Research progress of water responsive compound material in the field of green writing and anti-counterfeiting
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摘要: 水响应复合材料在水分子作用下能产生可逆的颜色或荧光发射变化，因其低成本、无毒害、与现有喷墨打印技术相兼容等多项优势，是实现可重复擦写材料的理想选择，同时在信息存储和安全防伪等领域展现了巨大的应用潜力。本综述主要对近五年来基于有机小分子的水响应复合材料的研究进展进行梳理，从水致质子转移、水致构型变化和水致质子转移诱导显色分子的构型变化等不同响应原理角度对水响应材料进行分类，归纳其在设计原理、光物理性能和信息存储应用等方面的成果和技术，希望能够为进一步开发水响应复合材料在绿色书写与防伪领域中的应用提供思路，推动相关产业发展。Abstract: Water stimulus responsive materials can undergo reversible color or fluorescence emission change process under the external stimulus of water. Because of its low cost, non-toxic, compatibility with existing inkjet printing technology and other advantages, it is an ideal choice to achieve rewritable. Meanwhile, it shows great application potential in information storage, security and anti-counterfeiting. In this review, the research progress of water responsive compound material based on organic small molecules in the past five years is systematically reviewed. Inductive materials are classified from the viewpoints of water induced proton transfer, water induced configuration change, water induced proton transfer combined with configuration change sensing principle. The achievements and technologies in design principles, optical physical properties and information storage applications are summarized. It is hoped to provide ideas for further developing the application of water responsive composites in the field of green writing and anti-counterfeiting, promoting the development of related industries.
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图 1 3种典型感应原理：(a) 水致质子转移；(b) 水致构型变化；(c) 水致质子转移诱导构型变化
Figure 1. Three typical sensing principle: (a) Water induced proton transfer; (b) Water induced configuration change; (c) Water induced proton transfer inducing configuration change
图 2 (a) 苏丹红(III) (1)和茜素红(2)的化学结构式；(b) 使用无墨水水笔在加入苏丹红(III).F的纸张上进行文本写入和擦除循环，文本信息在50℃温度下可被擦除[20]
Figure 2. (a) Structures of Sudan-III (1) and alizarin red S (2); (b) Rewritable (write and erase) text cycles carried out by ink-less water pen on paper incorporated with Sudan-III.F and the text erased by the temperature at 50℃[20]
图 3 (a) 基于质子转移机制的喷水重写纸(WJRP)氢致变色二元体系示意图；(b) 基于“SA-P (SA=2, 2'-双 (对甲苯磺酰胺基)-偶氮苯；P=H2PO4−)”的喷水打印可重写纸的结构示意图 (i) 和在WJRP上由EPSON L1119水打印的的打印文本图像 (ii)[21]
Figure 3. (a) Schematic illustration of the hydrochromic binary system for water-jet rewritable paper (WJRP) based on deprotonation and protonation mechanism in this work; (b) Schematic illustrations of structure of water jet print rewritable paper based on SA-P (SA=2, 2'-bis 4-methylbenzenesulfonamido azobenzene, P= H2PO4−) (i) and image of print text on WJRP printed by EPSON L1119 with water (ii)[21]
PEG—Polyethylene glycol
图 4 (a) 吲哚衍生偶氮苯化合物1~3的化学结构式；(b) 使用无墨水笔在加入偶氮苯酚类化合物(1-F)的纸张上进行文本写入和擦除循环，文本信息在60°C温度下可被擦除[22]
Figure 4. (a) Structures of indole-derived azobenzene compounds 1-3; (b) Rewritable (write and erase) text cycles carried out by a fountain pen filled with water on paper incorporated with azophenols (1-F) and the text erased by the temperature at 60℃[22]
图 7 (a) 2, 5-二羟基对苯二甲酸二乙酯(DDT)在氟离子存在下形成DDT-F；(b) 环境光和紫外线(365 nm)下DDT和DDT-F的照片(i)；DDT-F在无墨书写纸上的图像：(ii)未经PEG处理；(iii) 经PEG处理(ONOM字符通过一支蘸水的刷子书写)[25]
Figure 7. (a) Formation of DDT-F in the presence of the fluoride anion; (b) Photographs of DDT and DDT-F under ambient and UV lights (365 nm) (i); Images on inkless writing paper (Whatman No.2 filter paper) containing DDT-F without (ii) and with PEG treatment (iii) on the filter paper (The letters of ONOM were written with a brush containing water)[25]
DDT—2,5-dihydroxyterephthalate
图 8 (a) 氨基罗丹明(NH2-RhB)[26]和丙氨基罗丹明(Pr-N-RhB)[27]的合成方法和水刺激构型化示意图；(b) 照片、相应的紫外可见吸收光谱、荧光图像(在365 nm紫外光下)和CH3CN-H2O溶液(1×10−5 mol/L)中Pr-N-RhB的荧光发射光谱，其荧光强度随含水量的增加而增加(0vol%至90vol%，按体积计)[27]；(c) 结合Pr-N-RhB双模氢致变色染料和NH2-RhB可见氢致变色颜料的“两级加密”防伪图像[27]
Figure 8. (a) Schematic of the synthesis method and water-stimulated isomerization of NH2-RhB (3-NH2-rhodamine B)[26] and Pr-N-RhB (aminopropylrhodamine)[27]; (b) Photographs, corresponding UV-Vis absorption spectra, fluorescence images (under 365 nm UV light) and fluorescence emission spectra of Pr-N-RhB in CH3CN-H2O binary solutions (1×10−5 mol/L) with increasing the water content (0vol% to 90vol%, by volume)27]; (c) Demonstration of "two-level encryption" with the dual-mode hydrochromic dye of Pr-N-RhB and visible hydrochromic dye of NH2-RhB27]
λmax—Maximum wavelength
图 9 (a) 噁唑烷螺吡喃复合物1的结构设计和每个亚单位的变色构型化图解；(b) 通过纯水喷射打印在可擦写纸上显示的多色图像示例，其中纯水用于蓝色，咪唑乙醇溶液与紫外线照射相结合用于黄色，紫外线照射仅用于洋红色[29]
Figure 9. (a) Illustration of the structural design for oxazolidines-spiropyrans complex 1 and the color-changing isomerizations for each subunit; (b) Examples of muliticolor images displayed on the rewritable paper by water-jet printing with pure water for the blue color, a combination of an ethanol solution of imidazole with UV irradiation for the yellow color, and UV irradiation only for the magenta color[29]
OX—Oxazolidines; SP—Spiropyrans; hv—Irradiation with light; WJP—Water jet paper
图 10 (a) 水和热引发的光致变色分子(DASAs)和噁唑烷(OXs)分子构型化示意图、环状DASA·xH2O和线性DASAs的UV-Vis光谱、封闭OXs和开放OXs的UV-Vis光谱；(b) 在双重加密模式下通过加热将狗转换为猫的照片[30]
Figure 10. (a) Schematic illustration of molecular isomerization of DASAs (donor-acceptor stenhouse adducts) and OXs (oxazolidines) triggered by water and heat; UV-Vis spectra of cyclic DASA·xH2O and linear DASAs (The absorbance at 550 nm is normalized ([DASAs] = 0.04 mmol/L in DMSO-d6)); UV-Vis spectra of closed OXs and open OXs (The absorbance at 346 nm is normalized ([OXs] = 0.04 mmol/L in DMSO-d6)); (b) Photographic images of switching the dog to cat profile by heat in double-encryption mode[30]
图 14 (a) 基于酸致变色染料 (ODB-2) 和4-羟基苯甲酸苄酯 (B4 H)的喷水重写纸(WJRP)结构和组成(虚线：氢键)；(b) 水打印前后基于聚对苯二甲酸乙二醇酯(PET)基材的WJRP；(c) 其他WJRPs颜色[36]
Figure 14. (a) Preliminary structure of water-jet rewritable paper (WJRP) and the composition of this hydrochromic system in the imaging layer of WJRP (Dashed line: H-bonding); (b) WJRP based on polyethylene glycol terephthalate (PET) substrate before and after printed with water; (c) Other colours for WJRPs based on binary systems[36]
TFR—Fluorans; TFO—Fluorans; OXL—Spirooxazines; TFG—Fluorans; CVL—Triarylmethanes
图 15 (a) 在环境光和紫外光下，用纯水作为墨水在纸上书写图案的照片；(b) 可重写纸在多级安全信息中的应用； (c) 可重写纸在数据存储中的应用[37]
Figure 15. (a) Photographs of patterns written on the paper by using pure water as ink under ambient light and UV light; (b) Application of the produced rewritable paper in multilevel security information; (c) Application of the produced rewritable paper in data store [37]
图 16 (a) 三联吡啶配体(NUPT1、NUPT2)的结构式，NUPT3-Zn配合物结构；(b) 基于NUPT3-Zn配合物的可复写纸喷水无墨打印和擦除过程示意图[38]
Figure 16. (a) Structural formula of terpyridine derivatives (NUPT1, NUPT2), NUPT3-Zn complex structure; (b) Schematic diagram of water jet inkless printing and erasing process of reproducible paper based on NUPT3-Zn complex[38]
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