Preparation and Evaluation of 1,3-alternate 25,27-Bis-[p-nitrobenzyloxy]-26,28-bis-[3-propyloxy]-calix[4]arene-bonded Silica Gel Stationary Phase for LC

A novel 1,3-alternate 25,27-bis-[p-nitrobenzyloxy]-26,28-bis-[3-propyloxy]-calix[4]arene-bonded silica gel stationary phase has been prepared and used for separating various selected analytes by HPLC. The effect of organic modifier and pH of the mobile phase on retention and selectivity were studied using aromatic positional isomers as an example. Application examples have been provided for separation of alkylbenzenes, PAHs, xanthine derivatives, and purine and pyrimidine bases. A selectivity comparison of the novel phase versus CalixBz and Backerbond PhenylEthyl phases has been performed.     

Preparation and Evaluation of 1,3-alternate 25,27-Bis-[p-nitrobenzyloxy]-26,28-bis-[3-propyloxy]-calix[4]arene-bonded Silica Gel Stationary Phase for LC

A novel 1,3-alternate 25,27-bis-[p-nitrobenzyloxy]-26,28-bis-[3-propyloxy]-calix[4]arene-bonded silica gel stationary phase has been prepared and used for separating various selected analytes by HPLC. The effect of organic modifier and pH of the mobile phase on retention and selectivity were studied using aromatic positional isomers as an example. Application examples have been provided for separation of alkylbenzenes, PAHs, xanthine derivatives, and purine and pyrimidine bases. A selectivity comparison of the novel phase versus CalixBz and Backerbond PhenylEthyl phases has been performed.

     

1,3-Alternate 25,27-dibenzoiloxy-26,28-bis-[3-propyloxy]-calix[4]arene-bonded silica gel as a new type of HPLC stationary phase

A new 1,3-alternate 25,27-dibenzoiloxy-26,28-bis-[3-propyloxy]-calix[4]arene-bonded silica gel stationary phase (1,3-Alt CalixBn) has been prepared and used for the separation of aromatic positional isomers by high-performance liquid chromatography (HPLC). The effect of organic modifier content and pH of the mobile phase on retention and selectivity of these compounds were studied. Application examples were provided for separation of purine and pyrimidine bases and non-steroidal anti-inflammatory drugs.     

Preparation and evaluation of 1,3-alternate 25,27-bis-(pentafluorobenzyloxy)-26,28-bis-(3-propyloxy)-calix[4]arene-bonded silica gel high performance liquid chromatography stationary phase

A 1,3-alternate 25,27-bis-(pentafluorobenzyloxy)-26,28-bis-(3-propyloxy)-calix[4]arene-bonded silica gel stationary phase (CalixBzF₁₀) was synthesized, structurally characterized, and used as a selector in liquid chromatography. The selectivity study of this phase was done by using fluorine-containing compounds (fluorobenzenes, fluoro-pyrimidine bases), as well as non-fluorinated analytes (non-steroidal anti-inflammatory drugs, sulfonamides, xanthines and polynuclear aromatic hydrocarbons). The effects of organic modifiers on the retention of various compounds possessing basic, acidic and neutral characteristics were studied. It was shown that only basic analytes exhibit a “U-shaped” retention profile and that retention depends on the mobile phase pH. Selectivity comparisons of the novel phase vs. the 1,3-alternate 25,27-bis-(benzyloxy)-26,28-bis-(3-propyloxy)-calix[4]arene phase (CalixBz) were performed. The retention mechanism is also discussed. The results indicate that the fluorinated calixarene stationary phase behaves like reversed-phase packing material; however, fluorine–fluorine interactions seem to be involved in the separation process of fluorine-containing analytes.     

Preparation of a new 1,3-alternate-calix[4]arene-bonded HPLC stationary phase for the separation of phenols, aromatic amines and drugs

We have synthesized the 1,3-alternate 25,27-dioctyloxy-26,28-bis-[3-aminopropyloxy]-calix[4]arene and then immobilized onto γ-chloropropylsilica gel (CPS). The high-performance liquid chromatographic behavior of some aromatic hydrocarbons, phenolic compounds, aromatic amines and drug compounds was studied on this 1,3-alternate-calix[4]arene-bonded silica gel stationary phase (CIMS). The effect of organic modifier content and pH of the mobile phase on retention and selectivity of these compounds were investigated. According to chromatographic data, it can be concluded that the selectivity of CIMS for analytes ascribes to various interactions between CIMS and the analytes, such as hydrophobic interaction, hydrogen bonding interaction, π-π interaction and inclusion interaction.     

Electrochemical investigation of nano-baskets of calix[4]-1,3-crowns-5,6 complexes

Four nano-baskets of calixarene including cone 25,27-di(carboxymethoxy)calix[4]arene-crown-5, 1,3-alternate 25,27-di[carboxymethoxy]-calix[4]arene-crown-5, cone 25,27-bis[carboxymethoxy]calix[4]arene-crown-6 and 1,3-alternate 25,27-di[carboxymethoxy]-calix[4]arene-crown-6 were synthesized and their binding abilities towards alkali and alkaline earth metals as well as some lanthanides were studied using differential pulse voltammetry. The novelty of this study was investigation of those macrocyclic complexes by voltammetric behaviors of two acidic moieties in each scaffold during complexation of crown ether ring. Their voltammetric behaviors were closely related to the complex formation by entrapment of cation into crown ether cavity and ion–dipole interaction between cation and acidic moieties in calixcrowns. The results revealed the selective changes in voltammetric behavior of synthesized scaffolds toward the cations. Moreover, the position of crown ether in 1,3-alternate instead of cone enhanced the domain of binding ability to more cations. Furthermore, it was shown that those carboxylic acid moieties, which were far from the crown ether ring in the 1,3-alternate, did not affected by encapsulated cations in the coordination space of crown ether and showed no voltammetric behavior.     

Chromatographic behavior of a new hybrid type RP material containing silica bonded 1,3‐alternate 25,27‐bis‐[cyanopropyloxy]‐26,28‐bis‐[3‐propyloxy]‐calix[4]arene

A novel 1,3‐alternate 25,27‐bis‐[cyanopropyloxy]‐26,28‐bis‐[3‐propyloxy]‐calix[4]arene‐bonded silica gel stationary phase (CalixPrCN) was prepared and its structure was confirmed by ATR‐FTIR spectroscopy and elemental analysis. The CalixPrCN phase was characterized in terms of its surface coverage, hydrophobic selectivity, aromatic selectivity, shape selectivity, hydrogen bonding capacity, residue metal content, and silanol activity based on Tanaka, Lindner, and SMR 870 test protocols. The effect of the acetonitrile content on the retention and selectivity of the selected neutral, basic, and acidic solutes was studied. The neutral and acidic analytes exhibited classical RP behavior, in which retention time decreases with increasing acetonitrile content. In contrast, basic analytes showed an increase in retention at low and high percentages of acetonitrile, forming “U‐shaped” retention profiles. The new calixarene phase was compared with previously reported 1,3‐alternate 25,27‐bis‐[propyloxy]‐26,28‐bis‐[3‐propyloxy]‐calix[4]arene stationary phase and commercial cyanopropyl column. The results indicate that the CalixPrCN stationary phase behaves like RP packing; however, inclusion complex formation, dipole–dipole, and π–π interactions seem to be involved in the separation process. The selectivity of this phase was demonstrated in separation of polynuclear aromatic hydrocarbons, non‐steroidal anti‐inflammatory drugs, and sulfonamides as analytes.     

Synthesis of di-substituted calix[4]arene-based receptors for extraction of chromate and arsenate anions

The article describes the synthesis of a family of novel calix[4]arene ionophores, 25,27-bis-(2-aminomethylpyridine-propoxy)-26,28-dihydroxycalix[4]arene (5a), 25,27-bis-(3-aminomethylpyridine-propoxy)-26,28-dihydroxycalix[4]arene (5b) and two chromogenic calix[4]arenes, 5,17-dinitro-25,27-bis-(2-aminomethylpyridine-propoxy)-26,28-dihydroxycalix[4]arene (5c), 5,17-dinitro-25,27-bis-(3-aminomethylpyridine-propoxy)-26,28-dihydroxycalix[4]arene (5d) bearing pyridinium units. In the synthesis, the upper and lower rims of p-tert-butylcalix[4]arene were modified in order to acquire binding sites for the recognition of arsenate and dichromate anions. It has been observed that protonated alkylammonium forms of the ionophores showed high affinity toward dichromate and arsenate anions.     

Metallic macrocycle with a 1,3-alternate calix[4]arene phosphorus ligand

The preparation of an 1,3-alternate calix[4]arene phosphorus ligand, 25,27-bis(2-(diphenylphosphino)ethoxy)-26,28-bis(1-propyloxy)calix[4]arene (3), is presented. Ligand 3 is obtained in three steps in 64% overall yield. Reaction of 3 with [Rh(cot)2]BF4 produced the encapsulated rhodium complex [Rh[(P,P)-diphen-calix[4]arene]]BF4 (4). As revealed by a single-crystal X-ray diffraction study, the rhodium center has a bent coordination environment with a P-Rh-P angle of 135.66(3) degrees. Palladation of 3 employing [Pd(MeCN)4](BF4)2 yielded the chelate palladium complex 7 in which the palladium center has a slightly bent configuration. Treatment of the ligand with Pd(cod)Cl2 and [Pd(eta3-C4H7)(THF)2]BF4 leads to the isolation of the monometallic complex. Full characterization includes X-ray structural studies of compounds 3, 4, and 6.     

Lanthanoid coordination with a tetrazole-substituted calix[4]diquinone and calix[4]dihydroquinone

The tetrazole-functionalised calixdiquinone 5,17-di-tert-butyl-26,28-bis-(1H-tetrazole-5-ylmethoxy)-calix[4]-25,27-diquinone Q was synthesised by chemical oxidation of the bis-tetrazole calix[4]arene precursor using PbO₂/HClO₄. The single crystal X-ray structure determination of Q confirmed the structure and showed binding of a water molecule in the solid state. Chemical reduction of Q to the dihydroquinone QR was achieved using N,N-diethylhydroxylamine. Comparison of the solution phase photophysical properties of Q or QR in the presence of terbium ions showed significant excitation only with QR, suggesting redox switching of the photophysical response may be possible with this or similar receptor.     

Preparation and chromatographic characteristics of calix[4]arene polysiloxane as stationary phases for capillary gas chromatography

Summary Two new kinds of calix[4]arene derivatives, 5, 11, 17, 23-tetra-tert-butyl-25,27-bis(isopropylcarbamoyl-methoxy)-26,28-diundecenyloxy calix[4]arene (C[4]A) and 25,27-dibutoxy-5, 11, 17, 23-tetra-tert-butyl-26,28-diundecenyloxy calix[4]arene (C[4]B0, are prepared and then are polymized by two different processes. Three calix[4]arene polysiloxane stationary phases for capillary gas chromatography are obtained. Their chromatographic characteristics, including column efficiency, polarity, selectivity, glass-transition temperature and thermal stability are studied. Retention mechanisms are also discussed.     

Novel Triphenylamine Appended 1,3-Alternate-Calix[4]arenes: Synthesis and Characterization

In the present study, two novel calix[4]arene receptors containing triphenylamine units in 1,3-alternate conformation have been synthesized and characterized in detail. First, the 25,27-dipropoxy-26,28-bis[(3-aminopropyl)oxy]-calix[4]arene 4 and 25,26,27,28-tetra[(3-aminopropyl)oxy]-calix[4]arene 7 were prepared by using convenient reagents. Then, these amino derivatives of calix[4]arene were converted to Schiff base derivatives appended to triphenylamine of calix[4]arene (5 and 8) using 4-formyltriphenylamine via condensation. The 1,3-alternate conformation of the synthesized calix[4]arenes was determined by ¹H and ¹³C NMR analyses. Also, their structures have been characterized by using ¹H and ¹³C NMR, infrared, and elemental analyses.

Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file.     

酰胺型杯[4]聚硅氧烷用作气相色谱固定相的研究

将合成的两种酰胺型杯「４」聚硅氧烷（ＰＳＯ－Ｃ「４」Ａ和Ｍ－Ｃ「４」Ａ－ＰＳＯ）用作毛细管柱气相色谱固定液,考察了产的色谱特性,柱效、极性及选择性,相变温度和稳定性。结果表明,两种酰胺型杯「４」聚硅氧烷固定液具有优良的色谱性能、多环芳主一些芳香族位置异构体得到较好的分离。     

新型杯[4]芳烃高效液相色谱固定相的制备及表征

合成了一种新型的杯[4]芳烃高效液相色谱键合固定相,考察了它的反相色谱行为．通过对多环芳烃、二取代苯的位置异构体、苯甲酸酯和邻苯二甲酸酯的分离,发现该键合相具有显著的反相特征,对位置异构体具有很高的识别能力,其分离明显优于C18柱,并讨论了可能的分离机理．     

Selective synthesis and isolation of all possible conformational isomers of proximally para-disubstituted calix[4]arene

All six possible conformational isomers of the proximally p-dibrominated calix[4]arene tetraalkyl ether, 1a-f*, were selectively synthesized by appropriate control of stereochemistry during di-O-alkylation reactions of 5,11-dibromocalix[4]arene syn-dialkyl ethers, namely, 5,11-dibromo-27,28-dihydroxy-25,26-dipropoxy-, 5,11-dibromo-25,26-dihydroxy-27,28-dipropoxy-, 5,11-dibromo-25,28-dihydroxy-26,27-propoxy-, and 5,11-dibromo-26,28-dihydroxy-25,27-dipropoxycalix[4]arenes. Their conformations were confirmed by (1)H and (13)C NMR spectroscopy and are cone for 1a (u(Br)(Pr), u(Br)(Pr), u(H)(Pr),u(H)(Pr)), partial cone for 1b (u(Br)(Pr), d(Br)(Pr), u(H)(Pr),u(H)(Pr)) and 1d (u(Br)(Pr), u(Br)(Pr), u(H)(Pr),d(H)(Pr)), 1,2-alternate for 1c (u(Br)(Pr), u(Br)(Pr), d(H)(Pr),d(H)(Pr)) and 1e (u(Br)(Pr), d(Br)(Pr), d(H)(Pr),u(H)(Pr)), and 1,3-alternate for 1f (u(Br)(Pr), d(Br)(Pr), u(H)(Pr),d(H)(Pr)). Although both 1c and 1e are in the 1,2-alternate conformation, the conformation of 1e was found to be strongly distorted and distinct from that of 1c.     

Liquid chromatographic behavior of two alanine‐substituted calix[4]arene‐bonded silica gel stationary phases

Two new kinds of alanine‐substituted calix[4]arene stationary phases of 5,11,17,23‐p‐tert‐butyl‐25,27‐bis(l ‐alanine‐methylester‐N‐carbonyl‐methoxy)‐26,28‐dihyroxycalix[4]arene‐bonded silica gel stationary phase (BABS4) and 5, 11, 17, 23‐p‐tert‐butyl‐25,26,27,28‐tetra(l ‐alanine‐methylester‐N‐carbonyl‐methoxy)‐calix[4]arene‐bonded silica gel stationary phase (TABS4) were prepared and characterized in the present study. They were compared with each other and investigated in terms of their chromatographic performance by using polycyclic aromatic hydrocarbons, disubstituted benzene isomers, and mono‐substituted benzenes as solute probes. The results indicated that both BABS4 and TABS4 exhibited multiple interactions with analytes. In addition, the commonly used Tanaka characterization protocol for the evaluation of commercially available stationary phases was applied to evaluate the properties of these two new functionalized calixarene stationary phases. The Tanaka test results were compared with Zorbax Eclipse XDB C₁₈ and Kromasil phenyl columns, respectively. BABS4 has stronger hydrogen‐bonding capacity and ion‐exchange capacity than TABS4, and features weaker hydrophobicity and hydrophobic selectivity. Both of them behave similarly in stereoselectivity. Both BABS4 and TABS4 are weaker than C₁₈ and phenyl stationary phases in hydrophobicity and hydrophobic selectivity.     

Synthesis and Cesium Binding Affinity of New 25,27-Bis(alkyloxy)calix[4]arene-crown-6 Conformers in Relation to the Alkyl Pendent Moiety

The preparation of new 25,27-bis(alkyloxy)calix[4]arenes-crown-6 in the cone, partial-cone and 1,3-alternate conformation is reported. We have also investigated the alkylation of the cone monoalkylated calix[4]arene-crown-6 achieved using Cs 2 CO 3 . This reaction afforded a mixture of cone and partial-cone calix[4]arenes-crown-6 having an alkyl chain anti or syn to the polyether ring. Conformations have been probed using 1 H, 13 C, 2D-NMR and NOESY analysis, and using X-ray crystallography. Extraction experiments using a two-phase solvent method involving cesium picrate were performed for these newly synthesized conformers. They reveal and confirm the strong preference for the 1,3-alternate conformers. The affinity of 1,3-alternate calixarenes for Cs + has been assessed by complexation measurements (log g ) using a spectrophotometric technique. No significant Cs + extraction difference was observed in relation to the nature of the alkyl chains on the aromatic rings. 1 H NMR studies of the 1,3-alternate calixarene Cs + complexes confirms the cation's spacial position between the two aromatic rings, due to cation- ~ interactions.     

Selective adsorption of potassium and rubidium by metal–organic frameworks supported supramolecular materials

Journal of Radioanalytical and Nuclear Chemistry - A new MOFs-based adsorbent UiO-66@iPCC5 was prepared by hybridization of 25,27-bis(iso-propoxyl)-calix[4]arene-26,28-crown-5 (iPCC5) into the...     

First Synthesis of 1,3-Alternate 25,27-Dialkyloxy-5,17-diarylcalix[4]arenes-crown-6 as New Cesium Selective Extractants by Suzuki Cross-coupling Reaction

The synthesis of new 25,27-dialkyloxy-5,17-diarylcalix[4]arenes-crown-6 1a–f in 1,3-alternate conformation by Suzuki cross-coupling reaction is reported. Their conformation was determined using ¹H, ¹³C, 2D NMR and ROESY analysis, and X-ray crystallography. Extraction experiments using a two-phase solvent method involving sodium, potassium or cesium picrate showed good extraction of the cesium cation. The X-ray crystal structures of 1,3-alternate 25,27-dipropoxy-5,17-diphenylcalix[4]arene-crown-6 ether 1a and its cesium picrate complex were established. Solid-state data were used to determine the complexation behavior of these new ligands. The efficiency of calixarenes 1a–f for cesium ion extraction could be ascribed to the rigidity and flatness linkages caused by the aryl groups at the lower rim of the aromatic moieties in the calixarene skeleton. In addition, the introduction of these aromatic moieties in positions 5 and 17 enhanced the solubility of the metal complexes in organic media.     

Synthesis, Structure, and Extraction Properties of paco-Calix[4]arene Crown-6 Ethers

anti-25,27-Bis-n-octyloxycalix[4]arene, the paco-isomer of25,27-bis-n-octyloxycalix[4]arene crown-6 ether, and the paco- and1,3-alt isomers of 25,27-bis-n-octyloxycalix[4]arene t-butylbenzocrown-6 ether were prepared. The crystal structures of anti-25,27-bis-n-octyloxycalix[4]arene, paco-25,27-bis-n-octyloxycalix[4]arene crown-6, and 1,3-alt-25,27-bis-n-octyloxycalix[4]arene crown-6 were determined and thesolution structure of anti-25,27-bis-n-octyloxycalix[4]arene was studied by 2D- and VT-NMR. The extraction of alkali metal nitrates by thepaco-25,27-bis-n-octyloxycalix[4]arene crown-6 and t-butylbenzocrown-6 ethers in 1,2-dichloroethane was compared to that of the corresponding 1,3-alt isomers.