Nonprecious metal catalysts for the oxygen reduction reaction are the ultimate materials and the foremost subject for low-temperature fuel cells. A novel type of catalysts prepared by high-pressure pyrolysis is reported. The catalyst is featured by hollow spherical morphologies consisting of uniform iron carbide (Fe3 C) nanoparticles encased by graphitic layers, with little surface nitrogen or metallic functionalities. In acidic media the outer graphitic layers stabilize the carbide nanoparticles without depriving them of their catalytic activity towards the oxygen reduction reaction (ORR). As a result the catalyst is highly active and stable in both acid and alkaline electrolytes. The synthetic approach, the carbide-based catalyst, the structure of the catalysts, and the proposed mechanism open new avenues for the development of ORR catalysts.

Chemical synthesis of platinum-rare earth metal (Pt-RE) nanoalloys, one of the most active catalysts for the oxygen reduction reaction, has been a formidable challenge, mainly due to the vastly different standard reduction potentials of the two metals and high oxophilicity of the latter. Here we report a universal chemical process to prepare Pt-RE nanoalloys with tunable compositions and particle sizes. Pt and RE metal ions from the most common hydrated metal salts are first atomically embedded into an in-situ formed C-N network, yielding a stable compound insensitive to O 2 and H 2 O. The Pt-RE nanoalloys are subsequently obtained by heating the compound under a mild reducing atmosphere (e.g. 3.3% H 2 /Ar). The key intermediate step of the process is the formation of RE carbodiimides (RE 2 (CN 2 ) 3 ) along with Pt particles. This synthesis mechanism suggests an efficient strategy to prepare nanoalloys with highly reactive metals.

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Because of their biocompatibility, biodegradability, and unique bioactive properties, polysaccharides have been recognized and directly applied as excellent candidates for various biomedical applications. In order to introduce more functionalities onto polysaccharides, various modification methods were applied to improve the physical-chemical and biochemical properties. Grafting polysaccharides with functional polymers with limited reaction sites maximizes the structural integrity. To the best of our knowledge, great efforts have been made by scientists across the world, including our research group, to explore different strategies for the synthesis and design of controllable polymer-grafted polysaccharides. By the application of some reasonable strategies, a series of polymer-grafted polysaccharides with satisfactory biocharacteristics were obtained. The first strategy involves facile modification of polysaccharides with living radical polymerization (LRP). Functionalized polysaccharides with diverse grafts can be flexibly and effectively achieved. The introduced grafts include cationic components for nuclei acid delivery, PEGylated and zwitterionic moieties for shielding effects, and functional species for bioimaging applications as well as bioresponsive drug release applications. The second synthetic model refers to biodegradable polymer-grafted polysaccharides prepared by ring-opening polymerization (ROP). Inspired by pathways to introduce initiation sites onto polysaccharides, the use of amine-functionalized polysaccharides was explored in-depth to trigger ROP of amino acids. A series of poly(amino acid)-grafted polysaccharides with advanced structures (including linear, star-shaped, and comb-shaped copolymers) were developed to study and optimize the structural effects. In addition, biodegradable polyester-grafted polysaccharides were prepared and utilized for drug delivery. Another emerging strategy was to design polysaccharide-based assemblies with supramolecular structures. A variety of assembly techniques using non-covalent interactions were established to construct different types of polysaccharide-based assemblies with various bioapplications. On the basis of these strategies, polymer-grafted polysaccharides with controllable functions were reported to be well-suited for different kinds of biomedical applications. The exciting results were obtained from both in vitro and in vivo models. Viewing the rapid growth of this field, the present Account will update the concepts, trends, perspectives, and applications of functionalized polysaccharides, guiding and inspiring researchers to explore new polysaccharide-based systems for wider applications.

The bioreducible star-shaped gene vector (POSS-(SS-PDMAEMA)8) with well-defined structure and relatively narrow molecular weight distribution was synthesized via atom transfer radical polymerization (ATRP) of (2-dimethylamino)ethyl methacrylate (DMAEMA) from a polyhedral oligomeric silsesquioxane (POSS) macroinitiator. POSS-(SS-PDMAEMA)8 was composed of a biocompatible POSS core and eight disulfide-linked PDMAEMA arms, wherein the PDMAEMA chain length could be adjusted by controlling polymerization time. POSS-(SS-PDMAEMA)8 can effectively bind pDNA into uniform nanocomplexes with appropriate particle size and zeta potential. The incorporation of disulfide bridges gave the POSS-(SS-PDMAEMA)8 material facile bioreducibility. In comparison with POSS-(PDMAEMA)8 without disulfide linkage, POSS-(SS-PDMAEMA)8 exhibited much lower cytotoxicity and substantially higher transfection efficiency. The present work would provide useful information for the design of new POSS-based drug/gene carriers.