Recent advances in the radical cascade reaction for constructing nitrogen heterocycles using azides as radical acceptors.

Due to the high conversion properties, azide compounds are widely utilized in organic synthesis. For instance, azide compounds readily release nitrogen to form a new N-C bond when they function as radical acceptors for the active intermediates in the reaction. Over the past decade, strategies employing azides as radical acceptors to construct nitrogen heterocycles have been extensively developed. This approach has emerged as a crucial method for synthesizing nitrogen heterocycles. Therefore, this paper provides a review of the research advancements in tandem cyclization reactions using azides as radical acceptors, summarizing the process of reaction design, exploration, reasoning of the mechanism, and prospects for further research of these reactions.

Crystallization of Amorphous Nimesulide: The Relationship between Crystal Growth Kinetics and Liquid Dynamics.

Understanding crystallization and its correlations with liquid dynamics is relevant for developing robust amorphous pharmaceutical solids. Herein, nimesulide, a classical anti-inflammatory agent, was used as a model system for studying the correlations between crystallization kinetics and molecular dynamics. Kinetic parts of crystal growth (ukin) of nimesulide exhibited a power law dependence upon the liquid viscosity (η) as ukin~η-0.61. Bulk molecular diffusivities (DBulk) of nimesulide were predicted by a force-level statistical-mechanical model from the α-relaxation times, which revealed the relationship as ukin~Dbulk0.65. Bulk crystal growth kinetics of nimesulide in deeply supercooled liquid exhibited a fragility-dependent decoupling from τα. The correlations between growth kinetics and α-relaxation times predicted by the Adam-Gibbs-Vogel equation in a glassy state were also explored, for both the freshly made and fully equilibrated glass. These findings are relevant for the in-depth understanding and prediction of the physical stability of amorphous pharmaceutical solids.

Skin-Like Stretchable Fuel Cell Based on Gold-Nanowire-Impregnated Porous Polymer Scaffolds.

Skin-like energy devices can be conformally attached to the human body, which are highly desirable to power soft wearable electronics in the future. Here, a skin-like stretchable fuel cell based on ultrathin gold nanowires (AuNWs) and polymerized high internal phase emulsions (polyHIPEs) scaffolds is demonstrated. The polyHIPEs can offer a high porosity of 80% yet with an overall thickness comparable to human skin. Upon impregnation with electronic inks containing ultrathin (2 nm in diameter) and ultrahigh aspect-ratio (>10 000) gold nanowires, skin-like strain-insensitive stretchable electrodes are successfully fabricated. With such designed strain-insensitive electrodes, a stretchable fuel cell is fabricated by using AuNWs@polyHIPEs, platinum (Pt)-modified AuNWs@polyHIPEs, and ethanol as the anode, cathode, and fuel, respectively. The resulting epidermal fuel cell can be patterned and transferred onto skin as "tattoos" yet can offer a high power density of 280 µW cm-2 and a high durability (>90% performance retention under stretching, compression, and twisting). The results presented here demonstrate that this skin-thin, porous, yet stretchable electrode is essentially multifunctional, simultaneously serving as a current collector, an electrocatalyst, and a fuel host, indicating potential applications to power future soft wearable 2.0 electronics for remote healthcare and soft robotics.

In situ autologous growth of self-supporting NiFe-based nanosheets on nickel foam as an efficient electrocatalyst for the oxygen evolution reaction.

A highly efficient and low-cost oxygen evolution reaction electrocatalyst is essential for water splitting. Herein, a simple and cost-effective autologous growth method is developed to prepare NiFe-based integrated electrodes for water oxidation. In this method, a Ni(OH)2 nanosheet film is first developed on nickel foam by oxidative deposition in a chemical bath solution. The as-prepared nanosheet electrode is then immersed into a solution containing Fe(iii) cations to form an Fe-doped Ni(OH)2 electrode by utilization of the different solubility of metal cations. Benefiting from its unique and integrated nanostructure, this hierarchically structured electrode displays extremely high catalytic activity toward water oxidation. In 1 M KOH, the electrode can deliver a current density of 1000 mA cm-2 at an overpotential of only 330 mV. This work provides a facile way to produce an efficient, durable, and Earth-abundant OER electrocatalyst with no energy input, which is attractive for large-scale water splitting.

Two- and three-dimensional molecular organization of Schiff-base derivatives.

We have designed and synthesized a series of Schiff base derivatives, and studied their structural features in two-dimensional (2D) and three-dimensional (3D) states by combining scanning tunneling microscopy (STM) and X-ray diffraction experiments. The Schiff-base derivatives with short alkyl chains crystallize easily, which allows a detailed structural analysis by X-ray diffraction. Due to the strong adsorbate-substrate interactions, those bases with long alkyl chains easily form 2D assemblies on highly oriented pyrolytic graphite (HOPG). The STM images indicate also that the introduction of two methoxy groups into the molecule can change the structure of these 2D assemblies as a result of the increased steric hindrances, for example: the Schiff-base derivative, bearing both methoxy groups and C16H33 tails, forms 2D Moiré patterns, and an alignment of pairing Schiff-base molecules may be easily resolved. Conversely, the Schiff base derivative, bearing solely C16H33 tails, forms 2D non-Moiré patterns. It is demonstrated that the 3D structural features result from the compromise of intermolecular interactions of different molecular moieties. However, there is one more factor, which also governs the 2D structure: the adsorbate-substrate interaction. The 3D crystal structure may thus help to understand many factors involved in the formation of 2D structures, and would be helpful for designing new molecular assemblies with tailoring functions.