RESUMO
Azobenzene (azo)-based photothermal energy storage systems have garnered great interest for their potential in solar energy conversion and storage but suffer from limitations including rely on solvents and specific wavelengths for charging process, short storage lifetime, low heat release temperature during discharging, strong rigidity and poor wearability. To address these issues, an azo-based fabric composed of tetra-ortho-fluorinated photo-liquefiable azobenzene monomer and polyacrylonitrile fabric template is fabricated using electrospinning. This fabric excels in efficient photo-charging (green light) and discharging (blue light) under visible light range, solvent-free operation, long-term energy storage (706 days), and good capacity of releasing high-temperature heat (80-95 °C) at room temperature and cold environments. In addition, the fabric maintains high flexibility without evident loss of energy-storage performance upon 1500 bending cycles, 18-h washing or 6-h soaking. The generated heat from charged fabric is facilitated by the Z-to-E isomerization energy, phase transition latent heat, and the photothermal effect of 420 nm light irradiation. Meanwhile, the temperature of heat release can be personalized for thermal management by adjusting the light intensity. It is applicable for room-temperature thermal therapy and can provide heat to the body in cold environments, that presenting a promising candidate for wearable personal thermal management.
RESUMO
Development of renewable energy technologies has been a significant area of research amongst scientists with the aim of attaining a sustainable world society. Solar thermal fuels that can capture, convert, store, and release solar energy in the form of heat through reversible photoisomerization of molecular photoswitches such as azobenzene derivatives are currently in the limelight of research. Herein, we provide a state-of-the-art account on the recent advancements in solar thermal fuels based on azobenzene photoswitches. We begin with an overview on the importance of azobenzene-based solar thermal fuels and their fundamentals. Then, we highlight the recent advances in diverse azobenzene materials for solar thermal fuels such as pure azobenzene derivatives, nanocarbon-templated azobenzene, and polymer-templated azobenzene. The basic design concepts of these advanced solar energy storage materials are discussed, and their promising applications are highlighted. We then introduce the recent endeavors in the molecular design of azobenzene derivatives toward efficient solar thermal fuels, and conclude with new perspectives on the future scope, opportunities and challenges. It is expected that continuous pioneering research involving scientists and engineers from diverse technological backgrounds could trigger the rapid advancement of this important interdisciplinary field, which embraces chemistry, physics, engineering, nanoscience, nanotechnology, materials science, polymer science, etc.
RESUMO
It is highly challenging to achieve an optically deformable polymer with good controllability, stability, and self-healability for fabricating an optically controlled microrobotics. Here, we present a photo-responsive self-healing supramolecular assembly cross-linked by 3,3',5,5'-azobenzenetetracarboxylic acid (t-Azo) enabling the controllable and stable deformation. The network (PAA-u) of polyacrylic acid (PAA) grafted with 2-ureido-4[1 H]-pyrimidinone (UPy) is formed via multiple intermolecular hydrogen bonds (H-bonds) between UPy and t-Azo moieties. Molecular H-bonds stabilize the cis-isomer, enables stress transfer at the interface, and also contributes to fast healability. The PAA-u/t-Azo assembly shows a green-light-induced bending deformation, which recovers its shape under the irradiation of UV light. On the basis of this controllable and reversible deformation, the PAA-u/t-Azo "hand" realizes reversible light-driven grabbing and releasing of an object by optimizing bending and recovery. The assembly also shows a fast and excellent self-healing performance irradiated by green light during deformation. The multiple-H-bonding-cross-linked assembly with stable deformation and fast self-healability can be used for the development of a multitude of advanced microrobotics.
RESUMO
The development of electrochemical methods for enantioselective recognition is a focus of research in pharmaceuticals and biotechnology. In this study, a pair of water-soluble chiral 3,4-ethylenedioxythiophene (EDOT) derivatives, (R)-2'-hydroxymethyl-3,4-ethylenedioxythiophene ((R)-EDTM) and (S)-2'-hydroxymethyl-3,4-ethylenedioxythiophene ((S)-EDTM), were synthesized and electrodeposited on the surface of a glassy carbon electrode (GCE) via current-time (I-t) polymerization in an aqueous LiClO4 electrolyte. These chiral PEDOT polymers were used to fabricate chiral sensors and to investigate the enantioselective recognition of d-/l-3,4-dihydroxyphenylalanine, d-/l-tryptophan, and (R)-/(S)-propranolol enantiomers, respectively. The results indicated that the (R)-PEDTM/GCE sensor showed a higher peak current response toward the levo or (S) forms of the tested enantiomers, while the opposite phenomenon occurred for (S)-PEDTM/GCE. The mechanism of the stereospecific interaction between these enantiomers and the chiral polymers was determined. Therefore, a model of the chiral recognition by the chiral conducting polymer electrodes and an electrochemical method was proposed. The chirality of the enantiomers was confirmed by two parameters: the chirality of the electrode and the peak current response. These findings pave the way for the application of chiral PEDOT as electrode modification material in the electrochemical chiral recognition field.