纤维素纳米晶手性模板的研究进展

邓艳梅; 支云飞; 陕绍云; 胡帅; 张楚茹

doi:10.13801/j.cnki.fhclxb.20221030.001

纤维素纳米晶手性模板的研究进展

doi: 10.13801/j.cnki.fhclxb.20221030.001

昆明理工大学　化学工程学院，昆明 650500

基金项目: 国家自然科学基金(52163003；21766016；22068023；202307AC110001)；云南省“万人计划”基金(YNWR-QNBJ-2018-198)；昆明市科学技术局科技计划基金(2019-1-G-25318000003480)；昆明市科学技术局科技创新要素聚集计划重点项目(2019-1-A-24657)；云南省基础研究计划青年项目(202001AU070023)；云南省大学生创新创业计划国家级项目(201910674032)；云南省后备人才项目(2015HB014)

详细信息

通讯作者:
支云飞，博士，副教授，硕士生导师，研究方向为催化新材料与新技术　E-mail: zyf891123@163.com

陕绍云，博士，教授，博士生导师，研究方向为绿色高分子材料　E-mail: shansy411@163.com

中图分类号: TQ352
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出版历程
- 收稿日期: 2022-08-22
- 修回日期: 2022-10-06
- 录用日期: 2022-10-22
- 网络出版日期: 2022-10-31
- 刊出日期: 2023-04-15

Progress of study on cellulose nanocrystals as chiral templates

Faculty of Chemical Engineering, Kunming University of Science and Technology, Kunming 650500, China

Funds: National Natural Science Foundation of China (52163003; 21766016; 22068023; 202307AC110001); Yunnan Province "Ten Thousand People Plan" Fun (YNWR-QNBJ-2018-198); Science and Technology Program Fund of Kunming Science and Technology Bureau (2019-1-G-25318000003480); Key Projects of Science and Technology Innovation Factor Gathering Plan of Kunming Science and Technology Bureau (2019-1-A-24657); Youth Project of Yunnan Basic Research Program (202001AU070023); National Project of Yunnan University Students' Innovation and Entrepreneurship Program (201910674032); Reserve Talent Project of Yunnan Province (2015HB014)

摘要

摘要: 纤维素纳米晶(CNC)是由酸水解天然纤维素制得的具有高结晶度的一种纳米材料，CNC通过蒸发诱导自组装(EISA)能形成具有手性向列液晶相的虹彩薄膜。CNC制备工艺简单，具有生物可持续性和固有的手性向列结构，CNC的手性向列结构表现出特有的光学特性，以CNC为手性模板与聚合物或无机材料共组装可制得先进光学材料，在传感器、光电器件和智能显示等领域具有广阔的应用前景。本文介绍了CNC的制备、手性向列结构的形成及其作为模板的研究，简要综述了近年来CNC在制备有序介孔材料、功能纳米复合膜和新型光学材料领域的应用现状。最后，总结了基于目前CNC手性材料制备和应用存在的一些问题，以期为今后手性材料的应用研究提供参考。
- 纤维素纳米晶 /
- 手性模板 /
- 蒸发诱导自组装 /
- 光学材料 /
- 应用
Abstract: Cellulose nanocrystals (CNC) is a kind of nanocellulose with high crystallinity, which is prepared by the acid hydrolysis of natural cellulose. CNC can form iridescent films with chiral nematic liquid crystal phase through evaporation-induced self-assembly (EISA). The preparation process of CNC is simple, and CNC has biological sustainability and inherent chiral nematic structure that shows unique optical properties. Advanced optical materials can be prepared by co-assembling CNC as chiral templates with polymers or inorganic materials, which has a broad application prospect in the fields of sensors, photoelectric devices, and intelligent display. The preparation of CNC, the formation of chiral structure and the study of CNC as template are introduced in this paper, and the application status of CNC in the preparation fields of ordered mesoporous materials, functional nanocomposite membranes and new optical materials are briefly reviewed. Finally, some problems in the preparation and application of CNC chiral materials are summarized, which is expected to provide reference for the application of CNC chiral materials in the future.
- cellulose nanocrystals /
- chiral templates /
- evaporation-induced self-assembly /
- optical materials /
- applications

HTML全文

图 1 制备纤维素液晶膜的示意图^[5]：(a) 绿树；(b) 纤维素纤维；(c) 纤维素的结晶和非晶区；(d) 纤维素的分子结构；(e) 纤维素纳米晶 (CNC)的AFM图像；(f) CNC扭曲螺旋状外观；(g) 硫酸水解后CNC的分子结构；(h) 蒸发诱导自组装 (EISA)之前的CNC悬浮液；(i) EISA之后的CNC内部排列；(j) EISA后的纤维素液晶薄膜

Figure 1. Schematic diagram of preparing cellulose liquid crystal film^[5]: (a) Green trees; (b) Cellulose fiber; (c) Crystalline and amorphous regions of cellulose; (d) Molecular structure of cellulose; (e) AFM image of cellulose nanocrystals (CNC); (f) Twisted spiral appearance of CNC; (g) Molecular structure of CNC after sulfuric acid hydrolysis; (h) Picture of CNC suspension before evaporation-induced self-assembly (EISA); (i) Internal CNC arrangement after EISA; (j) Picture of cellulose liquid crystal film after EISA

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图 2 CNC作模板合成介孔材料的工艺流程^[21]

Figure 2. Process steps of mesoporous materials with CNC as template^[21]

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图 3 掺镧介孔碳材料(MC-La)合成示意图^[26]

Figure 3. Schematic of La-doped mesoporous carbon materials (MC-La)^[26]

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图 4 CNC与带电金纳米棒(GNRs)混合的胶体悬浮液制备手性等离子体杂化膜^[33]

Figure 4. Schematic of the chiral plasmonic hybrid films prepared by mixing colloidal suspensions of CNC and charged gold nanorods (GNRs)^[33]

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图 5 手性荧光聚乙二醇(PEG)-CNC-谷胱甘肽(GSH)-铜纳米团簇(CuNCs)复合薄膜的自组装过程^[37]

Figure 5. Self-assembly of chiral fluorescent polyethylene glycol (PEG)-CNC-glutathione (GSH)-copper nanoclusters (CuNCs) composite films^[37]

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图 6 在HCl蒸汽条件下，CNC与戊二醛(GA)通过EISA交联形成导电聚合物和金属氧化物的模板^[39]

Figure 6. Preparation template of conductive polymer and metal oxide formed by cross-linking of CNC with glutaraldehyde (GA) through EISA under the condition of HCl vapor^[39]

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图 7 GA交联CNC/聚乙烯醇(PVA)薄膜的制备过程示意图(a)和CNC ((b), (e), (h))、 CNC/PVA-70∶30 ((c), (f), (i)) 和CNC/PVA-GA ((d), (g), (j)) 薄膜的照片 ((b)~(d))、截面SEM图像 ((e)~(g))、偏振光学显微镜(POM)图像 ((h)~(j))^[12]

Figure 7. Schematic illustration of the preparation process of GA cross-linked CNC/polyvinyl alcohol (PVA) film (a) and photographs ((b)-(d)), cross-sectional SEM images ((e)-(g)), and polarized optical microscopy (POM) images ((h)-(j)) of CNC((b), (e), (h)), CNC/PVA-70∶30 ((c), (f), (i)), and CNC/PVA-GA ((d), (g), (j)) films^[12]

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图 8 荧光光子晶体膜的形成过程， [N-(3-N-苄基-N,N-二甲基丙基氯化铵)-1,8-萘酰亚胺]联氨(ANH)和PEG在CNC表面的组装及CNC在溶剂蒸发过程中定向有序形成液晶膜^[46]

Figure 8. Formation process of the fluorescent photonic crystal membranes, including the assembly of [N-(3-N-benzyl-N,N-dimethyl-propyl ammonium chloride)-1,8-naphthalimide] hydrazine (ANH) and PEG on the CNC surface and the orientational order of CNC during the solvent evaporation to form liquid crystal membranes^[46]

P/2—Half-helical pitch

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图 9 CNC手性向列光学复合膜的制备示意图，将CNC与葡萄糖、甘油和PVA共同组装，显示出对不同湿度(RH)的智能响应^[48]

Figure 9. Schematic diagram of CNC chiral nematic optical composite film preparation showing an intelligent response to different humidity (RH) by co-assembling CNC with glucose, glycerol and PVA^[48]

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