Functionalizing Single Crystals: Incorporation of Nanoparticles Inside Gel‐Grown Calcite Crystals

Liu, Yujing; Yuan, Wentao; Shi, Yijiang; Chen, Xiaoqiang; Wang, Yong; Chen, Hongzheng; Li, Hanying

doi:10.1002/ange.201310712

Cited by 22 publications

(21 citation statements)

References 52 publications

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“…[1][2][3][4][5][6][7][8] Taking inspiration from this biogenic strategy, the occlusion of nanoparticle additives within inorganic crystal hosts has recently gained increasing attention. [9][10][11][12][13][14][15] Not only do such synthetic routes provide a straightforward approach to the rational design of new hybrid materials with enhanced physical properties such as hardness, magnetism, color or strong fluorescence, [16][17][18][19][20] but they can also inform our understanding of biomineralization processes. [21][22][23][24] There is no doubt that the nanoparticle surface chemistry dictates their occlusion.…”

Section: Introductionmentioning

confidence: 99%

Model Anionic Block Copolymer Vesicles Provide Important Design Rules for Efficient Nanoparticle Occlusion within Calcite

et al. 2019

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Nanoparticle occlusion within growing crystals is of considerable interest because (i) it enhances our understanding of biomineralization and (ii) it offers a straightforward route for the preparation of novel nanocomposites. However, robust design rules for efficient occlusion remain elusive. Herein, we report the rational synthesis of a series of silica-loaded poly(glycerol monomethacrylate)-poly(2-hydroxypropyl methacrylate)-poly(ethylene glycol dimethacrylate)poly(methacrylic acid) tetrablock copolymer vesicles using polymerization-induced self-assembly. The overall vesicle dimensions remain essentially constant for this series, hence systematic variation of the mean degree of polymerization (DP) of the anionic poly(methacrylic acid) steric stabilizer chains provides an unprecedented opportunity to investigate the design rules for efficient nanoparticle occlusion within host inorganic crystals such as calcite. Indeed, the stabilizer DP plays a decisive role in dictating both the extent of occlusion and the calcite crystal morphology: sufficiently long stabilizer chains are required to achieve extents of vesicle occlusion of up to 41 vol% but overly long stabilizer chains merely lead to significant changes in the crystal morphology, rather than promoting further occlusion. Furthermore, steric stabilizer chains comprising anionic carboxylate groups lead to superior occlusion performance compared to those composed of phosphate, sulfate or sulfonate groups. Moreover, occluded vesicles are subjected to substantial deformation forces, as shown by the significant change in shape after their occlusion. It is also demonstrated that such T H-functional silica nanoparticles within calcite. In summary, this study provides important new physical insights regarding the efficient incorporation of guest nanoparticles within host inorganic crystals.

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Section: Introductionmentioning

confidence: 99%

Model Anionic Block Copolymer Vesicles Provide Important Design Rules for Efficient Nanoparticle Occlusion within Calcite

et al. 2019

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“…The incorporation of guest species into host crystals has gained considerable interest because this bio-inspired strategy provides an attractive route for the preparation of new functional nanocomposites with tailored properties. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] However, the precise design rules for efficient and versatile nanoparticle occlusion within inorganic crystals remain elusive. For example, Pasteris and co-workers 16 reported that poly(acrylic acid)-stabilized micelles merely adsorbed onto the surface of sodium chloride crystals.…”

Section: Introductionmentioning

confidence: 99%

What Dictates the Spatial Distribution of Nanoparticles within Calcite?

et al. 2019

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Crystallization is widely used by synthetic chemists as a purification technique because it usually involves the expulsion of impurities. In this context, the efficient occlusion of guest nanoparticles within growing host crystals can be regarded as an interesting technical challenge. Indeed, although there are various reports of successful nanoparticle occlusion within inorganic crystals in the literature, robust design rules remain elusive. Herein, we report the synthesis of two pairs of sterically-stabilized diblock copolymer nanoparticles with identical compositions but varying particle size, morphology, stabilizer chain length and stabilizer chain surface density via polymerization-induced self-assembly (PISA). The mean degree of polymerization of the stabilizer chains dictates the spatial distribution of these model anionic nanoparticles within calcite (CaCO3): relatively short stabilizer chains merely result in near-surface occlusion, whereas sufficiently long stabilizer chains are essential to achieve uniform occlusion. This study reconciles the various conflicting literature reports of occluded nanoparticles being either confined to surface layers or uniformly occluded and hence provides important new insights regarding the criteria required for efficient nanoparticle occlusion within inorganic crystals.

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“…另一方面, 近年来的研究发现, 在将功能性杂质引入单晶的过程中, 凝胶网络可以起到媒介的关键作用. Liu等人 [27] 成功能材料 . 这需要设计具有特定功能的凝胶体系 [59] , 也需要逐步研究功能性的单晶 (如半导体晶体 [51,52] Gel-grown method has been adopted to grow single crystals for over a century, and has triggered increasing interest with a large number of single crystals obtained.…”

Section: 体在硅胶中的生长研究发现 Naf与kdp晶体能很unclassified

“…有趣的是, 虽然凝胶法作为一种常用的晶体生长手段, 其悠久的历史可追溯到18世纪末 [25] , 但直到1969年, 凝胶法生长晶体过程中凝胶网络能嵌入单晶内部的现象才被发现并报道 [26] . 然而该现象仅在一种晶体-凝胶体系中发现, 被认为可能是特例 [25] , 而不具有普遍意义, 因此在发表后较长的时间里并如晶体-凝胶网络-粒子的复合体系, 为功能性第三组分(如纳米粒子)的引入创造了便利 [27] , 从而为实现单晶功能化提供了切实可行的途径和思路. 本文简要评述了凝胶法制备凝胶网络-单晶复合物的研究进展.…”

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