Piezoelectricity of the Transmembrane Protein ba3 Cytochrome c Oxidase

Controlling the electromechanical response of piezoelectric biological structures including tissues, peptides, and amino acids provides new applications for biocompatible, sustainable materials in electronics and medicine. Here, the piezoelectric effect is revealed in another class of biological materials, with robust longitudinal and shear piezoelectricity measured in single crystals of the transmembrane protein ba₃ cytochrome c oxidase from Thermus thermophilus. The experimental findings from piezoresponse force microscopy are substantiated using a range of control measurements and molecular models. The observed longitudinal and shear piezoelectric responses of ≈ 2 and 8 pm V⁻¹, respectively, are comparable to or exceed the performance of commonly used inorganic piezoelectric materials including quartz, aluminum nitride, and zinc oxide. This suggests that transmembrane proteins may provide, in addition to physiological energy transduction, technologically useful piezoelectric material derived entirely from nature. Membrane proteins could extend the range of rationally designed biopiezoelectric materials far beyond the minimalistic peptide motifs currently used in miniaturized energy harvesters, and the finding of robust piezoelectric response in a transmembrane protein also raises fundamental questions regarding the molecular evolution, activation, and role of regulatory proteins in the cellular nanomachinery, indicating that piezoelectricity might be important for fundamental physiological processes.     

Flexible,Mechanically Stable,Porous Self-Standing Microfiber Network Membranes of Covalent Organic Frameworks: Preparation Method and Characterization

Covalent organic frameworks (COFs) show advantageous characteristics, such as an ordered pore structure and a large surface area for gas storage and separation, energy storage, catalysis, and molecular separation. However, COFs usually exist as difficult-to-process powders, and preparing continuous, robust, flexible, foldable, and rollable COF membranes is still a challenge. Herein, such COF membranes with fiber morphology for the first time prepared via a newly introduced template-assisted framework process are reported. This method uses electrospun porous polymer membranes as a sacrificial large dimension template for making self-standing COF membranes. The porous COF fiber membranes, besides having high crystallinity, also show a large surface area (1153 m² g⁻¹), good mechanical stability, excellent thermal stability, and flexibility. This study opens up the possibility of preparation of large dimension COF membranes and their derivatives in a simple way and hence shows promise in technical applications in separation, catalysis, and energy in the future.     

Diluted chemical bath deposition of CdZnS as prospective buffer layer in CIGS solar cell

In this study, dilute chemical bath deposition technique has been used to deposit CdZnS thin films on soda-lime glass substrates. The structural, morphological, optoelectronic properties of as-grown films have been investigated as a function of different Zn²⁺ precursor concentrations. The X-ray diffractogram of CdS thin-film reveals a peak corresponding to (002) plane with wurtzite structure, and the peak shift has been observed with the increase of the Zn²⁺ concentration upon formation of CdZnS thin film. From morphological studies, it has been revealed that the diluted chemical bath deposition technique provides homogeneous distribution of film on the substrate even at a lower concentration of Zn²⁺. Optical characterization has shown that the transparency of the film is influenced by Zn²⁺ concentration and when the Zn²⁺ concentration is varied from 0 M to 0.0256 M, bandgap values of resulting films range from 2.42 eV to 3.90 eV while. Furthermore, electrical properties have shown that with increasing zinc concentration the resistivity of the film increases. Finally, numerical simulation validates and suggests that CdZnS buffer layer with composition of 0.0032 M Zn²⁺ concentration would be a promising candidate in CIGS solar cell.     

BMS Derivatives C7-Linked to β-Cyclodextrin and Hyperbranched Polyglycerol Retain Activity against R5-HIV-1NLAD8 Isolates and Can Be Deemed Potential Microbicides

Amides from indole-3-glyoxylic acid and 4-benzoyl-2-methylpiperazine, which are related to entry inhibitors developed by Bristol-Myers Squibb (BMS), have been synthesized with aliphatic chains located at the C7 position of the indole ring. These spacers contain an azido group suitable for the well-known Cu(I)-catalyzed (3+2)-cycloaddition or an activated triple bond for the nucleophilic addition of thiols under physiological conditions. Reaction with polyols (β-cyclodextrin and hyperbranched polyglycerol) decorated with complementary click partners has afforded polyol-BMS-like conjugates that are not cytotoxic (TZM.bl cells) and retain the activity against R5-HIV-1_NLAD8 isolates. Thus, potential vaginal microbicides based on entry inhibitors, which can be called of 4^th generation, are reported here for the first time.     

Impact of defects on the decomposition of chemical warfare agent simulants in Zr-based metal organic frameworks

Metal organic frameworks (MOFs) containing zirconium secondary building units (SBUs) in UiO-67 and related MOFs, are highly active for neutralizing both the chemical warfare agents and simulants, such as dimethyl methylphosphonate (DMMP). However, two recent publications gave conflicting reports of DMMP reaction with UiO-67 under ultra high vacuum (UHV) conditions, with one reporting chemisorption and reaction (Wang et al., J Phys Chem C, 2017, 121, 11261–11272) and the other reporting only physisorption and reversible desorption (Ruffley et al., J Phys Chem C, 2019, 123, 19748–19758) from very similar temperature programmed desorption experiments. We show that the discrepancy between these experiments may be explained by different levels of missing linker defects in the UiO-67 samples. We present density functional theory calculations showing that SBU sites having two-adjacent missing linkers exhibit reaction barriers that are about 30 kJ/mol lower than SBU sites having a single missing linker. We also show that topology of the undercoordinated sites plays an important role in the reaction barrier under UHV conditions.     

Deep-blue thermally activated delayed fluorescence emitter with a very high fluorescence rate

Conventional thermally activated delayed fluorescence (TADF) molecules achieve small energy differences between the lowest singlet and triplet excited states (ΔE_ST) by enhancing the intramolecular charge transfer, which inevitably leads to a wide emission spectrum and low fluorescence rate. Here, we prepared a deep blue TADF molecule via a small ΔE_ST pyridine-phenol fluoroboron complex as the acceptor. The small ΔE_ST is maintained when carbazole donors are attached to the 4-position of the phenyl rings in the fluoroboron complex. Benefiting from the strong electron coupling between the donor (D) and acceptor (A) moieties, the compound Cz-4-BF exhibits a high fluorescence rate of 4.8 × 10⁸ s⁻¹ and a small D-A dihedral angle change in the excited state. Consequently, a photoluminescence (PL) quantum yield of nearly 100% and a PL spectrum with full-width at half-maximum (FWHM) < 60 nm were obtained in solution and low-concentration doped films. A TADF-sensitized fluorescence (TSF) device containing Cz-4-BF achieves an external quantum efficiency of 21%, which is higher than the devices employing classical fluorescent emitters and multiple resonance-type TADF emitters. The Cz-4-BF-based TSF device shows significantly improved color coordinates of (0.14, 0.10) versus a control device without Cz-4-BF.     

Polylactide‐perylene derivative for blue biodegradable organic light‐emitting diodes

In this work we demonstrate, for the first time, the use of polylactic acid (PLA) as a biodegradable host matrix for the construction of the active emissive layer of organic light‐emitting diode (OLED) devices for potential use in bioelectronics. In this preliminary study, we report a robust synthesis of two fluorescent PLA derivatives, pyrene‐PLA ( AH10 ) and perylene‐PLA ( AH11 ). These materials were prepared by the ring opening polymerisation of l ‐lactide with hydroxyalkyl‐pyrene and hydroxyalkyl‐perylene derivatives using 1,8‐diazabicyclo[5.4.0]undec‐7‐ene as catalyst. OLEDs were fabricated from these materials using a simple device architecture involving a solution‐processed single‐emitting layer in the configuration ITO/PEDOT:PSS/PVK:OXD‐7 (35%): AH10 or AH11 (20%)/TPBi/LiF/Al (ITO, indium tin oxide; PEDOT:PSS, poly(3,4‐ethylenedioxythiophene) doped with poly(styrenesulfonic acid); PVK, poly(vinylcarbazole); OXD‐7, (1,3‐phenylene)‐bis‐[5‐(4‐tert‐butylphenyl)‐1,3,4‐oxadiazole]; TPBi, 2,2′,2″‐(1,3,5‐benzenetriyl)tris(1‐phenyl‐1H‐benzimidazole)). The turn‐on voltage for the perylene OLED at 10 cd m^–2 was around 6 V with a maximum brightness of 1200 cd m^–2 at 13 V. The corresponding external quantum efficiency and device current efficiency were 1.5% and 2.8 cd A^–1 respectively. In summary, this study provides proof of principle that OLEDs can be constructed from PLA, a readily available and renewable bio‐source. © 2020 The Authors. Polymer International published by John Wiley & Sons Ltd on behalf of Society of Industrial Chemistry.     

Achieving High Electroluminescence Efficiency and High Color Rendering Index for All-Fluorescent White OLEDs Based on an Out-of-Phase Sensitizing System

Sensitizing conventional fluorescence (CF) dopants with thermally activated delayed fluorescence (TADF) materials has achieved considerable progress, by which the advantages of TADF materials and CF dopants can be fully harnessed. However, the usually used co-phase configuration of CF dopant-engaged sensitizing systems often encounters exciton loss due to Dexter energy transfer (DET). Herein, an effective out-of-phase configuration is proposed to sensitize CF dopants in the fabrication of white organic light-emitting diodes (WOLEDs). Based on a new efficient sky-blue TADF luminogen DCP-BP-DPAC which has an electroluminescence (EL) peak at 486 nm and an EL efficiency of 26.6%, a green TADF material BDMAC-XT, and a red CF dopant DBP sensitized by BDMAC-XT through an out-of-phase configuration without interlayer, efficient WOLEDs are successfully fabricated. By further adopting orange TBRB or 4CzTPNBu as intermediate sensitizers, more efficient energy transfer to DBP is achieved via Förster energy transfer. Through step-by-step energy transfer and elimination of excess DET process, high-performance all-fluorescent WOLEDs are achieved, providing excellent EL efficiencies over 23.0%, and highly stable white light with a high color rendering index of 87. The outstanding EL performance and high-quality emission color demonstrate the great potential of the proposed out-of-phase design for sensitizing systems of WOLEDs.     

Furan fatty acid concentrations in tea infusions prepared from green,black, and herbal teas

Furan fatty acids (FuFAs) are valuable antioxidants with highly effective radical scavenging properties which are widely distributed at low levels in food. Previous research indicated that tea is a valuable source of FuFAs. However, tea is only consumed in form of infusions. To fill this gap, we prepared infusions from different herbal, green, and black teas. Initial measurements with GC-MSMS of tea verified previous findings that 11-(3,4-dimethyl-5-penylfuran-2-yl)-undecanoic acid (11D5) was the prevalent FuFA in tea matrix. Therefore, 11D5 was quantified in tea infusions by means of UHPLC-MSMS equipment after mild alkaline hydrolysis. While herbal tea infusions were low or free of FuFAs, 11D5 was detectable in all samples of green and black tea infusions. Amounts of 11D5 were higher in green tea than in black tea. Moreover, Darjeeling tea infusions were by ~30% richer in 11D5 than black and green teas from other regions. Each cup of green and black tea infusion may provide 20–60 μg 11D5, which is about 5% of the amounts found in tea samples. Spread over the day, regular tea consumption may contribute to the intake of valuable FuFAs.     

Methylcyclohexane production under fluctuating hydrogen flow rate conditions

Energy storage using liquid organic hydrogen carrier (LOHC) is a long-term method to store renewable energy with high hydrogen energy density. This study investigated a simple and low-cost system to produce methylcyclohexane (MCH) from toluene and hydrogen using fluctuating electric power, and developed its control method. In the current system, hydrogen generated by an alkaline water electrolyzer was directly supplied to hydrogenation reactors, where hydrogen purification equipment such as PSA and TSA is not installed to decrease costs. Hydrogen buffer tanks and compressors are not equipped. In order to enable MCH production using fluctuating electricity, a feed-forward toluene supply control method was developed and introduced to the system. The electrolyzer was operated under triangular waves and power generation patterns of photovoltaic cells and produced hydrogen with fluctuating flow rates up to 7.5 Nm³/h. Consequently, relatively high purity of MCH (more than 90% of MCH mole fraction) was successfully produced. Therefore, the simplified system has enough potential to produce MCH using fluctuating renewable electricity.