Synthesis of phosphorylated calix[4]arene derivatives for the design of solid phases immobilising uranyl cations

Bou-Maroun, Elias; Hagège, Agnès; Basset, Christian; Quéméneur, Éric; Vidaud, Claude; Asfari, Zouhair

doi:10.1080/10610270802588301

Cited by 3 publications

(3 citation statements)

References 36 publications

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“…Molecule CX8 consists of eight phosphonic acid functionalties, which are attached to the same calix[4]arene scaffold, and has a ratio of one phosphonic acid functional group per 3.5 carbons. Though functionalization of the calix[4]arene scaffold with phosphonate groups on either the lower , or upper , rims has been reported previously, synthesis of CX8 is unique in that it represents the first exhaustively phosphorylated calix[4]arene molecule, on upper and lower rims. Reaction of cone -tetrakis(4-Bromobutoxy)calix[4]arene 1 with N -bromosuccinimide synthesizes starting octabromo-calix[4]arene 2 in 86% yield, as shown in Figure .…”

Section: Results and Discussionmentioning

confidence: 99%

Silica-Supported Phosphonic Acids as Thermally and Oxidatively Stable Organic Acid Sites

et al. 2016

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Organic–inorganic materials consisting of organophosphonic-acid-supported-on-silica materials C3/SiO2 and C4/SiO2 are described, where C3 is propane-1,2,3-triphosphonic acid and C4 is butane-1,2,3,4-tetraphosphonic acid. Solid-state structures of both of these phosphonic acids are analyzed using single-crystal X-ray diffraction, and these data reveal extensive intermolecular hydrogen bonding and no intramolecular hydrogen bonds. Thermogravimetric analysis/mass spectroscopy (TGA/MS) data show a lack of combustion for these materials in air at temperatures below 400 °C, and only release of water corresponding to reversible organophosphonic acid condensation below 150 °C. A comparative series of silica-supported materials were synthesized, consisting of organophosphonic acid CX8, which represents a calixarene macrocycle that is decorated with a high density of organophosphonic-acid substituents on both the lower and upper rim, as well as polyvinylphosphoric acid (PVPA). Material CX8/SiO2 possesses a significantly lower thermal stability and lower combustion temperature of 300 °C in air, whereas PVPA demonstrates comparable thermal stability as observed with C3 and C4. TGA coupled with base-probe titration was used to determine the Brønsted acid site density of all silica-supported phosphonic acids at various coverages and temperatures. Material C4/SiO 2 -37% (corresponding to 37% (by mass) loading and half-monolayer coverage on silica) exhibited the highest Brønsted acid-site density of all materials, corresponding to 0.84 mmol/g at 150 °C, and 0.62 mmol/g at 300 °C. All supported phosphonic acids treated with pyridine at room temperature were strong enough acids to protonate pyridine at room temperature as exhibited by a distinct pyridinium cation band in the infrared spectrum; however, in contrast to much stronger acid sites in silica-supported phosphoric acid materials, almost all adsorbed pyridine was lost by 150 °C. Use of a stronger base for acid-site titration consisting of diisopropylamine (DIPA) demonstrates acid sites in all materials up to 300 °C, at which temperature the acid site was too weak to adsorb DIPA. Thus, these oxidatively stable materials are deemed to be useful in applications requiring weak Brønsted acid sites, while exhibiting high-temperature oxidative stability up to 400 °C.

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Section: Results and Discussionmentioning

confidence: 99%

Silica-Supported Phosphonic Acids as Thermally and Oxidatively Stable Organic Acid Sites

et al. 2016

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“…5c. Phosphonate groups are known to bind weakly with metallic cations 28,42 including uranyl cations 29,[43][44][45] which are used in the present work as a stain in the form of uranyl acetate. Thus, uranyl acetate is far more likely to be absorbed by the selfassemblies, conducting to positive staining (the particles appear dark in the TEM imaging, and even darker with increasing size) and not to a negative staining as usually observed with this contrast enhancer.…”

Section: Nanoprecipitation Methodsmentioning

confidence: 99%

Self-assembly of phosphorous containing oligomers: morphological features and pH-sensitiveness in suspension

2014

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Methacrylamide-based oligomers bearing phosphonate pending groups at the end of a long alkyl chain and originating from undecylenic acid synthons were subjected to direct oligomer dissolution. Size improvement towards much smaller objects was reached using the nanoprecipitation method: the oligomers were first dissolved in an organic solvent, and then precipitated in water using a syringe pump. Dynamic light scattering (DLS) showed phosphorous containing monomodal and quite narrow-sized self-assemblies in water with hydrodynamic diameters (DH) ranging from 80 to 280 nm (depending on the oligomer system). Direct visualization using transmission electron microscopy (TEM) and atomic force microscopy (AFM) showed filled and almost individual particles with spherical shape. They were considerably shrunk, suggesting the highly swollen character of the self-assemblies in suspension. Morphological information on the multi-scale self-assembled structures was complementarily obtained using static light scattering (SLS). Thus, at a low length-scale, highly segregated sub-units having sharp boundaries surrounded by water (Porod behaviour) were observed, whereas at a high length-scale random non-compact organization of these sub-units via weak interactions was found, forming a chaplet-like structure (Gaussian behaviour). Furthermore, the pH-sensitiveness of the suspensions obtained after the nanoprecipitation method was studied. Particularly, at pH = 12, the characteristic size drastically increased within few hours from typically ∼280 nm to 2 μm due to electrostatic repulsion between deprotonated hydroxyl groups. At longer times, the observed peculiar behaviour corresponded to the model of diffusion-limited cluster aggregation (DLCA) where the particles stuck easily together upon contact [continuation of the article by C. Bouilhac, C. Travelet, A. Graillot, S. Monge, R. Borsali and J.-J. Robin, Polym. Chem., 2014, 5, 2756-2767].

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“…118 The multistep synthesis of calix [4]arenes 168 in the 1,3alternate conformation was described. 119 These compounds contain several substituents of different nature, e.g., two chelating phosphonic acid groups and the carboxylic acid moiety in the form of N-oxysuccinimide ester.…”

Section: B C-phosphorylation Of Calixarenesmentioning

confidence: 99%

Phosphorus-containing macrocyclic compounds: synthesis and properties

Knyazeva¹,

Бурилов²,

Пудовик³

et al. 2013

Russ. Chem. Rev.

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Main trends in the development of methods for Main trends in the development of methods for the synthesis of phosphorus-containing macrocyclic com-the synthesis of phosphorus-containing macrocyclic compounds in the past 15 years are considered. Emphasis is pounds in the past 15 years are considered. Emphasis is given to reactions producing macrocyclic structures with the given to reactions producing macrocyclic structures with the participation of a phosphorus atom and other functional participation of a phosphorus atom and other functional groups involved in organophosphorus molecules and to groups involved in organophosphorus molecules and to modifications of macrocycles by phosphorus compounds modifications of macrocycles by phosphorus compounds in different valence states. Possibilities of the practical in different valence states. Possibilities of the practical application of phosphorus-containing macrocyclic com-application of phosphorus-containing macrocyclic compounds in difference areas of science and engineering are pounds in difference areas of science and engineering are discussed. The bibliography includes 205 references discussed. The bibliography includes 205 references. .

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Synthesis of phosphorylated calix[4]arene derivatives for the design of solid phases immobilising uranyl cations

Cited by 3 publications

References 36 publications

Silica-Supported Phosphonic Acids as Thermally and Oxidatively Stable Organic Acid Sites

Silica-Supported Phosphonic Acids as Thermally and Oxidatively Stable Organic Acid Sites

Self-assembly of phosphorous containing oligomers: morphological features and pH-sensitiveness in suspension

Phosphorus-containing macrocyclic compounds: synthesis and properties

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