Natural Phytic Acid-Assisted Polyaniline/Poly(vinyl alcohol) Hydrogel Showing Self-Reinforcing Features.

Polyaniline (PANi) hydrogels that combine advantages of hydrogels and conductive PANi have recently emerged in areas of wearable devices and personal healthcare. Nevertheless, their mechanical performance often gradually degrades after being used for a period, caused by destruction of the inner structures when external forces are applied. Inspired by biological structures with persistent durability, we develop here a phytic acid-assisted PANi/poly(vinyl alcohol) (PVA) hydrogel that shows self-reinforcing features. As a natural product holding plenty of phosphate groups, phytic acid (PA) plays two crucial roles when preparing this hydrogel: (1) aniline is salinized by PA in aqueous solution to promote in situ polymerization, making the resulting PANi conductive; (2) PA/PANi particles form hydrogen bonds with PVA, acting as stress concentration points to induce structure orientation. The optimal PVA/PA/PANi hydrogel displays dark green color with a uniform distribution of PA/PANi particles. After experiencing repetitive 4 × 100 stretching at a strain of 10%, the hydrogel exhibits an enhanced fracture strength (20.35 MPa), Young's modulus (22.66 MPa), and toughness (36.24 MJ·m-3) compared with the original hydrogel. This self-reinforcing feature is mainly attributed to the formation of anisotropic structures fixed by hydrogen bonds between PA/PANi particles and PVA chains upon repetitive external forces. Moreover, anisotropic structures can be disassembled by swelling the post-stretched hydrogel in water, and the swollen hydrogel shows similar self-reinforcing behaviors. The good mechanical durability and reusable characteristics make the PVA/PA/PANi hydrogel a reliable strain sensor. This work provides a structural growing-reviving approach for conductive hydrogels with persistent durability.

Incorporating Photochromic Viologen Derivative to Unprecedentedly Boost UV Sensitivity in Photoelectrochromic Hydrogel.

Developing ultraviolet (UV) radiation sensors featuring high sensitivity, ease of operation, and rapid readout is highly desired in diverse fields. However, the strategies to enhance sensitivity of UV detection remain limited particularly for photochromic materials, which show colorimetric response toward UV irradiation. Guided by our initial goal of facilitating easier handling, we formulated a viologen derivative ([H2L]-SC) incorporating hydrogel-based UV sensor which not only inherits the photochromism of [H2L]-SC but also engenders an unprecedented reversible photoelectrochromic response that is absent in either [H2L]-SC or hydrogel alone. Judicious synergy between photochromic [H2L]-SC and polyacrylamide (PAM) converts the colorimetric response of [H2L]-SC into the electrical resistance change of [H2L]-SC@PAM, which amplifies the UV sensitivity of [H2L]-SC by 2 orders of magnitude. Explicitly, the limit of detection (LOD) for UV decreases from 296.3 mJ/cm2 based on the UV-vis absorption spectra of [H2L]-SC to 2.83 mJ/cm2 derived from the resistance variation of [H2L]-SC@PAM. Moreover, linear correlation between the resistance reduction rate of [H2L]-SC@PAM and UV dose rate can be established, rendering it as a dual platform for quantifying both the accumulated UV dose and the instant dose rate. In addition, the proposed strategy based on constructing photoelectrochromic hybrids offers a new pathway to boost the UV sensitivity that could be universal for other photochromic materials.

Lignin Nanoparticles Produced from Wheat Straw Black Liquor Using γ-Valerolactone.

The valorization of the black liquor produced during the chemical pulping of wheat straw is the key to the sustainable use of this abundant agricultural waste. However, the silica problem has hampered the recovery process. Herein, nanoprecipitation technology was used to produce lignin nanoparticles (LNPs) from wheat straw black liquor using γ-valerolactone (GVL) as a solvent and water as an anti-solvent. The results showed that a uniform, well-dispersed, and stable LNP was produced. The particle size and Zeta potential of 161 nm and -24 mV of the LNP suspension were obtained at a GVL concentration of 87%. The chemical structure and bonding of the lignin were adequately preserved after nanoprecipitation based on two-dimensional heteronuclear single quantum coherence nuclear magnetic resonance (2D-HSQC NMR) spectroscopy, Fourier transform infrared (FTIR) analysis, and thermal stability was improved based on thermogravimetric analysis. In addition, the abundant phenolic hydroxyl groups of LNP quantified by 31P-NMR analysis are beneficial for chemical cross-linking and modification. This work not only achieved the valorization of wheat straw black liquor but also opened up a new avenue for advanced nanomaterials.

Natural Glycyrrhizic Acid-Tailored Homogeneous Conductive Polyaniline Hydrogel as a Flexible Strain Sensor.

Polyaniline (PANi) hydrogels often exhibit highly mechanical and electrochemical properties, which have received extensive attention in the fields of batteries, supercapacitors, and sensors. However, the shortcomings such as hydrophobicity and easy aggregation of PANi frequently result in deterioration of mechanical and electrochemical performance of PANi hydrogels. Here, a bifunctional natural product, glycyrrhizic acid (GL), is utilized to prepare the homogeneous conductive PANi hydrogel, because GL not only can assemble into supramolecular hydrogel as the biocompatible matrix but also can salinize aniline monomers to facilitate the polymerization in situ to form uniformly dispersed PANi within GL matrix. Accordingly, the resulting GL/PANi hydrogel shows the Tyndall effect caused by the nanoclusters entangled by nanofibers and exhibits an improved storage modulus G' (3.2 kPa) and loss modulus G″ (0.9 kPa), as well as the expected conductivity (0.17 S·m-1). In addition, the GL/PANi hydrogel is further reinforced by blending poly(vinyl alcohol) (PVA) for the required strength and stretchability as a flexible strain sensor. The results reveal that the obtained PVA/GL/PANi hydrogel has a fracture stress of 693 kPa at an elongation of 329%, with a fracture toughness of 82 MJ·m-3 and Young's modulus of 47.9 kPa. Its gauge factor (GF) is measured to be 2.5 at lower strain (<130%) and up to 4.3 at larger strain (>130%). This good sensitivity and sensing stability make the PVA/GL/PANi hydrogel effectively monitor relevant human motion detections. Our work provides an innovative strategy to manufacture the homogeneous conductive PANi hydrogel for high-performance soft electronic devices.