Contact Piezoresistive Sensors Based on Electro-Polymerized Polypyrrole and a Regulated Conductive Pathway.

The performance of contact resistive pressure sensors heavily relies on the intrinsic characteristics of the active layers, including the mechanical surface structure, conductivity, and elastic properties. However, efficiently and simply regulating the conductivity, morphology, and modulus of the active layers has remained a challenge. In this study, we introduced electro-polymerized polypyrrole (ePPy) to design flexible contact piezoresistive sensors with tailored intrinsic properties. The customizable intrinsic property of ePPy was comprehensively illustrated on the chemical and electronic structure scale, and the impact of ePPy's intrinsic properties on the sensing performance of the device was investigated by determining the correlation between resistivity, roughness, and device sensitivity. Due to the synergistic effects of roughness, conductivity, and elastic properties of the active layers, the flexible ePPy-based pressure sensor exhibited high sensitivity (3.19 kPa-1, 1-10 kPa, R2 = 0.97), fast response time, good durability, and low power consumption. These advantages allowed the sensor to offer an immediate response to human motion such as finger-bending and grasping movements, demonstrating the promising potential of tailorable ePPy-based contact piezoresistive sensors for wearable electronic applications.

A Photopatternable Conjugated Polymer with Thermal-Annealing-Promoted Interchain Stacking for Highly Stable Anti-Counterfeiting Materials.

Photoresponsive polymers can be conveniently used to fabricate anti-counterfeiting materials through photopatterning. However, an unsolved problem is that ambient light and heat can damage anti-counterfeiting patterns on photoresponsive polymers. Herein, photo- and thermostable anti-counterfeiting materials are developed by photopatterning and thermal annealing of a photoresponsive conjugated polymer (MC-Azo). MC-Azo contains alternating azobenzene and fluorene units in the polymer backbone. To prepare an anti-counterfeiting material, an MC-Azo film is irradiated with polarized blue light through a photomask, and then thermally annealed under the pressure of a photonic stamp. This strategy generates a highly secure anti-counterfeiting material with dual patterns, which is stable to sunlight and heat over 200 °C. A key for the stability is that thermal annealing promotes interchain stacking, which converts photoresponsive MC-Azo to a photostable material. Another key for the stability is that the conjugated structure endows MC-Azo with desirable thermal properties. This study shows that the design of photopatternable conjugated polymers with thermal-annealing-promoted interchain stacking provides a new strategy for the development of highly stable and secure anti-counterfeiting materials.

Photoswitches with different numbers of azo chromophores for molecular solar thermal storage.

We investigate three azo-chromophore-containing photoswitches (1, 2 and 3) for molecular solar thermal storage (MOST) based on reversible Z-E isomerization. 1, 2 and 3 are photoswitchable compounds that contain one, two and three azo chromophores, respectively. In solution, 1, 2 and 3 were charged via UV-light-induced E-to-Z isomerization. Among these three compounds, 2 exhibited an energy density as high as 272 ± 1.8 J g-1, which showed the best energy storage performance. This result originated from the low molecular weight, a high degree of photoisomerization, and moderate steric hindrance of 2, which demonstrated the advantages of the meta-bisazobenzene structure for MOST. In addition, we studied the performances of these photoswitches in the solvent-free state. Only 1 showed photoinduced reversible solid-to-liquid transitions, which enabled the charging of 1 in a solvent-free state. The stored energy density for 1 in a solvent-free state was 237 ± 1.5 J g-1. By contrast, 2 and 3 could not be charged in the solvent-free state due to the lack of solid-state photoisomerization. Our findings provide a better understanding of the structure-performance relationship for azobenzenebased MOST and pave the way for the development of high-density solar thermal fuels.

Designing Rewritable Dual-Mode Patterns using a Stretchable Photoresponsive Polymer via Orthogonal Photopatterning.

The fabrication of dual-mode patterns in the same region of a material is a promising approach for high-density information storage, new anti-counterfeiting technologies, and highly secure encryption. However, dual-mode patterns are difficult to achieve because the two patterns in one material may interfere with each other during fabrication and usage. The development of noninterfering dual-mode patterns requires new materials and patterning techniques. Herein, a novel orthogonal photopatterning technique is reported for the fabrication of noninterfering dual-mode patterns on an azopolymer P1. P1 is a unique material that exhibits both photoinduced reversible solid-to-liquid transitions and good stretchability. In the first step of orthogonal photopatterning, patterned photonic structures are fabricated on a P1 film via masked nanoimprinting controlled by photoinduced reversible solid-to-liquid transitions. In the second step, the P1 film is stretched and irradiated with polarized light through a photomask, which generates a chromatic polarization pattern. In particular, the photonic structures and chromatic polarization in the dual-mode pattern are noninterfering. Another feature of dual-mode patterns is that they are rewritable via photo-, thermal, or solution reprocessing, which are useful for recycling and reprogramming. This study opens an avenue for the development of novel materials and techniques for photopatterning.

KIT-related piebaldism in a Chinese girl.

Piebaldism is a rare, autosomal dominant and congenital pigmentary disorder characterized by stable depigmentation of the skin and white forelock. Mutations in KIT or SNAI2 genes result in piebaldism. Most individuals with piebaldism have a family history of the disorder. Herein, we report a 5-month-old Chinese girl with severe piebaldism but no family history thereof. She has white forelock and large patches of depigmentation in the jaw, central anterior trunk, perineum and extremities. We performed whole-exome and Sanger sequencing and identified a de novo KIT mutation (NM_000222.2: c.2657G>A, p.Gly886Val) in exon 18 of KIT in the proband. Currently, this mutation is located in the most extreme C-terminal of the tyrosine kinase domain 2 of the KIT gene amongst all reported mutations and causes a severe clinical phenotype. We further reviewed literature on piebaldism and summarized 79 KIT gene mutations that lead to this disease. Our study may expand knowledge on the genotype-phenotype correlation in piebaldism and serve as a reference for genetic counseling and prenatal diagnosis of affected families.

Photoinduced Reversible Solid-to-Liquid Transitions for Photoswitchable Materials.

Heating and cooling can induce reversible solid-to-liquid transitions of matter. In contrast, athermal photochemical processes can induce reversible solid-to-liquid transitions of some newly developed azobenzene compounds. Azobenzene is photoswitchable. UV light induces trans-to-cis isomerization; visible light or heat induces cis-to-trans isomerization. Trans and cis isomers usually have different melting points (Tm ) or glass transition temperatures (Tg ). If Tm or Tg of an azobenzene compound in trans and cis forms are above and below room temperature, respectively, light may induce reversible solid-to-liquid transitions. In this Review, we introduce azobenzene compounds that exhibit photoinduced reversible solid-to-liquid transitions, discuss the mechanisms and design principles, and show their potential applications in healable coatings, adhesives, transfer printing, lithography, actuators, fuels, and gas separation. Finally, we discuss remaining challenges in this field.

TfNHNHBoc as a SCF3 source for the sulfenylation of indoles.

An unprecedented use of trifluoromethanesulfonyl hydrazides as effective SCF3 sources has been established in the sulfenylation of indoles. A range of substituted indoles participated in CuCl-catalyzed oxidative sulfenylation reaction with TfNHNHBoc in the presence of dimethyl sulfoxide to furnish structurally diverse 3-indolyl trifluoromethyl thioethers in moderate to good yields with very high regioselectivity.

Three-component carboarylation of unactivated imines with arynes and carbon nucleophiles.

With 2-(trimethylsilyl)aryl triflates as aryne precursors, an unprecedented three-component carboarylation reaction of unactivated imines with arynes and carbon nucleophiles has been developed to access a variety of functionalized tertiary amines under transition metal-free conditions. Suitable carbon nucleophiles include chloroform, acetonitrile, and methyl propiolate.