141902-33-2Relevant articles and documents
Cationic amphiphilic calixarenes to compact DNA into small nanoparticles for gene delivery
Rodik, Roman V.,Anthony, Anne-Sophie,Kalchenko, Vitaly I.,Mély, Yves,Klymchenko, Andrey S.
, p. 1654 - 1664 (2015)
Macrocycles have been attracting increasing attention as scaffolds for preparation of non-viral vectors for gene delivery. Here, following our earlier report, a series of amphiphilic calixarenes bearing cationic choline or N-(2-aminoethyl)-N,N-dimethylammonium groups at the upper rim and alkyl chains at the lower rim were synthesized. The effect of the length of aliphatic chains and the structure of the head group on their self-assembly, interaction with DNA, properties of their DNA complexes, transfection efficiency and cytotoxicity was studied. It was found that longer alkyl chains favor formation of small virus-sized DNA nanoparticles with low polydispersity. Moreover, longer alkyl chains, such as dodecyl groups, significantly improved the transfection efficiency, so transfection was observed in the presence of fetal bovine serum as well as with or without a helper lipid. Finally, we observed that the cytotoxicity of these calixarenes clearly decreased with increase of the chain length. On the other hand, the presence of four additional amino groups, which could be protonated at pH 7, affected only the stoichiometry of the complexes with DNA without influencing their transfection efficiency or cytotoxicity. The results obtained provide new insights for designing non-viral vectors based on macrocyclic molecules.
Calixarene-based porous 3D polymers and copolymers with high capacity and binding energy for CO2, CH4and Xe capture
Bezuidenhout, Charl X.,Bracco, Silvia,Comotti, Angiolina,Pedrini, Alessandro,Perego, Jacopo,Sozzani, Piero
supporting information, p. 27353 - 27360 (2021/12/24)
The supramolecular capacity of calixarenes towards guests is largely consolidated; in contrast, the synthesis of porous calixarene-based frameworks by covalent bond formation is still a challenge. Our target was to yield 3D polymers and copolymers based on calixarenes for selective gas-capture, endowed with easy pore accessibility and specific sites, and builtviaa straightforward synthetic route. The covalent calixarene frameworks (CXFs) were prepared by the Yamamoto coupling reaction starting from tetrabromo calixarene propoxy- and methoxy-monomers of three stable calixarene (partial cone, effective cone, and 1,3-alternate) conformers and complete post-synthetic deprotection to achieve polar phenolic calixarene derivatives. Moreover, the copolymer of calixarene-based monomers with tetrabromo-tetraphenylmethane exhibited remarkable surface area up to about 3000 m2g?1. Smart architectures endowed with hierarchical porosity from micro- to meso-porosity showed notable sponge-like swellability by CO2, which was captured effectively at room temperature, even in competition with N2, yielding CO2removal in column breakthrough experiments. Indeed, CXFs displayed excellent CO2and CH4energy binding of 35 and 24 kJ mol?1, respectively. Ultramicropore sites were highlighted by Xe capture andin situdetection after a xenon diffusion time of a few milliseconds, by laser-assisted hyperpolarized129Xe NMR, revealing the accessibility of calixarene capsules and the available space. This synthetic route demonstrated the possibility to modulate at will the pore capacity and selectivity, displaying porous frameworks with two distinct pore families, wherein calixarene moieties play the role of small and selective sites. A contractile behavior of the frameworks was observed upon deprotection which produced more polar sites, due to the formation of hydrogen bond networks.
Selectivity of original C-hexopyranosyl calix[4]arene conjugates towards lectins of different origin
Ka?áková, Martina,Malinovská, Lenka,Klejch, Tomá?,Hlavá?ková, Martina,Dvo?áková, Hana,Fujdiarová, Eva,Rottnerová, Zdeňka,Ma?átková, Olga,Lhoták, Pavel,Wimmerová, Michaela,Moravcová, Jitka
, p. 60 - 72 (2018/10/15)
As a part of ongoing activities towards the design of ligands against pathogenic lectins, a synthesis of original α-C-galacto/α-C-manno/α-C-fucopyranosyl glycomimetics based on a calix[4]arene scaffold and their binding evaluation is described. The interactions of the glycomimetics with seven lectins of various origins were carried out using agglutination inhibition assays. The 1,3-alternate tetra-C-fucosylated ligand and its derivative having a tertBu group at the upper rim of the calix[4]arene scaffold were the most potent towards the AAL lectin family (RSL, AFL, AAL, AOL) and BC2L-C. As AFL and RSL originate from important human (Aspergillus fumigatus) and plant (Ralstonia solanacearum) pathogens, the inhibition potency of both leading structures was assessed by surface plasmon resonance. With AFL, both structures exhibited an approximately three orders of magnitude increase in affinity compared to the reference L-fucose. The role of tertBu groups as “aglycon-assisted” events was illustrated by NMR. Furthermore, both compounds showed significantly increased ability to inhibit BC2L-C (from human pathogen Burkholderia cenocepacia) cell agglutination and were able to cross-link whole B. cenocepacia cells. Although the ligands failed to significantly inhibit the agglutination activity of LecA and LecB from Pseudomonas aeruginosa, tetra-C-galactosylated calix[4]arene with tertBu groups at the upper rim of the 1,3-alternate conformation inhibited P. aeruginosa biofilm formation efficiently. This systematic and comprehensive study highlights the fact that hydrolytically stable polyvalent C-glycomimetics should be regarded as potent and selective ligands capable of acting as antiadhesive agents.
A general method for obtaining calix[4]arene derivatives in the 1,2-alternate conformation
Slavík, Petr,Eigner, Václav,Lhoták, Pavel
, p. 6348 - 6355 (2016/09/23)
The 1,2-alternate conformation, so far the least accessible atropisomer of calix[4]arene, is now easily available on a gram scale. The entire synthetic sequence consists of only two steps—(a) proximal dialkylation (R1-I, NaH/DMF), and (b) another subsequent dialkylation (R2-I, Me3SiOK/THF). The selection of appropriate base/solvent combinations in both stages was the key prerequisite for the successful preparation of the 1,2-alternate conformers, which are available without the use of any protecting groups.
Unexpected formation of disulfide-based biscalix[4]arenes
Stejskal, Franti?ek,Cu?ínová, Petra,Lhoták, Pavel
, p. 760 - 766 (2016/01/15)
Attempts at Pd-catalyzed bridging in sulfoxide-bearing calixarenes containing various substituents (phenyl, ethyl, pyrimidin-2-yl) gave the expected compound only in the case of the ethyl derivative. However, the reaction of sulfoxides with BuLi revealed
Synthesis and investigation of catalytic affinities of water-soluble amphiphilic calix[n]arene surfactants in the coupling reaction of some heteroaromatic compounds
Sayin, Serkan,Yilmaz, Mustafa
, p. 6528 - 6535 (2016/09/23)
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.
Cyanocalix[4]arenes: Synthesis, crystal structures and reactivity studies
Applewhite, Malcolm J.,Haynes, Delia A.,Arnott, Gareth E.
, p. 475 - 484 (2016/04/19)
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
Structure impact in antenna effect of novel upper rim substituted tetra-1,3-diketone calix[4]arenes on Tb(III) green and Yb(III) NIR-luminescence
Zairov, Rustem,Shamsutdinova, Nataliya,Podyachev, Sergey,Sudakova, Svetlana,Gimazetdinova, Gulnaz,Rizvanov, Ildar,Syakaev, Victor,Babaev, Vasily,Amirov, Rustem,Mustafina, Asiya
, p. 2447 - 2455 (2016/04/26)
Two novel calix[4]arene macrocyclic ligands functionalized with four 1,3-diketone groups at the upper and hydroxyl (3) or propyloxy-groups (6) at the lower rims were synthesized and characterized using NMR, IR spectroscopy, mass spectrometry, and elemental analysis. UV-vis spectrophotometry and ESI mass spectrometry studies indicate 1:1 complex formation of ligands 3 and 6 with Ln(III) (Ln=Tb, Yb) in alkaline DMF solutions resulted from coordination of Ln(III) with 1,3-diketonate groups. Luminescence study of Ln(III) complexes with 3 and 6 reveals significant difference in antenna effects of their deprotonated forms on both Tb(III)- and Yb(III)-centered luminescence. Comparison of ligand-centered emission for ligands 3 and 6 points to the latter as more efficient antenna for Tb(III) and Yb(III). Different conformational behavior of ligands 3 and 6 in alkaline media is assumed as a reason for the experimentally observed difference in sensitization pathways in Ln(III) complexes with 3 and 6.
A convenient synthetic route to partial- cone p-Carboxylatocalix[4]arenes
Fairbairna, Robyn E.,Teatb, Simon J.,Gagnonb, Kevin J.,Dalgarnoa, Scott J.
, p. 516 - 519 (2015/10/28)
p-Carboxylatocalix[n]arenes have emerged as useful building blocks for the construction of a diverse range of supramolecular assemblies. A convenient route to a p-carboxylatocalix[4]arene that is locked in a partial-cone conformation is presented. The conformation gives the molecule markedly different topological directionality relative to those previously used in self- And metal-directed assembly studies.
A multi-state, allosterically-regulated molecular receptor with switchable selectivity
Mendez-Arroyo, Jose,Barroso-Flores, Joaquín,Lifschitz, Alejo M.,Sarjeant, Amy A.,Stern, Charlotte L.,Mirkin, Chad A.
supporting information, p. 10340 - 10348 (2014/08/05)
A biomimetic, ion-regulated molecular receptor was synthesized via the Weak-Link Approach (WLA). This structure features both a calix[4]arene moiety which serves as a molecular recognition unit and an activity regulator composed of hemilabile phosphine alkyl thioether ligands (P,S) chelated to a Pt(II) center. The host-guest properties of the ion-regulated receptor were found to be highly dependent upon the coordination of the Pt(II) center, which is controlled through the reversible coordination of small molecule effectors. The environment at the regulatory site dictates the charge and the structural conformation of the entire assembly resulting in three accessible binding configurations: one closed, inactive state and two open, active states. One of the active states, the semiopen state, recognizes a neutral guest molecule, while the other, the fully open state, recognizes a cationic guest molecule. Job plots and 1H NMR spectroscopy titrations were used to study the formation of these inclusion complexes, the receptor binding modes, and the receptor binding affinities (Ka) in solution. Single crystal X-ray diffraction studies provided insight into the solid-state structures of the receptor when complexed with each guest molecule. The dipole moments and electrostatic potential maps of the structures were generated via DFT calculations at the B97D/LANL2DZ level of theory. finally, we describe the reversible capture and release of guests by switching the receptor between the closed and semiopen configurations via elemental anion and small molecule effectors.
