- Tuning and enhancing enantioselective quenching of calixarene hosts by chiral guest amines
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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.
- Lynam,Jennings,Nolan,Kane,McKervey,Diamond
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- Synthesis and toxicology of p-phosphonic acid calixarenes and O-alkylated analogues as potential calixarene-based phospholipids
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A series of p-phosphonic acid calix[n]arenes 1a-g bearing hydroxy groups, n=4 and 5, or alkyl chains of varying lengths at their lower rim, n=4, were synthesised, and in vitro assessments of their effect on cell viability in rat PC12 cells and primary cultures of mixed retinal cells were conducted. Compounds 1a and 1g, bearing hydroxy groups at their lower rim, displayed lower toxicity towards PC12 cells than their alkylated counterparts; concentrations of up to 1 mgmL-1 did not affect the number of viable cells. Mixed retinal cultures showed a higher susceptibility towards toxic effects for all calixarenes tested. Compound 1b self-assembles into nanofibres from a toluene solution, and 1c assembles into micelles from an aqueous solution, with these nanoscale architectures showing potential applications for various biological roles, such as solubilising p-nitrophenol and curcumin.
- Martin, Adam D.,Houlihan, Emma,Morellini, Natalie,Eggers, Paul K.,James, Eliza,Stubbs, Keith A.,Harvey, Alan R.,Fitzgerald, Melinda,Raston, Colin L.,Dunlop, Sarah A.
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- A Calixarene-Based Metal–Organic Framework for Highly Selective NO2 Detection
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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.
- Schulz, Marcel,Gehl, Adrian,Schlenkrich, Jakob,Schulze, Hendrik A.,Zimmermann, Stefan,Schaate, Andreas
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- A nanodrug to combat cisplatin-resistance by protecting cisplatin with p-sulfonatocalix[4]arene and regulating glutathione S-transferases with loaded 5-fluorouracil
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A nanodrug that can effectively combat cisplatin-resistant A549/CDDP cells was developed by protecting cisplatin from glutathione (GSH) detoxification trough a host-guest interaction between cisplatin and p-sulfonatocalix[4]arene. The enzymatic activity o
- Dai, Xin,Zhou, Xueying,Liao, Chunyan,Yao, Yongchao,Yu, Yunlong,Zhang, Shiyong
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- Synthesis of selectively formylated calixarene ethers
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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.
- Arora, Vandna,Chawla,Santra, Anuradha
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- A Calix[4]arene-Based Cyclic Dinuclear Ruthenium Complex for Light-Driven Catalytic Water Oxidation
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A cyclic dinuclear ruthenium(bda) (bda: 2,2’-bipyridine-6,6’-dicarboxylate) complex equipped with oligo(ethylene glycol)-functionalized axial calix[4]arene ligands has been synthesized for homogenous catalytic water oxidation. This novel Ru(bda) macrocycle showed significantly increased catalytic activity in chemical and photocatalytic water oxidation compared to the archetype mononuclear reference [Ru(bda)(pic)2]. Kinetic investigations, including kinetic isotope effect studies, disclosed a unimolecular water nucleophilic attack mechanism of this novel dinuclear water oxidation catalyst (WOC) under the involvement of the second coordination sphere. Photocatalytic water oxidation with this cyclic dinuclear Ru complex using [Ru(bpy)3]Cl2 as a standard photosensitizer revealed a turnover frequency of 15.5 s?1 and a turnover number of 460. This so far highest photocatalytic performance reported for a Ru(bda) complex underlines the potential of this water-soluble WOC for artificial photosynthesis.
- Noll, Niklas,Würthner, Frank
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- A new calix[4]azacrown ether based boradiazaindacene (Bodipy): Selective fluorescence changes towards trivalent lanthanide ions
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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
- Bayrakci, Mevlüt,Kursunlu, Ahmed Nuri,Güler, Ersin,Ertul, ?eref
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- Synthesis of flavin-calix[4]arene conjugate derivatives
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The synthesis of two new flavin substituted calix[4]arene derivatives, 9 and 10, is described. The first flavin substituted calix[4]arene derivative 9 was synthesized by the reaction of 3-methylalloxazine (5) with 25,27-bis(3-bromopropoxy)-26,28-dihydroxy-5,11,17,23-tetra(tert-butyl)calix[4] arene (4) in high yield (92%). The other derivative 10 was prepared from 3-methylalloxazine-1-acetic acid (7) and 25,27-bis(3-cyanopropoxy)calix[4]arene (3). All new compounds were characterized by a combination of FTIR and 1H-NMR spectroscopy, and elemental-analysis techniques.
- Sayin, Serkan,Akkus, Guelderen Uysal,Cibulka, Radek,Stibor, Ivan,Yilmaz, Mustafa
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- Complexation of calix[4]arene protected gold nanoparticles with pyridinium and bipyridinium compounds
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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.
- Pulkkinen, Petri M. S.,Wiktorowicz, Szymon,Aseyev, Vladimir,Tenhu, Heikki
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- A phenyl glycinol appended calix[4]arene film for chiral detection of ascorbic acid on gold surface
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This paper describes the synthesis of new chiral calix [4]arene derivative having (R)-2-phenylglycinol moiety (compound 6), and its chiral recognition studies for ascorbic acid (AA) enantiomers by using Quartz Crystal Microbalance (QCM). Initial experiments indicated that the outstanding selective chiral recognition (α) was observed as 2.61 for l-enantiomer of AA. The sensitivity (S) and the limit of detection (LOD) values for L-AA were calculated as 0.0226 Hz/μM and 0.63 μM, respectively. Furthermore, the sorption behavior and mechanism of AA onto compound 6 film were evaluated and the sorption data exhibited a good correlation with the Freundlich isotherm models. The maximum uptake of L-AA by the sensor was found as 5895.76 mg/g. In conclusion, chiral recognition of AA enantiomers as real-time, sensitive, selective and effective was performed by a calixarene derivative coated QCM sensor.
- Akpinar,Temel, Farabi,Tabakci,Ozcelik, Egemen,Tabakci, Mustafa
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- A novel fluorescent sensor for Fe3+ and Cr3+ based on a calix[4]arene bearing two coumarin units
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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.
- Wang, He-Wen,Feng, Ya-Qing,Meng, Shu-Xian
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- 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
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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.
- Ramakrishna, Vallu,Suresh,Boricha, Vinod P.,Bhatt, Anjani K.,Paul, Parimal
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- Dipyrenylcalix[4]arene-A fluorescence-based chemosensor for trinitroaromatic explosives
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A new chemosensor-based approach to the detection of nitroaromatics is described. It involves the analyte-induced quenching of excimer emission of a dipyrenyl calix[4]arene (L). The chemical and photophysical properties of the complexes formed between L and mono-, di-, and trinitrobenzene, and di- and trinitrotoluene were studied in acetonitrile and chloroform by using 1H NMR, UV/Vis, and fluorescence spectroscopy. Fluorescence spectroscopy revealed that the trinitroaromatics engendered the largest response among the various substrates tested, with the sensitivity for these analytes being correspondingly high. Quantitative analysis of the fluorescence titration profile generated from the titration of L with TNT provided evidence that this particular functionalized calix[4]arene receptor allows for the detection of TNT down to the low ppb level in CH3CN. A single-crystal X-ray diffraction analysis revealed that in the solid state the complex L·TNT consists of a supramolecular crystalline polymeric structure, the formation of which appears to be driven by intermolecular π-π interactions between two pyrene units and a TNT molecule held at a distance of 3.2-3.6 A, as well as by intra- and intermolecular hydrogen-bonds among the amide linkages. Nevertheless, the changes in the 1H NMR, UV/Vis, and fluorescence spectrum, including sharp color changes, are ascribed to a chargetransfer interaction arising from complementary π-π overlap between the pyrene subunits and the bound trinitroaromatic substrates. A number of ab initio calculations were also carried out and, considered in concert, they provide further support for the proposed charge-transfer interactions, particularly in the case of L·TNT.
- Lee, Young Hoon,Liu, Hongguang,Lee, Jin Yong,Kim, Sang Hoon,Kim, Sung Kuk,Sessler, Jonathan L.,Kim, Yang,Kim, Jong Seung
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- Study on thermal decomposition of calix[4]arene and its application in thermal stability of polypropylene
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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.
- Chennakesavulu,Basariya, M. Raviathul,Sreedevi,Bhaskar Raju,Prabhakar,Rao, S. Subba
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- Calixarene modified montmorillonite: A novel design for biosensing applications
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Here we report the synthesis, characterization and application of calixarene (Calix) modified montmorillonite (Mt) as a platform for bio-applications such as biomolecule immobilization and biosensing technologies. This modification enhanced the biomolecule immobilization capability of Mt. Initially, amino-functionalised calixarenes (Calix-NH2) were synthesized and used as a modifier. X-ray diffraction, Fourier transform infrared spectroscopy, zeta potential and thermal gravimetric analysis were performed to verify the modification of the clay minerals. For the biosensor construction, Calix-NH2 modified Mt (Calix-NH2/Mt), bovine serum albumin (BSA), glutaraldehyde (GA) and pyranose oxidase were immobilized on the surface of a glassy carbon electrode which was then referred to as a Calix-NH2/Mt/PyOx biosensor. After optimization of the enzyme amount and pH, analytical characteristics were investigated in detail.
- Sonmez, Burak,Sayin, Serkan,Yalcinkaya, Esra Evrim,Seleci, Didem Ag,Yildiz, Huseyin Bekir,Demirkol, Dilek Odaci,Timur, Suna
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- The light-driven macroscopic directional motion of a water droplet on an azobenzene-calix[4]arene modified surface
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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.
- Cheng, Jing,Dhinakaran, Manivannan Kalavathi,Li, Haibing,Tan, Shiliang,Zhu, Fei
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- Synthesis of di-substituted calix[4]arene-based receptors for extraction of chromate and arsenate anions
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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.
- Bayrakci, Mevlüt,Ertul, ?eref,Yilmaz, Mustafa
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- Mo(CO)6-mediated synthesis of calix[4]arenes carrying β-hydroxy ketones or α,β-unsaturated-β-amino ketones
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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
- Senthilvelan, Annamalai,Tsai, Ming-Tsung,Chang, Kai-Chi,Chung, Wen-Sheng
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- Carcinogenic direct azo dye removal from aqueous solution by amino-functionalized calix[4]arenes
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This study contains a convenient synthesis and azo dye extraction efficiency of amino-functionalized calix[4]arene derivatives. Two calix[4]arene derivatives bearing alkyl amino groups on their upper and lower rim have been successfully synthesized and used as extractant for dye removal in liquid-liquid extraction system. The effect of electrolyte concentration, contact time, and pH on azo dye extraction was also investigated for all calixarene derivatives. From the results, it has been deduced that the amino-functionalized calix[4]arenes showed a better affinity than other parent calix[4]arenes towards the selected azo dyes.
- Akceylan, Ezgi,Erdemir, Serkan
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- Membrane-active calixarenes: toward 'gating' transmembrane anion transport
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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.
- Okunola, Oluyomi A.,Seganish, Jennifer L.,Salimian, Kevan J.,Zavalij, Peter Y.,Davis, Jeffery T.
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- Synthesis, extraction and chromogenic properties of Amidoazocalix[4]arenes and their telomer derivatives
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The synthesis, extraction and chromogenic properties of calix[4]arenes, carrying phenylazo and amido groups on their upper and lower rims, respectively, are described. Novel azocalix[4]arene amides (1a-d, 2a-d, 3a-d) and some of their telomers (T1a-T1d) have been synthesised and characterised by spectroscopic methods as well as elemental analysis techniques. Compounds 1c and 2b were additionally characterised by two-dimensional nuclear magnetic resonance spectroscopic methods. Some of the compounds were examined by absorption spectra using different solvents. The colour changes of the resulting solutions can be observed by the naked eye. Metal extraction abilities of compounds have been investigated comparatively. Telomer structures of azocalix[n]arenes exhibited higher extraction rates compared to those of their monomers. Products obtained under this study, especially telomers, can be used in the field of ion-selective electrodes.
- Karaku, ?zlem ?zen,Delig?z, Hasalettin
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- Synthesis and structural analysis of an infinite linear coordination network formed by the self-assembly of tetracyanocalix[4]arene ligands and silver cations
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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.
- Mislin, Gilles,Graf, Ernest,Hosseini, Mir Wais,De Cian, Andre,Kyritsakas, Nathalie,Fischer, Jean
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- Spectroscopic investigation of the interaction of water-soluble azocalix[4]arenes with bovine serum albumin
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In this work, three hydrosoluble azocalix[4]arene derivatives, 5-(o-methylphenylazo)-25,26,27-tris(carboxymethoxy)-28-hydroxycalix[4]arene (o-MAC-Calix), 5-(m-methylphenylazo)-25,26,27-tris(carboxymethoxy)-28-hydroxycalix[4]arene (m-MAC-Calix) and 5-(p-methylphenylazo)-25,26,27-tris(carboxymethoxy)-28-hydroxycalix[4]arene (p-MAC-Calix) were synthesized. Their structures were characterized by infrared spectrum (IR), nuclear magnetic resonance spectrum (1H NMR and 13C NMR) and mass spectrum (MS). The interactions between these compounds and bovine serum albumin (BSA) were studied by fluorescence spectroscopy, UV-vis spectrophotometry and circular dichroic spectroscopy. According to experimental results, three azocalix[4]arene derivatives can efficiently bind to BSA molecules and the o-MAC-Calix displays more efficient interactions with BSA molecules than m-MAC-Calix and p-MAC-Calix. Molecular docking showed that the o-MAC-Calix was embedded in the hydrophobic cavity of helical structure of BSA molecular and the tryptophan (Trp) residue of BSA molecular had strong interaction with o-MAC-Calix. The fluorescence quenching of BSA caused by azocalix[4]arene derivatives is attributed to the static quenching process. In addition, the synchronous fluorescence spectroscopy indicates that these azocalix[4]arene derivatives are more accessible to Trp residues of BSA molecules than the tyrosine (Tyr) residues. The circular dichroic spectroscopy further verified the binding of azocalix[4]arene derivatives and BSA.
- Fan, Ping,Wan, Lu,Shang, Yunshan,Wang, Jun,Liu, Yulong,Sun, Xiaoyu,Chen, Chen
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- Competitive self and induced aggregation of Calix[4]arene ethers and their interaction with pinacyanol chloride and methylene blue in nonaqueous media
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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.
- Pandey, Shubha,Kar, Jyotsna R.,Azam, Amir,Pandey, Siddharth,Chawla
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- Synthesis and oxoanions (dichromate/arsenate) sorption study of N-methylglucamine derivative of calix[4]arene immobilized onto poly[(phenyl glycidyl ether)-co-formaldehyde]
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The article describes synthesis as well as the evaluation of sorption properties of new N-methylglucamine substituted calix[4]arene and its poly[(phenyl glycidyl ether)-co-formaldehyde] immobilized product. Firstly, 5,17-bis-[(N-methylglucamine)methyl]-25,26,27,28-tetrahydroxy-calix[4]arene (3) was synthesized by the treatment of calix[4]arene with a secondary amine N-methylglucamine and formaldehyde via Mannich reaction. The immobilization of 3 onto poly[(phenyl glycidyl ether)-co-formaldehyde] to form calixarene based polymer (4) was carried out under suitable reaction conditions via nucleophilic substitution reaction. All the new compounds were characterized by a combination of FT-IR, 1H-NMR spectroscopic and elemental analysis techniques. The sorption studies of 4 reveal that it is an excellent material for the removal of toxic oxoanions especially arsenate from aqueous environment. To understand the selectivity of 4, we also examined the retention of dichromate anions in the presence of Cl-, NO3- and SO42- anions at pH 1. 5. Springer Science+Business Media B.V. 2009.
- Sayin, Serkan,Ozcan, Fatih,Memon, Shahabuddin,Yilmaz, Mustafa
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- Ion sensing of sister sensors based-on calix[4]arene in aqueous medium and their bioimaging applications
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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.
- Alizada, Malak,Gul, Alev,Kursunlu, Ahmed Nuri,Oguz, Mehmet,Yilmaz, Mustafa
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- Synthesis of a functionalised calix[4]arene and its interactions with hemicucurbit[6,7]urils and cucurbit[8]uril
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In the present work, we synthesised a functionalised calix[4]arene with 5,11-di(N-methyl-E-(4-pyridylethylene) moiety (CX[4]), and investigated interactions of it with HemiMeQ[6], HemiMeQ[7], and Q[8]) in both water and DMSO using fluorescence spectrophotometry and 1H NMR spectroscopy. Titration 1H NMR spectra revealed that Q[n]s prefers to include the N-methyl-E-(4-pyridylethylene) moiety. In particular, the interaction of CX[4] with Q[8] in water resulted in intense fluorescence emission, and this interaction system can respond to compounds such as amantadine.
- Zhu, Jin Ming,Chen, Li Xia,Chen, Kai,Zeng, Xi,Tao, Zhu
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- Joining a host-guest platform and a light-emission motif: Pyrazinamide-calixarene hybrids
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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.
- 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
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- Reversible coloring/decoloring reactions of thermochromic leuco dyes controlled by a macrocyclic compound developer
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In this study, we examine macrocyclic compounds to determine whether they can provide a safer replacement and stable complex for BPA in thermochromic dyes. To achieve this objective, a series of macrocyclic compounds, Methyl-N-benzylhexahomotriazacalix[3]arene (MeAC3), p-Chloro-N-benzylhexahomo-triazacalix[3]arene (ClAC3), α-Cyclodexdrin (α-CD), β-Cyclodexdrin (β-CD), p-tert-Butylthiacalix[4]arene (TC4), Calix[4]arene (C4), and Resorcin[4]arene (RC4), were synthesized. Among these macrocyclic compounds, RC4 was determined to be the most appropriate candidate to replace BPA as the developer material used in thermochromic dyes. In tests of prepared thermochromic dyes, RC4 had results similar to those of BPA, achieving the best protonation/deprotonation equilibria and providing a dark contrast with the thermochromic dye. DFT calculations also showed stable complexes between RC4 and CVL via hydrogen-bond interactions.
- Chaodongbung, Tawatchai,Kaewtong, Chatthai,Pattavarakorn, Datchanee,Saenkham, Audchara,Sriphalang, Sanguansak,Wanno, Banchob
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- Synthesis of new calix[4]arene derivatives and evaluation of their cytotoxic activity
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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.]
- Oguz, Mehmet,Yildirim, Ayse,Durmus, Irem Mukaddes,Karakurt, Serdar,Yilmaz, Mustafa
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- Mathematical modeling studies for the adsorptive removal of ciprofloxacin drug from water samples using functionalized silica resin
-
The current research demonstrates the adsorptive removal of ciprofloxacin antibiotic drug from pharmaceutical wastewater samples using functionalized silica (FS) resin through batch adsorption experiments. The adsorption experiments were performed under the optimized parameters such as pH effect, FS-resin amount, ciprofloxacin concentration, equilibrium time and temperature. Results demonstrate that the maximum adsorption of ciprofloxacin was achieved at pH (6.5), while the effective resin dose was 20?mg?L?1. The Langmuir and Freundlich models were applied on equilibrium data, and it has been observed that the adsorption was best fit to the Freundlich model with a good correlation coefficient (R2 = 0.999). Moreover, the thermodynamic and kinetic parameters show that the adsorption of ciprofloxacin is endothermic and spontaneous in nature followed by pseudo-second-order kinetic model. To explore the efficiency of resin, the real wastewater samples were collected and it has been observed that resin has better potential to treat pharmaceutical effluents. Furthermore, the FS-resin and ciprofloxacin interaction were analyzed at a molecular level through quantum chemical calculation. Graphical abstract: [Figure not available: see fulltext.]
- Elik, Mustafa,Jalbani, Nida Shams,Junejo, Ranjhan,Kaya, Savas,Serdaroglu, Goncagül
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- Optimization of toxic metal adsorption on DEA-calix[4]arene appended silica resin using a central composite design
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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.
- Gul, Samiha,Memon, Fakhar N.,Memon, Shahabuddin
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p. 3448 - 3463
(2022/02/21)
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- IONOMERS WITH MACROCYCLIC MOIETIES FOR ION CONDUCTIVITY AND PERMSELECTIVITY
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Provided here are ion conducting materials including one or more macrocycles, and either one or more pendant groups or one or more backbone repeat units. The ion conducting materials exhibit distinctly high ion conductivity in thin film and bulk membrane
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Paragraph 00102
(2021/10/30)
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- CALIXARENE COMPOUND, CURABLE COMPOSITION, AND CURED PRODUCT
-
A calixarene compound represented by formula (1) below is provided. The calixarene compound contains, per molecule, at least one —CH2OH group or phenolic hydroxy group and at least one carbon-carbon unsaturated bond. R1's are a structural moiety (A), which has a —CH2OH group; a structural moiety (B), which has a carbon-carbon unsaturated bond; a structural moiety (C), which has a —CH2OH group and a carbon-carbon unsaturated bond; a monovalent organic group (D), which is different from (A), (B), and (C); or a hydrogen atom (E). R2's are (A), (B), (C), (D), or (E) provided that not all R2's are (E). R3's are one of a hydrogen atom, an aliphatic hydrocarbon group, and an aryl group. n is 2 to 10. * is a point of attachment to an aromatic ring. A curable composition including the calixarene compound is provided. A cured product of the curable composition is provided.
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Paragraph 0132
(2021/07/02)
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- Synthesis of new anthracene-substituted calix[4]triazacrown-5 as highly sensitive fluorescent chemosensor and extractant against hazardous dichromate anion
-
A new fluorogenic anthracene functionalized calix[4]triazacrown-5 (Ant-AzClx) was successfully synthesized using a simple Schiff’s base reaction. The 1H-NMR, 13C-NMR, ESI-MS, and elemental analysis techniques were performed to characterize its structure. Excited at 370 nm, Ant-AzClx reveals excimer emission at 418 nm. Therefore, its anion binding properties were investigated against F?, HCO3?, H2PO4?, NO3?, Cr2O72?, and SO42? ions. When hazardous dichromate anion was introduced into medium, the fluorescence intensity of Ant-AzClx was markedly quenched. The binding constant, stoichiometry, the detection limits and Stern–Volmer equation for the complex formed between Ant-AzClx and Cr2O72? ion were determined. Furthermore, the 1H-NMR technique was also performed to assess the mechanism of the complex (Ant-AzClx@Cr2O72?). Apart from its excellent fluorescent chemosensor properties for selective and sensitive recognition of Cr2O72? ion, Ant-AzClx was used as an efficient extractant towards dichromate anion. The extraction results indicated that Ant-AzClx exhibited high extraction capability, leading to it being a promising extractant for the removal of dichromate anions from water.
- Sayin, Serkan
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p. 1716 - 1724
(2021/07/14)
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- CALIXCROWNS AND USES THEREOF
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Provided herein are novel calixcrowns, such as those of Formula (I), which are useful for coating a solid substrate such as a protein chip, diagnostic kit or protein separation pack. Also provided herein are methods detecting protein-protein interactions with a solid substrate coated with the calixcrown herein and an immobilized protein.
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Paragraph 0061
(2020/10/09)
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- Investigation of high-performance adsorption for benzene and toluene vapors by calix[4]arene based organosilica (CBOS)
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The immobilization of a calix[4]arene derivative bearing methyl ester moieties onto mesoporous silica was successfully achieved to obtain calix[4]arene based organosilica (CBOS). IR spectroscopy, X-Ray powder diffraction, energy-dispersive spectroscopy, and scanning electron microscopy analysis were carried out for the characterization of the CBOS. After that, the proposed mesoporous silica-supported adsorbent was studied for the adsorption of benzene and toluene vapors, which are essential VOCs. The effects of operating parameters on the adsorption of these vapors with the CBOS adsorbent were analyzed and optimized by applying response surface methodology (RSM)-central composite design (CCD). According to initial experimental results, CBOS exhibited excellent performance for these vapors. The adsorption capacities of calix-3, GBS, and CBOS adsorbents were determined to be 203, 357, and 606 mg g-1 for benzene vapors, respectively, while they were found to be 258, 394 and 672 mg g-1 for toluene vapors, respectively. Thus, the proposed CBOS adsorbent showed better adsorption performance when compared to its precursors. In addition to the distinctive adsorptive behavior, the CBOS adsorbent exhibited a high reproducibility adsorption/desorption capacity after five consecutive cycles. After the fifth adsorption/desorption cycle, the CBOS retained 94.2% and 95.1% of its initial adsorption capacities for benzene and toluene, respectively. Finally, adsorption phenomena of benzene and toluene vapors onto CBOS were evaluated in terms of isotherm and kinetic parameters. This journal is
- Temel, Farabi,Kutluay, Sinan
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p. 12949 - 12961
(2020/08/28)
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- Synthesis and evaluation of the antitumor activity of Calix[4]arene L-proline derivatives
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The unique conformational properties, functionality, low toxicity, and low cost make calixarene-based compounds a valuable candidate against cancer. The aim of the present study is the synthesis of the upper rim and lower rim-functionalized L-proline-based calix[4]arene derivatives and evaluation of their cytotoxic potential for human cancerous cells as well as to determine the death mechanism. Synthesized calix[4]arene (3, 8a, 8b 13a, and 13b) derivatives were characterized by different spectroscopic techniques such as 1HNMR, 13CNMR, and FTIR. In vitro effects of compounds 3, 8a, 8b, 13a and 13b were tested on human cancerous cells (HEPG2, PC-3, A-549, and DLD-1) as well as human healthy epithelium cell (PNT1A). Results show that compounds 3, 8a, 8b and 13b have cytotoxic potential on human colorectal carcinoma cells (DLD-1) with IC50 values of 43 μM, 45.2 μM, 64.57 μM, and 29.35 μM respectively. Apoptosis ratios of cell death were investigated with flow cytometer using 7-AAD and Annexin-V as markers. Cytotoxic potential of 8a was found to be higher due to increased apoptosis, when compared with healthy cells the apoptotic cell death was significantly (p 0.0001) increased up to 1.7-fold and 2.4-fold in DLD-1 and A549 cells, respectively. In conclusion, these L-proline derived calix[4]arenes with their selective cytotoxic potential on human cancerous cells may be a potential candidate for the treatment of human CRC and lung cancer.
- Oguz, Mehmet,Gul, Alev,Karakurt, Serdar,Yilmaz, Mustafa
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- Effective Removal of the Direct Black-38 Dye from Wastewater Using a New Silica-Modified Resin: Equilibrium and Thermodynamics Modeling Studies
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In this study, the synthesis of p-diethanolaminomethylcalix[4]arene and its immobilization on a silica surface have been performed for the removal of the direct black (DB-38) dye from wastewater samples. The newly synthesized p-diethanolaminomethylcalix[4]arene-immobilized silica (DIS) resin has been analyzed and characterized by FTIR spectroscopy and SEM techniques. To check the efficiency of the DIS resin, batch and column adsorption procedures have been applied under the optimized parameters, i.e., resin dosage, pH, and temperature. To validate the experimental data, Langmuir, Freundlich, and D-R models have been applied. The results show that adsorption follows the Freundlich model well with a good correlation coefficient (R2 = 0.999). Moreover, the energy E (kJ/mol) was calculated with the help of the D-R model, which suggested that the adsorption has an ion exchange nature. The DIS resin was also applied to real industrial samples of DB-38 dye wastewater. The results show that the DIS resin removes 99% of the dye successfully. Thermodynamics studies were conducted to know the feasibility and the mechanism of the adsorption reaction. The thermodynamic parameters show that the adsorption is spontaneous and exothermic. The theoretical calculation was performed at the B3LYP/DZP calculation level of the ADF program, and the power of the interaction between adsorbent and dye molecules can be determined in the light of chemical reactivity analysis.
- Junejo, Ranjhan,Memon, Shahabuddin,Kaya, Savas
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p. 4805 - 4814
(2020/10/09)
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- Feeding a Molecular Squid: A Pliable Nanocarbon Receptor for Electron-Poor Aromatics
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A hybrid nanocarbon receptor consisting of a calix[4]arene and a bent oligophenylene loop ("molecular squid"), was obtained in an efficient, scalable synthesis. The system contains an electron-rich cavity with an adaptable shape, which can serve as a host
- Bury, Wojciech,Cybińska, Joanna,Frydrych, Rafa?,Lis, Tadeusz,St?pień, Marcin
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p. 15604 - 15613
(2020/10/18)
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- Building Covalent Molecular Capsules by Thiol-Michael Addition Click Reaction
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The thiol-Michael addition (TMA) is a powerful methodology to click several fragments together, despite having been underestimated in the synthesis of complex systems for supramolecular chemistry. Herein, a very fast and efficient method has been developed to make covalent molecular capsules by taking advantage of the TMA click reaction. Several scaffolds commonly used in supramolecular chemistry, such as calixarenes, CTV, or cavitands, have been used to quickly obtain covalent cages. Additionally, a 'click&click' procedure has been also developed, by sequential combination of TMA and CuAAC click reaction, as an easy and quick way to build complex molecular structures.
- Perretti, Marcelle D.,Pérez-Márquez, Lidia A.,García-Rodríguez, Raúl,Carrillo, Romen
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p. 840 - 850
(2019/01/24)
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- Water-soluble nitrogen-containing calixarene
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The invention relates to a water-soluble nitrogen-containing calixarene. The preparation method comprises: carrying out a dealkylation reaction on p-tert-butylcalix[4]arene as a raw material and phenol in the presence of anhydrous aluminum trichloride to
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-
Paragraph 0016-0017
(2019/05/16)
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- Method for preparing high-purity resveratrol
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The invention relates to a method for preparing high-purity resveratrol. The method comprises the following steps: synthesizing calixarene RS002 with capability of identifying 3,4'-dihydroxystilbene through aldol condensation, Friedel-Crafts reaction, est
- -
-
Paragraph 0024; 0025
(2019/04/13)
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- Water-soluble nitrogen-containing calixarene synthesis method
-
The invention relates to a water-soluble nitrogen-containing calixarene synthesis method, which comprises: carrying out a dealkylation reaction on p-tert-butylcalix[4]arene as a raw material and phenol in the presence of anhydrous aluminum trichloride to
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Paragraph 0016-0017
(2019/05/16)
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- Synthesis of macrocyclic polyphenol resin by methylene crosslinked calix[4]arene (MC-[4]H) for the adsorption of palladium and platinum ions
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A novel macrocyclic polyphenol resin, a calix[4]arene derivative, namely, a methylene crosslinked calix[4]arene (MC-[4]H), was successfully synthesised by demethylation of MC-[4]CH3. MC-[4]CH3 was prepared by crosslinking [4]CH3 with s-trioxane under acidic conditions. Methylation of calix[4]arene ([4]H) is strongly required to protect the oxygen atoms on the phenolic groups. It was found that the adsorption of palladium and platinum optimally occurred at low pH. The maximum loading capacity of palladium on the resin was found to be 0.41 mol kg-1 while that of platinum was 0.23 mol kg-1. The stoichiometries of metal ions were found to be 5:1 of the calix[4]arene unit in MC-[4]H to Pd(ii) and 3:1 of that in MC-[4]H to Pt(iv), respectively.
- Priastomo, Yoga,Morisada, Shintaro,Kawakita, Hidetaka,Ohto, Keisuke,Jumina
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supporting information
p. 8015 - 8023
(2019/06/07)
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- Investigation of hydrogen bonding in p-sulfonatocalix[4]arene and its thermal stability by vibrational spectroscopy
-
The vibrational spectra of p-sulfonatocalix [4] arene were studied. The geometrical parameters, the energies, the frequencies and the intensities of the bands in the IR and Raman spectra are calculated for four conformations. The most stable conformation of the p-sulfonatocalix[4]arene is the cone due to the cooperative cyclic intramolecular hydrogen bonding system. The strength of the hydrogen bonds depends on the type of substituent on the upper rim of the calixarene molecules. We studied the process of destruction of calixarenes using IR spectroscopy and TGA methods. Characteristic bands for each conformation were selected. HOMO covers aromatic units with notable conjugation, and LUMO belongs to sulfonate groups.
- Furer,Vandyukov,Khamatgalimov,Kleshnina,Solovieva,Antipin,Kovalenko
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p. 403 - 410
(2019/06/19)
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- CALIXARENE COMPOUND AND CURABLE COMPOSITION
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A compound useful as a release agent, and a release agent, a curable composition, and a nanoimprint lithography resin material each containing the compound are provided. More specifically, a calixarene compound with a molecular structure represented by the following structural formula (1) and a composition containing the calixarene compound are provided. wherein R1 denotes a structural moiety with a perfluoroalkyl group, R2 denotes a hydrogen atom, a polar group, a polymerizable group, or a structural moiety with a polar group or a polymerizable group, R3 denotes a hydrogen atom, an aliphatic hydrocarbon group that may have a substituent, or an aryl group that may have a substituent, n denotes an integer in the range of 2 to 10, and * denotes a bonding point with an aromatic ring.
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-
Paragraph 0141
(2019/09/20)
-
- Thermodynamic and Kinetic Studies for Adsorption of Reactive Blue (RB-19) Dye Using Calix[4]arene-Based Adsorbent
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A current study demonstrates the removal of Reactive Blue 19 (RB-19) from industrial wastewater by synthesizing p-piperdinocalix[4]arene-immobilized silica resin (PASR). The surface morphology and functional group analysis were performed with scanning electron microscopy and Fourier transform infrared spectroscopy. The dye removal efficiency of PASR was analyzed through adsorption studies. Different parameters were optimized such as the pH value of dye, amount of resin, concentration of dye, and effect of electrolyte on adsorption. The adsorption mechanism was analyzed with Langmuir, Freundlich, and Dubinin-Radushkevich (D-R) isotherms. It was found that experimental data follow the Freundlich isotherm, which suggests multilayer adsorption. The column adsorption study was also evaluated by breakthrough and Thomas models. The Thomas model rate constant kTH (cm3 mg-1 min-1) and maximum solid phase concentration was found to be qo = 2.702 mg·g-1. The thermodynamic study reveals that the adsorption process is exothermic and spontaneous in nature. The kinetic study suggests that the adsorption process follows the pseudo-second-order kinetic model.
- Junejo, Ranjhan,Memon, Shahabuddin,Memon, Fakhar N.,Memon, Ayaz Ali,Durmaz, Fatih,Bhatti, Asif Ali,Bhatti, Ashfaque Ali
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p. 3407 - 3415
(2019/08/28)
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- Phase transfer catalyst based on calixarene structure, preparation method thereof, and method for producing fluorinated organic compounds using the same
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When using a catalyst represented by chemical formula 1 according to the present invention in manufacturing an organic fluorinated compound by conducting a reaction of alkyl halide or alkyl sulfonate, potassium fluoride or cesium fluoride, which is a fluoride salt, an alkali positive ion is combined with a crown ether group and a fluorine negative ion is hydrogen-bonded with a hydroxy group to weaken ionic bonds of alkali metal fluoride to promote a fluorination reaction, and also to have an effect of significantly inhibiting the production of by-product alkenes.COPYRIGHT KIPO 2020
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-
Paragraph 0181-0182; 0185-0195
(2019/12/25)
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- CALIXARENE COMPOUND, WATER-SLIDING SURFACE MODIFIER, CURABLE RESIN COMPOSITION AND WATER-SLIDING COATING FILM
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PROBLEM TO BE SOLVED: To provide a surface modifier that makes it possible to obtain a surface having excellent water-sliding properties, and a curable resin composition using the same, and a water-sliding coating film using the same. SOLUTION: Used herein is a calixarene compound having a molecular structure represented by formula (1) (where R1 is a structural site having a C1-3 perfluoroalkyl group; R 2 is H, a polar group, or a structural site having a polymerizable group; R 3 is H, an optionally-substituted aliphatic hydrocarbon group, or the like; n is an integer of 2-10; * is a node with an aromatic ring). SELECTED DRAWING: None COPYRIGHT: (C)2020,JPOandINPIT
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Paragraph 0138-0139
(2020/01/30)
-
- Temperature Controls Guest Uptake and Release from Zn4L4 Tetrahedra
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We report the preparation of triazatruxene-faced tetrahedral cage 1, which exhibits two diastereomeric configurations (T1 and T2) that differ in the handedness of the ligand faces relative to that of the octahedrally coordinated metal centers. At lower temperatures, T1 is favored, whereas T2 predominates at higher temperatures. Host-guest studies show that T1 binds small aliphatic guests, whereas T2 binds larger aromatic molecules, with these changes in binding preference resulting from differences in cavity size and degree of enclosure. Thus, by a change in temperature the cage system can be triggered to eject one bound guest and take up another.
- Zhang, Dawei,Ronson, Tanya K.,Güryel, Songül,Thoburn, John D.,Wales, David J.,Nitschke, Jonathan R.
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supporting information
p. 14534 - 14538
(2019/10/11)
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- Inorganic-organic covalent hybrid of polyoxometalate-calixarene: Synthesis, characterization and enzyme mimetic activity
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The inorganic-organic hybrid based on covalently attached trilacunary phosphotungstate and calixarene conjugate (POM-Calix hybrid) has been synthesized via facile click chemistry approach. The characterization studies showed that both the moieties are present together in the hybrid upon covalent modification. The morphology of the hybrid was studied by SEM, TEM and AFM analyses suggesting spherical shaped nanoparticles of 40–60 nm size for the hybrid. The POM-Calix hybrid was successfully employed to demonstrate peroxidase-like activity for the oxidation of the model substrate, viz., o-phenylenediamine (OPD), for the enzyme. The activity of the POM-Calix hybrid was ~170% greater than that exhibited by simple POM and this is mainly attributed to the introduction of hydrophobic character by the covalently attached calixarene conjugate and the hydrophobicity is supported by the contact angle measurement. From the kinetic studies, the Michaelis constants, Km and Vmax were estimated to be 2.55 mM and 0.756 × 10?8 M s?1, respectively. It was observed that, the POM-Calix hybrid facilitates the formation of [rad]OH radicals when treated with H2O2 which eventually results in the oxidation of the substrate. The POM-Calix hybrid exhibits excellent enzyme-like activity over a wide pH range, which would enable its bio-applications at physiological conditions.
- Narkhede, Nilesh,Uttam, Bhawna,Rao, Chebrolu Pulla
-
supporting information
p. 337 - 342
(2018/09/11)
-
- Probe for detecting multi-target alkaline earth metal ions and application thereof
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The invention discloses a probe for detecting multi-target alkaline earth metal ions and application thereof. The probe has unique structural design. The upper side of calixarene is modified by a double bond with nitrogen iodide methyltetramethylpyridine, so as to not only constitute a large conjugated structure, but also improve luminous efficiency. At the same time, quaternary ammonium salt improves the water solubility of the probe. The carboxyl modification of the lower edge of calixarene provides more complexation sites; in addition, the probe can be used for detecting multiple targets independently. Fluorescence quenching and ratio absorption methods are used to selectively detect three alkaline earth metal target ions with high sensitivity and low detection limit. The detection method can be used to carry out both spectral detection and rapid visual colorimetric detection.
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-
Paragraph 0104; 0105
(2018/10/19)
-
- Quinolines: Microwave-assisted synthesis and their antifungal, anticancer and radical scavenger properties
-
An efficient method for the synthesis of quinolines using microwave irradiation was developed providing 28 quinolines with good yields. The reaction procedures are environmentally friendly, convenient, mild and of easy work-up. Quinolines were evaluated f
- Liberto, Natália Aparecida,Sim?es, Juliana Baptista,de Paiva Silva, Sarah,da Silva, Cristiane Jovelina,Modolo, Luzia Valentina,de Fátima, ?ngelo,Silva, Luciana Maria,Derita, Marcos,Zacchino, Susana,Zu?iga, Omar Miguel Portilla,Romanelli, Gustavo Pablo,Fernandes, Sergio Antonio
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supporting information
p. 1153 - 1162
(2017/02/05)
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- Preparation of calix[4]arene-embedded polysulphone membranes, and utilisation of its Cr(VI) transport efficiency
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In this study, a tetramine-substituted calix[4]arene derivative, which was synthesised from calix[4]arene by treatment with dimethylamine in one step via Mannich reaction, was used to fabricate a new calix[4]arene-embedded polysulphone membrane (calix@membrane). Its structure and surface morphology were determined using thermogravimetric analysis and scanning electron microscopy, and elemental analysis techniques. Moreover, a Donnan dialysis system was employed to investigate Cr(VI) transport efficacy of calix@membrane at different pH values. Results showed that calix@membrane represented a promising transport capability for HCr2O7 ? due to their efficient complexation behaviour.
- Engin, Mehmet Soner,Cay, Seydahmet,Sayin, Serkan,Eymur, Serkan,Sardohan Koseoglu, Tugba
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p. 455 - 461
(2017/03/24)
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- Effect of conformation, flexibility and intramolecular interaction on ion selectivity of calix[4]arene-based anion sensors: experimental and computational studies
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A number of calix[4]arene-based molecules were designed incorporating amide moiety with variation in conformation, rigidity at the binding sites and steric crowding at the upper rim to investigate the anion sensing property of this series of ionophores. These compounds were synthesised and characterised, molecular structures of two of the compounds were established by single-crystal X-ray study. Anion binding property of these ionophores, investigated with the aid of 1H NMR and UV–vis spectroscopy, revealed that three (1–3) out of four ionophores strongly interact with F?, in addition, ionophore 2 interacts with CN? and H2PO? 4, ionophore 3 interacts with CH3COO? and H2PO? 4 and ionophore 4 does not interact with any anions. NMR titration was carried out to determine binding constant with strongly interacting anions. Crystal structure analysis revealed that strong intramolecular N ? H · π interaction in 4 prevented the anions to interact with the N–H protons of the amide moiety. Interestingly, 2 with F? and CN? exhibits sharp colour change in acetonitrile–chloroform. Apparently, conformation of the calix moiety, flexibility of the binding sites and intramolecular H-bonding played critical role towards determination of selectivity. Computational study was performed to investigate the interaction site(s) and also to corroborate some of the experimental results.
- Maity, Debdeep,Bhatt, Madhuri,Desai, Mittal L.,Suresh,Si, Mrinal Kanti,Boricha, Vinod P.,Ganguly, Bishwajit,Paul, Parimal
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p. 600 - 615
(2017/03/30)
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- Functionalized calix[4]arene as a colorimetric dual sensor for Cu(II) and cysteine in aqueous media: Experimental and computational study
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A family of calix[4]arenes with variation in steric crowding at the upper rim and incorporating pyridine and amide moieties at two of the four OH groups located in the lower rim have been synthesized and their performance as sensors for metal ions has been investigated. Two of the compounds exhibited selective interaction with Cu2+ ions with sharp colour change, observed by the naked eye. Spectroscopic and computational studies revealed that two of the compounds form 1 : 2 complexes, in which one of the Cu2+ ions interacts strongly with the phenolic OH, resulting in a colour change due to strong absorption (ICT) in the visible region. For the third compound, the Cu2+ ions coordinate with the pyridine and amide nitrogen atoms, and the Cu2+ ion could not enter inside to interact with the OH group due to restricted flexibility at the lower rim because of the bulky groups at the upper rim. The Cu2+ complexes thus formed have been used for sensing of amino acids and interestingly, one of the complexes exhibits interactions selectively with cysteine out of eighteen amino acids tested with a sharp colour change in aqueous media. The formation of the Cu2+-cysteine complex is confirmed from mass data, and the surface morphology of the complex before and after the addition of cysteine is investigated by SEM study.
- Bhatt, Madhuri,Maity, Debdeep,Hingu, Vinayak,Suresh, Eringathodi,Ganguly, Bishwajit,Paul, Parimal
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p. 12541 - 12553
(2017/11/06)
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- Solvent-free synthesis of trisphenols as starting precursors for the synthesis of calix[4]arenes using sulfonated multi-walled carbon nanotubes
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The condensation of phenol derivatives (12 substrates) with 2,6-bis(hydroxymethyl)phenols (BMP) (6 examples) is reported using sulfonated multi-walled carbon nanotubes (SO3H@MWCNTs) under solvent-free conditions as starting precursors for the synthesis of macrocyclic molecules of calix[4]arenes. The new protocol provides a series of trisphenol derivatives (21 examples) in high yields (up to 94%) and relatively short reaction times (15-120 min). Also, direct synthesis of calix[4]arenes from different trisphenols by use of the catalyst was reported (5 examples). Furthermore, the synthesized calix[4]arene was obtained using a one-pot method from simple and easily available starting materials such as p-cresol for the synthesis of 5,11,17,23-tetramethylcalix[4]arene-25,26,27,28-tetraol. Also, in this process SO3H@MWCNTs can be reused for seven runs with almost consistent efficiency and can be recovered by easy filtration.
- Fareghi-Alamdari, Reza,Golestanzadeh, Mohsen,Zekri, Negar
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p. 3400 - 3412
(2016/05/09)
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- Synthesis and characterization of novel nanofiber based calixarene and its binding efficiency towards chromium and uranium ions
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The objective of this study is to obtain nanofibrous precursor based calixarene with high ion adsorption capacity by electrospinning of blended solution of polyacrylonitrile (PAN) and upper rim functionalized calix[4]arene bearing N-methylglucamine (Calix-NMG). The obtained electrospun fibers were characterized using fourier transform infrared (FT-IR-ATR), scanning electron microscope (SEM) equipped with energy-dispersive X-ray spectrometry (EDX) and thermogravimetric analyses (TGA and DSC). Analysis indicated that preparation of nanofibers based Calix-NMG was successfully achieved. The ion binding studies exhibited that the nanofiber based Calix-NMG could be efficiently used for the binding of chromate anions and uranium cations. Nanofiber based calix[4]arene with N-methylglucamine chelating groups may be a good candidate as a filter material for treatment of a large quantity of wastewater owing to their very large surface area as well as both the inclusion and donor–acceptor complexation capability of all surfaces associated with the calixarene skeleton.
- ?zcan, Fatih,Bayrakc?, Mevlüt,Ertul, ?eref
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- Cyanocalix[4]arenes: Synthesis, crystal structures and reactivity studies
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Herein, we describe an improved method to synthesise mono-, di- and tetra-cyanocalix[4]arene and report their crystal structure determinations. We also report our attempts to further functionalise the cyanocalix[4]arenes into dithiadiazolyl-calix[4]arenes
- Applewhite, Malcolm J.,Haynes, Delia A.,Arnott, Gareth E.
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p. 475 - 484
(2016/04/19)
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- P-Sulfonic acid calix[4]arene-functionalized alkyl-bridged organosilica in esterification reactions
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Two new p-sulfonic acid calix[4]arene- and p-sulfonic acid calix[6]arene-functionalized organosilica have been synthesized using a sol-gel method and applied as heterogeneous catalysts in esterification reactions. The catalytic performance was evaluated using the esterification of carboxylic acids with ethanol, and good catalytic activity (i.e., 55-88%) was observed under the optimum reaction conditions. This study reports the first promising example of the successful employment of calix[n]arenes as a heterogeneous catalyst for catalytic esterification. The catalyst was easily separated by filtration and reused five times without any significant loss of activity.
- De Assis,Abranches,Braga,Zu?iga,Sathicq,Romanelli,Sato,Fernandes
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p. 24285 - 24289
(2016/03/15)
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- Calix[n]arenes: Active organocatalysts for the synthesis of densely functionalized piperidines by one-pot multicomponent procedure
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An efficient, suitable and high yielding method has been developed for the synthesis of different densely functionalized piperidine derivatives via pseudo-five component, one-pot domino reaction through a combination of β-ketoesters, aromatic aldehydes, and various amines using p-sulfonic acid calix[n]arenes as catalysts. The reaction was carried out in refluxing methanol, affording very good yields of the expected piperidine. Atomic economy, environmentally benign procedure, reuse of catalysts, and short reaction time are some of the important features of this protocol.
- Palermo,Sathicq,Liberto,Fernandes,Langer,Jios,Romanelli
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supporting information
p. 2049 - 2054
(2016/04/26)
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- An Elaborate Supramolecular Assembly for a Smart Nanodevice for Ratiometric Molecular Recognition and Logic Gates
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Ingenious approaches to supramolecular assembly for fabricating smart nanodevices is one of the more significant topics in nanomaterials research. Herein, by using surface quaternized cationic carbon dots (CDots) as the assembly and fluorescence platform, anionic sulfonatocalix[4]arene with modifiable lower and upper rims as a connector, as well as in situ coordination of Tb3+ions, we propose an elaborate supramolecular assembly strategy for the facile fabrication of a multifunctional nanodevice. The dynamic equilibrium characteristics of the supramolecular interaction can eventually endow this nanodevice with functions of fluorescent ratiometric molecular recognition and as a nano-logic gate with two output channels. A smart nanodevice for ratiometric molecular recognition and nano-logic gates has been successfully fabricated by using an elaborate supramolecular assembly strategy that includes the precise assembly of a bifunctional connector sulfonatocalix[4]arene on quaternized cationic carbon dots by inclusion complexation and electrostatic interactions, and the incorporation of Tb3+ions by in situ coordination.
- Xie, Yu-Jie,Wu, Wen-Yu,Chen, Hao,Li, Xiang,Zhang, Hao-Li,Liu, Liang-Liang,Shao, Xing-Xin,Shan, Chang-Fu,Liu, Wei-Sheng,Tang, Yu
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supporting information
p. 8339 - 8345
(2016/06/15)
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- Synthesis, X-ray crystal structure and anti-tumor activity of calix[n]arene polyhydroxyamine derivatives
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Calixarene-based compounds are highly effective therapeutic agents against cancer. This study aims to prepare a series of calix [n]arene (n?=?4, 6, 8) polyhydroxyamine derivatives (3a–3m) and to study their potential antitumor activities. The single crystal structure of calixs[4]arene derivative 3a was determined through X-ray diffraction. We assessed the ability of the prepared calix [n]arene polyhydroxyamine derivatives to induce cytotoxicity in six cancer cell lines by performing cancer cell growth inhibition assays. Results demonstrated that compounds 3a–3d achieved IC50values ranging from 1.6?μM to 11.3?μM. Among the different compounds, 3a and 3b exerted the strongest cytotoxic effect in inhibiting the growth of SKOV3 cells. In relation to the underlying mechanisms of cytotoxic effects, cell cycle analysis revealed that the exposure of SKOV3 cells to 3a induced cell cycle arrest in the G0/G1 phase, suggesting a reduction in DNA synthesis. Immunofluorescent staining indicated that the protein expression levels of caspase-3 and p53 in cells significantly increased, whereas that of Bcl-2 was effectively suppressed. Meanwhile, no significant changes in Bax were observed in SKOV3 cells. These results highlight that calixarene 3a can be further studied as a potential anticancer agent.
- An, Lin,Han, Li-Li,Zheng, You-Guang,Peng, Xian-Na,Xue, Yun-Sheng,Gu, Xiao-Ke,Sun, Jing,Yan, Chao-Guo
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- Synthesis and investigation of catalytic affinities of water-soluble amphiphilic calix[n]arene surfactants in the coupling reaction of some heteroaromatic compounds
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Six water-soluble calix[n]arene-based Br?nsted acid-type catalysts with amphiphilic groups were successfully synthesized by incorporating sulfonic acid moieties. Their structures were characterized using FTIR,1H NMR,13C NMR, APT-NMR, and elemental analysis techniques. Moreover, their catalytic capabilities were evaluated in the coupling reaction of 2-methylfuran and/or N-methylindole with some sec-alcohols in aqueous media. The association of their surfactant abilities, and the effects of water amount used and reaction durations on the catalytic activities of these amphiphilic calix[n]arene derivatives were also investigated. Observations indicated that these amphiphilic calix[n]arene catalysts exhibited high catalytic activities in the coupling reactions of 2-methylfuran and N-methylindole with some alcohols in water.
- Sayin, Serkan,Yilmaz, Mustafa
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p. 6528 - 6535
(2016/09/23)
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- SYNTHESIS OF AMPHIPHILIC CALIXARENE GLYCOSIDE DETERGENTS AND USE OF SAME FOR EXTRACTING AND STABILIZING NATIVE FUNCTIONAL MEMBRANE PROTEINS
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Calixarene compound according to formula (I) wherein: R1 represents a linear or branched C(1-16) alkyl group; R2 represents an hydrogen atom or a methyl group; R3 is identical to R1 or R2 g
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Page/Page column 25
(2015/11/09)
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- P-Sulfonic acid calix[n]arenes as organocatalysts for the transesterification reaction of Passiflora seed oil
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The catalytic activity of p-sulfonic acid calix[4]arene was studied in the transesterification reactions of Passiflora seed oil with methanol or ethanol. Calix[n]arenes are highly versatile organocatalysts and conversion rates >98 % were obtained for the transformation of Passiflora seed oil to its methyl or ethyl esters after 5 h of reaction in the presence of p-sulfonic acid calix[4]arene (3.52 mol % in ethanol; 5.28 mol % in methanol). Moreover, the organocatalyst was recovered and reused in two subsequent cycles without a significant decrease in the activity or selectivity. The use of a non-corrosive and reusable organocatalyst is the positive aspect of this process.
- Almeida, Camila G.,Souza, Isabella F.,Liberto, Natália A.,Da Silva, Márcio J.,Fernandes, Sergio A.,Le Hyaric, Mireille
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p. 1927 - 1934
(2015/10/29)
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- Control of the rheological properties of clay nanosheet hydrogels with a guanidinium-attached calix[4]arene binder
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A 1,3-alternate calix[4]arene derivative 1 possessing four guanidinium moieties was synthesized as a molecular binder. The clay nanosheet (CNS) hydrogels were prepared upon addition of 1 and sodium polyacrylate (ASSP), and their mechanical properties were measured by rheometry. CNS hydrogels prepared by combining calix[4]arene 1 with dispersed CNSs surrounded by ASSPs showed an enhancement of mechanical properties such as viscosity and elasticity.
- Lee, Ji Ha,Kim, Chaelin,Jung, Jong Hwa
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supporting information
p. 15184 - 15187
(2015/10/12)
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- Roles of both amines and acid in supramolecular hydrogel formation of tetracarboxyl acid-appended calix[4]arene gelator
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A tetracarboxylic acid-appended calix[4]arene derivative 1 which were insoluble in water could form a supramolecular hydrogel upon addition of both amines and HCl. The added amines such as primary, secondary and tertiary amines efficiently acted as base to enhance the solubility of gelator. The stability of supramolecular gels is strongly dependent to the number of amino groups involved in the amines and the number of equivalents of amines added, relative to the equivalents of carboxylic acid groups in the calix[4]arene. In addition, the sequence of addition of both the amines and acid is critically important to form the supramolecular hydrogel from a gelator which, without any other additives, is insoluble in pure water. Furthermore, chiral gelator 1 formed a right-handed chiral arrangement of the amide chromophore in the presence of achiral amines. This journal is
- Choi, Heekyoung,Lee, Ji Ha,Jung, Jong Hwa
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p. 20066 - 20072
(2015/03/18)
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- Synthesis and structural characterization of bisazocalix[4]arene with melamine: Metal ion extraction studies
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In this study, the synthesis and characterization of novel bisazocalix[4]arene [2-amino-4,6-bis(5-azo-25,26,27- tribenzoyloxy-28-hydroxycalix[4]arene)-1,3,5-triazine] (5), symmetrically derived from the diazo coupling of 2,4,6-triamino-1,3,5-triazine (mel
- Elc?in, Serkan,Karaku?, ?zlem ?zen,Kara, Izzet,Delig?z, Hasalettin
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p. 134 - 140
(2015/02/19)
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