Reversible Properties Research Articles

Insight into the Antioxidant Activity of Ascorbic Acid-Containing Gelatin Nanoparticles in Simulated Chronic Wound Conditions.

Chronic wounds differ from acute wounds by remaining in the inflammatory phase for a long time. This chronic inflammation confers a high concentration of inflammatory cytokines, proteases, and ROS. Likewise, the pH environment of chronic wounds has been recorded within the range of 7.2-8.9 due to the alkaline by-products of bacterial proliferation. In this work, differences in pH between healthy skin and chronic cutaneous wounds have been used for the design and development of pH-responsive gelatin-based nanoparticles (NPs). Ascorbic acid (AA), as an antioxidant compound that can neutralize reactive oxygen species (ROS), has been the therapeutic model compound included in these NPs. The goal of the present work has been the preparation and characterization (physicochemical and biological properties) of NPs for the effective release of AA under simulated chronic wound conditions. In vitro experiments demonstrated total AA release at pH corresponding to the chronic wounds. The biocompatible character of these gelatin-based NPs based on their hemolytic and cytotoxicity responses has been highlighted under in vitro conditions. The reversible and protective antioxidant properties of the AA-including NPs in erythrocytes and skin cell lines, respectively, have been confirmed to be modulated by the gelatin A gel strength.

Thermally Induced Lattice-Defective Oxygen Breathing in Perovskite-Structure Stannates with High-Contrast Reversible Thermochromism.

Inorganic thermochromic materials exhibit a tunable color gamut and a wide chromatic temperature range, indicating their potential for intelligent adaptive applications in thermal warning, temperature indication, thermal regulation, and interactive light-to-thermal energy conversion. However, most metal-oxide-based thermochromic materials show weak chromaticity adaption with the change of temperature, which needs further understanding of the microscopic principle to clarify the potential route to improve the contrast and identifiability for fabricating better thermochromic materials. Using perovskite-structure (AMO3) alkaline earth metal stannate (Ba1-xSrxSnO3, 0.0 ≤ x ≤ 1.0) as a model system, this paper reports for the first time the mechanism of the properties of thermally induced defect-enhanced charge transfer-type (CTT) thermochromic materials and the strategy for regulating their thermochromic properties by A-site cations. BaSnO3 exhibits continuously reversible thermochromic properties with high contrast from weak light yellow (b* = 11) to strong bright yellow (b* = 58) between room temperature and 550 °C. In-situ high-temperature X-ray diffraction (in-situ XRD), in-situ UV-vis absorption spectroscopy (in-situ UV-vis), thermogravimetric (TG), and electron paramagnetic resonance (EPR) spectra indicate that this excellent thermochromic phenomenon is attributed to the weakening of Sn-O bond hybridization at high temperatures, as well as the formation of a large number of oxygen vacancies at the top of the valence band, and the enhanced charge transfer resulting from the generation of impurity levels in the Sn2+ 5s2 intermediate. Replacing Ba2+ by Sr2+ in Ba1-xSrxSnO3 successfully tuned the thermochromic properties, which is attributed to the Sr2+ doping level-directed oxygen defect concentration and deoxygenation rate. The demonstrated defect-enhanced charge transfer behavior promotes a feasible route for lattice oxygen-mediated thermochromic materials and provides a fundamental relationship between thermally induced defects and colorimetry.

Hydrochromic Nanocapsule with Real Time Visual In Situ Water Level Sensing Function and Toughening Effect for Plastic Materials

AbstractDespite the recent developments in hydrochromic materials, visual detection of water level in plastic materials without sacrificing mechanical properties remains a meaningful yet challenging topic. Currently, to optimize the sensitivity, hydrochromic agents are usually incorporated into hygroscopic matrixes to form bulk solids, which have restricted compatibility for the direct application inside other polymer materials. In this study, this challenge is tackled by nanoscale incorporation of hydrochromic agent into a hygroscopic polymer by miniemulsion polymerization. The obtained hydrochromic nanocapsule has an average diameter ≈110 nm, shows reversible hydrochromic property after 10 cycles, and can offer the first directly eye‐readable signal about the real time in situ water level in plastic materials with a water level below 4 wt.%, while achieving a 214% enhancement of the toughness at the same time. Comprehensive researches by investigating the composition and viscoelastic transition of the nanocapsules has shed light on the mechanisms concerning hydrochromic sensitivity and toughening effect. This simple methodology not only offers a new route for the nanoscale incorporation and application of different hydrochromic materials, but also inspires the development of smart nanoparticles with other stimuli‐responsive functionalities. All these aspects should render this work interesting for both scientific researches and engineering practices.

Force-activated ratiometric fluorescence switching of tensile mechano-fluorophoric polyurethane elastomers with enhanced toughnesses improved by mechanically interlocked [c2] daisy chain rotaxanes

The extended and contracted conformations of [c2] daisy chain rotaxanes were introduced in mechano-fluorophoric polyurethane (PU) scaffolds via step-growth polymerizations to obtain distinct mechanical and optical features upon external forces. Particularly, the inherent ductile and stretchable capabilities along with notable toughnesses of PU films containing very low contents of [c2] daisy chain moieties with long-range sliding motions were obviously improved. Furthermore, appealing Förster resonance energy transfer (FRET) behaviors with the optimum energy transfer efficiency ca. 26.02% between blue-emitting tetraphenylethylene (TPE) and yellow-orange-emitting rhodamine derivatives could be acquired in the PU film under tensile conditions, which could be assigned to the incorporation of bi-fluorophoric daisy chain rotaxane into PU frameworks to gain reversible dual fluorescence switching behaviors upon stretching and relaxation processes. Additionally, the stretching deformations of PU films were inspected by X-ray diffraction (XRD) and FTIR techniques for the verification of correlated morphological properties of stretching states in the oriented daisy chain rotaxane-based PU films. Interestingly, impressive shape recovery and reversible ratiometric mechano-fluorophoric fluorescence switching properties of [c2] daisy chain rotaxane-based PU films could be attained upon heating, suggesting potential applications of PU films comprising artificial molecular muscles with glorious mechanical and optical behaviors in advanced polymer networks.

Solution-recrystallization mechanism of g-C3N4 and its inhibitory effect on polysulfide shuttling through cross-linked porous network structure with carbon nanotubes

Lithium-sulfur batteries have the advantages of high specific capacitance density and high theoretical capacity, which are attracting more and more attention in the field of energy storage. However, in practice, there are still many difficulties, such as the poor conductivity of sulfur, the large volume expansion of sulfur, and the shuttle effect of polysulfides, which lead to rapid capacity degradation and poor cycling stability. Here, we utilize g-C3N4 which is soluble in concentrated H2SO4 and has a good solution-recrystallization reversible property, alcohol was used as deprotonation solvent, the g-C3N4/CNT composites were prepared by the method of solution-recrystallization as sulfur host. The dissolution and precipitation mechanism of g-C3N4 in concentrated sulfuric acid and the composite mechanism with CNT were revealed. The g-C3N4/CNT/S cathode exhibit excellent electrochemical properties. The capacity of SPCNT11 can still be maintained to 1013 mAh·g−1 after 200 cycles at 0.2 C, with a capacity retention rate of 73.2%. Even at rate of 4C, the SPCNT11 material still has a capacity of 547 mAh·g−1 after 450 cycles. The first-principle calculation results further reveal that the interaction between g-C3N4 and CNT produces conjugated effect, the constrain of g-C3N4 to electrons is weakened, enhances its conductivity, and thus realizes the effect of promoting polysulfide transformation.

AIE-active dyes based on Tröger's base: Synthesis and mechanochromic luminescence

Three fluorescent dyes (DI-TB, ICZ-TB and ITPA-TB) were synthesized based on 1,3-indindanedione substituted Tröger's base (TB). All the dyes exhibited AIE properties in the mixed system of chloroform and n-hexane. The compounds showed reversible MCL properties with obvious fluorescence changes, which were confirmed by XRD and DSC. The fluorescence of ITPA-TB showed high contrast (68 nm) before and after grinding, and the fluorescence changed from yellow (546 nm) to red (614 nm). In addition, the three solid compounds showed good thermal stability by thermogravimetric analysis. The TB dyes further opened up new ideas for the development of TB-based mechanochromic luminescent materials.

TGF-β blockade drives a transitional effector phenotype in T cells reversing SIV latency and decreasing SIV reservoirs in vivo

HIV-1 persistence during ART is due to the establishment of long-lived viral reservoirs in resting immune cells. Using an NHP model of barcoded SIVmac239 intravenous infection and therapeutic dosing of anti-TGFBR1 inhibitor galunisertib (LY2157299), we confirm the latency reversal properties of in vivo TGF-β blockade, decrease viral reservoirs and stimulate immune responses. Treatment of eight female, SIV-infected macaques on ART with four 2-weeks cycles of galunisertib leads to viral reactivation as indicated by plasma viral load and immunoPET/CT with a 64Cu-DOTA-F(ab’)2-p7D3-probe. Post-galunisertib, lymph nodes, gut and PBMC exhibit lower cell-associated (CA-)SIV DNA and lower intact pro-virus (PBMC). Galunisertib does not lead to systemic increase in inflammatory cytokines. High-dimensional cytometry, bulk, and single-cell (sc)RNAseq reveal a galunisertib-driven shift toward an effector phenotype in T and NK cells characterized by a progressive downregulation in TCF1. In summary, we demonstrate that galunisertib, a clinical stage TGF-β inhibitor, reverses SIV latency and decreases SIV reservoirs by driving T cells toward an effector phenotype, enhancing immune responses in vivo in absence of toxicity.

Identification of a 10-mer peptide from the death domain of MyD88 which attenuates inflammation and insulin resistance and improves glucose metabolism.

Insulin resistance (IR) is the key pathophysiological cause of type 2 diabetes, and inflammation has been implicated in it. The death domain (DD) of the adaptor protein, MyD88 plays a crucial role in the transduction of TLR4-associated inflammatory signal. Herein, we have identified a 10-residue peptide (M10), from the DD of MyD88 which seems to be involved in Myddosome formation. We hypothesized that M10 could inhibit MyD88-dependent TLR4-signaling and might have effects on inflammation-associated IR. Intriguingly, 10-mer M10 showed oligomeric nature and reversible self-assembly property indicating the peptide's ability to recognize its own amino acid sequence. M10 inhibited LPS-induced nuclear translocation of NF-κB in L6 myotubes and also reduced LPS-induced IL-6 and TNF-α production in peritoneal macrophages of BALB/c mice. Remarkably, M10 inhibited IL-6 and TNF-α secretion in diabetic, db/db mice. Notably, M10 abrogated IR in insulin-resistant L6 myotubes, which was associated with an increase in glucose uptake and a decrease in Ser307-phosphorylation of IRS1, TNF-α-induced JNK activation and nuclear translocation of NF-κB in these cells. Alternate day dosing with M10 (10 and 20 mg/kg) for 30 days in db/db mice significantly lowered blood glucose and improved glucose intolerance after loading, 3.0 g/kg glucose orally. Furthermore, M10 increased insulin and adiponectin secretion in db/db mice. M10-induced glucose uptake in L6 myotubes involved the activation of PI3K/AKT/GLUT4 pathways. A scrambled M10-analog was mostly inactive. Overall, the results show the identification of a 10-mer peptide from the DD of MyD88 with anti-inflammatory and anti-diabetic properties, suggesting that targeting of TLR4-inflammatory pathway, could lead to the discovery of molecules against IR and diabetes.

Liquid crystal-induced tunable circular dichroism in CdSe and ZnSe nanoplatelets

Induced circular dichroism in CdSe and ZnSe nanoplatelets (NPLs) was demonstrated using chiral thermotropic liquid crystals (LCs). Firstly, NPLs were easily dispersed in cholesteryl oleyl carbonate (COC) LC via a simple intercalation chemistry-based approach. Extensive circular dichroism (CD) studies showed remarkably strong and reversible chiroptical properties for these composites as a function of temperature. NPL-COC composites displayed strong exciton-induced CD as well as high anisotropy g-factor values (in the case of CdSe NPLs). Secondly, induced chirality in CdSe NPLs was also demonstrated using right-handed (RH) and left-handed (LH) blue phase LCs. LC-induced chirality in nanoparticles was corroborated by theoretical studies which revealed coupling between the chiral molecular excitons and nonchiral nanocrystals. The temperature-tunability is a useful tool to switch the chirality on/off. This study presents an alternative approach to realize exciton-induced tunable circular dichroism in nanomaterials.

Vulcanization kinetics and reinforcement behaviour of natural rubber-carbon black composites: Addition of Shea-butter versus aromatic oil as plasticizers

This work is a comparative study between Shea butter (SB) and treated distillate aromatic extract oil (TDAE) as plasticizers in the vulcanization of natural rubber (NR)- carbon black (CB) vulcanizates (—CB—S—NR—). The plasticized —CB—S—NR— composites extended scorch (Ts2) and optimum (T90) curing times. The delays in crosslinking reaction were suspected to be due to the increased viscosity (ML) and insulation of the reacting species (NR, CB, Sulfur and other curing aids) by the films of plasticizers. This effect increased the activation energy (Ea (KJ/mol)) for vulcanization. The —CB—S—NR— without plasticizer SB (SBO), showed higher ML, crosslinking density index (ΔM), rheological strength (MH) and low cure reversion properties than others. In comparison, the SB loaded —CB—S—NR— composites showed improvement in ML, ΔM, T90, with lowers Ea (KJ/mol) than TDAE samples. Also, the SB compounds exhibited higher Young's modulus Eo(MPa) than SBO and TDAE compounds. For instance, the Eo(MPa) of SB5 was over 7 and 1200 % higher than SBO and STD5 respectively. However, —CB—S—NR— filled with TDAE generally showed higher strength(MPa), attributed to stronger CB—NR interactions. Therefore, environmentally friendly SB could replace petroleum based oils for compounding rubbers.

Lanthanide-Polyoxometalate-Based Film with Reversible Photochromism and Luminescent Switching Properties for Erasable Inkless Security Printing.

Security printing is of the utmost importance in the information era. However, the excessive use of inks and paper still faces many economic and environmental issues. Thus, developing erasable inkless security printing materials is a remarkable strategy to save resources, protect the environment, and improve information security. To this endeavor, a photoresponsive lanthanide-polyoxometalate-doped gelatin film with high transparency was developed through the solution casting method. Attenuated total reflection Fourier-transform infrared spectroscopy confirmed the electrostatic and hydrogen bond interactions between gelatin and lanthanide-polyoxometalate. Absorption spectra, luminescent spectra, and digital images indicated that the film displayed reversible photochromism behavior and was accompanied by luminescent switching property upon exposure to UV irradiation and oxygen (in the dark) alternately, which allowed its potential application as a reprintable medium for inkless security printing. The printed information can be erased upon exposure to oxygen in the dark, and the film can be reused for printing again. The film exhibited excellent erasability, reprintability, renewability, and low toxicity. In addition, multiple encryption strategies were designed to improve information security. This work offers an attractive alternative strategy for constructing a reprintable film for inkless security printing in terms of simplifying the preparation process, saving resources, and protecting the environment.

Synthesis of Chiral Pyrene‐Based 1,4‐Dithiins

AbstractThe 1,4‐dithiin motif is known for its reversible redox properties to generate radical cations and diradical dications and thus is interesting for organic electronic applications. However, examples where this motif is embedded into chiral larger fused aromatic compounds are very rare. Here we describe the syntheses of several structurally related pyrene fused dithiins and their spectroscopic investigations with a focus on tuning circular dichroism, with respect to the g values, depending on their connectivity.

Synthesis of Chiral Pyrene-Based 1,4-Dithiins.

The 1,4-dithiin motif is known for its reversible redox properties to generate radical cations and diradical dications and thus is interesting for organic electronic applications. However, examples where this motif is embedded into chiral larger fused aromatic compounds are very rare. Here we describe the syntheses of several structurally related pyrene fused dithiins and their spectroscopic investigations with a focus on tuning circular dichroism, with respect to the g values, depending on their connectivity.

Flexible transparent wood with reversible photoresponsive property

Flexible photoresponsive transparent wood (FPTW) has potential applications in electronic equipment, sensors, and other fields. In this study, flexible and photoresponsive transparent wood was synthesized through the impregnation process, utilizing epoxy resin and a spiropyran solution. This process endowed the wood with intelligent response and flexible capabilities. Scanning electron microscopy (SEM) revealed the impregnation of the flexible polymer into the porous structure of natural wood. Further validation was conducted to affirm the sample responds to ultraviolet light, employing analyses of infrared spectroscopy, UV–visible spectroscopy, and X-ray photoelectron spectroscopy (XPS). Through the measurement of chromaticity parameters, encompassing lightness (L*), redness (a*), yellowness (b*), and total color difference (ΔE*), before and after UV irradiation, it is indicated that the wooden samples manifest commendable photoresponsive properties. Testing the fluorescence properties of the samples, the spiropyran completed the opened-loop and closed-loop transitions under irradiation with UV and visible light. In addition, the FPTW has excellent mechanical properties, with a tensile strength of 0.98 GPa and an elastic modulus of 0.65 GPa.

Ultrasensitive Ionic Conductors with Tunable Resistance Switching Temperature Enabled by Phase Transformation of Polymer Cocrystals.

Phase-transformable ionic conductors (PTICs) show significant prospects for functional applications due to their reversible resistance switching property. However, the representative design principle of PTICs is utilizing the melt-crystallization transition of ionic liquids, and the resistance switching temperatures of such PTICs cannot be tuned as desired. Herein, a new strategy is proposed to design PTICs with on-demand resistance switching temperatures by using the melt-crystallization transition of polymer cocrystal phase, whose melting temperature shows a linear relationship with the polymer compositions. Owing to the melt of polymer cocrystal domains and the tunable migration of ions in the resistance switching region, the obtained PTICs display ultrahigh temperature sensitivity with a superior temperature coefficient of resistance of -8.50% °C-1 around human body temperature, as compared to various ionic conductors previously reported. Therefore, the PTICs can detect tiny temperature variation, allowing for the intelligent applications for overheating warning and heat dissipation. It is believed that this work may inspire future researches on the development of advanced soft electrical devices.

A Highly Efficient and Energy Saving Electrochromic Platform for Adaptive Visible and Near-Infrared Light Modulation

Dual-band electrochromic devices (DBEDs) with reversible optical properties in visible (VIS) and near-infrared (NIR) spectral ranges are highly desirable for intelligent technologies (e.g. electrochromic smart windows, adaptive and military camouflages). However, most available DBEDs only have two optical states - namely the bleached and colored states, and efforts are committed to increasing the optical modulation between them, while durability of cycling is rarely reported. Herein, we report a novel multicolored rocking-chair DBED based on Prussian blue (PB) thin films as electrochromic layers and a conductive carbon cloth (CC) frame as the counter electrode. During the electrochromic process, cations from the electrolyte migrate back and forth between PB and CC, and electrolysis of aqueous electrolyte can be effectively avoided to extend device longevity. The PB-CC DBED exhibits superior dual-band electrochromic performance with a wide range of switchable colors, including transparent, blue, green and yellow, large optical modulation in VIS-NIR ranges, fast response speed, high coloration efficiency and long-term durability. Based on the diverse color change in the VIS range and thermal control in the NIR range, the camouflage ability of the device is also described. Finally, an adaptive optical modulation platform is demonstrated, obtained by connecting the PB-CC device to a voltage-controlled circuit module to realize intelligent and autonomous color switching of the device.

Eu3+-Directed Supramolecular Metallogels with Reversible Quadruple-Stimuli Response Behaviors.

Smart luminescent materials that have the ability to reversibly adapt to external environmental stimuli and possess a wide range of responses are continually emerging, which place higher demands on the means of regulation and response sites. Here, europium ions (Eu3+)-directed supramolecular metallogels are constructed by orthogonal self-assembly of Eu3+ based coordination interactions and hydrogen bonding. A new organic ligand (L) is synthesized, consisting of crown ethers and two flexible amide bonds-linked 1,10-phenanthroline moieties to coordinate with Eu3+. Synergistic intermolecular hydrogen bonding in L and Eu3+-L coordination bonding enable Eu3+ and L to self-assemble into shape-persistent 3D coordination metallogels in MeOH solution. The key to success is the utilization of crown ethers, playing dual roles of acting both as building blocks to build L with C2-symmetrical structure, and as the ideal monomer for increasing the energy transfer from L to Eu3+'s excited state, thus maintaining the excellent luminescence of metallogels. Interestingly, such assemblies show K+, pH, F-, and mechano-induced reversible gel-sol transitions and tunable luminescence properties. Above findings are useful in the studies of molecular switches, dynamic assemblies, and smart luminescent materials.

Co-immobilized multi-enzyme biocatalytic system on reversible and soluble carrier for saccharification of corn straw cellulose

Herein, three enzymes (cellulase, β-glucosidase, and pectinase) with synergistic effects were co-immobilized on the Eudragit L-100, and the recovery of co-immobilized enzymes from solid substrates were achieved through the reversible and soluble property of the carrier. The optimization of enzyme ratio overcomed the problem of inappropriate enzyme activity ratio caused by different immobilization efficiencies among enzymes during the preparation process of co-immobilized enzymes. The co-immobilized enzymes were utilized to catalytically hydrolyze cellulose from corn straw into glucose, achieving a cellulose conversion rate of 74.45% under conditions optimized for their enzymatic characteristics and hydrolytic reaction conditions. As a result of the reversibility and solubility of the carrier, the co-immobilized enzymes were recovered from the solid substrate after five cycles, retaining 54.67% of the enzyme activity. The aim of this study is to investigate the potential of co-immobilizing multiple enzymes onto the Eudragit L-100 carrier for the synergistic degradation of straw cellulose.

Reversible hydrochromic CsPbBr3/Cs4PbBr6@MCM-41 to enable organic solvent polarity detection

Hydrochromic materials have received much attention in anticounterfeiting due to their reversible photoemission properties toward water. However, existing hydrochromic materials usually suffer from slow hydrochromic response and limited stability, repeatability, and color tunability. This paper found for the first time that CsPbBr3/Cs4PbBr6 composites with quantum-limited domain effects had reversible hydrochromism. CsPbBr3/Cs4PbBr6 composites were successfully synthesized in molecular sieve MCM-41 using an improved mechanochemical method. The composites underwent a reversible phase transition from Cs4PbBr6/CsPbBr3 to CsPbBr3 upon treatment with a trace amount of water, the photoluminescence colors underwent a change from blue to green, and reversion occurred due to heating. Mechanistic investigation revealed that quantum dots underwent soft agglomeration due to van der Waals forces in polar solvent environments, affecting the action of quantum domain-limiting effects. Therefore, organic solvents with different polarities can cause different degrees of reversible discoloration of the material. This study provides new ideas for understanding the phase transition and agglomeration of metal halide perovskite quantum dots in polar solvent environments. Additionally, it offered new options for aqueous color-changing materials and organic solvent polar detection materials.

Towards Optical Information Recording: A Robust Visible-Light-Driven Molecular Photoswitch with the Ring-Closure Reaction Yield Exceeding 96.3 .

Diarylethene molecular photoswitches hold great fascination as optical information materials due to their unique bistability and exceptional reversible photoswitching properties. Conventional diarylethenes, however, rely on UV light for ring-closure reactions, typically with modest yields. For practical application, diarylethenes driven by visible lights are preferred but achieving high ring-closure reaction yield remains a significant challenge. Herein, we synthesized a novel all-visible-light-driven photoswitch, TPAP-DTE, by facilely endcapping the dithienylethene (DTE) core with triphenylamine phenyl (TPAP) groups. Owing to the electron-donating conjugation effect of TPAP, the open-form TPAP-DTE responds strongly to short-wavelength visible lights with considerable photocyclization quantum yields and molar absorption coefficient. Upon 405 nm visible-light irradiation, TPAP-DTE achieves a ring-closure reaction yield exceeding 96.3 % (confirmed by both nuclear magnetic resonance spectroscopy and high-performance liquid chromatography). Its ring-opening reaction yield is 100 % upon irradiation with long-wavelength visible light. TPAP-DTE could be regarded as a bidirectional "quasi"-quantitative conversion molecular switch. Furthermore, TPAP-DTE exhibits robust fatigue resistance over 100 full photoswitching cycles and great anti-aging property under 85 °C and 85 % humidity for at least 1000 h. Consequently, its rewritable QR-code, multilevel data storage, and anti-counterfeiting/encryption applications are successfully demonstrated exclusively using visible lights, positioning TPAP-DTE as a highly promising medium for information recording.