,3-alternate conformation owing to the presence of a 1,3-polyether chain.

Calixarenes↗
PubMed2006

Columnar and smectic liquid crystals based on crown ethers.

Unsymmetrical benzo[15]crown-5 ethers 5 with one lateral ortho-terphenyl unit bearing alkoxy side chains of varying chain lengths (C5-C14) were prepared from 3,4-dialkoxyphenylbromides 2. Complexation with metal salts MX (M = Na, Cs) afforded the corresponding derivatives MX5. The uncomplexed crown ethers 5 h and 5 i, with dodecyloxy and tetradecyloxy side chains, respectively, exhibit liquid crystalline properties. In the series of complexed crown ethers, liquid crystal properties appeared as early as NaI5 f with C9H19 side chains. Whereas the uncomplexed 5 h,i form smectic mesophases, the complexed NaI5 g and NaI5 h exhibit textures typical of columnar mesophases. These results were supported by X-ray diffraction measurements (WAXS, SAXS), which revealed smectic (5 h,i), rectangular columnar (NaI5 g), and hexagonal columnar (NaI5 h) mesophases. As the liquid crystalline phase might retain packing features of the solid-state structure, single-crystal X-ray analyses were also performed for some of the uncomplexed and complexed crown ether derivatives. The complex NaI(3)5 a displays a sandwich-type structure, with the crown ether cores mutually antiperiplanar and maintaining an almost perfect crown conformation. In contrast, non-mesogenic uncomplexed crown ether 5 b displays a layer-type ordering in the solid phase.

Journal Article↗
PubMed2004

[Preparation and properties of complex of europium lanthanum with crown ether and p-phthalic acid].

Two complexes of crown ether europium (EuL) and crown ether lanthanum (LaL) were synthesized by europium perchlorate and lanthanum perchlorate with 18-crown-6(18-C-6) respectively. The heternuclear complexes of europium-lanthanum p-phthalic acid crown ether were prepared by the two complexes (EuL and LaL) with p-phthalic acid. The elemental analysis shows that its composition is EuLaL2L'(ClO4)4.6H2O(L = 18-C-6 and L' = p-C6H4 (COO)2). The IR spectra, UV-spectra and molar conductor indicate that both ligands (L and L') coordinate rare earth ions (Eu3+ and La3+), but perchlorate group is free. The fluorescence spectra show that the fluorescence intensities of the complex of heternuclear (EuLaL2L'(ClO4)4.6H2O) are more than eight times that of the crown ether europium complex. It was shown that the linked ligand (p-phthalic acid) can transfer the absorbed energy of Lanthanum-crown ether to europium-crown ether with high efficiency.

Crown Ethers↗
PubMed2006

Exploring crown ethers as shift reagents for ion mobility spectrometry.

A series of crown ethers, 12-crown-4, 15-crown-5, 18-crown-6, and dibenzo-30-crown-10, are examined as a possible means of shifting the mobilities of peptide ions. In this approach, a crown ether is added to a solution containing a mixture of peptides and is electrosprayed into the gas phase in order to create distributions of peptide-crown complexes. The ion complexes have different mobilities than the naked peptide ions, and the crown ether molecules appear to interact specifically with basic sites in the peptides thus providing some sequence selectivity. After the peptide-crown complexes are separated by ion mobility spectrometry, the ions can be collisionally activated to dissociate the complex (forming the naked peptide ions) prior to m/z analysis. The overall effect is that complex formation shifts peptide ions to different regions of the mobility spectrum, extending the ability to resolve components. The approach is illustrated by examining isobaric dipeptides as well as a combinatorial library containing 27 tripeptides. Cross sections for the series of crown ether ions and complexes that are observed are reported.

Crown Ethers↗
PubMed1997

Chiral separation of primary amino compounds using a non-chiral crown ether with beta-cyclodextrin by capillary electrophoresis.

A non-chiral crown ether (18-crown-6) along with beta-cyclodextrin (beta-CD) was used to achieve enantioselective separations of primary amino compounds in capillary electrophoresis. In this new method, the amino group of these compounds is protonated in a low pH separation buffer and forms a selective host-guest complex with the crown ether (amino compound+18-crown-6). The hydrophobic portion of the host-guest complex is then incorporated into the cavity of the beta-cyclodextrin. The amino compound is sandwiched between the crown ether and the cyclodextrin (18-crown-6+amino compound+beta-CD) and thus determines or enhances the enantioselective recognition. It is postulated that the formation of this sandwich results in a more selective chiral interaction between the molecule and beta-cyclodextrin. The chiral recognition is dependent upon the formation of this sandwich complex. This method has been used to achieve enantioselectivity of primary amino compounds with a wide variety of substitutions.

Amines↗
PubMed2003

Synthesis of light-harvesting dendrimers focally anchored with crown ethers or terpyridine ligands.

Crown ethers and terpyridine ligands have been successfully attached to the focal point of light harvesting phenylacetylene monodendrons through Pd-catalyzed coupling reactions. The structures of these functional monodendrons were characterized by 1H and 13C NMR spectroscopy, mass spectrometry and elemental analysis. Such binding-ligand anchored dendrons exhibit broad absorption, large molar extenction coefficients and high fluoresence quantum yields. Coordination of crown ethers with alkali ions results in a significant increase in absorption strength in the UV range, but little alteration in either intensity or position of fluorescence emission. Coordination of terpyridine ligands with Ru2+, however, does efficiently quench the fluorescence from the dendrons,albeit only the smallest dendron exhibits efficient binding.

Ethers, Cyclic↗
PubMed2002

Cyclitol-based metal-complexing agents. Effect of the relative orientation of oxygen atoms in the ionophoric ring on the cation-binding ability of myo-inositol-based crown ethers.

myo-Inositol-derived crown ethers having varying relative orientations (1,3-diaxial, 1,2-diequatorial, and 1,2-axial-equatorial) of the oxygen atoms in the ionophoric ring were synthesized and the extent of their binding with picrates of alkali metals, ammonia, and silver were estimated. These crown ethers bind very well with potassium and silver picrates and show good to moderate binding toward lithium, sodium, cesium, and ammonium picrates. These myo-inositol-derived crown ethers exhibit very strong binding for silver, even though they do not have sulfur or nitrogen coordinating sites in them, which are known to have high affinity for silver. The ratio of binding constants for silver to other ions tested varies from 10(2) to 10(5). The ion selectivity and the strength of binding are dependent on the relative orientation of the oxygen atoms in the ionophoric ring as well as on the size of the macrocyclic ring.

Ammonia↗
PubMed2002

Supramolecular cation assemblies of hydrogen-bonded (NH4+/NH2NH3+)(crown ether) in [Ni(dmit)2]-based molecular conductors and magnets.

Hydrogen-bonded supramolecular cation assemblies of (NH4+/NH2-NH3+)(crown ether), where the crown ether is [12]crown-4, [15]crown-5, or [18]crown-6, were incorporated into electrically conducting [Ni(dmit)2] salts (dmit2- = 2-thioxo-1,3-dithiole-4,5-dithiolate). (NH4+)([12]crown-4)[Ni(dmit)2]3(CH3CN)2 had a pyramidal shape, while ionic channels were observed in (NH4+)(0.88)([15]crown-5)[Ni(dmit)(2)]2 and (NH4+)(0.70)([18]crown-6)[Ni(dmit)(2)]2. Both (NH4+)(0.88)([15]crown-5) and (NH4+)(0.70)([18]crown-6) contained regularly spaced [Ni(dmit)(2)] stacks formed by N-H.O hydrogen bonding between the oxygen atoms in crown ethers and the NH4+ ion. NH4+ occurred nonstoichiometrically; there were vacant ionic sites in the ionic channels. The ionic radius of NH4+ is larger than the cavity radius of [15]crown-5 and [18]crown-6. Therefore, NH4+ ions could not pass through the cavity and were distributed randomly in the ionic channels. The static disorder caused the conduction electrons to be randomly localized to the [Ni(dmit)2] stacks. Hydrazinium (NH2-NH3+) formed the supramolecular cations in (NH2-NH3+)([12]crown-4)2[Ni(dmit)2]4 and (NH2-NH3+)2([15]crown-5)3[Ni(dmit)2]6, possessing a sandwich and club-sandwich structure, respectively. To the best of our knowledge, these represent the first hydrazinium-crown ether assemblies to be identified in the solid. In the supramolecular cations, hydrogen bonding was detected between the ammonium or the amino protons of NH2-NH3+ and the oxygen atoms of crown ethers. The sandwich-type cations coexisted with the [Ni(dmit)2] dimer stacks. Although the assemblies were typically semiconducting, ferromagnetic interaction (Weiss temperature = +1 K) was detected in the case of (NH2-NH3+)2([15]crown-5)3[Ni(dmit)2]6. The (NH2-NH3+)0.8([18]crown-6)[Ni(dmit)2]2 and (NH4+)0.76([18]crown-6)[Ni(dmit)2]2 crystals were isomorphous. The large and flexible [18]crown-6 allowed for maintaining the same ionic channel structure through replacement of the NH4+ cation by NH2-NH3+.

Journal Article↗
PubMed1992

Genotoxic potential of crown ethers in mammalian cells: induction of sister-chromatid exchanges.

Crown ethers are macrocyclic polyethers which possess ionophoric properties. These compounds are currently being studied for potential use as pharmaceutical agents as well as antibacterials. Though crown ethers have been shown to be highly toxic in prokaryotes and eukaryotes, there have been few investigations into the potential genotoxicity of these compounds. When sister-chromatid exchanges (SCEs) were quantitated after exposure to crown ethers, the results reflected no significant genotoxic effects on Chinese hamster V79 cells at any of the crown ether concentrations utilized. One crown ether, dicyclohexyl 21-crown-7, did appear to possess antigenotoxic activity. The data on the induction of SCEs by crown ethers reported herein suggest that these compounds are not genotoxic in mammalian cells despite their cytotoxicity.

Analysis of Variance↗