Room Temperature Ca2+-Initiated Free Radical Polymerization for the Preparation of Conductive, Adhesive, Anti-freezing and UV-Blocking Hydrogels for Monitoring Human Movement.

In recent years, conductive hydrogels have received increasing attention as wearable electronics due to the electrochemical properties of conductive polymers combined with the softness of hydrogels. However, conventional hydrogels are complicated to prepare, require high temperature or UV radiation to trigger monomer polymerization, and are frozen at low temperatures, which seriously hinder the application of flexible wearable devices. In this paper, a conductive sensor integrating mechanical properties, adhesion, UV shielding, anti-dehydration, and anti-freeze was prepared based on Ca2+-initiated radical polymerization at room temperature using the synergy of sodium lignosulfonate, acrylamide (AM), and calcium chloride (CaCl2). Metal ions can activate ammonium persulfate to generate free radicals that allow rapid gelation of AM monomers at room temperature without external stimuli. Due to ionic cross-linking and non-covalent interaction, the hydrogels have good tensile properties (1153% elongation and 168 kPa tensile strength), high toughness (758 KJ·m-3), excellent adhesive properties (48.5 kPa), high ionic conductivity (7.2 mS·cm-1), and UV resistance (94.4%). CaCl2 can inhibit ice nucleation, so that the hydrogels have anti-dehydration and frost resistance properties and even at -80 °C can maintain flexibility, high conductivity, and adhesion. Assembled into a flexible sensor, it can sense various large and small movements such as compression, bending, and talking, which is a flexible sensing material with wide application prospects.

Intelligent hydrogel with both redox and thermo-response based on cellulose nanofiber for controlled drug delivery.

The purpose of this study is to develop a hydrogel with temperature and redox response to control drug delivery. However, the strength of temperature sensitive N-isopropylacrylamide (NIPAM) hydrogel is weak. Therefore, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) oxidized cellulose nanofiber (CNF) is introduced to improve this problem. The compressive strength of hydrogels increased by 360% after CNF addition. Meanwhile, N,N'-bis(acryloyl)cystamine (BACy) is introduced into the hydrogels as a cross-linker, imparting redox responsive properties to the hydrogels. Tumor therapeutic drugs are used as model drugs for in vitro release studies. The drug release rate of hydrogel is regulated by temperature and reducing environment. The maximum cumulative release rate of doxorubicin (DOX) is 39.56%, and the Berberine (BBR) is 99.50% after 60 h. The swelling and transparency of hydrogels showed dramatic changes in the range of 30-40 °C. Cytotoxicity experiments demonstrated that the hydrogel had almost no cytotoxicity.

Characterization of bacterial cellulose composite films incorporated with bulk chitosan and chitosan nanoparticles: A comparative study.

Ternary composite films containing bulk chitosan (CS) and chitosan nanoparticles (CSNPs) with different concentrations were prepared using bacterial cellulose/poly(vinyl alcohol) as the base film and the composites films were compared. The micromorphology and mechanical, physical, chemical, antibacterial, and optical barrier properties of the composite films were compared. CS incorporation improved the mechanical properties, as the maximum tensile strength was increased to 130.55 ± 9.42 MPa. The dense structure of CSNPs prevented water diffusion and lessened the water content of the composite membranes. The inclusion of CS and CSNPs both reduced the water solubility and water vapor permeability. CS-doped films possessed good transparency, while CSNPs had better ultraviolet-barrier properties (3.84 % of transmittance at 200-280 nm). In addition, CSNPs-embedded membranes exhibited prominent antibacterial properties against Escherichia coli and Staphylococcus aureus, which were much greater than those of CS composite membranes with a maximum bacteriostatic diameter of 10.33 ± 1.55 mm.

Preparation and properties of a highly elastic galactomannan- poly(acrylamide- N, N-bis (acryloyl) cysteamine) hydrogel with reductive stimuli-responsive degradable properties.

An oxidation-reduction responsive degradable highly elastic galactomannan hydrogel was synthesized from galactomannan (GA), N,N-bis (acryloyl) cysteamine (BAC) and acrylamide by grafting polymerization in aqueous solution. The microstructure, degradability and mechanical properties of the hydrogels were emphatically investigated using Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), ultraviolet spectroscopy and differential scanning calorimetry (DSC). The mechanical properties of hydrogels can be improved by adjusting the content of GA. Continuous cyclic compression tests showed that the hydrogel did not rupture under 60 %,70 %,80 % strain and quickly recovered to its original shape. The degradation rate and drug release rate of hydrogel can be adjusted by the concentration of the reductant and the reduction time. These hydrogels broaden the scope of application of GA and can be tuned with a broad range of mechanical, degradation and release properties and therefore hold potential applications in drug carriers, tissue engineering scaffolds, extracellular matrix and other fields.

Preparation and Drug Release Properties of a Thermo Sensitive GA Hydrogel.

A high-strength galactomannan (GA)-based hydrogel with thermal response and pH response is introduced in this paper. GA, N-isopropylacrylamide (NIPAM), N-[3-dimethylamino)propyl]methylacrylamide (DMAPMA), and montmorillonite were used to form hydrogels through a simple mixed static system. Fourier-transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM) were used to characterize the structure and properties of the hydrogels. The compressive strength of the the hydrogel increased from 23.9 to 105.61 kPa with the increase of GA dosage from 0 to 1.5 wt%. When the NIPAM content in the monomer increased from 75% to 95%, the lower critical solution temperature (LCST) of the hydrogel changed from 36.5 to 45.8 °C. When the monomer content was higher than 10wt%, the swelling kinetics of the sample changed from the second-order equation to the first-order equation. With the increase of the proportion of NIPAM monomer, the release rate of bovine serum album in the early stage was faster, and the cumulative release rate was close to 100%.The release rate of bovine serum albumin at 37 °C was higher than that at 25 °C. The release rate of the hydrogel containing bovine serum albumin was the fastest under the condition of pH 7.4, followed by those at pH 6.6 and pH 5.0. The results showed that this thermal-responsive hydrogel has potential applications as a drug carrier for colon delivery.

Design of diversified self-assembly systems based on a natural rosin-based tertiary amine for doxorubicin delivery and excellent emulsification.

A novel rosin-based ester tertiary amine (RETA) with three hydrophilic groups and a rigid hydrophobic group was synthesized from rosin by Diels-Alder addition, acylation and esterification reactions. RETA was characterized by infrared spectroscopy (FT-IR) and proton nuclear magnetic resonance spectroscopy (13C NMR). Results from testing surface tension, zeta potential, and transmission electron spectroscopy showed that RETA had unique pH responsiveness. RETA self-assembled into worm-like micelles, spherical micelles 130 nm in diameter and big spherical worm-like aggregates with diameter of 2 µm at pH = 5.76, 8.04 and 9.38, respectively. The critical micelle concentration (CMC) of RETA was 0.42 mmol/L, and the surface tension at CMC (γcmc) was 38.73 mN/m when pH was 8.04. The RETA had a potential application in delivering doxorubicin hydrochloride (DOX) due to the pH responsiveness. Self-assembly mixed systems of RETA and rosin-based phosphoric acid (DDPD) were designed to improve emulsification. The mixed systems had obvious synergistic effects and unexpected emulsification. The γcmc and CMC of mixtures were 41.74 mN/m and 0.20 mmol/L, the size of mixture micelles increased up to 300 nm in the optimum molar ratio of RETA/DDPD (7:3) by TEM and cryo-TEM. It was worth noting that the mixture system formed vesicles in the RETA/DDPD molar ratio of 5:5. The stability time of emulsion with RETA and DDPD as emulsifier were only 63 s and 52 s respectively, but the stability time increased to 234 s in the optimum molar ratio. In addition, the formation mechanisms of micelles at different pH and in various mixtures were discussed in detail. What's more, cytotoxicity results showed that the toxicity of RETA was lower significantly than that of lecithin, a food ingredient in egg yolk and soybean. The cell viability was more than 83% in the high concentration of RETA (4000 µg/ml).

Characterization of Fractional Polysaccharides from Gleditsia sinensis and Gleditsia microphylla Gums.

The seeds of Gleditsia sinensis and Gleditsia microphylla, widespread in China, are an important source of galactomannans. G. sinensis gum (GSG) and G. microphylla gum (GMG) were purified and precipitated using different concentrations of ethanol and isopropanol. The GSG and GMG, precipitated in different stages, presented different characteristics, including polymer recovery, mannose/galactose ratio, chemical composition, molecular weight, and morphological appearance. The galactomannan recovery of GSG and GMG in 33.3% ethanol was 81.7% and 82.5%, respectively, while that in 28.8% isopropanol was 81.3% and 82.9%, respectively. To achieve similar precipitation efficiency, the amount of isopropanol should be lower than that of ethanol because of the lower dielectric constant of isopropanol (20 vs. 25 for ethanol). The precipitation behavior of galactomannans in polar organic solvents was dependent on the molecular structures and properties of the solvent. A higher mannose/galactose ratio and a higher molecular weight was obtained in a lower concentration of alcohols.

Enhancement of Gleditsia sinensis gum rheological properties with pressure cell treatment in semi-solid state.

The apparent viscosity, molecular weight, and molecular weight distribution are important physical properties that determine the functional properties of galactomannan gum. Gleditsia sinensis gum (GSG) in semi-solid state was pressure cell treated over a range of temperature (30-110 °C) under nitrogen maintained at a pressure of 1.0-4.0 MPa. Physicochemical properties of GSG samples both before and after the pressure cell treatment were characterized. These include measurements of rheological properties by LVDV-III Ultra Rheometer, molecular weight and radius of gyration by light scattering, and changes in surface morphology by scanning electron microscopy. GSG had the highest apparent viscosity at a treatment temperature of 30 °C; further increase in temperature led to decrease in apparent viscosity. The apparent viscosity of GSG can be efficiently improved at room temperature and low pressure. The process of pressure cell treatment of GSG in semi-solid state could be industrialized for enhancement of rheological properties of galactomannan gum.

In situ grafting silica nanoparticles reinforced nanocomposite hydrogels.

Highly flexible nanocomposite hydrogels were prepared by using silica nanoparticles (SNPs) as fillers and multi-functional cross-links to graft hydrophilic poly(acrylic acid) (PAA) by free radical polymerization from an aqueous solution. The SNPs were collected by neighboring polymer chains and dispersed uniformly within a PAA matrix. The mechanical properties of the nanocomposite hydrogels were tailored by the concentration of SNPs according to the percolation model. It was proposed that covalent bonds of adsorbed chains on the filler surface resulted in the formation of a shell of an immobilized glassy layer and trapped entanglements, where the glassy polymer layer greatly enhanced the elastic modulus and the release of trapped entanglements at deformation contributed to the viscoelastic properties.

Mechanical and viscoelastic properties of cellulose nanocrystals reinforced poly(ethylene glycol) nanocomposite hydrogels.

The preparation and mechanical properties of elastomeric nanocomposite hydrogels consisting of cellulose nanocrystals (CNCs) and poly(ethylene glycol) (PEG) are reported. The aqueous nanocomposite CNC/PEG precursor solutions covalently cross-linked through a one-stage photocross-linking process. The mechanical properties of nanocomposite hydrogels, including Young's modulus (E), fracture stress (σ), and fracture strain (ε), were measured as a function of CNC volume fraction (φCNC, 0.2-1.8%, v/v) within polymeric matrix. It was found that the homogeneously dispersed nanocomposite hydrogels can be prepared with φCNC being less than 1.5%, whereas the heterogeneous nanocomposite hydrogels were obtained with φCNC being higher than 1.5%. The nanocomposite hydrogels exhibited higher strengths and flexibilities when compared with neat PEG hydrogels, where the modulus, fracture stress, and fracture strain enhanced by a factor of 3.48, 5, and 3.28, respectively, over the matrix material alone at 1.2% v/v CNC loading. Oscillatory shear data indicated the CNC-PEG nanocomposite hydrogels were more viscous than the neat PEG hydrogels and were efficient at energy dissipation due to the reversible interactions between CNC and PEG polymer chains. It was proposed that the strong gel viscoelastic behavior and the mechanical reinforcement were related to "filler network", where the temporary interactions between CNC and PEG interfered with the covalent cross-links of PEG.