Molecularly Designed Nanoparticles by Dispersion of Self‐Assembled Organosiloxane‐Based Mesophases

Sakamoto, Shigeru; Tamura, Yasuhiro; Hata, Hideo; Sakamoto, Yasuhiro; Shimojima, Atsushi; Kuroda, Kazuyuki

doi:10.1002/anie.201404515

Cited by 7 publications

(7 citation statements)

References 23 publications

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“…35 The retrievability of the fluorescent porous polymers making them different from traditional fluorescent compounds and polymers. 36 High specific surface area and the highest fluorescence intensity and micropore volume ratio in LPOPs encouraged us to select LPOP-2 for exploration on NAC detection strategies. 4-Nitrotoluene (NT), 2,4-dinitrotoluene (DNT), and 2,4,6-trinitrotoluene (TNT) were selected to investigate luminescence response by adding various concentrations of NACs to LOPO-2 suspension.…”

Section: Resultsmentioning

confidence: 99%

“…NACs are closely related to agricultural chemicals, medicament, and military applications and is harmful to personal health, public security, and ecological environment if misapplied. , Therefore, monitoring and detecting NACs is important to decrease and prevent the occurrence of related accidents . The retrievability of the fluorescent porous polymers making them different from traditional fluorescent compounds and polymers . High specific surface area and the highest fluorescence intensity and micropore volume ratio in LPOPs encouraged us to select LPOP-2 for exploration on NAC detection strategies.…”

Section: Resultsmentioning

confidence: 99%

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Siloxane-Based Nanoporous Polymers with Narrow Pore-size Distribution for Cell Imaging and Explosive Detection

Gou

Zuo

Tian

et al. 2018

ACS Appl. Mater. Interfaces

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Porous polymers are among the most promising porous materials for various application because they show the combined advantages of fluorescent porous materials and polymers. This study developed a cell imaging technique based on luminescent porous organosilicon polymers (LPOPs) that were synthesized via Friedel-Crafts reaction of octaphenylcyclotetrasiloxane with octavinylsilsesquioxanes. The porous organosilicon polymers possessed narrow pore-size distribution, high surface area, and monomodal nanopores centered at approximately 0.59 nm. The excellent properties to the porous polymers can be attributed to the fine structures of LPOPs. LPOP-2 owned the highest fluorescence intensity and micropore volume ratio in LPOPs and showed high selectivity for Fe detection and excellent sensitivity to nitroaromatic compound detection. Interestingly, these porous polymers still exhibited excellent responsiveness to Fe ion even when inside of living cells. We also fabricated a paper-based sensor using LPOP-2 to develop a simple method for visual detection of explosives. This rapid and visual paper sensor demonstrates promising application for explosive detection and can be expanded for the detection of other analytes.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Siloxane-Based Nanoporous Polymers with Narrow Pore-size Distribution for Cell Imaging and Explosive Detection

Gou

Zuo

Tian

et al. 2018

ACS Appl. Mater. Interfaces

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“…3 nm in size with dense outer alkyl chains through the self-assembly of oligosiloxane compounds possessing a trialkylsilyl group. 20 The large hydrophobic moiety covalently bonded to the hydrophilic oligosiloxane favors the formation of reverse-type silica-organic hybrid mesostructures by the EISA process, and the mesostructures can be successfully dispersed into discrete nanoparticles in hexane. However, the synthesis of such precursors is rather complicated, and the outer surfaces of the resulting particles cannot be postmodified.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Recently, we have reported the formation of silica nanoparticles ca. 3 nm in size with dense outer alkyl chains through the self-assembly of oligosiloxane compounds possessing a trialkylsilyl group . The large hydrophobic moiety covalently bonded to the hydrophilic oligosiloxane favors the formation of reverse-type silica-organic hybrid mesostructures by the EISA process, and the mesostructures can be successfully dispersed into discrete nanoparticles in hexane.…”

Section: Introductionmentioning

confidence: 99%

Formation of Single-Digit Nanometer Scale Silica Nanoparticles by Evaporation-Induced Self-Assembly

et al. 2018

Self Cite

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There are emerging demands for single-digit nanoscale particles in multidisciplinary fields, such as nanomedicine, optics, catalysis, and sensors, to create new functional materials. Here, we report a novel route to prepare silica nanoparticles less than 3 nm in size via the evaporation-induced self-assembly of silicate species and quaternary trialkylmethylammonium surfactants, which usually form reverse micelles. The solvent evaporation induces a local concentration increase and simultaneous polycondensation of silicate species within the hydrophilic region of the surfactant mesophases. Extremely small silica nanoparticles in the silica-surfactant mesostructures can be stably dispersed in organic solvents by destroying the mesostructure, which is in clear contrast to the preparation of silica nanoparticles using the conventional reverse micelle method. The surface chemical modification of the formed silica nanoparticles is easily performed by trimethylsilylation. The particle size is adjustable by changing the ratio of the surfactants to the silica source because the hydrophobic/hydrophilic ratio determines the curvature and diameter of the resulting spherical silica-surfactant domains in the mesostructure. The versatility of this method is demonstrated by the fabrication of very small titania nanoparticles. These findings will increase the designability of oxide nanoparticles at the single-digit nanoscale because conventional methods based on the generation and growth of nuclei in a solution cannot produce such nanoparticles with highly regulated sizes.

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“…Herein, we report a general and facile strategy for preparing hybrid NBBs composed of silica-like heads decorated by well-defined polymer tethers. Silica NPs with controllable size/morphology/porosity, chemical stability, and excellent biocompatibility are widely used as building blocks in material science. , Our method is based on the intramolecular folding of single polymer chains using the hydrolysis and polycondensation of trimethoxysilane in di-BCPs (Figure a). BCPs are designed with one reactive block of poly(3-(trimethoxysilyl)propyl methacrylate) (PTMSPMA) and poly(methyl methacrylate) (PMMA) (denoted as P(TMSPMA- co -MMA) block) and one inert block of poly(ethylene oxide) (PEO).…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Self-Assembly of Amphiphilic Hybrid Nano Building Blocks via Self-Collapse of Polymer Single Chains

Kuo

Kanyó

et al. 2014

Macromolecules

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Nano building blocks (NBBs) decorated with well-defined polymer tethers have emerged as a promising type of building blocks for constructing hierarchical materials through programmable self-assembly. We present a general and facile strategy for preparing hybrid NBBs composed of silica-like heads decorated with well-defined polymer tethers by the self-collapse of polymer single chains. Using amphiphilic block copolymers (BCPs) of poly(ethylene oxide)-block-[poly(methyl methacrylate)-co-poly(3-(trimethoxysilyl)propyl methacrylate)] (PEO-b-P(MMA-co-TMSPMA)), the intramolecular hydrolysis and polycondensation of silane moieties led to the formation of hybrid NBBs with silica-like heads and PEO tethers. The formation of hybrid NBBs was carefully characterized by gel permeation chromatography, nuclear magnetic resonance spectroscopy, transmission electron microscopy, and static/dynamic light scattering. In a mixed solvent of THF/water, amphiphilic NBBs could assemble into spherical micelles, vesicles, and large compound micelles, depending on the size of silica heads and the initial concentrations. The intramolecular cross-linking of P(MMA-co-TMSPMA) blocks significantly altered the assembly behavior of linear BCPs. The rigid hydrophobic heads of NBBs could not be stretched/compressed, and the selfassembly of NBBs behaved surfactant-like. Furthermore, we observed that the mismatched dimensions of NBBs and linear BCPs would give rise to the formation of unprecedented phase-separated bilayer vesicles when coassembling two amphiphiles. Our study of NBBs may bridge the study of nanoparticles and polymeric building blocks and offer new opportunities to synthesize hybrid NBBs with controlled functionalities for use in novel functional materials and devices.

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Molecularly Designed Nanoparticles by Dispersion of Self‐Assembled Organosiloxane‐Based Mesophases

Cited by 7 publications

References 23 publications

Siloxane-Based Nanoporous Polymers with Narrow Pore-size Distribution for Cell Imaging and Explosive Detection

Siloxane-Based Nanoporous Polymers with Narrow Pore-size Distribution for Cell Imaging and Explosive Detection

Formation of Single-Digit Nanometer Scale Silica Nanoparticles by Evaporation-Induced Self-Assembly

Synthesis and Self-Assembly of Amphiphilic Hybrid Nano Building Blocks via Self-Collapse of Polymer Single Chains

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