RESUMEN

As sustainable and eco-friendly replacements to conventional paper, rewritable paper is a very attractive alternative for communication, information circulation, and storage. Development is made for rewritable paper using chromogenic materials that change its color in presence of external stimuli. However, the new techniques have faced several major challenges including feasible operational method, eco-friendly approach. Herein, a simple, convenient, and eco-friendly strategy is described for the preparation of rewritable paper substrate, and multi colored ink for efficient use in writing, painting or printing purpose. In addition, writing with "invisible ink" on the rewritable paper can be realized for potential anti-counterfeiting application. The written, painted, or printed information on the paper substrate can be easily erased using an aqueous solution. Thus, the original paper can be retrieved and the paper substrate can be reused multiple times. Besides, the written or printed information can be retained for a prolonged time at ambient conditions. Overall, this approach shows the rewritable paper as a prototype of multicolor writing/painting application, offering a sustainable solution for reducing paper waste and promoting environmental stewardship.

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The chemically triggered reversible switching of pH-responsive hydrazones involves rotary motion-induced configurational changes, serving as a prototype for constructing an array of molecular machines. Typically, the configurational isomerization of such switches into two distinct forms (E/Z) occurs through the alteration of the pH the medium, achieved by successive additions of acid and base stimuli. However, this process results in intermittent operation due to the concomitant accumulation of salt after each cycle, limiting switching performance to only a few cycles (5-6). In this context, we introduce a novel strategy for the autonomous E/Z isomerization of hydrazones in acetonitrile using pulses of trichloroacetic acid as a chemical fuel. The use of this transient acid enabled reversible switching of hydrazones even after 50 cycles without causing significant fatigue. To test the broad viability of the fuel, a series of ortho/para-substituted hydrazones were synthesized and their switching performance was investigated. The analysis of kinetic data showed a strong dependency of switching operations including the lifetime of transient state, on the electronic properties of substituents. Finally, a distinct color change from yellow to orange due to reversible switching of the para-methoxy substituted hydrazone was employed for the creation of rewritable messages on commercially available paper.

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To alleviate the negative effects of resource waste and environmental pollution caused by the excessive use of paper, technologies for rewritable paper have received widespread attention and in-depth research. Despite the growing interest in rewritable paper, meeting the requirements of large-scale preparation, long-lasting information storage time, high reversibility, and good environmental stability remains a huge challenge for this technology. This study developed a solvent-responsive copolymerized polyurethane-based rewritable paper with an inverse photonic glass structure (co-PUIPG paper). Comprehensive writing modes, including handwriting, spraying, and printing, were realized by using the swelling effect of different solvents and the local force field formed by capillary force to control the deformation degree of the inverse photonic glass structure. Co-PUIPG paper can persistently store high-resolution information and has a green and environmentally friendly "write-erase" method. Meanwhile, it exhibits good rewritability, as well as high mechanical strength and exceptional resistance to environmental factors, such as friction, high temperature, and sunlight. Because the spraying method can prepare templates quickly and extensively and polyurethane materials are economical, co-PUIPG rewritable paper possesses great potential as a substitute for commercial fiber paper and its industrialization is full of great possibilities.

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Rewritable paper, which can be used multiple times as an effective solution for sustainable development and lessen the heavy environment pollution, has received widespread attention. A photonic crystal with dye-free character and tunable structure color has attracted significant interest in this area. Generally, handwriting on the photonic crystal structure containing a responsive polymer or hydrogel ingredient was based on the change of lattice spacing. It is necessary to enrich the diversities of color adjustment mechanism for further application. Herein, a flexible rewritable photonic crystal structurally colored paper with excellent mechanical strength based on the hollow SiO2 (h-SiO2) particle and polyurethane was developed. Owning to the varied optical response of h-SiO2 photonic crystal film in different solvents, handwriting on this paper was realized by applying polarity solvents such as EG as colorless ink directly, which could also be erased by resoaking the film in water. Writing and erasing on this paper were totally reversible. The color adjustment mechanism and the realization of handwriting on this paper are totally different from those of the previous reported photonic crystal-based rewritable paper. The combination of quick handwriting and flexibility is significant for potential application as rewritable paper.

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Pristine titanium dioxide (TiO2 ) changes color from white to black when it is reduced from TiIV to TiIII by photoexcited electrons. However, the black coloration requires substantial light energy to create, and it vanishes instantaneously upon exposure to air. This work reports the synthesis of surface-functionalized N-doped TiO2 nanocrystals that rapidly change color (i.e., within seconds) from whitish to black under low-power irradiation with excellent color stability in atmospheric conditions. The N-doping plays a critical role in promoting the surface-adsorption of polyol groups to stabilize the TiIII species and accelerate the coloration process. A rewritable paper fabricated using these nanocrystals exhibits excellent writing and erasing reversibility in response to UV irradiation and oxygen exposure. The low-cost, rapid response, excellent reversibility, and good color stability are vital advantages of N-doped TiO2 nanocrystals for color-switching applications.

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Smart color switching materials that can change color with a fast response and a high reversibility have attracted increasing attention in color-on-demand applications. However, most of them can only respond to a single stimulus from their external environment, which dramatically limits their broad applications. To address this problem, we report a new strategy in developing a dual pH-/photo-responsive color switching system by coupling the pH-dependent and redox-driven color switchable neutral red (NR) with photoreductive TiO2-x nanoparticles. The biodegradable TiO2-x nanoparticles/NR/agarose gel film shows a rapid color switching between yellow and red upon stimulation with acidic/basic vapors in more than 20 cycles because of the protonation and deprotonation process of NR. Moreover, the film shows interesting photoreversible color switching properties under both acidic and basic conditions, including a fast response time and a high reversibility. Taking advantage of the excellent dual pH-/photo-responsive color switching properties, we demonstrated the potential applications of the TiO2-x nanoparticles/NR/agarose gel film in dynamic rewritable paper, in which the created patterns by photo-printing produce dynamic color changing upon applying an acidic or a basic vapor. We believe that the result will enable a new path for the development of dual- and even multi-responsive color switching systems, broadening their new applications.

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Luminescent security printing is of particular importance in the information era. However, the use of conventional paper still carries a lot of economic and environmental issues. Therefore, developing new environmentally friendly security printing material with a low cost is imperative. To achieve the aforementioned goals, novel lanthanide polyoxometalate doped gelatin/glycerol films with high transparency, high strength, and good flexibility have been developed via a solution-casting method. The electrostatic interaction between zwitterionic gelatin and polyoxometalate was confirmed by attenuated total reflection Fourier transform infrared spectroscopy. Luminescent spectra and digital images indicated that the films exhibited reversible luminescent switching properties through association and dissociation of hydrogen bonds between glycerol and water molecules, allowing its potential application as water-jet rewritable paper for luminescent security printing. Furthermore, the printed information can be conveniently "erased" by heating, and the film can be reused for printing. The film exhibited excellent ability to be both rewritten and re-erased. A QR code pattern and hybrid printing were employed to improve the security of information. In addition, the rewritable films possessed excellent regeneration ability and low toxicity, as well as good stability against UV irradiation and organic solvents. The water-jet rewritable film based on lanthanide polyoxometalate for luminescent security printing, to the best of our knowledge, has not yet been reported up to date. This work provides an attractive alternative strategy on fabricating rewritable films for luminescent security printing in terms of cutting down the cost, simplifying the preparation process, and protecting the environment.

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Inkless printing based on rewritable papers has recently made great progress because it can improve the utilization rate of papers, which is of great significance for saving resources and protecting the environment. Among them, light-responsive rewritable papers (LRPs) are a hot research topic because light is clean, easily available, wavelength and intensity adjustable, and noncontacting. However, the photochromic material, as the imaging substance of LRPs, is easily affected by environmental conditions, resulting in insufficient time to read the information. In view of this, we designed and constructed an acid/base tunable diarylethene molecular system that can effectively adjust the photochromic properties by reversibly changing the electron density of the diarylethene photoreaction center through protonation and demonstrated its potential as an imaging material with a longer legible time. What makes us more satisfied is that the acidification can not only extend the legible time of carrying information but also bring a clear and stable absorption/fluorescence imaging dual mode, which can better reflect details and improve contrast. Therefore, we believe that this tunable photochromic diarylethene molecule is a potential imaging material for the development of new LRPs.

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Rewritable paper has greatly promoted the sustainable development of society. However, the hydrophilicity/lipophilicity of the poly(3,4-ethylenedioxythiophene) (PEDOT) film limits its application as the rewritable paper. Herein, we constructed a repeatable writing/erasing pattern on a PEDOT film (rewritable PEDOT paper) by combining wettability control, water-induced dedoping, and an electrochemical redox reaction. The treatment with a medium-polarity/high-volatility solvent (MP/HVS) adjusted the wettability of the PEDOT film (water contact angle increased from 6.5° to 146.2°), contributing to the formation of a hydrophobic writable substrate. The treatment with a high-polarity solvent (HPS) induced the dedoping of anions in the PEDOT chain, resulting in the film's color changed from blue to purple and serving as a writing process. The intrinsic electrochemical redox (elimination of color change by doping/dedoping of lithium ions in the PEDOT chain) of the PEDOT film enabled the erasing process. This writing/erasing process can be repeated at least 10 times. The patterned PEDOT film maintained excellent stability to standing diverse solvents (low-polarity solvent (LPS) and MP/HVS), high temperatures (350 °C), and irradiation of different light wavelengths (wavelengths of 365, 380, 460, 520, and 645 nm). Additionally, the conductivity of the PEDOT film was quantitatively measured (impedance: LPS, increased 8.84%; MP/HVS, decreased 6.67%; and HPS, increased 27.97%) by fabricating a micropatterned PEDOT electrode. This work will provide a method for the fabrication of PEDOT-based optoelectronic functional materials.

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Rewritable paper is meaningful to the recyclable and sustainable utilization of environmental resources and thus has been extensively investigated for several decades. In this work, we demonstrated an efficient and convenient strategy to fabricate rewritable paper based on reversible hydrochromism of donor-acceptor Stenhouse adducts (DASAs). The kinetics and efficiency of isomerization could be well-controlled by adjusting the surrounding temperature and humidity. Monocolored rewritable paper was prepared by coating cyclic DASA·xH2O on the paper surface. Writing, printing, stamping and patterning were realized on the rewritable paper. The information could be controllably erased by treatment in a humid atmosphere. More importantly, the rewritable paper was upgraded to multicolored by combination of two DASA materials. The color of chirography was switched by controlling the writing speed.

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Two typical molecular switches of spiropyran (SP) and benzoxazine (OX) were fused by sharing an indole to achieve a new dual-addressable molecular switch (SP-OX-NO2 ). Through proper molecular modification with NO2 , the transformation from merocyanine (MC) to ring-closed SP or ring-closed OX can be controlled separately with visible light or base stimuli in solution, respectively, and these processes are verified by UV-vis and NMR spectroscopy as well as control experiments. The cis-merocyanine (cis-MC) form is involved in the basochromic process in solution. DFT calculation suggests that the bidirectional switching property of the fused SP-OX molecular switch can be controlled separately, when the OX isomer is more stable than the deprotonated SP isomer. Because of the significant color variations in solution, the simple dual-addressable switch has been further successfully applied to construct a multicolor reversible display on paper.

RESUMEN

Paper, for writing and printing, is consumed a lot in modern life. However, the production of conventional paper could cause many problems, such as deforestation and environmental pollution. Therefore, it is necessary and urgent to explore novel strategies to solve these problems. In this work, a polyoxometalate-doped gelatin film with high strength, excellent transparency, and fast photochromic properties is designed and prepared. The film can display different colors by using a variety of reagents, exhibiting its potential application as a paper medium. Its rapid photochromic properties allow complex high-resolution images to be displayed by UV light printing. It is found that the mechanical and photochromic properties could be regulated by the introduction of triethylene glycol, and the fading process could be controlled by changing the temperature and humidity. Moreover, it is rewritable, self-repairable, and recyclable, and can also achieve long-term preservation without fading. It is envisioned that the environmentally friendly films with low cost, ease of preparation, and recycling advantages have the potential to be an alternative to conventional paper for writing and printing.

RESUMEN

Nowadays, urged by the high demand to reduce paper consumption, rewritable paper receives more and more attention. However, it is a great challenge to conveniently fabricate the rewritable paper which has long legible time of information and is easy to use simultaneously. Here, we report a new type of long-lasting rewritable paper based on color-memorizing thermochromic dye and photothermal-converting toner, which is fabricated by a two-step printing process. The rewritable paper demonstrates excellent rewriting performances (legible time > 6 months and reversibility > 100 times). The thermochromic effect is based on a temperature-driven phase change mechanism, accompanied by a lactone ring tautomerism of crystal violet lactone. The color of the rewritable paper rapidly changes from blue to colorlessness when the temperature is higher than 65 °C, and the colorless state can be maintained at room temperature. The color returns to blue when the temperature is lower than -10 °C. By using an electrothermal pen, a thermal printer, and near infrared (NIR) light, characters and images with high resolution can be handwritten, thermal-printed, and photoprinted on the rewritable paper. The written/printed information can be cleaned under lower temperature or can be quickly erased by NIR light. This rewritable paper is easy for large-scale production and will have promising opportunities in practical applications, such as long-lasting information recording and reading, rewritable label, reprintable displays, and so on.

RESUMEN

Rewritable paper based on switchable molecules has attracted great attention in both academic research and marketplace. However, most available switchable dyes have single switchable color state only, which cannot meet the long-awaited multicolor reversible displays. Herein, through simple introduction of phenolic hydroxyl group, we develop a series of new oxazolidines with one switch unit, which could reversibly display two different as well as their mix-gradient colors by treating with water and mild acid, respectively, both in solution and solid substrate. The structures and mechanism for the formation of two colors had been studied in detail via UV-vis/NMR spectroscopy, skillfully designing contrast molecules, and kinetics experiments. This multiple switchable colors of the dyes have been further applied to construct a rewritable paper for ink-free printing with multi/gradient-color display.

RESUMEN

Reversible multicolor displays on solid media created from single-molecule pigments are a long-awaited goal. Herein, a new and simple molecular dyad, which can undergo switchable cyan (C), magenta (M), and yellow (Y) color changes in both solution and the solid state upon exposure to light, water/acid, and nucleophiles, has been designed and synthesized. The stimuli used herein can be applied independent of each other, which is beneficial for color changes without mutual interference. For comparison, mixtures of the two molecular switching motifs that form the basis of the dyad were also studied. The dyad greatly outperforms the corresponding mixed system with respect to reversible color switching on the paper substrate. Its potential for full-color rewritable paper with excellent reversibility has been demonstrated. Legible multicolor prints, that is, high color contrast and resolution, good dispersion, and excellent reversibility, were achieved by using common water-jet and light-based printers. This work provides a very promising approach for the further development of full-color switchable molecules, materials, and displays.

RESUMEN

"Paper" has greatly contributed to the development and spread of civilization. Even in today's "digitalized" world, paper continues to play a key role in socioeconomic growth, as is evidenced by the growth in global paper consumption. Unfortunately, the use of paper has its cost in terms of the exhaustion of world's natural resources. Consequently, new, cost-effective technologies that preserve natural resources are required for this purpose. Functional materials have revolutionized the way people think about developing new technologies. Especially important in this regard are "smart reactive materials," which are capable of actively responding to external stimuli such as heat, light, mechanical stress, and specific molecular orientations. Moreover, functionalized chromogenic materials, which undergo reversible color switching upon external stimulation, have attracted great attention in the context of developing rewritable paper. Here, investigations of various materials and systems that are devised for use as rewritable paper are reviewed with the hope that the coverage will stimulate and guide future studies in this area.

RESUMEN

Owing to its benefits to reducing paper production and consumption, ink-free rewritable paper has attracted great attention and it is desirable to develop rewritable paper based on its low-cost, robust, and environmentally benign color switching systems. Herein, we report the fabrication of a rewritable paper based on novel poly(vinylpyrrolidone)/hexatungstic acid (HTA) hybrids with fast dual-mode color switching. As-prepared rewritable paper shows fast and reversible colorless-blue or blue-colorless color switching upon photo- or hydroprinting, owing to the fast redox transformations of the unique HTA clusters. More interestingly, the rewritable paper can be used as a template for noble-metal reduction and the noble metal can be deposited on the reduced area of the paper to form well-ordered patterns in high resolution. This rewritable paper can be produced in large scale, and the composition can be facilely tuned with various polyoxometalates or polymers. It may not only be an attractive alternative to current paper prints but also be potentially used for noble-metal reduction to prepare photolithographic circuits and optoelectronic devices.

RESUMEN

Interest and effort toward new materials for rewritable paper have increased dramatically because of the exciting advantages for sustainable development and better nature life cycle. Inspired by how nature works within living systems, herein, we have used fluorans, as a concept verification, to endow original acidochromic, basochromic or photochromic molecules with broader properties, such as switchable with solvent, water, heat, electricity, stress, other force, etc., via simplified methods (i.e., via variation of submolecular structure or microenvironments). The hydrochromic visual change and reversible behavior of selected molecules have been explored, and the primary mechanism at the atomic or subatomic level has been hypothesized. In addition, several newly demonstrated hydrochromic fluorans have been utilized for water-jet rewritable paper (WJRP), which exhibit great photostability, high hydrochromic contrast, and fast responsive rate and which can be reused at least 30 times without significant variation. The water-jet prints have good resolution and various colors and can keep legibility after a few months or years. This improved performance is a major step toward practical applications of WJRP.

Asunto(s)

RESUMEN

Developing efficient photoreversible color switching systems for constructing rewritable paper is of significant practical interest owing to the potential environmental benefits including forest conservation, pollution reduction, and resource sustainability. Here we report that the color change associated with the redox chemistry of nanoparticles of Prussian blue and its analogues could be integrated with the photocatalytic activity of TiO2 nanoparticles to construct a class of new photoreversible color switching systems, which can be conveniently utilized for fabricating ink-free, light printable rewritable paper with various working colors. The current system also addresses the phase separation issue of the previous organic dye-based color switching system so that it can be conveniently applied to the surface of conventional paper to produce an ink-free light printable rewritable paper that has the same feel and appearance as the conventional paper. With its additional advantages such as excellent scalability and outstanding rewriting performance (reversibility >80 times, legible time >5 days, and resolution >5 µm), this novel system can serve as an eco-friendly alternative to regular paper in meeting the increasing global needs for environment protection and resource sustainability.