113215-72-8Relevant articles and documents
A new chiral stationary phase for gas chromatography by use of a chiral thiacalix[4]arene derivative
Iki, Nobuhiko,Narumi, Fumitaka,Suzuki, Tomohiro,Sugawara, Atsushi,Miyano, Sotaro
, p. 1065 - 1066 (1998)
A new chiral stationary phase for capillary gas chromatography based on a chirally modified p-tert-butylthiacalix[4]arene with (S)-1-phenylethylamine was prepared to show good separations of enantiomeric amino acid, amine and alcohol derivatives, while the corresponding p-tert-butylcalix[4]arene counterpart did not differentiate the enantiomers.
An integrated approach (thermodynamic, structural, and computational) to the study of complexation of alkali-metal cations by a lower-rim calix[4]arene amide derivative in acetonitrile
Horvat, Gordan,Stilinovic, Vladimir,Hrenar, Tomica,Kaitner, Branko,Frkanec, Leo,Tomisic, Vladislav
, p. 6264 - 6278 (2012)
The calix[4]arene secondary-amide derivative L was synthesized, and its complexation with alkali-metal cations in acetonitrile (MeCN) was studied by means of spectrophotometric, NMR, conductometric, and microcalorimetric titrations at 25 °C. The stability constants of the 1:1 (metal/ligand) complexes determined by different methods were in excellent agreement. For the complexation of M+ (M = Li, Na, K) with L, both enthalpic and entropic contributions were favorable, with their values and mutual relations being quite strongly dependent on the cation. The enthalpic and overall stability was the largest in the case of the sodium complex. Molecular and crystal structures of free L, its methanol and MeCN solvates, the sodium complex, and its MeCN solvate were determined by single-crystal X-ray diffraction. The inclusion of a MeCN molecule in the calixarene hydrophobic cavity was observed both in solution and in the solid state. This specific interaction was found to be stronger in the case of metal complexes compared to the free ligand because of the better preorganization of the hydrophobic cone to accept the solvent molecule. Density functional theory calculations showed that the flattened cone conformation (C2 point group) of L was generally more favorable than the square cone conformation (C4 point group). In the complex with Na+, L was in square cone conformation, whereas in its adduct with MeCN, the conformation was slightly distorted from the full symmetry. These conformations were in agreement with those observed in the solid state. The classical molecular dynamics simulations indicated that the MeCN molecule enters the L hydrophobic cavity of both the free ligand and its alkali-metal complexes. The inclusion of MeCN in the cone of free L was accompanied by the conformational change from C2 to C4 symmetry. As in solution studies, in the case of ML+ complexes, an allosteric effect was observed: the ligand was already in the appropriate square cone conformation to bind the solvent molecule, allowing it to more easily and faster enter the calixarene cavity.
Preparation and investigation of temperature-responsive calix[4]arene-based molecular gels
Cai, Xiuqin,Xu, Yunhua,Yang, Rong,Yang, Hui
, p. 28476 - 28482 (2017)
A novel calix[4]arene-based tetracholesteryl derivative was synthesized, and its gelation behaviours in 30 organic solvents were studied. It showed that 1 gelled long chain alkane, some of alcohol, kerosene, ethyl acetate benzene and toluene. Interestingly the gel of 1/kerosene possessed special property, which was that the mixture solution of the compound 1/kerosene heating for a while was put on the flat contact heater and formed a gel film at 25 °C and 65 °C. Unlike ordinary film, gel film had higher strength and toughness at 65 °C, by contrast other was fragile and broken easily at 25 °C, this phenomenon was few reported before. In order to explore the phenomenon, the mechanism of the gel of 1/kerosene was discussed by Scanning Electron Microscope (SEM), High Nuclear Magnetic Resonance (H NMR), Fourier Transform Infrared Spectrometer (IR) and micro-rheology. SEM revealed that the xerogel of 1/kerosene assembled network through some long and thick fibers at 65 °C, with concentration reducing fibers become thin and its networks were clearly observed. In contrast the morphology of xerogel was porous at low concentration and was a bulk at high temperature system. According to EI data in micro-rheology, the gelation process could be divided into three stages at 65 °C and they could be that some cholesterol segments in the gelator interacting with each other formed some small aggregation in the first stage, and other cholesterol section of the gelator sufficiently were cross-linked with time and assembled into large assembly in the second plateau. In the final moment the large assembly build gel network and the system of gel tended to stable. But there are two stages at low temperature and could be some cholesterol segments that didn't take part in assembly, which may be the cause that the performance of gel was fragile.
Synthesis and extraction properties of new 'proton-switchable' tri-?and tetra-substituted calix[4]arene derivatives bearing pyridinium units
Tabakci, Mustafa,Memon, Shahabuddin,Yilmaz, Mustafa
, p. 6861 - 6865 (2007)
The article describes the syntheses and complexation properties of new calixarene-based extractants, which have been synthesized?from 5,11,17,23-tetra-tert-butyl-25,26,27-tris(chlorocarbonylmethoxy)-28- hydroxycalix[4]arene and 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis(chlorocarbonylmethoxy) calix[4]arene by treatment with isoniazid (isonicotinic acid hydrazide) in the presence of pyridine, respectively. p-tert-Butylcalix[4]arene teraamide was converted to its methyl iodide salt by refluxing with methyl iodide in acetonitrile. In this synthesis it was thought to explore the role of pyridinium sites in the extraction of HCr2O7-/Cr2O7 2- anions. The complexing properties of the extractants toward selected alkali/transition metal cations and HCr2O7-/Cr2O7 2- anions are reported. It has been observed that both receptors do not extract alkali metal cations but show excellent selectivity toward transition metals. The protonated pyridinium forms of the receptors are effective for transferring the HCr2O7-/Cr2O7 2- anions from an aqueous into a dichloromethane layer.
FRET-based Solid-state Luminescent Glyphosate Sensor Using Calixarene-grafted Ruthenium(II)bipyridine Doped Silica Nanoparticles
Ashwin, Bosco Christin Maria Arputham,Saravanan, Chokalingam,Stalin, Thambusamy,Muthu Mareeswaran, Paulpandian,Rajagopal, Seenivasan
, p. 2768 - 2775 (2018)
Calixarene-functionalized luminescent nanoparticles were successfully fabricated for the FRET-based selective and sensitive detection of the organophosphorus pesticide glyphosate (GP). p-Tert-butylcalix[4]arene was grafted on the surface of [Ru(bpy)3]2+ incorporated SiNps to produce self-assembled nanosensors (RSC). FRET was switched on in the presence of GP by means of energy transfer due to binding with p-tert-butylcalix[4]arene grafted on the surface of the RSC. The FRET efficiency of the GP-RSC system was increased gradually with the addition of GP. The FRET efficiency was evaluated as 87.69 % and a high binding affinity was established by the binding constant value, 1.16×107 M?1, using a Langmuir binding isotherm plot. The estimated limit of detection (LOD) was 7.91×10?7 M, which was lower than the Environmental Protection Agency (EPA) recommendation. The probe also effectively responds to real sample analysis. The sensitivity and selectivity was realized due to the efficient FRET towards the fluorescence properties of the [Ru(bpy)3]2+ complex.
A Novel Calixarene Tetraester with Fluorescent Response to Complexation with Alkali Metal Cations
Perez-Jimenez, Consuelo,Harris, Stephen J.,Diamond, Dermot
, p. 480 - 483 (1993)
A new metal sensing compound, a calixarene having four anthracene moieties on the lower rim has been synthesized; the intensity of its fluorescence spectrum is markedly affected by alkali metal ion complexation.
4-tert-Butylcalix[4]arenes containing azacrown ether substituents at the narrow rim as membrane carriers
Ivanova,Prokhorova,Morzherin,Lukyanenko,Alekseeva,Basok
, p. 905 - 908 (2015)
Calixarenes substituted at the narrow rim with one or four N-methoxycarbonylmonoaza12-crown-4 moieties were used in liquid membranes to transport transition metal chlorides.
Synthesis and cation binding properties of fluorescent calix[4]arene derivatives bearing tryptophan units at the lower rim
Galic, Nives,Buric, Natas,Tomas, Renato,Frkanec, Leo,Tomisic, Vladislav
, p. 389 - 397 (2011)
The fluorescent peptidocalixarenes, 5,11,17,23-tetra-tert-butyl-25,26,27, 28-tetrakis(O-methyl-L-tryptophanylcarbonylmethoxy) calix[4]arene (1) and 5,11,17,23-tetra-tert-butyl-25,27-di(O-methyl)-26,28-bis(O-methyl-L- tryptophanylcarbonylmethoxy) calix[4]arene (2), were prepared by introducing tryptophan subunits at a lower calixarene rim. Coordination abilities of 1 and 2 towards Eu(III) and alkali metal cations were studied by spectrophotometric, spectrofluorimetric, conductometric and potentiometric titrations in acetonitrile at 25°C. Rather strong complexation was observed for smaller alkali metal cations Li+ and Na+ (logKLi1 > 6, log KLi2 > 6, log KNa1 = 8.25, logKNa2 = 6.94), and moderate for K+ (logKK1 = 5.09, log K K2 = 4.09). Larger Rb+ and Cs+ cations did not fit in the ion binding site of 1 so no complexation was detected, whereas the more flexible ligand 2 accommodated Rb+ cation (logKRb2 = 3.44). The fluorescence of 1 (λex = 280 nm, λem = 340 nm) was remarkably quenched by Eu(III). Stability constant of 1:1 (Eu3+:1) complex determined spectrofluorimetrically amounted to log KEu1 = 6.16.
Low-generation dendrimers with a calixarene core and based on a chiral C2-symmetric pyrrolidine as iminosugar mimics
Marradi, Marco,Cicchi, Stefano,Sansone, Francesco,Casnati, Alessandro,Goti, Andrea
, p. 951 - 957 (2012)
The preparation of low-generation dendrimers based on a simple calix[4]arene scaffold by insertion of the iminosugar-analogue C 2-symmetric 3, 4-dihydroxypyrrolidine is described. This methodology allows a rapid incorporation of a considerable number of iminosugar-like moieties in a reduced volume and in a well-defined geometry. The inclusion of alkali-metal ions (sodium and potassium) in the polar cavity defined by the acetamide moieties at the lower rim of the calixarene was demonstrated, which allows also the rigidification of the dendrimer structure and the iminosugar presentation in the clusters. The combination of the supra-molecular properties of calixarenes with the advantage of a dendrimeric presentation of repetitive units opens up the possibility of generating well-defined multivalent and multifaceted systems with more complex and/or biologically relevant iminosugars.
Molecular scaffolds for di-metallic complexation: The synthesis, characterisation and complexation properties of tetrakis-terpyridinyl-calix[4]arene
Molard, Yann,Parrot-Lopez, Hélène
, p. 6355 - 6358 (2002)
The ligand tetrakis-terpyridinyl-calix[4]arene is used as a rigid scaffold and pre-organiser of supramolecular assemblies by complexation of the Ni(II), Cu(II) and Co(II) cations. The ligand synthesis was carried out using peptide synthesis conditions by coupling 4′-(2-aminoethoxy)-2,2′/6′,2′′-terpyridine to the tetra-succinimidoyl activated ester of p-tert-butylcalix[4]arene. The studies on complexation by UV show the existence of M2L-type complexes.
