Unique Optical Properties of Cellulosic Materials

IF 14 Q1 CHEMISTRY, MULTIDISCIPLINARY Accounts of materials research Pub Date : 2024-07-08 DOI:10.1021/accountsmr.4c0001310.1021/accountsmr.4c00013
Jade Poisson,  and , Kai Zhang*, 
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Abstract

Our natural environment inspires much of our innovation in all fields of research and application. In particular, unique optical properties are observed in natural systems such as bioluminescence and structural colors generated by bioengineering specific nanostructures. Cellulose is one such naturally occurring material that has been particularly surprising and impactful. Cellulose is one of the most abundant biopolymers with incredible versatility and distinct optical properties. Cellulose nanomaterials can readily self-assemble into chiral nematic phases which induces birefringence resulting in unique optical properties as well as causing incident irradiation to be circularly polarized. These properties unlock possibilities for cellulose materials to be used in encryption and sensing applications to name a few. Thus, cellulose materials have been used extensively as chiral scaffolds in composites but not as luminophores themselves in circularly polarized luminescent (CPL) materials. Recent discovery of the intrinsic luminescence of cellulose has expanded the use of cellulose materials in optical applications.

In addition to structural colors, the study of luminescent properties of cellulose is a perfect example of the scientific method. For many years it was presumed that such materials would only emit if they were contaminated with other luminophores. Researchers stress tested this hypothesis and found that not just cellulose but many everyday, biological and even very structurally simple molecules emit UV and visible light via a clustering triggered emission (CTE) mechanism. This phenomenon employs through-space conjugation of heteroatoms wherein the electron clouds of nearby electron moieties can overlap. CTE combines aspects of aggregation-induced emission (AIE) and crystallization-induced phosphorescence (CIP). There are several characteristic features observed in materials demonstrating CTE. These include concentration-dependent emission, excitation wavelength-dependent and multicolor emission, and room temperature phosphorescence.

The optical properties of cellulose are found to be particularly sensitive to environmental stimuli such as pH, humidity, temperature, etc. thus making them ideal for luminescent sensing applications. Cellulose-derived materials have also been used in a broad spectrum of other applications including encryption, bioimaging, and analytical tools. However, there are several aspects of the field that have yet to be explored. Arguably, the most important of these is the lack of specificity in the CTE mechanism. It is currently unknown what the specific requirements for cluster sizes are and what the maximum spacer length is in order for the cellulose materials to still enable effective heteroatom electronic overlap. Additionally, the materials can often suffer from low quantum yields.

This account includes a brief overview of some of the most impactful optical properties of cellulose materials, including birefringence, CPL and CTE, as well as their applications and perspectives on future research opportunities.

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纤维素材料的独特光学特性
自然环境激发了我们在各个研究和应用领域的创新灵感。特别是,我们在自然系统中观察到了独特的光学特性,如生物发光和生物工程特定纳米结构产生的结构色彩。纤维素就是这样一种自然生成的材料,尤其令人惊奇,影响深远。纤维素是最丰富的生物聚合物之一,具有惊人的多功能性和独特的光学特性。纤维素纳米材料可以很容易地自组装成手性向列相,从而产生双折射,形成独特的光学特性,并使入射光产生圆偏振。这些特性为纤维素材料应用于加密和传感等领域提供了可能性。因此,纤维素材料已被广泛用作复合材料中的手性支架,但在圆偏振发光(CPL)材料中还没有被用作发光体。最近发现的纤维素固有发光特性扩大了纤维素材料在光学应用中的用途。除了结构颜色之外,对纤维素发光特性的研究也是科学方法的完美体现。多年来,人们一直认为只有当这种材料受到其他发光体的污染时才会发光。研究人员对这一假设进行了压力测试,发现不仅是纤维素,许多日常分子、生物分子甚至结构非常简单的分子都会通过聚类触发发射(CTE)机制发出紫外线和可见光。这种现象利用了杂原子的通空共轭,其中附近电子分子的电子云可以重叠。CTE 结合了聚集诱发发射(AIE)和结晶诱发磷光(CIP)的各个方面。在显示 CTE 的材料中可以观察到几个特征。纤维素的光学特性对 pH 值、湿度、温度等环境刺激特别敏感,因此非常适合发光传感应用。纤维素衍生材料还被广泛应用于其他领域,包括加密、生物成像和分析工具。不过,该领域还有几个方面有待探索。可以说,其中最重要的是 CTE 机制缺乏特异性。目前尚不清楚对簇大小的具体要求是什么,也不知道最大间隔长度是多少,以便纤维素材料仍能实现有效的杂原子电子重叠。本报告简要概述了纤维素材料的一些最有影响的光学特性,包括双折射、CPL 和 CTE,以及它们的应用和对未来研究机会的展望。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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