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The self-discharge and effumability of supercapacitors with aqueous electrolytes are prevalent problems. In this study, we used Na2S2O3·5H2O as the electrolyte for aqueous supercapacitors. Na2S2O3 in Na2S2O3·5H2O can dissolve in crystalline water molecules by itself and the transformation between the solid and liquid states of Na2S2O3·5H2O electrolytes is reversible. The electrolyte based on liquating Na2S2O3 in 5H2O electrolytes has better thermal stability than that based on 2 M Na2S2O3 and 2 M KOH electrolytes. The electrochemical result indicates that the energy storage mechanism of a supercapacitor based on liquating Na2S2O3 in 5H2O leads to a double-layer supercapacitor via Na+ and S2O32− ion adsorption. The self-discharge behavior of the supercapacitor using liquating Na2S2O3 in 5H2O is effectively suppressed by the slow charge redistribution of Na+ and S2O32− ions in solid electrolytes formed from the liquid state. Finally, the supercapacitor using liquating Na2S2O3 in 5H2O has good cycling stability. [ABSTRACT FROM AUTHOR]

C–H activation provides a straightforward approach to construct new chemical bonds and privileged heterocycles. However, due to common deficiencies, C–H activation still faces a great challenge towards sustainability and applications. Described herein is a robust and convenient rhodium-catalyzed regioselective C–H activation/[4 + 2] annulation for the synthesis of isoquinolones with salient features including a recyclable catalytic reaction system, unique regioselectivity, gram-scale synthesis with low catalyst loading (e.g., 0.5 mol%), ethanol as the green solvent, air and water compatibility, and simple purification processes. The roles of the hydroxy group and the pivaloyl part in both substrates, the additional pivotal function of propargyl alcohol partners, and the origin of the unique chemoselectivity are clarified based on integrated experimental and DFT studies. Additionally, a propargyl alcohol-connected distinctive hydrogen bonding network with the hydroxy group and the pivaloyl part is also rationally deduced for conferring the observed reverse regioselectivity by subsequent IGMH analysis. [ABSTRACT FROM AUTHOR]

The formation of natural structures found in biological systems is wonderful and can be completed at ambient temperatures in contrast to artificial technologies wherein harsh conditions are common prerequisites. A new research direction, "bioprocess inspired manufacturing", is proposed for fabricating advanced materials with novel structures and functions. Nacre consists of an ordered multilayer structure of crystalline calcium carbonate lamellae separated by organic layers exhibiting mechanical toughness, which transcends that of its constituent components. Inspired by the nacre formation process, a microscale additive manufacturing mineralization method is proposed for achieving a multilayered organic–inorganic layered structure. In this work, layered calcite was synthesized on the surface of chitosan (CS) films at room temperature under the coordinated control of magnesium ions (Mg2+) and polyacrylic acid (PAA). The CS films and layered calcite are sequentially assembled in a layer-by-layer deposition approach to form an organic–inorganic hybrid structure. The nacre-like chitosan/CaCO3 (CS/CaCO3) composites exhibit high transparency and underwater superoleophobicity. Impressively, the hardness (2.35 ± 0.03 GPa) and Young's modulus (58.1 ± 0.5 GPa) of the as-prepared (CS/CaCO3) composites are comparable to those of their biological counterparts. This study provides a rational bioprocess-inspired room-temperature mineralization method to develop advanced composite materials with good performance. [ABSTRACT FROM AUTHOR]

Pigmented rodent tooth enamel is mainly composed of parallel hydroxyapatite nanorods and a small amount of organic matrix. These hydroxyapatite nanorods tend to be carbonated and contain traces of iron, fluorine, and magnesium. The pigmented rodent tooth enamel which contains trace iron is stronger and more resistant to acid corrosion than unpigmented rodent enamel, which could provide inspiration for the preparation and synthesis of high performance and corrosion resistant artificial materials. However, the regulatory role and mechanical enhancement of iron ions in enamel growth are unclear. Here, we synthesized enamel-like fluorapatite nanorod arrays in vitro using a mineralization technique at room-temperature. To investigate the regulatory effect of iron ions on the fluorapatite nanorod arrays (FAP-Fe), the phosphate solution is slowly transfused dropwise in the calcium ion solution, and different concentrations of iron ions are added to the calcium ion solution in advance. We demonstrated that fluorapatite nanorod arrays (FAP) can be epitaxially grown from amorphous calcium phosphate nanoparticles and iron ions can improve the microstructure of FAP nanorod arrays and obtain the same enamel bundle structure as the natural enamel. Moreover, high concentration of iron ions can inhibit the crystallization of fluorapatite. The FAP-Fe nanorod arrays controlled by 0.02 mM Fe 3+ have good mechanical properties. Their hardness is 1.34 ± 0.02 GPa and Young's modulus is 65.3 ± 0.4 GPa, respectively. This work is helpful to understand the role of trace elements in natural enamel in the regulation of enamel formation and to provide a theoretical foundation for the preparation of high strength artificial composites, which can play a greater role in the fields of biological alternative materials, anti-oil coating, oil/water separation, anti-bioadhesion and so on., Competing Interests: The authors declare no conflict of interest, (This journal is © The Royal Society of Chemistry.)

Organisms can synthesize heterogeneous structures with excellent mechanical properties through mineralization, the most typical of which are teeth. The tooth is an extraordinarily resilient bi-layered material that is composed of external enamel perpendicular to the tooth surface and internal dentin parallel to the tooth surface. The synthesis of enamel-like heterostructures with good mechanical properties remains an elusive challenge. In this study, we applied a biomimetic mineralization method to grow fluorapatite/CaCO 3 (FAP/CaCO 3 ) heterogeneous structured thin films that mimic their biogenic counterparts found in teeth through a three-step pathway: coating a polymer substrate, growing a layered calcite film, and mineralization of a fluorapatite columnar array on the calcite layer. The synthetic heterostructure composites combine well and exhibit good mechanical properties comparable to their biogenic counterparts. The FAP/CaCO 3 heterogeneous structured composite exhibits excellent mechanical properties, with a hardness and Young's modulus of 1.99 ± 0.02 GPa and 47.5 ± 0.6 GPa, respectively. This study provides a reasonable new idea for unique heterogeneous structured materials designed at room temperature., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The formation of natural structures found in biological systems is wonderful and can be completed at ambient temperatures in contrast to artificial technologies wherein harsh conditions are common prerequisites. A new research direction, "bioprocess inspired manufacturing", is proposed for fabricating advanced materials with novel structures and functions. Nacre consists of an ordered multilayer structure of crystalline calcium carbonate lamellae separated by organic layers exhibiting mechanical toughness, which transcends that of its constituent components. Inspired by the nacre formation process, a microscale additive manufacturing mineralization method is proposed for achieving a multilayered organic-inorganic layered structure. In this work, layered calcite was synthesized on the surface of chitosan (CS) films at room temperature under the coordinated control of magnesium ions (Mg2+) and polyacrylic acid (PAA). The CS films and layered calcite are sequentially assembled in a layer-by-layer deposition approach to form an organic-inorganic hybrid structure. The nacre-like chitosan/CaCO3 (CS/CaCO3) composites exhibit high transparency and underwater superoleophobicity. Impressively, the hardness (2.35 ± 0.03 GPa) and Young's modulus (58.1 ± 0.5 GPa) of the as-prepared (CS/CaCO3) composites are comparable to those of their biological counterparts. This study provides a rational bioprocess-inspired room-temperature mineralization method to develop advanced composite materials with good performance.