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仿生法在静电纺丝醋酸纤维素纤维支架上诱导碳酸钙涂层结晶及其相应的碳酸钙微管网络。

Bioinspired crystallization of CaCO3 coatings on electrospun cellulose acetate fiber scaffolds and corresponding CaCO3 microtube networks.

机构信息

Division of Nanomaterials & Chemistry, Hefei National Laboratory for Physical Sciences at Microscale, School of Chemistry & Materials, University of Science and Technology of China, Hefei 230026, PR China.

出版信息

Langmuir. 2011 Jun 7;27(11):7199-206. doi: 10.1021/la200738n. Epub 2011 May 2.

Abstract

This article describes the mineralization behavior of CaCO(3) crystals on electrospun cellulose acetate (CA) fibers by using poly(acrylic acid) (PAA) as a crystal growth modifier and further templating synthesis of CaCO(3) microtubes. Calcite film coatings composed of nanoneedles can form on the surfaces of CA fibers while maintaining the fibrous and macroporous structures if the concentration of PAA is in a suitable range. In the presence of a suitable concentration of PAA, the acidic PAA molecules will first adsorb onto the surface of CA fibers by the interaction between the OH moieties of CA and the carboxylic groups of PAA, and then the redundant carboxylic groups of PAA can ionically bind Ca(2+) ions on the surfaces of CA fibers, resulting in the local supersaturation of Ca(2+) ions on and near the fiber surface, which can induce the nucleation of CaCO(3) on the CA fibers instead of in bulk solution. Calcite microtube networks on the macroscale can be prepared by the removal of CA fibers after the CA@CaCO(3) composite is treated with acetone. When the CA fiber scaffold is immersed in CaCl(2) solution with an extended incubation time, the first deposited calcite coatings can act as secondary substrate, leading to the formation of smaller calcite mesocrystal fibers. The present work proves that inorganic crystal growth can occur even at an organic interface without the need for commensurability between the lattices of the organic and inorganic counterparts.

摘要

本文描述了通过使用聚丙烯酸 (PAA) 作为晶体生长调节剂,在静电纺丝醋酸纤维素 (CA) 纤维上诱导碳酸钙 (CaCO3) 晶体的矿化行为,进一步模板合成 CaCO3 微管。如果 PAA 的浓度在合适的范围内,可在 CA 纤维表面形成由纳米针组成的方解石薄膜涂层,同时保持纤维状和大孔结构。在合适浓度的 PAA 存在下,通过 CA 纤维上的 OH 基团与 PAA 的羧酸基团之间的相互作用,酸性 PAA 分子将首先吸附在 CA 纤维表面上,然后 PAA 的多余羧酸基团可以离子键合 CA 纤维表面上的 Ca2+离子,导致纤维表面及其附近的 Ca2+离子局部过饱和度增加,从而诱导 CaCO3 在 CA 纤维上而非在本体溶液中形核。在 CA@CaCO3 复合材料用丙酮处理后,去除 CA 纤维即可制备宏观尺度上的方解石微管网络。当 CA 纤维支架在 CaCl2 溶液中浸泡更长时间时,最初沉积的方解石涂层可以作为二次衬底,导致形成更小的方解石介晶纤维。本工作证明,即使在有机界面上,无机晶体生长也可以发生,而无需有机和无机对应物晶格之间的协调性。

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