Aryl Crown Ethers Based on d-Glucose Scaffold – Highly Selective Receptors of Amino Acid Ester Hydrochlorides

Amino acids are important biomolecules with a broad scope of applications in chemical and biological sciences. Their functions and properties depend on their absolute configuration. Therefore, methods for chiral recognition and separation of amino acids are highly sought after. For the purposes of diagnostic and medicinal applications chiral recognition of amino acids in water is particularly relevant. However synthetic receptors for enantioselective binding of amino acids in aqueous media are rare. Recently we reported a d -glucose-based crown ether for chiral recognition of amino acid esters in water. We achieved enantioselectivities towards amino acids with hydrophobic sidechains which were among the highest ever reported for a small molecule receptor. The binding affinities were however moderate. Herein we disclose analogs of that receptor, containing aryl functionalities in the crown ether fragment. The new receptors show considerably improved binding affinities for amino acid ester hydrochlorides in water, while retaining high enantio- or chemoselectivities.     

Cytochrome c-crown ether complexes as supramolecular catalysts: cold-active synzymes for asymmetric sulfoxide oxidation in methanol

A series of supramolecular complexes of various cytochrome c proteins with 18-crown-6 derivatives behave as cold-active synzymes in the H2O2 oxidation of racemic sulfoxides. This interesting behavior contrasts with native functionality, where the employed proteins act as electron transfer carriers. ESI-MS. UV, CD, and Raman spectroscopic characterizations reveal that four or five 18-crown-6 molecules strongly bind to the surface of the cytochrome c and also that nonnatural low-spin hexacoordinate heme structures are induced in methanol. Significantly, crown ether complexation can convert catalytically inactive biological forms to catalytically active artificial forms. Horse heart, pigeon breast, and yeast cytochromes c all stereoselectively oxidize (S)-isomers of methyl tolyl sulfoxide and related sulfoxides upon crown ether complexation. These supramolecular catalysts show the highest efficiency and enantiomer selectivity at -40 degrees C in the H202-dependent sulfoxide oxidation, while oxidative decomposition of the heme moieties predominantly occurs at room temperature. The oxidation reactivity of the employed sulfoxides is apparently related to steric constraints and electrochemical oxidation potentials of their S=O bonds. Among the cytochrome c complexes, yeast cytochrome c demonstrates the lowest catalytic activity and degradation reactivity. It has a significantly different protein sequence, suggesting that crown ether complexation effectively activates heme coordination but may additionally alter the native backbone structure. The proper combination of cytochrome c proteins, 18-crown-6 receptors, and external circumstances can be used to successfully generate "protein-based supramolecular catalysts" exhibiting nonbiological reactivities.     

Thermocontrolling ion permeation through binary component membrane composed of crown ether liquid crystal/PVC

In view of the nature of orderness in structure and the mesomorphism in property of liquid crystal, the function of which is further exploited by integrating it with the feature of crown ether. The monoarmed crown ether liquid crystals are successfully applied to the imitation of biomembrane transport. Binary component membrane composed of crown ether liquid crystal and PVC was first developed. Such a novel model of biomimetic membrane is capable of imitating ingeniously the thermocontrolling transport of biomembrane, thus the essential function of liquid crystal in membane transport is more fully exploited. It was suggested, consequently, that the molecules of the crown ether liquid crystal could assemble themselves to form ionic channels, as they exist in mesophase.Of still more significance is that the thermocontrolling transport of ions through the membrane is found to be operative selectively and the permeation of ion is under the direct influence of the thermal turmoil of the crown ether liquid cr     

Chemical ionization mass spectrometry of crown ether acetals using isobutane as reagent gas

Isobutane chemical ionization mass spectrometry of crown ether acetals (M), derived from ethanal, give [MH]⁺ ions from which species corresponding to 44 u are successively eliminated. Mechanisms are presented in which these units correspond to (i) ethanal and (ii) oxirane. An accompanying process is the elimination of ethyne. Similar reactions occur in the chemical ionization mass spectrometry of benzo crown ether acetals.     

Chemical activation of cytochrome c proteins via crown ether complexation: cold-active synzymes for enantiomer-selective sulfoxide oxidation in methanol

Supramolecular complexation with 18-crown-6 significantly converted catalytically inactive cytochrome c (biological form) to catalytically active synzyme (artificial form). Although a family of cytochrome c proteins does not work as enzymes in nature, crown ether complexation modified their heme coordination structures and functionally activated them to promote the asymmetric oxidation of racemic sulfoxides at low temperature. Horse heart, pigeon breast, and yeast cytochrome c proteins were demonstrated to form supramolecular complexes with 18-crown-6 in methanol, which effectively oxidized (S)-isomers of naphthyl methyl sulfoxide, methyl tolyl sulfoxide, isopropyl phenyl sulfoxide, benzyl methyl sulfoxide, and 4-methylsulfenyl acetophenone at -40 degrees C. Because horse heart and pigeon breast cytochromes c exhibited more efficient and higher enantiomer-selective activities than yeast cytochrome c, a proper combination of cytochrome c and crown ether offers a new class of cold-active synzymes promoting nonbiological asymmetric oxidation.     

Preparation and characterization of novel crown ether functionalized ionic liquid-based solid-phase microextraction coatings by sol-gel technology

A novel crown ether functionalized ionic liquid (IL), 1-allyl-3-(6'-oxo-benzo-15-crown-5 hexyl) imidazolium hexafluorophosphate was synthesized and used as selective stationary phase to prepare task-specific IL-based solid phase microextraction (SPME) fibers by sol-gel method and free radical cross-linking technology. The underlying mechanism of the sol-gel reaction was proposed and the successful chemical bonding of the crown ether functionalized IL to the formed hybrid organic-inorganic copolymer coating was confirmed by FT-IR spectroscopy. The performance of this in situ created crown ether functionalized IL-based SPME fibers, was investigated in detail. The coating has porous surface structure, stable performance in high temperature (to 340 °C) and in different solutions (water, organic solvent, acid and alkali), and good coating preparation reproducibility. In contrast to the sol-gel derived 1-allyl-3-methyl imidazolium hexafluorophosphate-based coating prepared in our previous work with the identical procedure, the extraction performance of this newly developed sol-gel crown ether functionalized IL-based coating was superior for alcohols, phthalate esters, phenolic environmental estrogens, fatty acids and aromatic amines due to the introduction of benzo-15-crown-5 functional group in IL structure. Moreover, it was shown to provide higher or comparable extraction efficiencies for most analytes studied than did the commercial PDMS, PDMS/DVB and PA fibers.     

Preconcentration of lanthanides from natural waters with a lipophilic crown ether carboxylic acid

Lipophilic crown ether carboxylic acids such as 2-(sym-dibenzo-16-crown-5-oxy)stearic acid with a cavity size comparable to the ionic radius of rare-earth elements are selective chelation agents for preconcentration and separation of lanthanides from natural waters for NAA. Interfering matrix elements such as sodium and bromine can be simultaneously eliminated during the extraction. The lanthanides can be back-extracted into a dilute acid solution for NAA, thus providing a large preconcentration factor. This two-step extraction method appears suitable for the determination of lanthanides in natural waters and in biological samples.     

Lead‐sensitive PNIPAM microgels modified with crown ether groups

A series of lead‐sensitive poly(N‐isopropylacrylamide) microgels with pendant crown ether groups were prepared. Their cation‐sensitive behaviors were studied by dynamic light scattering. When ionic strength is not controlled, adding salts causes the microgel particles to deswell. However, when the salt effect is ruled out by keeping a constant ionic strength, adding Pb²⁺ results in much larger swelling. The Pb²⁺‐induced swelling was explained by the formation of host–guest complex between Pb²⁺ and the pendant crown ether groups, which increases the hydrophilicity of the polymer and accordingly the degree of swelling. The lead sensitivity of the microgels increases with increasing crown ether content. For the modified microgel with the highest crown ether content, it swells to ～430% of its original volume at [Pb²⁺] = 10 mM. Other cations also increase the swelling degree of the modified microgels. The extent of the cation‐induced swelling mainly depends on their affinity to the pendant crown ether groups. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4120–4127, 2010     

Finkelstein Reaction in Functionalized Crown-ether Ionic Liquids

Recent years, crown ethers have been used in many fields, including phase transfer catalysis, chromatography stationary phase, ionselective electrode, and concentration of metal ions, etc1.. However, the toxicity of free crown ethers makes them unsuitable for industrial use2. Introduction of a crown ether as a functional group to functionalized ionic liquids has been reported3. These functionalized ionic liquids will combine the excellent properties of crown ether and ionic liquids without los…     

Crown Ether Phase Transfer Catalysts for An Ionic Polymerization of Bisphenol A / 4,4′‐Dichlorodiphenyl Sulfone

Various crown ethers were prepared and applied as phase transfer catalysts for the an ionic copolymerization of bisphenol A and 4,4′‐dichlorodiphenyl sulfone monomers with alkali salts, e.g., NaNH₂, NaOH and KOH, as initiators. The catalytic abilities of various crown ethers for the an ionic polymerization of bisphenol A / 4,4′‐dichlorodiphenyl sulfone were found to be in the order: 15‐crown‐5 ? monobenzo‐15‐crown‐5 > 18‐crown‐6 > Dicyclohexano‐18‐crown‐6 > Dibenzo‐18‐crown‐6 > 12‐crown‐4 with sodium amide (NaNH₂) as initiator. Sodium amide was shown to be a better initiator than NaOH or KOH with monobenzo‐ 15‐crown‐5 as a catalyst. Effects of solvents and temperature on the crown ether catalytic polymerization were also investigated. Dimethyl sulfoxide (DMSO) exhibited much better for the polymerization than other organic solvents, e.g., toluene, p‐xylene, dimethyl formamide and dioxane. Higher polymerization was found at higher temperatures and about 100% yield of poly(bisphenol A / sulfone) was obtained at 125 °C in 3 hr. The molecular weight of poly(bisphenol A / sulfone) as a function of reaction time was determined with gel permeation chromatography. Concentration effects of crown ether on % yield and molecular weight of poly(bisphenol A / sulfone) were also investigated and discussed.     

Inter- and Intra-Molecular Organocatalysis of SN2 Fluorination by Crown Ether: Kinetics and Quantum Chemical Analysis

We present the intra- and inter-molecular organocatalysis of S_N2 fluorination using CsF by crown ether to estimate the efficacy of the promoter and to elucidate the reaction mechanism. The yields of intramolecular S_N2 fluorination of the veratrole substrates are measured to be very small (<1% in 12 h) in the absence of crown ether promoters, whereas the S_N2 fluorination of the substrate possessing a crown ether unit proceeds to near completion (~99%) in 12 h. We also studied the efficacy of intermolecular rate acceleration by an independent promoter 18-crown-6 for comparison. We find that the fluorinating yield of a veratrole substrate (leaving group = −OMs) in the presence of 18-crown-6 follows the almost identical kinetic course as that of intramolecular S_N2 fluorination, indicating the mechanistic similarity of intra- and inter-molecular organocatalysis of the crown ether for S_N2 fluorination. The calculated relative Gibbs free energies of activation for these reactions, in which the crown ether units act as Lewis base promoters for S_N2 fluorination, are in excellent agreement with the experimentally measured yields of fluorination. The role of the metal salt CsF is briefly discussed in terms of whether it reacts as a contact ion pair or as a “free” nucleophile F⁻.     

Analysis of First-Order Reactions with Distributed Parameters

Simple methods of analysis of first-order kinetic processes controlled by distributions of parameters (activation energies and/or frequency factors) are presented. Both the isothermal and nonisothermal regimes are considered. The procedures make use of numerically calculated time derivatives of the concentrations of decaying species (reactants in the case of chemical reactions). They do not require any adjustable initial or boundary values of parameters (like concentration at the infinite time) being thus more accurate and reliable than earlier methods in which kinetic parameters were determined from the concentration, and not from its time derivative. The methods were successfully employed in analysis of the thermally driven cis–trans isomerization of a photochromic crown ether containing the azobenzene moiety incorporated in the crown.     

Mass and charge state assignment for proteins and peptide mixtures via noncovalent adduction in electrospray mass spectrometry

A method has been developed that takes advantage of the formation of noncovalent compounds in electrospray mass spectrometry. Mixtures of proteins and peptides are shown to produce an intense ion that corresponds to a 1:1 complex with a crown ether (18-crown-6). Although the crown ether may be added directly to the solution, for the current experiments it is introduced via the methanol liquid sheath. The spacing of these complexed species in the mass spectrum allows unambiguous determination of the charge state of the ions and their actual mass. Through constant neutral loss scans, charge state may be determined, mass assigned, spectra simplified, and chemical noise may be reduced for the analysis of complex peptide samples without chromatographic separation. Finally, the prevalence of single complexation permits mass assignments based on the mass difference of a single protein ion and its complexed form at any charge state. In essence, the method performs a separation based on charge state. It can be used to complement chromatographic separation and deconvolution algorithms for the electrospray mass spectrometry analysis of peptide-protein mixtures.     

Solvent extraction of amino acids into a room temperature ionic liquid with dicyclohexano-18-crown-6

Amino acids Trp, Gly, Ala, Leu are extracted efficiently from aqueous solution at pH 1.5–4.0 (Lys and Arg at pH 1.5–5.5) into the room temperature ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (BmimPF₆) with dicyclohexano-18-crown-6 (CE). The most hydrophilic amino acids such as Gly are extracted as efficiently as the less hydrophilic (92–96%). The influence of pH, amino acid and crown ether concentration, volume ratio of aqueous and organic phases, and presence of some cations on amino acid recovery were studied. The ratio of amino acid to crown ether in the extracted species is 1:1 for cationic Trp, Leu, Ala, and Gly and to 1:2 for dicationic Arg and Lys. This ionic liquid extraction system was used successfully for the recovery of amino acids from pharmaceutical samples and fermentation broth, and was followed by fluorimetric determination.These results were published in part in Smirnova SV (2002) Ph.D. Thesis, Moscow State University.     

基于冠醚衍生物的超分子聚合物

自组装现象是生命科学最本质的内容之一,生物体系可以精确地利用非共价键相互作用形成高度有序的功能组装体.受到大自然的启发,近年来利用分子自组装构筑包括超分子聚合物在内的有序聚集体是超分子科学的研究热点.此类组装体不仅在拓扑学上具有重要的意义,而且可以用来制备动态的超分子功能材料.冠醚作为第一代超分子主体化合物,由于其结构...     

Synthesis of new polysilane-crown ether

This paper presents the synthesis of new polysilane with pendant crown ether groups. The polymer was obtained through the addition reaction of 4^′-allylbenzo-15-crown-5 to poly[methyl(H)-co-methylphenylsilane] copolymer in anhydrous toluene solution using hexachloroplatinic acid as a catalyst. The allyl functionalization of the crown ether was achieved by the coupling of the crown ether bromide with allyl magnesium chloride. The availability of the crown ether sites in complexation reactions with Cu(II) cations was tested.The chemical structures of all products and intermediates were studied using spectral methods (IR, ¹H-NMR, ¹³C-NMR, UV), gel permeation chromatography (GPC) and thermogravimetric analysis (TGA).     

Plant proteins and their colloidal state

Plant proteins are characterized by a complex colloidal state in their physiological environment. The main reasons are related to the multiple functions of plant proteins as well as the different architectures encountered in the plant cells from various sources. During extraction process to produce ingredients, plant proteins reorganize in several native or denatured colloidal states depending on the energy and the physico–chemical changes applied to the system. In most cases, an equilibrium between the native (soluble monomers or oligomers) and denatured (mostly insoluble) oligomeric/aggregated states is reached. Further, processing of the plant protein ingredients during food production, introducing new hydrophobic phases (e.g., gas, oil), energy (pressure, temperature, shear), and physico–chemical conditions (pH, ionic salts) will lead to a final colloidal state, specific to the structural features of the considered final food product.     

苯并-12-冠-4磺酰氯接枝聚苯胺及其锂盐络合固体电解质的合成与性能研究

合成了侧链悬挂苯并-12-冠-4小环冠醚功能基的接枝聚苯胺,经锂盐络合和十二烷基苯磺酸(DBSA)掺杂,得到新型的电子-离子混合导体.用四探针法测得其室温电导率高达10-2S/cm.采用红外光谱分析化学结构,扫描电镜观察了表面形貌.X射线衍射分析证明此种混合导体为无定形态,有利于离子导电.热分析表明它有良好的热稳定性.     

Stability of divalent europium in an ionic liquid: spectroscopic investigations in 1-methyl-3-butylimidazolium hexafluorophosphate

In this work, devoted to 1-methyl-3-butylimidazolium hexafluorophosphate ionic liquid (BumimPF(6)), the importance of the purity of the solvent for spectroscopic investigations is highlighted. Results from small angle X-ray scattering indicate that the pure solvent exhibits a local organization. Europium(II), which appears to be unusually stable in BumimPF(6), is characterized by spectroscopic techniques (absorption, luminescence). Solvation of Eu(II) in BumimPF(6) and complexation effects in the presence of the crown ether 15C5 solubilized in the ionic liquid are discussed.     

Synthesis of poly(vinyl alcohol)-based poly(crown ether)s and permeability of their polymeric membranes

Polymers that contain crown ether moieties at the side chain and are capable of forming rather tough film were synthesized by the polymer reaction of poly(vinyl alcohol) with formyl derivatives of aliphatic crown ethers such as 12-crown-4, 15-crown-5, and 18-crown-6. In the passive transport of alkali metal picrates across the poly(crown ether) membranes the permeation, particularly of alkali metals which tend to form intramolecular sandwich-type complexes with the crown ether rings, was retarded, compared with a poly(vinyl alcohol) membrane. The cation selectivities in the permeation of poly(crown ether) membranes differed significantly from those of poly(vinyl alcohol).