High‐Internal‐Phase Pickering Emulsions Stabilized Solely by Peanut‐Protein‐Isolate Microgel Particles with Multiple Potential Applications

High‐internal‐phase Pickering emulsions have various applications in materials science. However, the biocompatibility and biodegradability of inorganic or synthetic stabilizers limit their applications. Herein, we describe high‐internal‐phase Pickering emulsions with 87 % edible oil or 88 % n‐hexane in water stabilized by peanut‐protein‐isolate microgel particles. These dispersed phase fractions are the highest in all known food‐grade Pickering emulsions. The protein‐based microgel particles are in different aggregate states depending on the pH value. The emulsions can be utilized for multiple potential applications simply by changing the internal‐phase composition. A substitute for partially hydrogenated vegetable oils is obtained when the internal phase is an edible oil. If the internal phase is n‐hexane, the emulsion can be used as a template to produce porous materials, which are advantageous for tissue engineering.     

pH‐Sensitive Mechanical Properties of Elastin‐Based Hydrogels

Ionizable amino acids in protein‐based hydrogels can confer pH‐responsive behavior. Because elastin‐like polypeptides (ELPs) have an established sequence and can crosslink to form hydrogels, they are an ideal system for creating pH‐sensitive materials. This study examines different parameters that might affect pH‐sensitive behavior and characterizes the mechanical and physical properties between pH 3 and 11 of three ELP‐based crosslinked hydrogels. The first finding is that varying the amount of crosslinker affects the overall stiffness and resilience of the hydrogels but does not strongly affect water content, swelling ratio, or pH sensitivity. Second, the choice of two popular tag sequences, which vary in histidine and aspartic acid content, does not have a strong effect on pH‐sensitive properties. Last, selectively blocking lysine and tyrosine residues through acetylation significantly decreases the pH‐sensitive zeta potential. Acetylated hydrogels also demonstrate different behavior at low pH values with reduced swelling, reduced water content, and higher stiffness. Overall, this work demonstrates that ELP hydrogels with ionizable groups are promising materials for environmentally‐responsive applications such as drug delivery, tissue engineering, and microfluidics.     

Alcohol‐Soluble Electron‐Transport Materials for Fully Solution‐Processed Green PhOLEDs

Two alcohol‐soluble electron‐transport materials (ETMs), diphenyl(4‐(1‐phenyl‐1H‐benzo[d]imidazol‐2‐yl)phenyl)phosphine oxide (pPBIPO) and (3,5‐bis(1‐phenyl‐1H‐benzo[d]imidazol‐2‐yl)phenyl)diphenylphosphine oxide (mBPBIPO), have been synthesized. The physical properties of these ETMs were investigated and they both exhibited high electron‐transport mobilities (1.67×10^?4 and 2.15×10^?4 cm² V^?1 s^?1), high glass‐transition temperatures (81 and 110 °C), and low LUMO energy levels (?2.87 and ?2.82 eV, respectively). The solubility of PBIPO in n‐butyl alcohol was more than 20 mg mL^?1, which meets the requirement for fully solution‐processed organic light‐emitting diodes (OLEDs). Fully solution‐processed green‐phosphorescent OLEDs were fabricated by using alcohol‐soluble PBIPO as electron‐transport layers (ETLs), and they exhibited high current efficiencies, power efficiencies, and external quantum efficiencies of up to 38.43 cd A^?1, 26.64 lm W^?1, and 10.87 %, respectively. Compared with devices that did not contain PBIPO as an ETM, the performance of these devices was much improved, which indicated the excellent electron‐transport properties of PBIPO.     

New soybean oil‐Styrene‐Divinylbenzene thermosetting copolymers—IV. Good damping properties

New polymeric materials have been prepared by the cationic copolymerization of regular soybean oil, low saturation soybean oil, i.e. LoSatSoy oil, or conjugated LoSatSoy oil with styrene and divinylbenzene, norbornadiene or dicyclopentadiene initiated by boron trifluoride diethyl etherate (BF ₃·OEt ₂) or related modified initiators. The effects of the stoichiometry, the type of soybean oil and the alkene comonomer on the damping behavior of the resulting polymers have been investigated. The damping properties have been quantitatively evaluated by the loss tangent maximum (tan δ) _max, ­the temperature range ΔT for efficient damping (tan δ > 0.3), and the integrals of the linear tan δ v. temperature curves (tan δ area, TA). These bulk materials are composed primarily of soybean oil‐styrene‐divinylbenzene random copolymers with considerable variability in the backbone compositions. The good damping properties of the soybean oil polymers are presumably determined by the presence of fatty acid ester side groups directly attached to the polymer backbone and the segmental heterogeneities resulting from crosslinking. In general, crosslinking reduces the (tan δ) _max and the TA values, but broadens the region of efficient damping (ΔT). Soybean oil polymeric materials with appropriate compositions and crosslink densities are capable of efficiently damping over a temperature region in excess of 110 °C and provide noise and vibration attenuation over broad temperature and frequency ranges. Copyright © 2002 John Wiley & Sons, Ltd.     

Robust Aqua Material: A Pressure‐Resistant Self‐Assembled Membrane for Water Purification

“Aqua materials” that contain water as their major component and are as robust as conventional plastics are highly desirable. Yet, the ability of such systems to withstand harsh conditions, for example, high pressures typical of industrial applications has not been demonstrated. We show that a hydrogel‐like membrane self‐assembled from an aromatic amphiphile and colloidal Nafion is capable of purifying water from organic molecules, including pharmaceuticals, and heavy metals in a very wide range of concentrations. Remarkably, the membrane can sustain high pressures, retaining its function. The robustness and functionality of the water‐based self‐assembled array advances the idea that aqua materials can be very strong and suitable for demanding industrial applications.     

Three‐Dimensional Nitrogen‐Doped Hierarchical Porous Carbon as an Electrode for High‐Performance Supercapacitors

A facile and sustainable procedure for the synthesis of nitrogen‐doped hierarchical porous carbons with a three‐dimensional interconnected framework (NHPC‐3D) was developed. The strategy, based on a colloidal crystal‐templating method, utilizes nitrogenous dopamine as the precursor due to its unique properties, including self‐polymerization under mild alkaline conditions, coating onto various surfaces, a high carbonization yield, and well‐preserved nitrogen doping after heat treatment. The obtained NHPC‐3D possesses a high surface area of 1056 m² g^?1, a large pore volume of 2.56 cm³ g^?1, and a high nitrogen content of 8.2 wt %. The NHPC‐3D is implemented as the electrode material of a supercapacitor and exhibits a specific capacitance as high as 252 F g^?1 at a current density of 2 A g^?1. The device also shows a high capacitance retention of 75.7 % at a higher current density of 20 A g^?1 in aqueous electrolyte due to a sufficient surface area for charge accommodation, reversible pseudocapacitance, and minimized ion‐transport resistance, as a result of the advantageous interconnected hierarchical porous texture. These results showcase NHPC‐3D as a promising candidate for electrode materials in supercapacitors.     

Freeze‐Drying‐Assisted Synthesis of Hierarchically Porous Carbon/Germanium Hybrid for High‐Efficiency Lithium‐Ion Batteries

Herein, an approach is reported to prepare porous a carbon/Ge (C/Ge) hybrid. In this hybrid, Ge nanoparticles are closely embedded in a highly conductive and flexible carbon matrix. Such a hybrid features a high surface area (128.0 m² g^?1) and a hierarchical micropore–mesopore structure. When used as an anode material in lithium‐ion batteries (LIBs), the as‐prepared hybrid [C/Ge (60.37 %)] exhibits an improved lithium storage performance with regard to its capacity and rate capability compared to its counterparts. More specifically, it can maintain a specific capacity as high as 906 mAh g^?1 at a high current density of 0.6 A g^?1 after 50 cycles. The excellent lithium storage performance of the C/Ge (60.37 %) sample can be attributed to synergetic effects between the carbon matrix and Ge nanoparticles. The method we adopted is simple and effective, and can be extended to fabricate other nanomaterials.     

3D Microporous Base‐Functionalized Covalent Organic Frameworks for Size‐Selective Catalysis

The design and synthesis of 3D covalent organic frameworks (COFs) have been considered a challenge, and the demonstrated applications of 3D COFs have so far been limited to gas adsorption. Herein we describe the design and synthesis of two new 3D microporous base‐functionalized COFs, termed BF‐COF‐1 and BF‐COF‐2, by the use of a tetrahedral alkyl amine, 1,3,5,7‐tetraaminoadamantane (TAA), combined with 1,3,5‐triformylbenzene (TFB) or triformylphloroglucinol (TFP). As catalysts, both BF‐COFs showed remarkable conversion (96 % for BF‐COF‐1 and 98 % for BF‐COF‐2), high size selectivity, and good recyclability in base‐catalyzed Knoevenagel condensation reactions. This study suggests that porous functionalized 3D COFs could be a promising new class of shape‐selective catalysts.     

A simple hydrated salt with a complex hydrogen‐bonding network: tetrakis(5‐amino‐3‐carboxy‐4H‐1,2,4‐triazol‐1‐ium) hexachloridocadmate(II) tetrahydrate

In the title cadmium chloride salt, (C₃H₅N₄O₂)₄[CdCl₆]·4H₂O, the asymmetric unit comprises two N‐protonated 5‐amino‐3‐carboxy‐4H‐1,2,4‐triazol‐1‐ium cations, half a [CdCl₆]⁴⁻ anion and two molecules of water. The Cd²⁺ cation is located on a centre of inversion and is coordinated by six chloride anions, forming a distorted octahedron. In the crystal structure, alternating layers of cations and anions are arranged along the [101] direction, forming a three‐dimensional supramolecular network via a combination of hydrogen‐bonding and aromatic stacking interactions.     

Energetic Materials Based on 5,5′‐Diamino‐4,4′‐dinitramino‐3,3′‐bi‐1,2,4‐triazole

A simple and straightforward synthesis of 5,5′‐diamino‐4,4′‐dinitramino‐3,3′‐bi‐1,2,4‐triazole by the selective nitration of 4,4′,5,5′‐tetraamino‐3,3′‐bi‐1,2,4‐triazole is presented. The interaction of the amino and nitramino groups improves the energetic properties of this functionalized bitriazole. For a deeper investigation of these properties, various nitrogen‐rich derivatives were synthesized. The new compounds were investigated and characterized by spectroscopy (¹H and ¹³C NMR, IR, Raman), elemental analysis, mass spectrometry, differential thermal analysis (DTA), X‐ray analysis, and impact and friction sensitivities (IS, FS). X‐ray analyses were performed and deliver insight into structural characteristics with which the stability of the compounds can be explained. The standard enthalpies of formation were calculated for all compounds at the CBS‐4M level of theory, revealing highly positive heats of formation. The energetic performance of the new molecules was predicted with the EXPLO5 V6.02 computer. A small‐scale shock reactivity test (SSRT) and a toxicity test gave a first impression of the performance and toxicity of selective compounds.     

1,1′‐Nitramino‐5,5′‐bitetrazoles

1,1′‐Dinitramino‐5,5′‐bitetrazole and 1,1′‐dinitramino‐5,5′‐azobitetrazole were synthesized for the first time. The neutral compounds are extremely sensitive and powerful explosives. Selected nitrogen‐rich salts were prepared to adjust sensitivity and performance values. The compounds were characterized by low‐temperature X‐ray diffraction, IR and Raman spectroscopy, multinuclear NMR spectroscopy, elemental analysis, and DTA/DSC. Calculated energetic performances using the EXPLO5 code based on calculated (CBS‐4M) heats of formation and X‐ray densities support the high performances of the 1,1′‐dinitramino‐5,5′‐bitetrazoles as energetic materials. The sensitivities toward impact, friction, and electrostatic discharge were also explored. Most of the compounds show sensitivities in the range of primary explosives and should only be handled with great care!     

New Energetic Materials: Functionalized 1‐Ethyl‐5‐aminotetrazoles and 1‐Ethyl‐5‐nitriminotetrazoles

A new way to make a bang : Several functionalized 1‐ethyl‐5‐aminotetrazoles, 1‐ethyl‐5‐nitrimino‐tetrazoles, and copper complexes have been synthesized and their chemical and energetic properties have been comprehensively characterized. The compounds belong to all classes of “energetic materials”: explosives, propellants, and pyrotechnics.

     

Fluorescence Emission from 2,6‐Naphthylene‐Bridged Mesoporous Organosilicas with an Amorphous or Crystal‐Like Framework

We report that 2,6‐naphthylene‐bridged periodic mesoporous organosilicas exhibit unique fluorescence behavior that reflects molecular‐scale periodicities in the framework. Periodic mesoporous organosilicas consisting of naphthalene–silica hybrid frameworks were synthesized by hydrolysis and condensation of a naphthalene‐derived organosilane precursor in the presence of a template surfactant. The morphologies and meso‐ and molecular‐scale periodicities of the organosilica materials strongly depend on the synthetic conditions. The naphthalene moieties embedded within the molecularly ordered framework exhibited a monomer‐band emission, whereas those embedded within the amorphous framework showed a broad emission attributed to an excimer band. These results suggest that the naphthalene moieties fixed within the crystal‐like framework are isolated in spite of their densely packed structure, different from conventional organosilica frameworks in which only excimer emission was observed for both the crystal‐like and amorphous frameworks at room temperature. This key finding suggests a potential to control interactions between organic groups and thus the optical properties of inorganic/organic hybrids.