Nanoarchitectonics composite hydrogels with high toughness, mechanical strength, and self-healing capability for electrical actuators with programmable shape memory properties.

Hydrogel materials show promise in various fields, including flexible electronic devices, biological tissue engineering and wound dressing. Nevertheless, the inadequate mechanical properties, recovery performance, and self-healing speed still constrain the development of intelligent hydrogel materials. To tackle these challenges, we designed a composite hydrogel with high mechanical strength, rapid self-recovery and efficient self-healing ability based on multiple synergistic effects. With the synergistic effect of hydrogen bonds, metal coordination bonds and electrostatic interaction, the synthesized hydrogel could reach a maximum tensile strength of 6.2 MPa and a toughness of 50 MJ m-3. The interaction between the weak polyelectrolyte polyethyleneimine and polyacrylic acid aided in improving the elasticity of the hydrogel, thereby endowing it with prompt self-recovery attributes. The multiple reversible effects also endowed the hydrogel with excellent self-healing ability, and the fractured hydrogel could achieve 95% self-healing within 4 h at room temperature. By the addition of glycerol, the hydrogel could also cope with a variety of extreme environments in terms of moisture retention (12 h, maintaining 80% of its water content) and freeze protection (-36.8 °C) properties. In addition, the composite hydrogels applied in the field of shape memory possessed programmable and reversible shape transformation properties. The polymer chains were entangled at high temperatures to achieve shape fixation, and shape memory was eliminated at low temperatures, which allowed the hydrogels to be reprogrammed and achieve multiple shape transitions. In addition, we also assemble composite hydrogels as actuators and robotic arms for intelligent applications.

Multifunctional polylactic acid biocomposite film for active food packaging with UV resistance, antioxidant and antibacterial properties.

Antibacterial packaging used to control the growth of microorganisms in food is of great value for prolonging the shelf life of food. In this study, a bio-based antibacterial agent PDI based on zwitterionic and stereochemical synergistic antibacterial was designed and synthesized, and it was simultaneously introduced into polylactic acid (PLA) matrix with antioxidant o-vanillin (oVL) and plasticizer glycerol (GL). A series of PLA/oVL/PDI composite membranes with antibacterial, antioxidant and anti-ultraviolet properties were prepared by solution casting method. The results showed that the mechanical properties of the composite film were significantly improved compared with pure PLA (tensile strength increased by 37 %, elongation at break increased by 209 %), which was mainly attributed to the microphase separation structure induced by synthetic bio-based antibacterial agent, which improved the mechanical strength of PLA matrix, and the hydrogen bond formed by glycerol, o-vanillin and carbonyl group in PLA molecules plasticized PLA matrix. At the same time, the antibacterial rate of PLA/oVL/PDI composite membrane against Escherichia coli and Staphylococcus aureus can reach >95 %. Packaging experiments showed that PLA/oVL/PDI series composite films could effectively extend the shelf life of fresh bananas and apples for 5 days, and had great application prospects in preservative food packaging.

Poly(lactic acid) based Pearl Layer Moistureproof Membrane for Flexible Laminated Packaging.

The development of bio-based polymer materials, such as polylactic acid (PLA) -based polymers, is an effective strategy to reduce dependence on petrochemical-based polymers. However, the preparation of bio-based polymers with high barrier properties is a major challenge. To overcome this challenge, a nacreous layer structure with a ' brick and mud ' pattern is mimicked to improve the overall performance of the material. In this paper, Poly (L -lactic acid) (PLLA) and Polypropylene Glycol (PPG) was combined to prepare bio-based polyurethane (PU-PLLA), which is used as the slurry structure of nacreous layer. The bio-based biomimetic composite membrane (PU-PLLA/BN) is then obtained by adding boron nitride (BN, brick structure of pearl layer) to it. The water vapor permeability test results show that the permeability of PU-PLLA material can be reduced by more than 50% by 5 wt.% BN, which is because the addition of BN can increase the length and tortuosity of the gas molecular diffusion path in the composite. Therefore, this pearl-inspired PU-PLLA/BN film has excellent moisture resistance, which opens up a broad road for the practical application of PLLA in flexible laminated packaging.

Tannic Acid Crosslinked Self-Healing and Reprocessable Silicone Elastomers with Improved Antibacterial and Flame Retardant Properties.

Silicone elastomers are widely used in aviation, electronics, automotive, and medical device fields, and their overuse inevitably causes recycled problems. In addition, the elastomers are subject to attack by bacteria and fire during use in some application scenarios, which is a safety hazard. Therefore, there is a great need to prepare silicone elastomers with improved antibacterial, flame retardant, self-healing, and recyclable functions. A new strategy is proposed to prepare silicone elastomers with bio-based tannic acid as cross-linkers to solve this problem by using polydimethylsiloxane as a soft chain segment and 2,2-bis(hydroxymethyl)propionic acid as an intermediate chain extender. Based on the phenol carbamate bonding and hydrogen bonding interactions, the elastomer has efficient self-healing ability and can achieve dynamic dissociation at 120 °C for complete recovery. In addition, due to the unique spatial structure and polyphenolic hydroxyl groups of tannic acid, the mechanical properties of the elastomer are greatly improved with an antimicrobial efficiency of over 90% and a final oxygen index of 25.5%. The multifunctional silicone elastomer has great potential applications in recyclable refractory materials and antimicrobial materials.

Highly Sensitive Zwitterionic Hydrogel Sensor for Motion and Pulse Detection with Water Retention, Adhesive, Antifreezing, and Self-Healing Properties.

The design and synthesis of conductive hydrogels with antifreezing, long-term stable, highly sensitive, self-healing, and reusable is a critical procedure to enable applications in flexible electronics, medical monitoring, soft robotics, etc. Herein, a novel zwitterionic composite hydrogel possessing antifreezing, fast self-healing performance, water retention, and adhesion was synthesized via a simple one-pot method. LiCl, as an electrolyte and antifreeze, was promoted to dissociate under the electrostatic interaction with zwitterions, resulting in the composite hydrogels with high electrical conductivity (7.95 S/m) and excellent antifreeze ability (-45.3 °C). Meanwhile, the composite hydrogels could maintain 97% of the initial water content after exposed to air (25 °C, 55% RH) for 1 week due to the presence of salt ions. Moreover, the active groups of zwitterions could form conformal adhesion between the composite hydrogels and skin, which was particularly crucial for the stable signal output of the sensor. The dynamic borate ester bonds, active group of zwitterions, and the hydrogen bond between different components could achieve rapid self-healing (2 h, self-healing efficiency to 97%) without any external intervention. Notably, the developed PBAS-Li (poly(vinyl alcohol) Borax/acrylamide/zwitterionic-LiCl) hydrogel not only succeeded in sensitively detecting human motions but also could precisely captured handwritings signals and subtle pulse waves on the neck and wrist. The above findings demonstrated the great potential of PBAS-Li hydrogels in the field of flexible electronic devices.

Poly (lactic acid)-based pH responsive membrane combined with chitosan and alizarin for food packaging.

A poly (lactic acid) (PLA) -based functional partition composite membrane (PLA/CA) containing chitosan (CS) and alizarin (AL) was designed by solution casting method. The PLA/CA membrane contains the antibacterial zone of the edge part (PLA/CS) and the pH response detection zone of the central part (PLA/AL). At the same time, the environmentally friendly plasticizer tributyl citrate (TBC) was added to make the prepared PLA/CA composite membrane have good flexibility and high transparency. The results of FE-SEM and FTIR showed that CS and AL were uniformly dispersed in PLA matrix and had good compatibility with PLA. The antioxidant activities of PLA/CS and PLA/AL composite films were 43.3 % and 72.8 %, respectively. At the same time, the inhibitory rates of PLA/CS membrane against Escherichia coli and Staphylococcus aureus were as high as 87.91 % and 75.17 %, respectively. PLA/AL films exhibit excellent UV barrier properties. When the environmental pH (ammonia and acetic acid vapor) changed repeatedly, the PLA/AL membrane showed reversible color change of yellow under acidic condition and purple under alkaline condition. During the packaging and storage of chicken breast meat, the freshness of chicken breast meat can be detected by the color change of functional PLA/CA composite membrane.

Biomimetic structure of chitosan reinforced epoxy natural rubber with self-healed, recyclable and antimicrobial ability.

Inspired by biomaterials with hard and soft structures, we reported a type of self-healed, recyclable and antimicrobial elastomers material (ECTS) which exhibited both strong mechanical strength and high toughness. ECTS was designed by furfuryl amine modified epoxy natural rubber (ENR-FA) and furaldehyde modified chitosan (CTS-FUR) through Diels-Alder (D-A) reaction. The dynamic loading capacity of the chitosan skeleton, the stress ductility of the matrix and the dynamic cross-linking between the hard and soft components gave the elastomer excellent mechanical strength, toughness and self-healing ability. The tensile strength and the elongation at break could reach up to 7.55 MPa and 487%, respectively. In addition, due to the reversibility of the covalent bond between chitosan framework and rubber matrix, the crosslinking network destroyed by external force could be reestablished under high temperature stimulation. The mechanical properties of the sample could be restored to more than 90% of the original sample, whether it was complete fracture, cyclic damage or recyclable. ECTS exhibited excellent antibacterial activity against both gram-positive bacteria (Staphylococcus aureus) and gram-negative bacteria (Pseudomonas aeruginosa), with antibacterial efficiency more than 99%. So, ECTS might has a promising application prospect in medical materials, intelligent devices, 4D-printing, etc.

A NIR laser induced self-healing PDMS/Gold nanoparticles conductive elastomer for wearable sensor.

Self-healing conductive elastomers have been widely used in smart electronic devices, such as wearable sensors. However, nano fillers hinder the flow of polymer segments, which make the development of conductive elastomer with rapid repair and high ductility a challenge. In this work, thioctic acid (TA) was grafted onto amino-modified polysiloxane (PDMS-NH2) by dehydration condensation of amino group and carboxyl group. By introducing gold nanoparticles, a dynamic network based on S-Au interaction was constructed. The dynamic gold cross-linking could effectively dissipate the energy exerted by external force and improve the extensibility of conductive elastomer. In addition, S-Au interaction had a good optothermal effect, so that the elastomer rapidly healed under NIR irradiation, and the repair efficiency reached 92%. We further evaluated the performance of the conductive elastomer as a strain sensor. The sample could accurately monitor the bending of human joints and small muscle state changes. This kind of self-healable conductive elastomer based on dynamic S-Au interaction has great potential in the fields of interpersonal interaction and health monitoring.

Comprehensive analysis of important parameters of choline chloride-based deep eutectic solvent pretreatment of lignocellulosic biomass.

Choline chloride based deep eutectic solvents have showed great potential in lignocellulosic biomass pretreatment. In this study, for DES pretreatment with different hydrogen bond donners of different raw materials under different reaction conditions, multivariate analysis methods including principal component analysis and partial least squares analysis were used for reveal the pretreatment mechanism by evaluating the inner relationships among 42 key process factors. Furthermore, based on molecular simulation, the detailed relationships between key variables were further analyzed. Meanwhile, four-dimensional color graphs were used to intuitively reveal the synergistic influence of multivariate conditions variables on pretreatment effect to obtain better economic benefits and energy consumption indicators for DES pretreatment. The results showed that HBD hydrophilic ability, HBD polarity, HBD acidity, HBD ability to form hydrogen bonds, molar ratio of HBD to choline chloride and pretreatment severity had great influence on the Choline chloride based deep eutectic solvents pretreatment effect.

Self-Healing Ti3C2 MXene/PDMS Supramolecular Elastomers Based on Small Biomolecules Modification for Wearable Sensors.

Flexible conductive composites can be used as wearable strain sensors, which are widely used in the fields of new-generation robotics, electronic skin, and human detection. However, how to make conductive composites that simultaneously possess flexibility, stretchability, self-healing, and sensing capability is challenging research. In this work, we innovatively designed and prepared a silicone polymer conductive composite. MXenes and amino poly(dimethylsiloxane) were modified by small biomolecules via an esterification reaction and a Schiff base reaction, respectively. The modified MXenes are uniformly dispersed, which endows the composite with good electrical conductivity. The reversibility of multiple hydrogen bonds and imine bonds in the composite system makes it have ideal tensile properties and high-efficiency self-healing ability without external stimulation. The conductive composite containing 10 wt % A-MXenes showed an elongation of 81%, and its mechanical strength could reach 1.81 MPa. After repair, the tensile properties and the electrical conductivity could be restored to 98.4 and 97.6%, respectively. In addition, the conductive composite is further evaluated for the value of wearable strain sensors. Even after cut-healed processes, the conductive composite can still accurately detect tiny human movements (including speaking, swallowing, and pressing). This kind of self-healing MXene/PDMS elastomers based on the modification of small biomolecules has great potential as wearable strain sensors. This simple preparation method provides guidance for future multifunctional flexible electronic materials.

A facile preparation of FePt-loaded few-layer MoS2 nanosheets nanocomposites (F-MoS2-FePt NCs) and their application for colorimetric detection of H2O2 in living cells.

BACKGROUND: Rapid and sensitive detection of H2O2 especially endogenous H2O2 is of great importance for series of industries including disease diagnosis and therapy. In this work, uniform FePt nanoparticles are successfully anchored onto Few-layer molybdenum disulfide nanosheets (F-MoS2 NSs). The powder X-ray diffraction, transmission electron microscopy, UV-Vis spectra and atomic force microscopy were employed to confirm the structure of the obtained nanocomposites (F-MoS2-FePt NCs). The prepared nanocomposites show efficient peroxidase-like catalytic activities verified by catalyzing the peroxidation substrate 4,4'-diamino-3,3',5,5'-tetramethylbiphenyl (TMB) with the existence of H2O2. RESULTS: The optimal conditions of the constructed colorimetric sensing platform is proved as 35 °C and pH 4.2. Under optimal catalytic conditions, the detection limit for H2O2 detection reaches 2.24 µM and the linear ranger is 8 µM to 300 µM. Furthermore, the proposed colorimetric sensing platform was successfully utilized to detect the intracellular H2O2 of cancer cells (MCF-7). CONCLUSIONS: These findings indicated that the F-MoS2-FePt-TMB-H2O2 system provides a potential sensing platform for hydrogen peroxide monitoring in living cells.

Itaconic Acid Based Surfactants: I. Synthesis and Characterization of Sodium n-Octyl Sulfoitaconate Diester Anionic Surfactant.

A novel itaconate-based surfactant, namely sodium n-octyl sulfoitaconate diester (SOSID), has been synthesized from itaconic acid (IA) and n-octanol by sulfonation and esterification reaction processes. The effects of reaction temperature, reaction time, molar ratios of n-octanol to IA and the catalyst dosage on the esterification were investigated. The chemical structure of the surfactants SOSID was characterized by means of LC-MS and confirmed by FT-IR and 1H NMR spectroscopy. The surface tension γ and the critical micelle concentration (CMC) were determined as 25.02 mN/m and 4.0 × 10-4 mol/L by using surface tensiometer at 20 °C. Further investigations showed that SOSID possess excellent wetting, emulsifying and lime soap dispersing properties.