Innovative Synthesis of Photo-Responsive, Self-Healing Silicone Elastomers with Enhanced Mechanical Properties and Thermal Stability.

Photo-responsive materials have garnered significant interest for their ability to react to non-contact stimuli, though achieving self-healing under gentle conditions remains an elusive goal. In this research, an innovative and straightforward approach for synthesizing silicone elastomers is proposed that not only self-heal at room temperature but also possess unique photochromic properties and adjustable mechanical strength, along with being both transparent and reprocessable. Initially, aldehyde-bifunctional dithiophene-ethylene molecules with dialdehyde groups (DTEM) and isocyanurate (IPDI) is introduced into the aminopropyl-terminated polydimethylsiloxane (H2N-PDMS-NH2) matrix. Subsequently, palladium is incorporated to enhance coordination within the matrix. These silicone elastomers transition to a blue state under 254 nm UV light and revert to transparency under 580 nm light. Remarkably, they demonstrate excellent thermal stability at temperatures up to 100 °C and show superior fatigue resistance. The optical switching capabilities of the silicone elastomers significantly affect both their mechanical characteristics and self-healing abilities. Notably, the PDMS-DTEM-IPDI-@Pd silicone elastomer, featuring closed-loop photo-switching molecules, exhibits a fracture toughness that is 1.3 times greater and a room temperature self-healing efficiency 1.4 times higher than its open-loop counterparts. This novel photo-responsive silicone elastomer offers promising potential for applications in data writing and erasure, UV protective coatings, and micro-trace development.

A metal-organic framework and quantum dot-based ratiometric fluorescent probe for the detection of formaldehyde in food.

A green and sensitive ratio fluorescence strategy was proposed for the detection of formaldehyde (FA) in food based on a kind of metal-organic frameworks (MOFs), MIL-53(Fe)-NO2, and nitrogen-doped Ti3C2 MXene quantum dots (N-Ti3C2 MQDs) with a blue fluorescence at 450 nm. As a type of MOFs with oxidase-like activity, MIL-53(Fe)-NO2 can catalyze o-phenylenediamine (OPD) into yellow fluorescent product 2,3-diaminophenazine (DAP) with a fluorescent emission at 560 nm. DAP has the ability to suppress the blue light of N-Ti3C2 MQDs due to inner filter effect (IFE). Nevertheless, Schiff base reaction can occur between FA and OPD, inhibiting DAP production. This results in a weakening of the IFE which reverses the original fluorescence color and intensity of DAP and N-Ti3C2 MQDs. So, the ratio of fluorescence intensity detected at respective 450 nm and 560 nm was designed as the readout signal to detect FA in food. The linear range of FA detection was 1-200 µM, with a limit of detection of 0.49 µM. The method developed was successfully used to detect FA in food with satisfactory results. It indicates that MIL-53(Fe)-NO2, OPD, and N-Ti3C2 MQDs (MON) system constructed by integrating the mimics enzyme, enzyme substrate, and fluorescent quantum dots has potential application for FA detection in practical samples.

Toughening Hydrogels by Forming Robust Hydrazide-Transition Metal Coordination Complexes.

Energy dissipation based on dynamic fracture of metal ligands is an effective way to toughen hydrogels for specific applications in biomedical and engineering fields. Exploration of new kinds of metal-ligand coordinates with robust bonding strength is crucial for the facile synthesis of tough gels. Here a hydrogel toughening strategy based on the formation of robust coordination complexes between the hydrazide ligands and zinc ions is reported. The resultant hydrogels exhibit high strength and toughness at room temperature. Their mechanical properties show temperature dependence due to the dynamic nature of coordination bonds. In addition, the amine group of hydrazides in the gel matrix provides a reactive site for Schiff's base reaction, enabling surface modification without influence on overall mechanical performances of the gel. The hydrazide ligands are easy to synthesize and can coordinate very well with several transition metals. Such a metal-ligand coordination should be suitable to develop tough soft materials with versatile applications.

Synthesis of a core-shell magnetic covalent organic framework for the enrichment and detection of aflatoxin in food using HPLC-MS/MS.

A porous magnetic covalent organic framework, Fe3O4@TPBD-TPA (terephthalaldehyde (TPA) , N, N, N', N'-tetrakis(p-aminophenyl)-p-phenylenediamine (TPBD)), was synthesized using the Schiff base reaction under mild reaction conditions. This adsorbent exhibited excellent adsorption performance for aflatoxins. The adsorption capacity of Fe3O4@TPBD-TPA for aflatoxins ranged from 64.4 to 84.4 mg/g. A magnetic solid-phase extraction combined with high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method based on Fe3O4@TPBD-TPA was developed for the efficient determination of four types of aflatoxins in food samples (maize, maize oil, peanut, and peanut oil). The determination coefficients (R2) were ≥0.9972. The method exhibited detection limits ranging from 0.01 to 0.06 µg/kg and spiked recoveries of 80.0 to 113.1%. The intra-day and inter-day precision were less than 6.77%, indicating good repeatability. The adsorbent showed promising prospects for the efficient enrichment of trace amounts of aflatoxins in complex food matrices.

Schiff Base Reaction in a Living Cell: In Situ Synthesis of a Hollow Covalent Organic Polymer To Regulate Biological Functions.

Artificially performing chemical reactions in living biosystems to attain various physiological aims remains an intriguing but very challenging task. In this study, the Schiff base reaction was conducted in cells using Sc(OTf)3 as a catalyst, enabling the in situ synthesis of a hollow covalent organic polymer (HCOP) without external stimuli. The reversible Schiff base reaction mediated intracellular Oswald ripening endows the HCOP with a spherical, hollow porous structure and a large specific surface area. The intracellularly generated HCOP reduced cellular motility by restraining actin polymerization, which consequently induced mitochondrial deactivation, apoptosis, and necroptosis. The presented intracellular synthesis system inspired by the Schiff base reaction has strong potential to regulate cell fate and biological functions, opening up a new strategic possibility for intervening in cellular behavior.

Highly Efficient Photocatalytic Reduction of CO2 to CO by In Situ Formation of a Hybrid Catalytic System Based on Molecular Iron Quaterpyridine Covalently Linked to Carbon Nitride.

Efficient and selective photocatalytic CO2 reduction was obtained within a hybrid system that is formed in situ via a Schiff base condensation between a molecular iron quaterpyridine complex bearing an aldehyde function and carbon nitride. Irradiation (blue LED) of an CH3 CN solution containing 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH), triethylamine (TEA), Feqpy-BA (qpy-BA=4-([2,2':6',2'':6'',2'''-quaterpyridin]-4-yl)benzaldehyde) and C3 N4 resulted in CO evolution with a turnover number of 2554 and 95 % selectivity. This hybrid catalytic system unlocks covalent linkage of molecular catalysts with semiconductor photosensitizers via Schiff base reaction for high-efficiency photocatalytic reduction of CO2 , opening a pathway for diverse photocatalysis.

Mixed Dimensional Nanostructure (UiO-66-Decorated MWCNT) as a Nanofiller in Mixed-Matrix Membranes for Enhanced CO2 /CH4 Separation.

Mixed-matrix membranes (MMMs) with combination of two distinct dimensional nanofillers (such as 1D-3D, 2D-3D, or 3D-3D, etc.) have drawn special attention for gas separation applications due to their concerted effects on gas permeation and mechanical properties. An amine-functionalized 1D multiwalled carbon nanotube (NH2 -MWCNT) with exceptional mechanical strength and rapid gas transport was crosslinked with an amine-functionalized 3D metal-organic framework (UiO-66-NH2 ) with high CO2 affinity in a Schiff base reaction. The resultant crosslinked mixed-dimensional nanostructure was used as a nanofiller in a polysulfone (PSf) polymer matrix to explore the underlying synergy between 1D and 3D nanostructures on the gas separation performance of MMMs. Cross-sectional scanning electron microscopy and mapping revealed the homogenous dispersion of UiO-66@MWCNT in the polymer matrix. The MMM containing 5.0 wt. % UiO-66@MWCNT demonstrated a superior permeability 8.3 Barrer as compared to the 4.2 Barrer of pure PSf membrane for CO2 . Moreover, the selectivity (CO2 /CH4 ) of this MMM was enhanced to 39.5 from the 28.0 observed for pure PSf under similar conditions of pressure and temperature.

Advances in Injectable and Self-healing Polysaccharide Hydrogel Based on the Schiff Base Reaction.

Injectable hydrogel possesses great application potential in disease treatment and tissue engineering, but damage to gel often occurs due to the squeezing pressure from injection devices and the mechanical forces from limb movement, and leads to the rapid degradation of gel matrix and the leakage of the load material. The self-healing injectable hydrogels can overcome these drawbacks via automatically repairing gel structural defects and restoring gel function. The polysaccharide hydrogels constructed through the Schiff base reaction own advantages including simple fabrication, injectability, and self-healing under physiological conditions, and therefore have drawn extensive attention and investigation recently. In this short review, the preparation and self-healing properties of the polysaccharide hydrogels that is established on the Schiff base reaction are focused on and their biological applications in drug delivery and cell therapy are discussed.

Surface Confined Synthesis of Hydroxy Functionalized Two-Dimensional Polymer: The Effect of the Position of Hydroxy Groups.

We report on the on-surface synthesis of a series of two-dimensional polymers (2DPs) and macrocycles containing hydroxyl groups on a highly oriented pyrolytic graphite surface. The formed 2DPs and macrocycles were visualized through scanning tunneling microscopy. By varying the solvent and reaction temperature, structural evolution from oligomers to well-ordered 2DPs or discrete macrocycles was directly followed. In addition, we discovered that the reaction outcome can be steered from extended 2DPs to discrete macrocycles or catenular structures by exchanging the position of the hydroxyl and aldehyde group. These results indicate that the relative positions of hydroxyl and aldehyde groups on the biphenyl ring play a determining role in the control and selection of the final products of the surface-confined Schiff base coupling reaction.

Ionic-liquid-stabilized fluorescent probe based on S-doped carbon dot-embedded covalent-organic frameworks for determination of histamine.

An ionic-liquid-stabilized fluorescent probe for histamine is described. Sulfur-doped carbon dots (S-CDs) were incorporated into a covalent organic framework (COF) that was prepared from 1,3,5-triformylphloroglucinol and 2,5-dimethyl-p-phenylenediamine by one-pot hydrothermal polymerization in the dark. The blue fluorescence of the S-CDs (with excitation/emission maxima at 350/440 nm) is enhanced (compared to undoped CDs) due to element doping by ionic-liquid modification. The COF is resistant to acids, bases, and boiling water. The fluorescence of the probe is statically quenched by histamine, and quenching follows the Stern-Volmer equation. The normalized fluorescence of the probe drops in the 10 to 1000 µg kg-1 histamine concentration range, and the limit of detection is 5.3 µg kg-1. The probe was successfully applied to the analysis of wine and fermented meat products. The recoveries from spiked samples range between 84.6 and 115.3%. The method is selective, sensitive, stable and repeatable. The mechanisms of the fluorometric response and molecular recognition were explored. Graphical abstractSchematic presentation of ionic-liquid-stabilized fluorescent probe based on S-doped carbon dot-embedded covalent organic framework for determination of histamine. The ionic liquid [VBIm][BF4] reacts with MPTS-modified carbon dots to enhance the fluorescence signal for analyte recognition.

Ultrastiff Hydrogels Prepared by Schiff's Base Reaction of Bis(p-Formylphenyl) Sebacate and Pillar[5]arene Appended with Multiple Hydrazides.

Herein a facile method is reported to prepare polymer gels based on the formation of acylhydrazone bond under mild conditions. A pillar[5]arene derivative appended with ten hydrazide groups provides multiple sites for the reaction with the aldehyde groups of bis(p-formylphenyl) sebacate in the presence of a small amount of HCl as the catalyst in dimethyl sulfoxide (DMSO), producing transparent polymer organogels. The mechanical properties of gels can be easily tuned by the molar ratio of the reactant compounds. After solvent exchange from DMSO to water, translucent polymer hydrogels with dramatically enhanced strength and stiffness are obtained. The tensile breaking stress and Young's modulus of hydrogels are 20-60 and 1.2-2.7 MPa, respectively, 100 and 20 times those of the corresponding organogels. These robust hydrogels with ultrahigh stiffness should find applications such as in load-bearing artificial organs. This work should merit designing functional materials using other macrocycles.

An injectable, chitosan-based hydrogel prepared by Schiff base reaction for anti-bacterial and sustained release applications.

Injectable hydrogels, providing sustained release as implanted materials, have received tremendous attention. In this study, chitosan-based hydrogels were prepared via Schiff base reaction of the aldehyde groups on Poly(NIPAM-co-FBEMA) and the amine groups on chitosan. Owing to the dynamic covalent linkage, the SC/PNF hydrogels exhibit pH-responsive, reversible sol-gel transition, injectable, and self-healing capacity. The mechanical strength of SC/PNF hydrogels can be operated simply by switching the composition or solid content of Poly(NIPAM-co-FBEMA) copolymers. Rheological analyses, including frequency sweeps, strain sweep scanning, and dynamic time sweeps, were employed to demonstrate the relationship between storage modulus (G'), loss modulus (G″), and composition of the SC/PNF hydrogels. In vitro release behaviors reveal that vancomycin-loaded SC/PNF hydrogel could contribute to both the initial burst release (over 1000 ppm within 4 h) and the sustained release (3000 ppm for at least 30 days). Pristine SC/PNF hydrogel holds good biocompatibility toward L929 cells and S. aureus that it degrades as incubated with S. aureus. However, vancomycin-wrapped SC/PNF hydrogel possesses a rapid bacterial-killing effect with a clear inhibition zone. In short, the SC/PNF hydrogels deliver not only sustainable release ability but also tunable physical properties, which are expected to be an outstanding candidate for non-invasive, anti-infection applications.

Highly sensitive detection of tryptophan based on Schiff base reaction and surface-enhanced Raman spectroscopy.

In this study, a simple, rapid and sensitive method combining surface-enhanced Raman spectroscopy and Schiff base reaction was developed for the detection of tryptophan. This method does not require product separation to obtain a significant Raman signal of the derivatized product, and the derivatization reaction can be controlled by experimental parameters such as reaction temperature, time, concentration of derivatization reagent and concentration of sodium nitrite. The characteristic peak of the derivative of tryptophan (1620 cm-1) was selected for quantitative analysis, and the intensity of the characteristic Raman spectrum peak showed a linear relationship with the concentration of tryptophan (10-8-10-4 mol/L) in the range of with a correlation coefficient R2 of 0.9922. This assay combines surface-enhanced Raman spectroscopy and Schiff base reaction, which is characterized by high sensitivity and easy operation, and has good application prospects in the detection of tryptophan in food.

Facile preparation of interpenetrating network hydrogel adsorbent from starch- chitosan for effective removal of methylene blue in water.

Hydrogels based on biopolymers have attracted considerable interest in the last decades. Herein, an interpenetrating network hydrogel (IPN-Gel) adsorbent from starch-chitosan was fabricated facilely in one-pot through tandem Schiff base reaction and photopolymerization. First, aldehyde starch (DAS) was synthesized by the reaction of soluble starch with sodium periodate. Afterward, acrylamide (AM), 2-acrylamido-2-methylpropanesulfonic acid (AMPS), polyethylene glycol dimethacrylate (PEGDMA), photoinitiator, chitosan and DAS were dissolved in water to obtain a clear solution. Schiff base reaction between chitosan and DAS took place quickly to form the first network, and then photopolymerization of AM, AMPS, and PEGDMA occurred under ultraviolet radiation to form the second network. The preparation conditions of the as-prepared IPN-Gel were optimized with two indexes of gel mass fraction and swelling ratio. Its swelling behavior with pH and temperature change was explored. Finally, its adsorption performance was characterized with methylene blue (MB) as a model contaminant. The maximum adsorption capacity of IPN-Gel can reach 2039 mg·g-1 at pH =10. Its adsorption performance accords with Langmuir isothermal model and pseudo-second-order kinetic model and it was mainly controlled by chemisorption. This strategy is expected to found broad application prospects in the preparation of hydrogel adsorbents.

Fabrication of injectable, adhesive, self-healing, superabsorbent hydrogels based on quaternary ammonium chitosan and oxidized pullulan.

Injectable hydrogels, which are polymeric materials that are characterized by their ability to be injected in a liquid form into cavities and subsequently undergo in situ solidification, have garnered significant attention. These materials are extensively used in a range of biomedical applications. This study synthesized several injectable composite hydrogels through the mild Schiff base reaction while imposing different concentrations of quaternary ammonium chitosan and oxidized pullulan. Subsequent characterizations revealed a consistent and coherent porous structure within the hydrogels with smooth inner walls. The hydrogels were also determined to possess good adhesion, mechanical properties, self-healing ability, and injectability. Furthermore, antimicrobial tests against Escherichia coli and Staphylococcus aureus demonstrated antibacterial properties, which improved with increasing concentrations of quaternary ammonium chitosan. Co-culturing with skin fibroblasts demonstrated that the injectable hydrogels exhibited favourable biocompatibility and the capacity to boost cellular activity, thus underscoring its potential for use in biomedical applications.

In situ forming alginate/gelatin hydrogel scaffold through Schiff base reaction embedded with curcumin-loaded chitosan microspheres for bone tissue regeneration.

In this study, we developed a biocompatible composite hydrogel that incorporates microspheres. This was achieved using a Schiff base reaction, which combines the amino and aldehyde groups present in gelatin (Gel) and oxidized alginate (OAlg). We suggest this hydrogel as a promising scaffold for bone tissue regeneration. To further boost its osteogenic capabilities and mechanical resilience, we synthesized curcumin (Cur)-loaded chitosan microspheres (CMs) and integrated them into the Gel-OAlg matrix. This formed a robust composite gel framework. We conducted comprehensive evaluations of various properties, including gelation time, morphology, compressive strength, rheological behavior, texture, swelling rate, in vitro degradation, and release patterns. A remarkable observation was that the inclusion of 30 mg/mL Cur-CMs significantly enhanced the hydrogel's mechanical and bioactive features. Over three weeks, the Gel-OAlg/Cur-CMs (30) composite showed a cumulative curcumin release of 35.57%. This was notably lower than that observed in standalone CMs and Gel-OAlg hydrogels. Additionally, the Gel-OAlg/Cur-CMs (30) hydrogel presented a reduced swelling rate and weight loss relative to hydrogels devoid of Cur-CMs. On the cellular front, the Gel-OAlg/Cur-CMs (30) hydrogel showcased superior biocompatibility. It also displayed increased calcium deposition, alkaline phosphatase (ALP) activity, and elevated osteogenic gene expression in human bone marrow mesenchymal stem cells (hBMSCs). These results solidify its potential as a scaffold for bone tissue regeneration.

Preparation and antitumor study of intelligent injectable hydrogel: Carboxymethyl chitosan-aldehyde gum Arabic composite graphene oxide hydrogel.

In this study, we used polyaldehyde gum Arabic (OGA) and carboxymethyl chitosan (CMCS) as a gel matrix to form an injectable self-healing hydrogel by Schiff-base bonding. Further, graphene oxide (GO) was loaded with doxorubicin (DOX) to the hydrogel, which resulted in a CMCS-OGA/GO@DOX hydrogel. We achieved a DOX drug loading capacity of 43.80 ± 1.13 %. Rheological studies showed that GO hydrogels have improved mechanical properties. The in vitro release profile showed pH responsiveness with 88.21 % DOX release at pH 5.5. Biocompatibility studies showed that the hydrogel composition had good cytocompatibility with L929 cells. The 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay showed a cell survival rate of 93.88 % within 48 h. The DOX-loaded hydrogel exhibited higher cell mortality in breast cancer cells (4 T1), with an inhibition rate of 79.4 % at 48 h. Acridine orange/ethidium bromide staining experiments on 4 T1 cells showed that when loaded with the same DOX concentration, the hydrogel significantly reduced the toxic effects on normal cells, whereas it had significant cytotoxic effects on cancer cells. This result indicates that the prepared GO hydrogel drug delivery system can serve as a novel approach for localized breast cancer treatment.

Skin-like dual-network gelatin/chitosan/emodin organohydrogel sensors mediated by Hofmeister effect and Schiff base reaction.

Conductive gels have been extensively explored in the field of wearable electronics due to their excellent flexibility and deformability. Traditional gels constructed from synthetic networks pose risks to biosecurity due to residual monomers like acrylamide, while pure biological hydrogels are plagued by inadequate mechanical performance. This study explores an innovative strategy, employing a dual-network (DN) system with purely biological components, as a superior alternative to conventional synthetic networks. By integrating gelatin and chitosan, two natural polymers with inherent biocompatibility and advantageous biomedical properties, this approach successfully avoids the toxic risk of synthetic polymers. By utilizing emodin, a natural extract from Rheum officinale, as a cross-linking agent for chitosan by Schiff base reactions, and Hofmeister effect of gelatin induced by sodium carbonate, the DN gelatin/chitosan/emodin organohydrogels achieve ultrahigh tensile strength (up to 9.45 MPa), tunable moduli (ranging from 0.07 to 3.42 MPa), excellent toughness (∼9.64 MJ/m3), and high ionic conductivity (7.63 mS/cm). Remarkably, these conductive organohydrogels also exhibit high sensitivity (gauge factor up to 1.5) and ultrahigh linearity (R2 up to 0.9995), making them promising candidates for soft human-motion sensors capable of accurately detecting and monitoring human movements in real time with high sensitivity and durability.

Assembly of polysaccharide-based polymer brush for supramolecular hydrogel dressing.

Extracted from Platycodon grandiflorum, platycodon grandiflorum polysaccharides (PGPs) with diverse biological functions have been extensively employed for modification and fabrication of hydrogels for biomedical applications, such as wound dressings. However, since the lack of effective structural design, the reported polysaccharide-based hydrogel dressings are still suffered from structural failures and limited bio-functionality. Herein, we demonstrate a facile and general strategy to fabricate a supramolecular hydrogel composed of PGP-based polymer brush as building blocks combined with a Ca2+-mediated self-assembly process. The specific polymer brush with high branch functionality was achieved with polyacrylamide arms evenly grown on the PGP (grafting efficiency as high as 80 %) with series of chemical modifications. With above structural merits, the resulting hydrogel with densely crosslinked polymer brush featured enhanced mechanical strength as well as self-healing, and shear-thinning behaviors. Further biocompatible investigation indicated the as-prepared hydrogels with admirable performances in self-adhesion (adhesive strength of 16.7-79.5 kPa), a pH-responsive swelling ratio as high as 44 at pH 5.4, and pH-responsive degradation. They also showed antioxidant capacity by scavenging DPPH activity of nearly 80 % in 20 min, hemocompatibility, cell viability and cell migration. Impressively, the PGP-based polymer brush hydrogel served as a wound dressing revealed significant acceleration on wound closure.

High internal phase Pickering emulsions stabilized by Zein-hyaluronic acid conjugate particles and their application in active substances protection.

In recent years, active substances have been extensively applied in the fields of food, cosmetics, and pharmaceuticals. However, their preservation and transportation have posed challenges due to issues such as oxidation and photodegradation. This study proposes a method for synthesizing Zein-Hyaluronic Acid (Zein-HA) conjugate particles via the Schiff base reaction, utilizing these conjugate particles to encapsulate and protect active substances within a stable emulsion system. Compared to zein, the modified conjugate particles exhibit significantly improved dispersibility, amphiphilicity, interfacial affinity, and emulsifying properties. Consequently, these particles are capable of stabilizing high internal phase Pickering emulsions with an oil phase volume fraction of up to 80 (v/v)%, thereby enabling the carriage of a higher load of active components. Furthermore, the prepared emulsions demonstrate excellent storage stability, resistance to ionic strength (250-2000 mM NaCl), and outstanding antioxidative characteristics. Moreover, after 8 h of UV light exposure, the retention rates of the active substances (curcumin, astaxanthin, and resveratrol) exceed 60 %. Therefore, these emulsions hold substantial potential to be applied as a carrier system in the food, cosmetics, and pharmaceutical industries.