Achieving Controllable Thermochromic Fluorescence via Synergistic Intramolecular Charge Transfer and Molecular Packing.

Thermochromic fluorescent materials (TFMs) have attracted significant attention due to their unique fluorescent colorimetric response to temperature. However, existing TFMs still suffer from weak stimulus responsiveness, broad temperature response ranges, uncontrollable emission color changes, and low quantum yields. In this study, we address these issues by designing and synthesizing three diketone-boron complexes with distinct emission wavelengths (NWPU-(2-4)). Utilizing a molecular engineering strategy to manipulate intramolecular charge transfer transitions and molecular packing modes, our synthesized complexes exhibit efficient fluorescence emission in both solution and solid states. Moreover, their emission wavelengths are highly sensitive to environmental polarity. By incorporating these compounds into thermosensitive matrices of long-chain alkanes, we produced TFMs with varied fluorescence emission peak variation ranges. Notably, the TFM based on NWPU-4, owing to its strong charge transfer transitions and dense J-aggregate packing configuration, not only exhibits intense fluorescence emission spanning the deep red to near-infrared spectrum but also displays a remarkable 90 nm broad range of thermochromic properties. Ultimately, it was successfully applied to programmable, thermally controlled, multi-level information encryption.

Oxindolyl-based Radicals with Tunable Mechanochromic and Thermochromic Behavior.

Organic radicals based dynamic covalent chemistry is promising in preparing stimuli-responsive chromic materials, due to their simplicity of dissociation/association, accompanied with distinct color changes during the process. However, suitable organic radicals for dynamic covalent chemistry have not been widely explored yet. Herein, a series of oxindolyl-based mono-radicals (OxRs) with different substituents were successfully synthesized and studied systematically as potential building blocks for stimuli-responsive chromic materials. These OxRs would dimerize spontaneously to form their corresponding dimers. The structures of dimers were unambiguously confirmed through low-temperature 1H-NMR and single-crystal X-ray diffraction analyses. Dynamic interconversion between monomers and dimers was achieved by reversible cleavage and recovery of the σ-bond upon soft external stimuli (temperature, pressure, and solvent polarity), accompanied by significant color changes. It is interesting that the stability of the mono-radical could be tuned through changing different substituents, and consequently altering the bond dissociation energy of the dynamic covalent bond between monomers. These new OxRs characterized by appreciable properties are entitled to more opportunities in developing mechanochromic and thermochromic materials, where their responsiveness to stimuli can be readily controlled by the substituents adhered.

An imidazole-copper(I) metallacycle complex exhibiting thermochromic fluorescence.

In this paper, we firstly report the synthesis and structural characterization of a discrete coordination metallacycle complex, [CuI (bipy)]2 (1). The x-ray diffraction structure, temperature-dependent electronic absorption, and photoluminescence spectra have been investigated. The solid-state fluorescence at variable temperatures shows that complex 1 exhibits an obvious thermochromic fluorescence. At low temperature, the dual fluorescence with peaks at 590 and 694 nm was observed. The emission color significantly changes from red at 77 K to yellow at 200 K and blue-green at 330 K. The thermochromic fluorescent molecular materials show great potential as temperature sensing.

Dual parameter smart sensor for nitrogen and temperature sensing based on defect-engineered 1T-MoS2.

In general, defects are crucial in designing the different properties of two-dimensional materials. Therefore large variations in the electric and optical characteristics of two-dimensional layered molybdenum disulphide might be attributed to defects. This study presents the design of a temperature and nitrogen sensor based on few-layer molybdenum disulfide sheets (FLMS), which was developed from bulk MoS2 (BMS) through an exfoliation approach. The produced sulfur defect, molybdenum defect, line defect, and plane defect were characterized by scanning transmission electron microscopy (STEM), which substantially impacts the sensing characteristics of the resulting FLMS. Our theoretical analysis validates that the sulfur vacancies of the MoS2 lattice improve sensing performance by promoting effective charge transfer and surface interactions with target analytes. The FLMS-based sensor showed a high sensitivity for detecting nitrogen gas with a detection limit (LOD) of ~ 0.18 ppm. Additionally, temperature-detecting capabilities were assessed over various temperatures, showing outstanding stability and repeatability. To the best of our knowledge, this material is the first of its kind, demonstrating visible N2 gas sensing with chromic behaviour.

Creation of Excitation-Driven Hypervalent Tin(IV) Compounds For Aggregation-Induced Emission and Application to Thermoresponsive Luminescent Films below Freezing Point.

Although many researchers have devoted their much effort to establish the strategy for developing a stimuli-responsive molecule and tuning of their properties according to the preprogrammed design, it is still challenging to create desired molecules from the scratch. We recently demonstrated that the molecules with a large structural difference between the theoretically optimized structures in the ground and excited states have a potential to exhibit stimuli-responsive luminescent properties. We defined these molecules as an excitation-driven molecule and have shown that they are a versatile platform for designing stimuli-responsive luminescent molecules. Herein, based on the concept of excitation-driven molecules, we show that the hypervalent tin-fused azomethine (TAm) compounds possessing aggregation-induced emission (AIE) properties can be obtained by simple chemical modification with a methyl group although conventional TAm derivatives are well known to be highly luminescent compounds in solution. Furthermore, by combining the solid-state luminescence property of AIE and the coordination number shifts of the hypervalent tin atom, the thermoresponsive films operating below the freezing point are fabricated with the polymer. In this study, we apply the concept of excitation-driven molecules to the hypervalent compounds and demonstrate to obtain the novel functional materials.

3D printing of thermochromic multilayer flexible film for multilevel information encryption.

Flexible thermal-responsive encryption devices are widely employed in information encryption and anti-counterfeiting due to their cost-effectiveness and dynamic data encryption and decryption capabilities. However, most current devices are limited to a single layer of encryption, resulting in restricted decryption methods and storage capacity, as well as reliance on external heating. In this study, we integrate multiple layers of encryption within a single device and introduce self-heating thermochromic technology along with infrared thermal imaging encryption to establish a novel concept of a multilayer flexible encryption system. By combining infrared encryption and thermochromic encryption in three-dimensional space enhances the difficulty level for decryption while achieving high storage capacity for information. The internally integrated conductive heating layer within the multilayer structure facilitates rapid and adjustable heating for thermochromic patterns, eliminating the need for external heat sources. Furthermore, we employ a low-cost customizable multi-material integrated 3D printing process for manufacturing multilayer flexible encryption devices. This research presents an innovative solution for designing and fabricating high-density multilevel flexible encryption devices.

Assessment of thermochromic phantoms for characterizing microwave ablation devices.

BACKGROUND AND PURPOSE: Thermochromic gel phantoms provide a controlled medium for visual assessment of thermal ablation device performance. However, there are limited studies reporting on the comparative assessment of ablation profiles assessed in thermochromic gel phantoms against those in ex vivo tissue. The objective of this study was to compare microwave ablation zones in a thermochromic tissue-mimicking gel phantom and ex vivo bovine liver and to report on measurements of the temperature-dependent dielectric and thermal properties of the phantom. METHODS: Thermochromic polyacrylamide phantoms were fabricated following a previously reported protocol. Phantom samples were heated to temperatures in the range of 20°C-90°C in a temperature-controlled water bath, and colorimetric analysis of images of the phantom taken after heating was used to develop a calibration between color changes and the temperature to which the phantom was heated. Using a custom, 2.45 GHz water-cooled microwave ablation antenna, ablations were performed in fresh ex vivo liver and phantoms using 65 W applied for 5 min or 10 min (n = 3 samples in each medium for each power/time combination). Broadband (500 MHz-6 GHz) temperature-dependent dielectric and thermal properties of the phantom were measured over the temperature range of 22°C-100°C. RESULTS: Colorimetric analysis showed that the sharp change in gel phantom color commences at a temperature of 57°C. Short and long axes of the ablation zone in the phantom (as assessed by the 57°C isotherm) for 65 W, 5 min ablations were aligned with the extents of the ablation zone observed in ex vivo bovine liver. However, for the 65 W, 10 min setting, ablations in the phantom were on average 23.7% smaller in the short axis and 7.4 % smaller in the long axis than those observed in ex vivo liver. Measurements of the temperature-dependent relative permittivity, thermal conductivity, and volumetric heat capacity of the phantom largely followed similar trends to published values for ex vivo liver tissue. CONCLUSION: Thermochromic tissue-mimicking phantoms provides a controlled, and reproducible medium for comparative assessment of microwave ablation devices and energy delivery settings. However, ablation zone size and shapes in the thermochromic phantom do not accurately represent ablation sizes and shapes observed in ex vivo liver tissue for high energy delivery treatments (65 W, 10 min). One cause for this limitation is the difference in temperature-dependent thermal and dielectric properties of the thermochromic phantom compared to ex vivo bovine liver tissue, as reported in the present study.

Unveiling the structural influence of nematic mesogens on customizable temperature and spectral responses.

Rapid and accurate detection and visualization of temperature variations near the human body hold significant importance. This study presents thermochromic colloids capable of adjusting the detectable temperature range and reflection wavelength over a wide spectrum. The systematic investigation focuses on understanding the influence of the molecular structure of nematic mesogens on the morphological dynamics of cholesteric liquid crystal droplets and their associated thermochromic behaviors. A tunable colorimetric temperature range (i.e., from 10 to 40 °C) and high sensitivity (i.e., Δλ ΔT-1 > 100nm °C-1) are realized through precise modulation of the alkyl chain lengths in cyanobiphenyls molecules, combined with a cholesteryl oleyl carbonate as a chiral dopant. We demonstrate the efficiency of a binary mixture of different mesogens, enabling customized structural colors with desired temperature responses. Finally, inspired by the ability of the octopus to camouflage through the elongation or contraction of its pigment cells, thermochromic droplets are embedded within a polymer matrix, resulting in a portable skin patch that offers quick, reversible, and direct temperature visualization of the human body.

Shape-stabilized flexible thermochromic films with one-sided adhesion via gradient crosslinking strategy for temperature indicating.

Thermochromic dyes (TCDs) based on a three-component color change system suffer from solid rigidity and liquid leakage issues because of the intrinsic solid-liquid phase change performance, resulting in difficulty in temperature visualization applications for smart wearable fields. Despite considerable efforts in microencapsulation of thermochromic dyes, designing and fabricating essentially flexible thermochromic phase change films still need to be explored. Herein, a one-sided adhesive gradient-crosslinked thermochromic film is reported to address these issues to make a trade-off between stability and flexibility, excellent thermochromic performance, and temperature visualization. The thermochromic wearable films have been fabricated exploiting tea polyphenol thermochromic dyes, vinyl dimethylsiloxane, and hydrosilicone oil via the salt-template-assisted method and gradient crosslinking strategy, which have porous structures with an average pore size of 12.8 µm and a porosity of 28 %. Due to the spatial limiting threshold effect of the porosity structure, interconnected 3D polysiloxane porous networks can provide ample support for tea polyphenol thermochromic dyes and effectively prevent liquid leakage. Upon heating, the thermochromic film changes from blue to white with the K/S value decreasing from 7.69 to 0.78 and the ΔE* increasing from 2.7 to 16.1 at 610 nm, and the color-changing temperature is 42 °C. Gradient crosslinked thermochromic films exhibit excellent temperature-responsive color change properties, desirable one-side adhesion, and thermal energy storage, enabling multicolor temperature displays and temperature-controlled multilevel information transfer.

Rationally Integrating Charge-Transfer Cocrystal and Ni(II) Organometallics for Visualized Photo/Thermochromic Sensors.

Smart materials demonstrate fascinating responses to environmental physical/chemical stimuli, including thermal, photonic, electronic, humidity, or magnetic stimuli, which have attracted intensive interest in material chemistry. However, their limited/harsh stimuli-responsive behavior or sophisticated postprocessing leads to enormous challenges for practical applications. Herein, we rationally designed and synthesized thermochromic Ni(II) organometallic [(C2H5)2NH2]2NiCl4-xBrx via a facile mechanochemical strategy, which demonstrated a reversible switch from yellow to blue color with a tunable phase-transition temperature from 75.6 to 61.7 °C. The simple electrospinning technology was applied to fabricate thermochromic Ni(II) organometallic-based nanofiber membranes for temperature monitoring. Furthermore, the organic charge-transfer cocrystal with a wide spectral absorption of 300-1950 nm and a high-efficiency photothermal conversion was combined with thermochromic Ni(II) organometallics for the desired dual-stimuli photo/thermochromism. This work supplies a new strategy for realizing multiple stimuli-responsive applications, such as thermal/light sensor displays and information storage.

A deep learning-based real-time hypothermia and hyperthermia monitoring system with a simple body sensor.

A real-time hypothermia and hyperthermia monitoring system with a simple body sensor based on a Convolutional Neural Network (CNN) is presented. The sensor is produced with 3D-printed thermochromic material. Due to the color change feature of thermochromic materials with temperature, 3D-printed thermochromic Polylactic Acid (PLA) material was used to monitor temperature changes visually. In this paper, we have used the transfer learning technique and fine-tuned the AlexNet CNN. Thirty images for each temperature class between 28-44°C and 510 image data were used in the algorithm. We used 80% and 20% of the data for training and validation. We achieved 96.1% accuracy of validation with a fine-tuned AlexNet CNN. The material's characteristics suggest that it could be employed in delicate temperature sensing and monitoring applications, particularly for hypothermia and hyperthermia.

Tunable thermoresponsive and stretchable hydrogel sensor based on hydroxypropyl cellulose for human motion/health detection, visual signal transmission and information encryption.

Thermoresponsive hydrogels can be used as smart flexible sensors. However, the design and facile preparation of multifunctional thermoresponsive hydrogel sensors still face great challenges. Herein, a tunable thermoresponsive, thermochromic and stretchable poly(2-hydroxypropyl acrylate-co-acrylamide) (P(HPA-co-AM))/hydroxypropyl cellulose (HPC)/lithium chloride (LiCl) hydrogel with the networks constructed from non-covalent interaction was fabricated by photopolymerization. PHPA exhibits excellent thermoresponsiveness. HPC endows the hydrogel with outstanding mechanical performance and enhanced temperature-sensitivity. LiCl not only provides good conductivity, but also regulates the lower critical solution temperature (LCST) of the hydrogel. The hydrogel shows tensile strength up to 300 kPa and maximum strain up to 790 %. The LCST value of the hydrogel can be adjusted from 38 to 75 °C. Therefore, the thermoresponsive conductive hydrogel can realize the information encryption, and be used as sensor through strain and temperature changes in the external environment to realize the motion and health detection, and visual signal transmission. This work is expected to provide ideas for the next generation of smart multifunctional electronic skin and information encryption device.

Assessment of Gel-Based Thermochromic Glazing for Energy Efficiency in Architectural Applications.

With the increasing global focus on energy efficiency and environmental sustainability, intelligent building materials such as thermochromic glazing have emerged as a hot topic of research. The intent of this paper is to explore the utilization of gel-type thermochromic glazing within the realm of architectural energy conservation calculations. It conducts an exhaustive examination of the material's attributes, its capacity for energy savings, and the obstacles encountered in real-world applications. Through simulation studies and case analyses, this paper assesses the energy efficiency of gel-type thermochromic glazing across various climates and suggests strategies for optimization. The study revealed that the incorporation of gel-based thermochromic glazing leads to a marked reduction in energy usage within buildings, an improvement in indoor comfort levels, and significant environmental advantages.

Development of Advanced Solid-State Thermochromic Materials for Responsive Smart Window Applications.

This study introduces the synthesis and detailed characterization of a novel thermochromic material capable of reversible alterations in its thermotropic transmittance. Through an emulsion polymerization process, this newly developed material is composed of 75-85% octadecyl acrylate and 0-7% allyl methacrylate, demonstrating a pronounced discoloration effect across a narrow yet critical temperature range of 24.5-39 °C. The synthesized powder underwent a battery of tests, including differential scanning calorimetry and thermogravimetric analysis, as well as scanning electron microscopy. These comprehensive evaluations confirmed the material's exceptional thermal stability, uniform particle size distribution, and strong anchoring properties. Building upon these findings, we advanced the development of thermochromic polyvinyl butyral films and laminated glass products. By utilizing a coextrusion technique, we integrated these films into laminated glass, setting a new benchmark against existing glass technologies. Remarkably, the incorporation of thermochromic PVB films into laminated glass led to a significant reduction in solar irradiance of 20-30%, outperforming traditional double silver low-emissivity glass. This achievement demonstrates the exceptional shading and thermal insulation properties of the material. The research presented herein not only pioneers a valuable methodology for the engineering of smart materials with tunable thermotropic transmittance but also holds the key to unlocking enhanced energy efficiency across a spectrum of applications. The potential impact of this innovation on the realm of sustainable building materials is profound, promising significant strides toward energy conservation and environmental stewardship.

Energy-Efficient Smart Window Based on a Thermochromic Hydrogel with Adjustable Critical Response Temperature and High Solar Modulation Ability.

Thermochromic smart windows realize an intelligent response to changes in environmental temperature through reversible physical phase transitions. They complete a real-time adjustment of solar transmittance, create a livable indoor temperature for humans, and reduce the energy consumption of buildings. Nevertheless, conventional materials that are used to prepare thermochromic smart windows face challenges, including fixed transition temperatures, limited solar modulation capabilities, and inadequate mechanical properties. In this study, a novel thermochromic hydrogel was synthesized from 2-hydroxy-3-butoxypropyl hydroxyethyl celluloses (HBPEC) and poly(N-isopropylacrylamide) (PNIPAM) by using a simple one-step low-temperature polymerization method. The HBPEC/PNIPAM hydrogel demonstrates a wide response temperature (24.1-33.2 °C), high light transmittance (Tlum = 87.5%), excellent solar modulation (ΔTsol = 71.2%), and robust mechanical properties. HBPEC is a functional material that can be used to adjust the lower critical solution temperature (LCST) of the smart window over a wide range by changing the degree of substitution (DS) of the butoxy group in its structure. In addition, the use of HBPEC effectively improves the light transmittance and mechanical properties of the hydrogels. After 100 heating and cooling cycles, the hydrogel still has excellent stability. Furthermore, indoor simulation experiments show that HBPEC/PNIPAM hydrogel smart windows have better indoor temperature regulation capabilities than traditional windows, making these smart windows potential candidates for energy-saving building materials.

Encapsulation of thermochromic tetradecyl myristate/methyl red composite via full poplar-based cellulose/lignin/SiO2 framework for preparation of thermochromic wood with thermal response and storage.

Thermochromic wood (TW), a smart material that can respond to temperature changes and store thermal energy, holds broad potential for application in the construction industry. This study fabricated thermochromic poplar (TP) by encapsulating a thermochromic phase change material (TPCM), consisting of tetradecyl myristate and methyl red, within a full poplar-based cellulose/lignin/SiO2 framework. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analyses indicate that the poplar matrix and the incorporated SiO2 formed an integrated cellulose/lignin/SiO2 framework, which encapsulated the TPCM within the poplar ducts. The TP exhibits a color change from light purple to dark purple within the temperature range of 30-48 °C, with a pronounced shift at approximately 42 °C, correlating with the sensation of scalding. Thus, TP-based products can alert users to the risk of scalding through a noticeable color change. The full poplar-based framework mitigates the impact of ultraviolet (UV) radiation on the TP and prevents the loss of TPCM during thermal processing. The mechanical properties of TP are enhanced to a strength grade comparable to that of Manchurian ash wood, making it suitable for load-bearing components in wooden structures. Additionally, the average temperature of TP is around 10 °C higher than that of untreated poplar within 25 min after the same thermal treatment. Consequently, TP can serve as a building material with capabilities for temperature response, thermal energy storage, and structural load-bearing.

Preparation of thermochromic ink from anthocyanidin-encapsulated alginate nanoparticles for anticounterfeiting applications.

In order to make commercial products less vulnerable to counterfeiting, thermochromic inks have proven to be a viable authentication strategy. Herein, we developed a thermochromic ink for authentication by combining an anthocyanidin (ACYD) extract with alginate (ALG). To increase the anthocyanidin/alginate ink stability, a mordant (ferrous sulfate) was employed to tie up the anthocyanidin biomolecules with alginate. ACYD was extracted from red-cabbage and then immobilized into alginate to serve as an environmentally friendly spectroscopic probe. Thermochromic composite inks (ACYD@ALG) were made by adjusting the content of anthocyanidin. A homogenous blue film (608 nm) was printed on a paper surface and investigated by the CIE Lab coordinate system. The blue color transformed into reddish (477 nm) when heated from 35°C to 65°C. Nanoparticles (NPs) of anthocyanidin/mordant (ACYD/M) were examined for their size and morphology to indicate diameters of 80-90 nm, whereas the ACYD/M-encapsulated alginate nanoparticles showed diameters of 120-150 nm. Multiple analytical techniques were utilized to examine the printed papers. The mechanical and rheological performance of both stamped sheets and ink fluid were explored. The cytotoxicity and antimicrobial efficacy of ink (ACYD@ALG) were investigated.

Thermochromic Polymer Nanocomposites for the Heat Detection System: Recent Progress on Properties, Applications, and Challenges.

Reversible thermochromic polymers have emerged as compelling candidates in recent years, captivating attention for their application in heat detection systems. This comprehensive review navigates through the multifaceted landscape, intricately exploring both the virtues and hurdles inherent in their integration within these systems. Their innate capacity to change colour in response to temperature fluctuations renders reversible thermochromic nanocomposites promising assets for heat detection technologies. However, despite their inherent potential, certain barriers hinder their widespread adoption. Factors such as a restricted colour spectrum, reliance on external triggers, and cost considerations have restrained their pervasive use. For instance, these polymer-based materials exhibit utility in the domain of building insulation, where their colour-changing ability serves as a beacon, flagging areas of heat loss or inadequate insulation, thus alerting building managers and homeowners to potential energy inefficiencies. Nevertheless, the limited range of discernible colours may impede precise temperature differentiation. Additionally, dependency on external stimuli, such as electricity or UV light, can complicate implementation and inflate costs. Realising the full potential of these polymer-based materials in heat detection systems necessitates addressing these challenges head-on. Continuous research endeavours aimed at augmenting colour diversity and diminishing reliance on external stimuli offer promising avenues to enhance their efficacy. Hence, this review aims to delve into the intricate nuances surrounding reversible thermochromic nanocomposites, highlighting their transformative potential in heat detection and sensing. By exploring their mechanisms, properties, and current applications, this manuscript endeavours to shed light on their significance, providing insights crucial for further research and potential applications.

Edible thermochromic beads from flavonoid, fatty acid, and lecithin for smart packaging.

Enzymatic browning and microbial growth are two natural phenomena that occur when fruits and vegetables are exposed to abnormal conditions, i.e., temperatures in the range of 12-22 °C, leading to their spoilage. Controlling the temperatures during the supply chain aims to optimize the product's shelf life. Irreversible thermochromic beads were fabricated using a simple extrusion technique containing fatty acid, lecithin, and anthocyanin solution-alginate. The pigmentation durability was adjusted based on electrostatic interactions, as evidenced by the reduction in dye leaching in the case of the produced bead at pH = 6 to less than 0.007 after 45 min. Characterization shows that the chosen combination of fatty acids and the quinonoid molecule is useful for producing thermochromic beads, with a color change at 12 °C-22 °C, from blue to purple. Using the prepared thermochromic beads in the supply chain of fresh-cut salad and brussels sprouts showed a great result for monitoring their freshness after 21 ± 1 min.

Carbon Dots-Inked Paper with Single/Two-Photon Excited Dual-Mode Thermochromic Afterglow for Advanced Dynamic Information Encryption.

Achieving thermochromic afterglow (TCAG) in a single material for advanced information encryption remains a significant challenge. Herein, TCAG in carbon dots (CDs)-inked paper (CDs@Paper) is achieved by tuning the temperature-dependent dual-mode afterglow of room temperature phosphorescence (RTP) and thermally activated delayed fluorescence (TADF). The CDs are synthesized through thermal treatment of levofloxacin in melting boric acid with postpurification via dialysis. CDs@Paper exhibit both TCAG and excitation-dependent afterglow color properties. The TCAG of CDs@Paper exhibits dynamic color changes from blue at high temperatures to yellow at low temperatures by adjusting the proportion of the temperature-dependent TADF and phosphorescence. Notably, two-photon afterglow in CDs-based afterglow materials and time-dependent two-photon afterglow colors are achieved for the first time. Moreover, leveraging the opposite emission responses of phosphorescence and TADF to temperature, CDs@Paper demonstrate TCAG with temperature-sensing capabilities across a wide temperature range. Furthermore, a CDs@Paper-based 3D code containing color and temperature information is successfully developed for advanced dynamic information encryption.