Amphiphilic Polyoxometalates for the Controlled Synthesis of Hybrid Polystyrene Particles with Surface Reactivity

Haye, Jennifer Lesage de la; Guigner, Jean‐Michel; Marceau, Éric; Ruhlmann, Laurent; Hasenknopf, Bernold; Lacôte, Emmanuel; Rieger, Jutta

doi:10.1002/chem.201405708

Cited by 28 publications

(19 citation statements)

References 73 publications

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“…In this type of POM-surfactant crystals, amphiphilic POMs are synthesized by grafting a long alkyl chain covalently into pre-modified or lacunary POM anion by condensation reaction such as esterification [22,23]. Several types of POMs with amphiphilic moiety (moieties) have been synthesized [98][99][100]112,[142][143][144][145][146][147][148][149] from Lindqvist-, Anderson-, and Keggin-type anions. However, the amphiphilic POMs analyzed from single crystals have been limited to hexavanadate and hexamolybdate derivatives so far.…”

Section: Hybrid Single Crystals Composed From Polyoxometalate Modifiementioning

confidence: 99%

Inorganic–Organic Hybrid Surfactant Crystals: Structural Aspects and Functions

Ito

2016

Crystals

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Hybrid single crystals consisting of an organic surfactant and an inorganic moiety are promising functional materials. Layered crystals composed from alternate inorganic and surfactant layers are obtained by the template effect of long alkyl chain moiety. The composition, crystal packing, and molecular arrangement of the hybrid single crystals are controllable by changing the inorganic constituent and the surfactant molecular structure. The types of hybrid surfactant single crystals are twofold: (i) crystals consisting of discrete inorganic cation coordinated by ligands having amphiphilic moiety; and (ii) crystals comprising a surfactant cation and a discrete inorganic anion including polyoxometalate (POM) oxide clusters. The POM-surfactant hybrid single crystals are rather rare, and therefore promising as unprecedented functional materials. Their structural variation and functional properties are discussed.

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Section: Hybrid Single Crystals Composed From Polyoxometalate Modifiementioning

confidence: 99%

Inorganic–Organic Hybrid Surfactant Crystals: Structural Aspects and Functions

Ito

2016

Crystals

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“…The combination of POM clusters and polymers has facilitated the realization of a series of POM–polymer hybrids. These may be prepared in a number of different ways to produce materials that are covalently bound or are the result of physical mixing . POM–polymer hybrids exhibit the functions of the precursor POM clusters and also have the high processability of polymers.…”

Section: Introductionmentioning

confidence: 99%

Twining Poly(polyoxometalate) Chains into Nanoropes

Zhang

Miao

Ren

et al. 2019

Chemistry A European J

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Organic polymers and inorganic clusters belong to two different disciplines and have completely different properties and structures. When a cluster is attached to the backbone of a polymer as a pendant, the resultant hybrid polymers (polyclusters) exhibit unique behaviours totally different from those of conventional polymers owing to the nanoscale size of the cluster and its particular interactions. Herein, the aggregation of a poly(polyoxometalate)—a polynorbornene backbone with inorganic polyoxometalate cluster pendants—upon addition of a non‐solvent to its dilute solution is reported. A three‐dimensional network of tangled and snake‐like nanothreads was observed. Direct visualisation of individual nanoscale clusters enabled identification of single chains within the nanothreads. These observations suggest that during the process of aggregation, the hybrid polymer forms curved or extended chains as a consequence of an armouring effect in which the collapsed cluster pendants wrap around the backbone. The collapse occurs because they become less soluble in the solvent/non‐solvent mixture. The extended chains then become entwined and form nanoropes consisting of multiple chains wound around each other. This study provides a deeper understanding of the nature of polyclusters and should also prove useful for their future development and application.

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“…The samples were dissolved in water to 1 wt% ~24 h before analysis (unless indicated differently below the figure). According to protocols reported elsewhere [44][45][46] Small-angle neutron scattering (SANS) measurements were made at the LLB (Saclay, France) on the PA20 SANS instrument, at three sample to detector distances 1.5, 8 and 18.5 m and fixed wavelength equal to 6 Å to cover the 2.5 10 -3 to 0.44 Å -1 q-range, where the scattering vector q is defined as usual, assuming elastic scattering (q = (4π/λ)sin(θ/2), where θ is the angle between incident and scattered beam). Data were corrected for the empty cell signal, the solute and solvent incoherent background.…”

Section: Introductionmentioning

confidence: 99%

Bisurea-Functionalized RAFT Agent: A Straightforward and Versatile Tool toward the Preparation of Supramolecular Cylindrical Nanostructures in Water

et al. 2018

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Bis-ureahydrophilic polymer sticker RAFT polymerizationTTC unit Hydrogen bonding unit , , , … µm ABSTRACTWe report a versatile and simple approach to produce cylindrical micelles by the direct dissolution of polymers in water. The developed strategy relies on a RAFT agent functionalized by a bisurea sticker that allowed to synthesize a series of α-bisurea functionalized poly(N,Ndimethylacrylamide) (PDMAc), poly(acrylic acid) (PAA), polyacrylamide (PAM) and poly(2-(N,N-dimethylamino)ethyl acrylate) (PDMAEA) with number-average degrees of polymerization (DPn) varying from about 10 to 50. Their spontaneous self-assembly in water was studied by electron microscopy (cryo-TEM), neutron scattering (SANS) and calorimetry (ITC) analyses that showed that long cylindrical micelles are spontaneously formed in water.The crucial role of the bisurea sticker end-groups was established by comparison with the corresponding bisurea-free model polymers that only formed spherical micelles. Finally, we have shown that it is possible to trigger reversibly the assembly/disassembly of the nanofibers by pH changes. AUTHOR INFORMATIONCorresponding authors *

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Amphiphilic Polyoxometalates for the Controlled Synthesis of Hybrid Polystyrene Particles with Surface Reactivity

Cited by 28 publications

References 73 publications

Inorganic–Organic Hybrid Surfactant Crystals: Structural Aspects and Functions

Inorganic–Organic Hybrid Surfactant Crystals: Structural Aspects and Functions

Twining Poly(polyoxometalate) Chains into Nanoropes

Bisurea-Functionalized RAFT Agent: A Straightforward and Versatile Tool toward the Preparation of Supramolecular Cylindrical Nanostructures in Water

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