A summary of calixarene-based fluorescent sensors developed during the past five years

Ren, Haixian; Wang, Hongliang; Wen, Wei; Li, Sha; Li, Nana; Huo, Fangjun; Yin, Caixia

doi:10.1039/d3cc04179d

Cited by 9 publications

(3 citation statements)

References 72 publications

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“…In the last three decades, the field of calixarenes-based host-guest chemistry has garnered significant scientific interest due to its diverse applications in the domain of supramolecular chemistry, including sensor chemistry, catalysis, and drug delivery [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17].…”

Section: Introductionmentioning

confidence: 99%

Pseudo-Polymorphism in 2-Pyridylmethoxy Cone Derivatives of p-tert-butylcalix[4]arene and p-tert-butylhomooxacalix[n]arenes

Joshi,

Hickey,

Marcos

et al. 2024

Crystals

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This paper investigates pseudo-polymorphism in 2-pyridylmethoxy derivatives of p-tert-butylcalix[4]arene (PyC4), p-tert-butyldihomooxa-calix[4]arenes (PyHOC4), and p-tert-butylhexahomotrioxacalix[3]arenes (PyHO3C3), presenting 11 crystal structures with 15 crystallographically independent molecules. The macrocycle of PyC4 is smaller and less flexible with respect to those of PyHOC4 and PyHO3C3, and in solution, the cone conformation of these three molecules exhibits different point symmetries: C4, Cs, and C3, respectively. A correlation is observed between the macrocycle’s structural rigidity and the number of pseudo-polymorphs formed. The more rigid PyC4 displays a higher number (six) of pseudo-polymorphs compared to PyHOC4 and PyHO3C3, which exhibit a smaller number of crystalline forms (three and two, respectively). The X-ray structures obtained show that the conformation of the macrorings is primarily influenced by the presence of an acetonitrile guest molecule within the cavity, with limited impact from crystal packing and intermolecular co-crystallized solvent molecules. Notably, both calix[4]arene derivatives produce a host–guest complex with acetonitrile, while the most flexible and less aromatic PyHO3C3 does not give crystals with acetonitrile as the guest. Intertwined 1D and 2D solvent channel networks were observed in the PyHOC4-hexane and in the PyHO3C3-H2O-MeOH crystal structures, respectively, while the other pseudopolymorphs of PyHOC4 and PyHO3C3 and all PyC4 crystal forms exhibit closely packed crystal structures without open channels.

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Section: Introductionmentioning

confidence: 99%

Pseudo-Polymorphism in 2-Pyridylmethoxy Cone Derivatives of p-tert-butylcalix[4]arene and p-tert-butylhomooxacalix[n]arenes

Joshi,

Hickey,

Marcos

et al. 2024

Crystals

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“…Calix [4]arenes are macrocyclic compounds formed by condensation of four molecules of phenol and four molecules of formaldehyde, which, after adequate functionalization, could be used as building blocks for applications in host-guest chemistry, coordination chemistry, homogeneous catalysis, and materials or medicinal sciences [1][2][3][4][5][6][7][8][9][10][11][12].…”

Section: Introductionmentioning

confidence: 99%

Optically Pure Calixarenyl Phosphine via Stereospecific Alkylation on Evans’ Oxazolidinone Moiety

Bauder,

Sémeril

2024

Molecules

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A convenient protocol for the synthesis of 25,26,27-tribenzoyl-28-[((S)-1-diphenylphos- phanyl-propan-2-yl)oxy]-calix[4]arene via stereospecific methylation on Evans’ oxazolidinone moiety was reported. According to the 13C NMR analysis of this phosphine, the calix[4]arene skeleton adopted a 1,3-alternate conformation. The latter conformation of the macrocycle and the (S)-chirality of the carbon atom bearing the methyl substituent were confirmed by a single-crystal X-ray diffraction study. After coordination of the phosphinated ligand to the dimeric [RuCl2(p-cymene)]2 organometallic precursor, the resulting arene–ruthenium complex was tested in the asymmetric reduction of acetophenone and alcohol was obtained with modest enantiomeric excess.

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“…Fluorescence stands out as a powerful tool for designing chemosensors, particularly due to its remarkable sensitivity, thus enabling the detection of chemical species even at nanomolar concentrations. , In the field of fluorescence-based chemosensing, two classical strategies prevail: direct sensing, where fluorophores are grafted onto the receptor, and indicator displacement assays, involving the replacement of a bound fluorophore by the analyte. , Homooxacalix[3]arenes are bowl-shaped receptors whose cavity is closed at the level of the narrow rim as the 18C3 macrocycle is too small to let a molecule thread through it . An ideal design for a homooxacalix[3]arene-based fluorescent chemosensor devoted to the sensing of ammonium ions accommodated into the polyaromatic cavity would thus consist of the introduction of fluorophores on the wide rim.…”

Section: Introductionmentioning

confidence: 99%

Development of a Cone Homooxacalix[3]arene-Based Fluorescent Chemosensor for the Selective Detection of Biogenic Ammonium Ions in Protic Solvents

Lambert,

Carpentier,

Lepeintre

et al. 2024

J. Org. Chem.

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We report here on the development of a fluorescent cone homooxacalix [3]arene-based receptor with a pyrene unit on the wide rim of the macrocycle (Ox3F) for the selective detection of primary ammonium ions, including those of biological importance. Ox3F was synthesized efficiently via an innovative strategy that enables the regio-and iteroselective wide rim functionalization of the readily available p-tBu-substituted homooxacalix[3]arene precursor. Nuclear magnetic resonance studies and in silico methods highlighted the endo-complexation of primary ammonium ions, including the protonated form of biogenic dopamine, tryptamine, serotonin, mexamine, and 3-iodothyronamine. The binding mode is similar for all guests with the ion deeply inserted into the polyaromatic cavity, enabling the NH 3 + head to establish three hydrogen bonds with the ethereal oxygens of the macrocycle. Fluorescence quenching of the pyrene unit was observed following the π−π interaction between the pyrene moiety and the aromatic groups of serotonin, mexamine, and 3-iodothyronamine. No quenching was observed upon complexation of the smaller aromatic neurotransmitter dopamine as well as aliphatic amines and polyamines. This study presents a novel approach for biologically relevant ammonium ion chemosensing with ongoing efforts focused on translating these systems for aqueous environment applications.

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A summary of calixarene-based fluorescent sensors developed during the past five years

Abstract: Calixarenes are “chalice like” phenol-based macrocycles that are ones of the most fascinating studied scaffolds in supramolecular chemistry. Their preorganized nonpolar cavities and ionbinding sites, and their well-defined conformations all...

Cited by 9 publications

References 72 publications

Pseudo-Polymorphism in 2-Pyridylmethoxy Cone Derivatives of p-tert-butylcalix[4]arene and p-tert-butylhomooxacalix[n]arenes

Pseudo-Polymorphism in 2-Pyridylmethoxy Cone Derivatives of p-tert-butylcalix[4]arene and p-tert-butylhomooxacalix[n]arenes

Optically Pure Calixarenyl Phosphine via Stereospecific Alkylation on Evans’ Oxazolidinone Moiety

Development of a Cone Homooxacalix[3]arene-Based Fluorescent Chemosensor for the Selective Detection of Biogenic Ammonium Ions in Protic Solvents

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