In-situ preparation and electrochromic properties of TiO2/PTPA-HTAN core-shell nanocomposite film

A new star-shaped structure conjugated microporous polymers, poly (2,8,14-tri[4-diphenyl-benzene]-hexaazatrinaphthylene) (PTPA-HATN), was designed and in-situ electrochemically polymerized on the surfaces of FTO electrodes with a directional alignment TiO₂ nanorod array to obtain TiO₂/PTPA-HATN core-shell nanocomposite films. Compared with the PTPA-HATN film, the TiO₂/PTPA-HATN composite film exhibits higher optical contrast and faster response time, with contrast of 57% at 783 nm, coloring time of 3.62 s and discoloring time of 2.55 s (43%, 4.63 s and 4.77 s for PTPA-HATN film, respectively). After 400 cycles, the contrast of nanocomposite film decreased by 28%, while the PTPA-HATN film basically lost its electrochromic properties. A simple three-layer EC prototype device based on TiO₂/PTPA-HATN nanocomposite film constructed with hydrogel electrolyte clearly shows color changes at different voltages. On the one hand, the formation of core-shell porous nanostructure of TiO₂/PTPA-HATN composite film provides a larger ion doping/de-doping interface, shortening the average diffusion length of ions. On the other hand, the large indented polymer-nanorods contact interface makes it difficult for the polymer to detach from the electrode, thus significantly improving the cyclic stability of the composite film.     

丙烯酸水溶液聚合法制备PTFE/PAA/Nafion膜及其性能

采用廉价的多孔聚四氟乙烯(PTFE)膜作为基底, 用少量的Nafion与PTFE膜复合可制备低成本的质子膜. 但疏水性的PTFE膜与亲水性的Nafion膜结合性不佳. 基于此, 本文对疏水性的PTFE膜材料表面进行设计, 先采用丙烯酸对疏水性的PTFE膜表面进行亲水性改性, 再喷涂亲水性Nafion膜, 完成低成本PTFE/PAA/Nafion膜的制备. 实验结果表明, 改性前的PTFE膜材料水接触角为150°, 改性后的膜接触角变为55.6°, 亲水性大幅上升, 膜的机械强度和尺寸稳定性(断裂强度为25.2 MPa, 80 ℃下的溶胀率为11.9%)均优于Nafion117膜, 而 Nafion用量则节省了60%. PTFE/PAA/Nafion膜具有高质子导通率(80 ℃下达到131.9 mS/cm), 接近于Nafion117膜, 最大功率密度可以达到404.2 mW/cm².     

Stealth Liposomes (PEGylated) Containing an Anticancer Drug Camptothecin: In Vitro Characterization and In Vivo Pharmacokinetic and Tissue Distribution Study

Numerous attempts to overcome the poor water solubility of cam ptothecin (CPT) by various nano drug delivery systems are described in various sources in the literature. However, the results of these approaches may be hampered by the incomplete separation of free CPT from the formulations, and this issue has not been investigated in detail. This study aimed to promote the solubility and continuous delivery of CPT by developing long-lasting liposomes using various weights (M.W. 2000 and 5000 Daltons) of the hydrophilic polymer polyethylene glycol (PEG). Conventional and PEGylated liposomes containing CPT were formulated via the lipid film hydration method (solvent evaporation) using a rotary flash evaporator after optimising various formulation parameters. The following physicochemical characteristics were investigated: surface morphology, particle size, encapsulation efficiency, in vitro release, and formulation stability. Different molecular weights of PEG were used to improve the encapsulation efficiency and particle size. The stealth liposomes prepared with PEG₅₀₀₀ were discrete in shape and with a higher encapsulation efficiency (83 ± 0.4%) and a prolonged rate of drug release (32.2% in 9 h) compared with conventional liposomes (64.8 ± 0.8% and 52.4%, respectively) and stealth liposomes containing PEG₂₀₀₀ (79.00 ± 0.4% and 45.3%, respectively). Furthermore, the stealth liposomes prepared with PEG₅₀₀₀ were highly stable at refrigeration temperature. Significant changes were observed using various pharmacokinetic parameters (mean residence time (MRT), half-life, elimination rate, volume of distribution, clearance, and area under the curve) of stealth liposomes containing PEG₂₀₀₀ and PEG₅₀₀₀ compared with conventional liposomes. The stealth liposomes prepared with PEG₅₀₀₀ showed promising results with a slow rate of release over a long period compared with conventional liposomes and liposomes prepared with PEG₂₀₀₀, with altered tissue distribution and pharmacokinetic parameters.     

Vanadium-Substituted Dawson-Type Polyoxometalate–TiO2 Nanowire Composite Film as Advanced Cathode Material for Bifunctional Electrochromic Energy-Storage Devices

Polyoxometalates (POMs) demonstrate potential for application in the development of integrated smart energy devices based on bifunctional electrochromic (EC) optical modulation and electrochemical energy storage. Herein, a nanocomposite thin film composed of a vanadium-substituted Dawson-type POM, i.e., K₇[P₂W₁₇VO₆₂]·18H₂O, and TiO₂ nanowires were constructed via the combination of hydrothermal and layer-by-layer self-assembly methods. Through scanning electron microscopy and energy-dispersive spectroscopy characterisations, it was found that the TiO₂ nanowire substrate acts as a skeleton to adsorb POM nanoparticles, thereby avoiding the aggregation or stacking of POM particles. The unique three-dimensional core−shell structures of these nanocomposites with high specific surface areas increases the number of active sites during the reaction process and shortens the ion diffusion pathway, thereby improving the electrochemical activities and electrical conductivities. Compared with pure POM thin films, the composite films showed improved EC properties with a significant optical contrast (38.32% at 580 nm), a short response time (1.65 and 1.64 s for colouring and bleaching, respectively), an excellent colouration efficiency (116.5 cm² C⁻¹), and satisfactory energy-storage properties (volumetric capacitance = 297.1 F cm⁻³ at 0.2 mA cm⁻²). Finally, a solid-state electrochromic energy-storage (EES) device was fabricated using the composite film as the cathode. After charging, the constructed device was able to light up a single light-emitting diode for 20 s. These results highlight the promising features of POM-based EES devices and demonstrate their potential for use in a wide range of applications, such as smart windows, military camouflage, sensors, and intelligent systems.     

Photocatalytic and antifouling properties of TiO2-based photocatalytic membranes

Photocatalysis has been extensively studied due to its potential ability to avoid the excessive use of chemical reagents and reduce the energy consumption by employing solar energy. Moreover, to alleviate the reduction in the membrane permeation selectivity, separation efficiency, and membrane service life caused by the emerging micro-pollutants and membrane fouling, membrane technology is often coupled with microbial, electrochemical, and catalytic processes. However, although physical/chemical cleaning and membrane module replacement can overcome the inherent limitations caused by membrane fouling and other membrane separation processes, high operating costs limit their practical applications. In this review, common preparation methods for TiO₂ photocatalytic membranes are described in detail, and the main approaches to enhancing their photocatalytic performance are discussed. More importantly, the mechanism of the TiO₂ photocatalytic membrane antifouling process is elucidated, and some applications of photocatalytic membranes in other areas are described. This review systematically outlines future research directions in the field of photocatalytic membrane modification, including metal and non-metal doping, fabrication of heterojunction structures, control over reaction conditions, increase in hydrophilicity, and increase in membrane porosity.     

石墨烯玻璃透明薄膜加热特性

Graphene has become a research focus in recent years owing to its excellent characteristics, and glass is a commonly used material with high transparency and low cost. Graphene glass combines the excellent properties of both graphene and glass; graphene glass has not only high thermal conductivity, high electrical conductivity, and good surface hydrophobicity but also exhibits superior electrothermal conversion and wide-spectrum high-light-transmittance characteristics. Therefore, the study of graphene glass films is of theoretical value and practical significance. In this study, a high-purity glass-based (JGS1 quartz glass) multilayer graphene film was developed based on an atmospheric-pressure chemical vapor deposition (APCVD) method, and its electrical characteristics, light transmittance, and electrical heating characteristics were experimentally investigated in detail. The results show that graphene glass with different surface resistance values obtained through direct growth on a high-purity quartz glass substrate using the APCVD method, not only has excellent uniformity and quality, but also has considerably flat and high transmittance across the entire visible light region and exhibits excellent heating performance and fast response time. For graphene glass with a surface resistance of 1500 Ω·sq^-1, the light transmittance can reach 74%, and the saturation temperature can rise to 185 ℃ by applying a bias voltage of 40 V. In addition, when the resistance value of the graphene glass is 420 Ω·sq^-1, the graphene glass reaches a high saturation temperature of 325 ℃ in 40 s, and the corresponding heating rate can exceed 18 ℃·s^-1, achieving a significantly higher heating rate than other heating films at the same voltage. Compared with the polyethylene-terephthalate- (PET-) based and silicon-based graphene films obtained by the transfer, graphene glass has a higher saturation temperature, shorter thermal response time, and faster heating rate. Furthermore, graphene glass exhibits better heating cycle stability and longer-term heating stability at a constant voltage. In addition, an experiment using the graphene glass to thermally tune the wavelength of a vertical-cavity surface-emitting laser was conducted and gave good results. The position of the laser peak controlled by the graphene glass was red-shifted by 1.78 nm by applying a voltage of 20 V, and the wavelength tuning efficiency reached 0.059 nm·℃^-1. Compared with PET-based and silicon-based graphene films, the actual electrical heating capacity of graphene glass increased by 195%. These experimental findings demonstrate that graphene glass transparent films with excellent electric heating characteristics can be used in various transparent electric heating fields and have relatively wide application prospects.     

铋基钙钛矿(CH3NH3)3Bi2I9薄膜的制备及在光伏电池中的应用

铋基钙钛矿由于稳定性强及毒性低,被认为是未来极具发展潜力的环保型钙钛矿材料。(CH₃NH₃)₃Bi₂I₉(MBI)因具有优异的光吸收性能而引起人们的普遍关注。本文介绍了MBI钙钛矿晶体的结构及性能,总结了其薄膜的制备方法,并重点叙述了不同方法制备的MBI钙钛矿薄膜在光伏电池中的应用情况。MBI钙钛矿与铅基钙钛矿的效率相比还有很大差距,如何提高其光电转换效率仍是今后研究的主要方向。     

Regular conjugated terpolymers comprising two different acceptors and bithiophene donor in repeating group: Effect of strong and weak acceptors on semiconducting properties

Diketopyrrolopyrrole (DPP)‐based terpolymers—P(DPP‐TPyT) and P(DPP‐T3MTT)—bearing bithiophene donating groups and weak accepting units such as pyridine (Py) or methyl thiophene‐3‐carboxylate (3MT), in the polymer backbone, were successfully synthesized. Although the two polymers had similar physical and electrochemical properties, grazing incidence X‐ray diffraction patterns of P(DPP‐TPyT) and P(DPP‐T3MTT) showed mixed and edge‐on orientations, respectively, in thermally annealed films. Accordingly, the P(DPP‐T3MTT) showed twice the hole mobility of P(DPP‐TPyT) in a thin‐film transistor, and a blended film of P(DPP‐T3MTT) and [6,6]‐phenyl‐C71‐butyric acid methyl ester (PC₇₁BM) showed better power conversion efficiency in a polymer solar cell. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1339‐1347     

Thickness dependence of thermally induced changes in surface and bulk properties of Nafion® nanofilms

Thermally induced changes in surface wettability, dewetting behavior, and proton transport of “self‐assembled” nanothin Nafion^® films (4–300 nm) on SiO₂ substrate is reported. Thermal annealing induces switching of the surface wettability of 55 nm and thinner films from hydrophilic to super‐hydrophobic. Thickness dependence of this behavior is observed with higher annealing temperature required for lower thickness films, indicating highly restrictive mobility of Nafion^® ionomer as film thickness decreases. Dewetting is only observed for 4‐nm thin film. Significant suppression in proton conductivity upon thermal annealing was noted. Similarly, two other bulk properties, water uptake and swelling, were found to decrease upon annealing. This work reports a systematic examination of the thickness dependence of thermally induced changes in both surface and bulk properties of ultra‐thin Nafion^®. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1267–1277     

How preparation and modification parameters affect PB‐PEO polymersome properties in aqueous solution

The effect of formation and modification methods on the physical properties of polymersomes is critical for their use in applications relying on their ability to mimic functional properties of biological membranes. In this study, we compared two formation methods for polymersomes made from polybutadiene‐polyethylene oxide diblock copolymers: detergent‐mediated film rehydration (DFR) and solvent evaporation (SE). DFR‐prepared polymersomes showed a three times higher permeability compared to SE‐prepared polymersomes as revealed by stopped‐flow light scattering. SE‐prepared polymersomes broke down faster to structures <50 nm diameter when processed with extrusion, which was more pronounced at 5 mg mL^?1, compared to 10, 20, and 25 mg mL^?1. Our results indicate that the bilayer of SE‐prepared polymersomes has a lower apparent fluidity. We also investigated the role of n‐octyl‐β‐d ‐glucopyranoside (OG), a detergent typically used for reconstitution of membrane proteins into lipid bilayers. Specifically, we compared dialysis and biobeads for OG removal to investigate the influence of these methods on bilayer conformation and polymer rearrangement following detergent removal. There was no significant difference found between method, temperature, or time within each method. Our findings provide insight on how biocompatible polymersome production affects the physical properties of the resulting polymersomes. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1581–1592