248590-47-8Relevant articles and documents
Tuning and enhancing enantioselective quenching of calixarene hosts by chiral guest amines
Lynam,Jennings,Nolan,Kane,McKervey,Diamond
, p. 59 - 66 (2002)
The synthesis of a propranolol amide derivative of p-allylcalix[4]arene is described, which has been designed to behave as a molecular sensor capable of distinguishing chiral amines on the basis of their shape and chirality. This molecule can discriminate between the enantiomers of phenylalaninol through the quenching of the fluorescence emission in methanol in contrast to an (S)-dinaphthylprolinol calix[4]arene derivative, which can discriminate between the enantiomers of phenylglycinol, but not phenylalaninol. The separation between the naphthyl fluorophores and the hydrogen-bonding sites within the chiral cavity can be tuned to recognize guest amines with similar separation between aryl groups and hydrogen-bonding sites. The formation of metal ion complexes of the p-allylcalix[4]arene propranolol amide derivative is shown to induce a more regular and rigid cone conformation in the calix[4]arene macrocycle, which generates a significant enhancement in the observed enantiomeric discrimination.
A Calixarene-Based Metal–Organic Framework for Highly Selective NO2 Detection
Schulz, Marcel,Gehl, Adrian,Schlenkrich, Jakob,Schulze, Hendrik A.,Zimmermann, Stefan,Schaate, Andreas
, p. 12961 - 12965 (2018)
A calixarene-based metal–organic framework (Zr-cal, [Zr6O4(OH)4(FA)6]2(cal)3], FA=formate, cal=1,3-alt-25,26,27,28-tetrakis[(carboxy)methoxy]calixarene) was synthesized and characterized by single-crystal X-ray diffraction. The three-dimensional framework is a 4,6-connected network of gar topology and exhibits two equal but nonintersecting three-dimensional pore systems. It has a specific BET surface area of 670 m2 g?1, and the calixarene cavities are accessible through the pore systems. The exposed calixarenes can be used for the visual detection and encapsulation of NO2 through the formation of deeply colored charge–transfer complexes inside the MOF. The highly selective complexation was analyzed by UV/Vis and IR spectroscopy, and the stability of the material was confirmed by powder X-ray diffraction and 1H NMR spectroscopy. Finally, the MOF was used as a sensor material in a home-made sensor cell and showed high sensitivity for NO2.
Synthesis of selectively formylated calixarene ethers
Arora, Vandna,Chawla,Santra, Anuradha
, p. 5591 - 5597 (2002)
By careful choice of a catalyst (TiCl4 or SnCl4), temperature, reaction time and mole ratio of the substrate to dichloromethylmethylether, it has been possible to obtain new functionalized formylated calix[n]arenes in the cone or partial cone conformation. Optimized general reaction procedures for obtaining mono-, di-, tri- and tetraformylated derivatives of calix[4]arenes as exemplified by formylation of tetramethoxy-, tetrakis(2-ethoxyethoxy)-, bis(ethoxycarbonylmethoxy)- and bis(hexadecyloxy)-calix[4]-arenes have been reported.
A new calix[4]azacrown ether based boradiazaindacene (Bodipy): Selective fluorescence changes towards trivalent lanthanide ions
Bayrakci, Mevlüt,Kursunlu, Ahmed Nuri,Güler, Ersin,Ertul, ?eref
, p. 268 - 274 (2013)
We report on the synthesis and photophysical properties of a new calix[4]azacrown derivative, capped with two amide bridges, in the cone conformation bearing two boradiazaindacene (Bodipy) groups at the narrow rim. Its binding properties towards trivalent
Complexation of calix[4]arene protected gold nanoparticles with pyridinium and bipyridinium compounds
Pulkkinen, Petri M. S.,Wiktorowicz, Szymon,Aseyev, Vladimir,Tenhu, Heikki
, p. 733 - 742 (2013)
Calix[4]arene and calix[4]arene/alkanethiol protected gold nanoparticles with narrow size distributions were synthesised and characterized with NMR, thermogravimetric analysis (TGA) and a transmission electron microscope (TEM). NMR and light scattering (LS) were used to study the complexation of the nanoparticles with a pyridinium modified polyethylene oxide (Pyr-PEO2k-Pyr) complexant and a small 16 carbon pyridinium compound (Pyr-C16). Results give clear evidence of complexation induced aggregation of the nanoparticles as pyridinium proton signals shift upon changing the host: guest ratio and LS shows a change from a narrow size distribution into a broad one. The addition of alkanethiols with longer dimensions than that of the calixarene derivative and the type of the complexant can be used to tune the complexation. The studies also provide evidence of induced fit complexation into calix[4]arene cavities and solution phase interdigitation (secondary monolayer formation) when the nanoparticles are complexed with Pyr-C16.
A novel fluorescent sensor for Fe3+ and Cr3+ based on a calix[4]arene bearing two coumarin units
Wang, He-Wen,Feng, Ya-Qing,Meng, Shu-Xian
, p. 587 - 589,3 (2012)
A novel turn-on fluorescent sensor based on a calix[4]arene with two coumarin units as fluorophores and iminogroups as ionophores on the upper rim has been synthesised. Its recognition properties towards heavy and transition metal ions have been studied by UV-Vis and fluorescence spectrometry. The compound showed an enhanced fluorescent intensity in the presence of Fe 3+ or Cr3+ ion, a high selectivity to Fe3+ or Cr3+ ions and a complexation ratio towards Fe3+ or Cr 3+ of 1:1. The association constant for Fe3+ was 5.37×105 M-1 and for Cr3+ was 9.18×105 M-1.
Synthesis, crystal structures and competitive binding property of a family of calix[4]arene-biscrown-5/6 and their application in extraction of alkali metal ions from sea bittern
Ramakrishna, Vallu,Suresh,Boricha, Vinod P.,Bhatt, Anjani K.,Paul, Parimal
, p. 65 - 77 (2015)
Abstract A family of calix[4]arene compounds containing crown moieties at both the upper and lower rims of the calix unit with different substituents attached to the nitrogen atom of the aza-crown moiety have been synthesized, characterized and their competitive binding property towards Li+, Na+, K+, Mg2+, Ca2+ and Sr2+ in aqueous media has been investigated. These ionophores exhibit high selectivity towards K+, assessed by two-phase extraction method followed by ion chromatographic assay of the metal ions in the extract. Isothermal calorimetric titration for complex formation with K+ was carried out to evaluate stoichiometry, binding constant and other thermodynamic parameters (ΔH, ΔS and ΔG). For structural elucidation in solution, detail 1H NMR study was carried out and K+ complexes were isolated for solid state characterization. Molecular structures of two of the ionophores and K+-complex of one of the ionophores has been established by single crystal X-ray study. 1H NMR, ITC and single crystal XRD studies suggest 1:1 complex formation with encapsulation of K+ in the crown-6 ring at the upper rim. These ionophores have been applied for extraction of metal ions from bittern.
Study on thermal decomposition of calix[4]arene and its application in thermal stability of polypropylene
Chennakesavulu,Basariya, M. Raviathul,Sreedevi,Bhaskar Raju,Prabhakar,Rao, S. Subba
, p. 24 - 31 (2011)
Thermal decomposition kinetics of calix[4]arene (C4) was investigated using thermogravimetric analysis (TGA) and derivative of TG curve (DTG). TG experiments were carried out under static air atmosphere with nominal heating rates of 1.0, 2.5, 5.0 and 10.0 K/min. Model-fitting methods and model-free methods such as Friedman and Ozawa-Flynn-Wall methods were employed to evaluate the kinetic parameters such as activation energy (Ea), exponential factor (ln A) and reaction order (n). To determine the antioxidant property of C4 the non-isothermal kinetics of polypropylene (PP) with C4 as additive was studied. The FTIR, ESR and 13C NMR CP-MAS techniques were used to propose the decomposition mechanism of C4 in the presence of PP.
The light-driven macroscopic directional motion of a water droplet on an azobenzene-calix[4]arene modified surface
Cheng, Jing,Dhinakaran, Manivannan Kalavathi,Li, Haibing,Tan, Shiliang,Zhu, Fei
, p. 10922 - 10925 (2020)
A novel photo-responsive surface was constructedviamodifying azobenzene-calix[4]arene (ABC4) on a microstructured silicon surface. Asymmetric UV light irradiation could drive the macroscopic directional motion of a water droplet on this photo-responsive surface.
Mo(CO)6-mediated synthesis of calix[4]arenes carrying β-hydroxy ketones or α,β-unsaturated-β-amino ketones
Senthilvelan, Annamalai,Tsai, Ming-Tsung,Chang, Kai-Chi,Chung, Wen-Sheng
, p. 9077 - 9081 (2006)
Mo(CO)6-mediated ring opening reactions of calix[4]arene isoxazolines/isoxazoles provide a new synthetic methodology for calix[4]arenes carrying bifunctional β-hydroxy ketones or α,β-unsaturated-β-amino ketones. Mo(CO)6 is a highly s
Membrane-active calixarenes: toward 'gating' transmembrane anion transport
Okunola, Oluyomi A.,Seganish, Jennifer L.,Salimian, Kevan J.,Zavalij, Peter Y.,Davis, Jeffery T.
, p. 10743 - 10750 (2007)
This paper describes on-going efforts to develop calixarene amides as transmembrane anion transporters. We report on the transport of Cl- anions across phospholipid membranes as mediated by some lipophilic calixarenes, all fixed in the cone conformation. We present significant findings regarding use of these calixarenes as transmembrane Cl- transporters: (1) the cone conformer cone-H 2a, like its 1,3-alt and paco isomers, transports Cl- across liposomal membranes; (2) the conformation of the calixarene (paco-H 1 vs cone-H 2a) is important for modulating Cl- transport rates; (3) the substitution pattern on the calixarene's upper rim is crucial for Cl- transport function; and (4) at least one of the four arms of the calixarene can be left unmodified without loss of function, enabling development of a pH-sensitive anion transporter (TAC-OH 3). This last finding is useful given the interest in gating the activity of synthetic ion transporters with external stimuli.
Synthesis and structural analysis of an infinite linear coordination network formed by the self-assembly of tetracyanocalix[4]arene ligands and silver cations
Mislin, Gilles,Graf, Ernest,Hosseini, Mir Wais,De Cian, Andre,Kyritsakas, Nathalie,Fischer, Jean
, p. 2545 - 2546 (1998)
Using the O-alkylation of the lower rim of the calix[4]arene to impose the 1,3-alternate conformation and the functionalisation of the upper rim to set-up four nitrile groups pointing in a divergent fashion, an exo-ligand capable of forming linear coordination networks was obtained; upon self-assembly of the latter and silver cation, a linear coordination polymer was obtained and structurally analysed in the solid state by an X-ray study.
Competitive self and induced aggregation of Calix[4]arene ethers and their interaction with pinacyanol chloride and methylene blue in nonaqueous media
Pandey, Shubha,Kar, Jyotsna R.,Azam, Amir,Pandey, Siddharth,Chawla
, p. 107 - 120 (2010)
Long chain calix[4]arene ethers have been examined for aggregation in nonaqueous solvents by using UV-vis molecular absorbance spectroscopy. It has been observed that tetraalkylated (alkyl = hexadecyl and octadecyl, respectively) calix[4]arene ethers tend to aggregate in chloroform and tetrahydrofuran, possibly via π-π stacking interactions of the phenyl moieties, and the aggregation process appears to be facilitated by the alkyl chains. The analogous dialkylated compounds do not show any self-aggregation, plausibly due to strong hydrogen bonding between the -OH and the -O- of calix aryl ether which seems to disrupt the aggregation process. Addition of the anionic surfactant sodium dodecylsulfate (SDS) appears to hinder the aggregation process in nonpolar chloroform but the same surfactant facilitates aggregation in the polar tetrahydrofuran. The cationic surfactant (cetyltrimethyl ammonium bromide) and the nonionic surfactant (Brij-35) have no effect on this aggregation process. Unexpectedly, SDS induces aggregation of dialkylated calix[4]arene ethers in chloroform. It has been observed that the aggregated form of the tetraalkylated calix[4]arene ethers tend to increase the dimerization efficiency of cationic dyes (pinacyanol chloride and methylene blue) in chloroform.
Ion sensing of sister sensors based-on calix[4]arene in aqueous medium and their bioimaging applications
Alizada, Malak,Gul, Alev,Kursunlu, Ahmed Nuri,Oguz, Mehmet,Yilmaz, Mustafa
, (2021)
Here, sister calix[4]arene derivatives containing two NBD (7-nitro-benzofurazan) units in 1,3-(distal) derivatives (sensors 4&8) were prepared and characterized by 1H, 13C NMR, FTIR, elemental analysis, and fluorescence spectroscopy. The ion binding properties of multi-channel sensors 4&8 were performed in the presence of various cations and anions. Both sensor compounds, 4&8, showed “on–off” type fluorescence response towards Cu2+ cation and H2PO4?&F? anions with high selectivity in aqueous solution (CH3CN/H2O, 4/1, v/v). The connected spectroscopic parameters were investigated as the complex stoichiometry, binding constant etc. for a better result. Moreover, the lowest detection limit of 4 for sensing Cu2+ and H2PO4?&F? were obtained 2.4 × 10?8, 9.1 × 10?7, 9.7 × 10?7 mol/L respectively. the lowest detection limit of Cu2+ and H2PO4?&F? by 8 was obtained as 2.9 × 10?8, 9.7 × 10?7, 8.9 × 10?7 mol/L respectively. The confocal microscope was performed to investigate the sensor properties of 4&8 towards ions on living cells. Sensors 4 and 8 showed fluorescence properties on the A549 cell line, while it was observed to turn off the fluorescence intensity in cells treated with H2PO4?, F? and Cu2+ ions. Besides, compounds 4 and 8 can be used to identify H2PO4?, F? and Cu2+ ions in living cells.
Joining a host-guest platform and a light-emission motif: Pyrazinamide-calixarene hybrids
Alvarenga, Meiry Edivirges,Alves, Rosemeire Brondi,Guimar?es, Freddy Fernandes,Lara, Thiago Vinicius Costa,Maia, Lauro June Queiroz,Martins, Felipe Terra,da Silva, Cleiton Moreira,de Santana, Ricardo Costa
, (2022/03/07)
Calixarenes are macrocyclic polyphenols widely used as hosts in supramolecular chemistry approaches. Recently, aminopyrazine has emerged as a high-efficiency blue light emitting moiety. Inspired by this knowledge, here we prepared two pyrazinamide-calixarene hybrids, in order to join in a single molecular platform both host-guest and light-emission properties. Both compounds were decorated with pyrazinamide at the upper rim, on two phenyl rings alternated into the four-units of the calixarene macrocycle. Their difference was the t?butyl substitution on the other two alternate phenyl rings. The t?butyl substituted derivative crystallized in two crystal forms, a non-solvated and a DMF mono-solvate phase, both with just one crystallographically independent hybrid molecule, while the compound without t?butyl moieties crystallized with three hybrid conformers and four DMF molecules. The molecular substitution pattern has also impacted on the crown conformation, being related to more inclined pyrazinamide-phenyl average planes in the absence of the t?butyl substituents. The coplanarity pattern between pyrazinamide and its bonded phenyl ring and the conformational profile of this substituent changed among the three conformers of derivative without the t?butyl group and between those assembling the two crystals forms of the other compound, which was also found in our DFT calculations. Under an excitation wavelength of 388 nm, a broad band emission between 400 nm and 550 nm was found for the three crystal forms, with maxima at ca. 500 nm, with low quantum yields of up to 0.4%. TD-DFT absorption spectra were overlaid to the experimental excitation spectra, while the low efficiency was rationalized both as an effect of the DMF guest and the tail-to-tail π…π stacking interactions between coplanar pyrazinamide-phenyl moieties of the centrosymmetric related molecules.
Synthesis of new calix[4]arene derivatives and evaluation of their cytotoxic activity
Oguz, Mehmet,Yildirim, Ayse,Durmus, Irem Mukaddes,Karakurt, Serdar,Yilmaz, Mustafa
, p. 52 - 59 (2021/11/03)
Since calixarenes are more easily synthesized and functionalized than other supramolecules, they are compounds of interest in organic chemistry. In this study, the dihydrazide (3a and 3b) and diamino propyl (6a and 6b) derivatives of p-tert-butylcalix[4]arene and calix[4]arene were synthesized. Then the L-proline methyl ester substituted chlorocyclopropenium was reacted with the calix[4]arene derivatives (3a, 3b, 6a, and 6b) at room temperature in CH2Cl2 to obtain calix[4]arene superbase derivatives (4a, 4b, 7a, and 7b) in 75%, 60%, 70%, and 55% yield, respectively. The synthesized compounds’ structure was elucidated using spectroscopic techniques (FTIR, 1H NMR, and 13C NMR). The cytotoxic properties of the calix[4]arene superbase derivatives were investigated against different human cancer cell, including A549, DLD-1, HEPG2, and PC-3 and human healthy epithelium cell line PNT1A. The cytotoxicity results showed that calix[4]arene superbase derivatives inhibited the proliferation of DLD-1, A549, HEPG2, and PC-3 cells in a dose-dependent manner. Compound 7a had the highest toxic effect on colorectal carcinoma (IC50: 4.7 μM), and the IC50 values were 18.5 μM and 74.4 μM against human prostate and lung cancer cells, respectively. Furthermore, compound 4b was found more effective on hepatocellular carcinoma cells (IC50: 210.2 μM). As a result, the synthesized calix[4]arene superbase derivatives can be developed to treat different human cancer cell. They can be considered as a preliminary result for molecular-level research. [Figure not available: see fulltext.]
Optimization of toxic metal adsorption on DEA-calix[4]arene appended silica resin using a central composite design
Gul, Samiha,Memon, Fakhar N.,Memon, Shahabuddin
, p. 3448 - 3463 (2022/02/21)
The present study is devoted to the application of Central Composite Design (CCD) to purify water contaminated with toxic metal ions (Pb2+, Cd2+ and Hg2+) using a p-tert-diethanolaminomethylcalix[4]arene (DEA-C4) based silica resin. The synthesized material was characterized using SEM, FTIR and EDX techniques. Three effective parameters (pH, adsorbent dosage and concentration of metal ion) were optimized by assessment with CCD. The data was analyzed using the quadratic model and the obtained results revealed the highest % adsorptions for Pb2+ (92.7), Cd2+ (93.7) and Hg2+ (88.2) at the optimum points for pH (5.4, 3.18 and 3.89), adsorbent dosage (23.8, 25.5 and 26.12 mg) and metal ion concentration (5.3, 7.62 and 7.18 ppm), respectively. Analysis of variance (ANOVA) results show a good fit for the regression model, showing R2 values of 0.99 for Pb2+, 0.99 for Cd2+ and 0.98 for Hg2+. Furthermore, the results from Freundlich adsorption isotherms suggest its favorability, as the values for n are >1 (i.e., 7.06, 8.85 and 13.2) and there are higher values for R2 = 0.97, 0.99 and 0.98 for Pb2+, Cd2+ and Hg2+, respectively. However, for the Langmuir isotherm, the value of the separation factor RL is >1 (1.01, 1.02 and 1.05 for Pb2+, Cd2+ and Hg2+, respectively), revealing its un-favorability. In kinetics, the pseudo-second-order kinetic model (Ho and McKay) shows R2 values of 0.998, 0.999 and 0.999 for Pb2+, Cd2+ and Hg2+, suggesting the chemical reaction seems significant in the rate controlling step. The thermodynamic results concluded that the reaction is spontaneous and exothermic in nature.
