Versatile light‐responsive organogels: Evaluation of their dye releasing and photoinitiation behaviors

Light‐responsive crosslinked structures were prepared by a straightforward quaternization strategy using chloride functional polystyrene copolymers and commercially available Michler's ketone with varying feed ratios. Resulting organogels demonstrated excellent solvent absorption and their swelling characteristics were altered by UV‐light irradiation. According to scanning electron microscope images, UV‐illuminated samples showed an obvious photodecomposition, which enhanced their solvent uptake capacity with increase of UV exposure. Additionally, release behavior of eosin Y as a model compound was determined by UV–vis and fluorescence spectrometers. Achieved photoactive gels were also employed as the reusable heterogeneous initiators for photoinduced free‐radical polymerization of methyl methacrylate. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1275–1282     

A Near-Infrared-Controllable Artificial Metalloprotease Used for Degrading Amyloid-β Monomers and Aggregates

Proteolysis of amyloid-β (Aβ) is a promising approach against Alzheimer's disease. However, it is not feasible to employ natural hydrolases directly because of their cumbersome preparation and purification, poor stability, and hazardous immunogenicity. Therefore, artificial enzymes have been developed as potential alternatives to natural hydrolases. Since specific cleavage sites of Aβ are usually embedded inside the β-sheet structures that restrict access by artificial enzymes, this strongly hinders their efficiency for practical applications. Herein, we construct a NIR (near-IR) controllable artificial metalloprotease (MoS₂-Co) using a molybdenum disulfide nanosheet (MoS₂) and a cobalt complex of 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (Codota). Evidenced by detailed experimental and theoretical studies, the NIR-enhanced MoS₂-Co can circumvent the restriction by simultaneously inhibition of β-sheet formation and destroying β-sheet structures of the preformed Aβ aggregates in living cell. Furthermore, our designed MoS₂-Co is an easy to graft Aβ-target agent that prevents misdirected or undesirable hydrolysis reactions, and has been demonstrated to cross the blood brain barrier. This method can be adapted for hydrolysis of other kinds of amyloids.     

Photocatalytic decolourization of a new water-insoluble organic dye based on phenothiazine by ZnO and TiO2 nanoparticles

A new water-insoluble organic dye, namely, 2-((10-decyl-10H-phenothiazin-3-yl)methylene)malononitrile, was synthesized and fully characterized. It was envisioned that photocatalytic decolourization of a dye-containing long chain would pave the way for the photocatalytic remediation of wastewater containing toxic hydrophobic organic pollutants. Two commercially available nanoparticles, ZnO and TiO₂, were selected, and their photocatalytic decolourization of the dye from aqueous medium were compared. The black UV light irradiation of the colored samples in the presence of TiO₂ (P25) or ZnO resulted in their decolourization and the photocatalytic activity observed for TiO₂ (P25) was better than that of ZnO. The kinetic of decolourization indicated that the process was first-order from which the rate constant was calculated. Also, the effect of pHs on the kinetic of decolourization revealed a negligible effect, indicating that the pH, although it affects the catalysts but has no effect on the organic-based hydrophobic dye and thus no effect on the photocatalytic process.     

Dye Sensitization Offers a Brighter Afterglow Nanoparticle Future for in vivo Recharged Luminescent Imaging

While concerns about improving recharged afterglow intensity in vivo still motivate further exploration, afterglow nanoparticles (AGNP) offer unique optical merit for autofluorescence-free biological imaging. Apart from efforts enhancing the afterglow emission properties of AGNP, improving afterglow excitation response to visible or near infrared light is important but has lacked success. Dye sensitization has been used to improve the optical response of photovoltaic nanomaterials and to enhance upconversion luminescence efficiency. This concept has recently been expanded and applied to AGNPs. As a new multifunctional nanoprobe, such dye-sensitized AGNP takes advantage of both high spatial resolution fluorescence imaging and sensitive afterglow imaging. This Concept introduces the background, the concept, mechanism, and related imaging application, as well as reviewing existing challenges and proposing future developmental directions for the dye-sensitized AGNPs.     

染料敏化太阳能电池载流子传输的数值模拟

由于在染料敏化太阳能电池(dye-sensitized solar cell, DSSC)中存在染料弛豫、半导体薄膜中电子与氧化态染料分子发生反应和电子在电解质中与氧化态离子复合等不利反应,利用一个更完善的DSSC载流子传输模型对电池的光电性能进行模拟就显得非常重要。为此,本文基于由多重俘获理论建立的DSSC中的包括电子、染料阳离子、碘化物和三碘化物在内的载流子传输模型,数值模拟得到了不同TiO₂薄膜厚度、不同入射光强度与不同染料分子吸收系数下DSSC的J-V曲线。结果表明,随着TiO₂薄膜厚度的增加,太阳能电池的短路电流密度增大,开路电压减小,光电转换效率先增大后减小。当DSSC的TiO₂薄膜厚度为20 μm时,光电转换效率达到最大值7.41%,同时光电转换效率随入射光强度与染料分子吸收系数的增大均有一定程度提高,其中在吸收系数为4 500 cm^-1时,光电转换效率为6.73%。以上结果可以为改进DSSC的光电性能提供理论指导。     

An Easy Access to Organic Salt‐Based Stimuli‐Responsive and Multifunctional Supramolecular Hydrogels

By exploiting orthogonal hydrogen bonding involving supramolecular synthons and hydrophobic/hydrophilic interactions, a new series of simple organic salt based hydrogelators derived from pyrene butyric acid and its β‐alanine amide derivative, and various primary amines has been achieved. The hydrogels were characterised by microscopy, table‐top rheology and dynamic rheology. FTIR, variable‐temperature ¹H NMR and emission spectroscopy established the role of various supramolecular interactions such as hydrogen bonding and π–π stacking in hydrogelation. Single‐crystal X‐ray diffraction (SXRD) studies supported the conclusion that orthogonal hydrogen bonding involving amide–amide and primary ammonium monocarboxylate (PAM) synthons indeed played a crucial role in hydrogelation. The hydrogels were found to be stimuli‐responsive and were capable of sensing ammonia and adsorbing water‐soluble dye (methylene blue). All the hydrogelators were biocompatible (MTT assay in RAW 264.7 cells), indicating their suitability for use in drug delivery.     

Dye‐Sensitized Solar Cell Counter Electrodes Based on Carbon Nanotubes

Dye‐sensitized solar cells (DSSCs) have received significant attention from the scientific community since their discovery in 1991. However, the high cost and scarcity of platinum has motivated researchers to seek other suitable materials for the counter electrode of DSSCs. Owing to their exceptional properties such as high conductivity, good electrochemical activity, and low cost, carbon nanotubes (CNTs) have been considered as promising alternatives to expensive platinum (Pt) in the counter electrode of DSSCs. Herein, we provide a Minireview of the CNTs use in the counter electrode of DSSCs. A brief overview of Pt‐based counter electrodes is also discussed. Particular attention is given to the recent advances of counter electrodes with CNT‐based composite structures.     

How Does Peripheral Functionalization of Ruthenium(II)–Terpyridine Complexes Affect Spatial Charge Redistribution after Photoexcitation at the Franck–Condon Point?

Ruthenium polypyridine‐type complexes are extensively used sensitizers to convert solar energy into chemical and/or electrical energy, and they can be tailored through their metal‐to‐ligand charge‐transfer (MLCT) properties. Much work has been directed at harnessing the triplet MLCT state in photoinduced processes, from sophisticated molecular architectures to dye‐sensitized solar cells. In dye‐sensitized solar cells, strong coupling to the semiconductor exploits the high reactivity of the (hot) singlet/triplet MLCT state. In this work, we explore the nature of the ¹MLCT states of remotely substituted Ru^II model complexes by both experimental and theoretical techniques. Two model complexes with electron‐withdrawing (i.e. NO₂) and electron‐donating (i.e. NH₂) groups were synthesized; these complexes contained a phenylene spacer to serve as a spectroscopic handle and to confirm the contribution of the remote substituent to the ¹MLCT transition. [Ru(tpy)₂]²⁺‐based complexes (tpy=2,2′:6′,2′′‐terpyridine) were further desymmetrized by tert‐butyl groups to yield unidirectional ¹MLCTs with large transition dipole moments, which are beneficial for related directional charge‐transfer processes. Detailed comparison of experimental spectra (deconvoluted UV/Vis and resonance Raman spectroscopy data) with theoretical calculations based on density functional theory (including vibronic broadening) revealed different properties of the optically active bright ¹MLCT states already at the Franck–Condon point.     

Maintenance of residual activity of Bt toxin by using natural and synthetic dyes: a novel approach for sustainable mosquito vector control

Mosquito control protein from Bacillus thuringiensis gets inactivated with exposure to sunlight. To address this issue, the potential of synthetic and natural dye was investigated as sunlight protectants. Bt SV2 in absence of dyes when exposed to sunlight showed reduced effectiveness against the fourth instars of mosquito larvae. Whereas acriflavin, congo red and violacein were able to maintain 86.4%, 91.6% and 82.2% mosquito larvicidal efficacy of Bt SV2 against IVth instars larvae of Anopheles stephensi Meigen after exposure to sunlight. Similarly, beetroot dye, acriflavin, congo red and violacein maintained 98.4%, 97.1%, 90.8% and 70.7% larvicidal activities against Aedes aegypti Linnaeus after sunlight exposure. Prodigiosin was found to be the best photo-protectant by simultaneously protecting and enhancing Bt activity by 6.16% and 22.16% against A. stephensi and A. aegypti, respectively. Combination of dyes with Bt formulations can be a good strategy for mosquito control programmes in tropical and sub-tropical regions.