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The introduction of dipoles on gold nanoparticle surfaces provides the formation of chain-like nanoparticle assemblies in solution under ambient conditions. Here, we present studies on influencing and controlling the strength of the induced dipole by thiols. Aromatic thiols lead to enhanced surface dipoles, where electron-donating functions can further increase the interaction. Thereby, particle–particle distances and chemical environment at the particle interface were manipulated, which resulted in different tunneling resistances Rg in these 1D structures. Here, Rg seemed to be mostly dominated by the interparticle distance rather than the type of ligand. Temperature-dependent current–voltage measurements of thiol-bearing nanoparticle chains revealed two different transport mechanisms. For temperatures <170 K, a thermally activated electron tunneling takes place, which depends on the charging energy Ec. Whereas for higher temperatures, a transition to an electron hopping process occurs determined by the involved thiol and nanoparticle shape. For structures with strong interparticle electronic coupling, the conduction mechanism is almost temperature-independent, which makes them promising candidates for highly sensitive chemiresistor sensors. [ABSTRACT FROM AUTHOR]

Understanding the crystallization of cement-binding phases, from basic units to macroscopic structures, can enhance cement performance, reduce clinker use, and lower CO2 emissions in the construction sector. This review examines the crystallization pathways of C–S–H (the main phase in PC cement) and other alternative binding phases, particularly as cement formulations evolve toward increasing SCMs and alternative binders as clinker replacements. We adopt a nonclassical crystallization perspective, which recognizes the existence of critical intermediate steps between ions in solution and the final crystalline phases, such as solute ion associates, dense liquid phases, amorphous intermediates, and nanoparticles. These multistep pathways uncover innovative strategies for controlling the crystallization of binding phases through additive use, potentially leading to highly optimized cement matrices. An outstanding example of additive-controlled crystallization in cementitious materials is the synthetically produced mesocrystalline C–S–H, renowned for its remarkable flexural strength. This highly ordered microstructure, which intercalates soft matter between inorganic and brittle C–S–H, was obtained by controlling the assembly of individual C–S–H subunits. While large-scale production of cementitious materials by a bottom-up self-assembly method is not yet feasible, the fundamental insights into the crystallization mechanism of cement binding phases presented here provide a foundation for developing advanced cement-based materials. [ABSTRACT FROM AUTHOR]

Aging society demands advanced bone implants that can achieve long‐term success through osseointegration at the bone‐implant interface. Polyetheretherketone (PEEK), a bioinert implant material, often struggles with connecting to existing bone tissue, leading to inflammation and implant replacement. Following nature's lessons, a new strategy is introduced that masks the surface of bio‐ and chemically inert Polyetheretherketone implants with a covalently anchored bone‐mimetic surface. This method transforms PEEK into a bone‐integrative material by grafting a ≈300 nm thick gelatin layer onto its surface, subsequently mineralized with calcium phosphate. Herein, it is showed that this surface modification for implant materials combines excellent bulk implant properties with the characteristic structure and functional properties of natural bone. In vitro biocompatibility assays, employing NIH‐3T3 fibroblast and MC3T3‐E1 osteoblast cell lines, confirm the enhanced biocompatibility of the modified material. This strategy offers promising prospects for improving bone implants and exemplifies the adaptation of a non‐osseointegrative material to a bone‐like interface. [ABSTRACT FROM AUTHOR]

Field and laboratory observations show that crystals commonly form by the addition and attachment of particles that range from multi-ion complexes to fully formed nanoparticles. The particles involved in these nonclassical pathways to crystallization are diverse, in contrast to classical models that consider only the addition of monomeric chemical species. We review progress toward understanding crystal growth by particle-attachment processes and show that multiple pathways result from the interplay of free-energy landscapes and reaction dynamics. Much remains unknown about the fundamental aspects, particularly the relationships between solution structure, interfacial forces, and particle motion. Developing a predictive description that connects molecular details to ensemble behavior will require revisiting long-standing interpretations of crystal formation in synthetic systems, biominerals, and patterns of mineralization in natural environments.

Field and laboratory observations show that crystals commonly form by the addition and attachment of particles that range from multi-ion complexes to fully formed nanoparticles. The particles involved in these nonclassical pathways to crystallization are diverse, in contrast to classical models that consider only the addition of monomeric chemical species. We review progress toward understanding crystal growth by particle-attachment processes and show that multiple pathways result from the interplay of free-energy landscapes and reaction dynamics. Much remains unknown about the fundamental aspects, particularly the relationships between solution structure, interfacial forces, and particle motion. Developing a predictive description that connects molecular details to ensemble behavior will require revisiting long-standing interpretations of crystal formation in synthetic systems, biominerals, and patterns of mineralization in natural environments.

Mineral plastics are a promising class of bio‐inspired materials that offer exceptional properties, like self‐heal ability, stretchability in the hydrogel state, and high hardness, toughness, transparency, and non‐flammability in the dry state along with reversible transformation into the hydrogel by addition of water. This enables easy reshape‐ability and recycling like the solubility in mild acids to subsequently form mineral plastics again by base addition. However, current mineral plastics rely on petrochemistry, are hardly biodegradable, and thus persistent in nature. This work presents the next generation of mineral plastics, which are bio‐based and biodegradable, making them a promising, new class of polymers for the development of environmentally friendly materials. Physically cross‐linked (poly)glutamic‐acid (PGlu)‐based mineral plastics are synthesized using various alcohol‐water mixtures, metal ion ratios and molecular weights. The rheological properties are easily adjusted using these parameters. The general procedure involves addition of equimolar solution of CaCl2 to PGlu in equal volumes followed by addition of iPrOH (iPrOH:H2O = 1:1) under vigorous stirring conditions. The ready biodegradability of PGlu/CaFe mineral plastic is confirmed in this study where the elements N, Ca, and Fe present in it tend to act as additional nutrients, supporting the growth of microorganisms and consequently, promoting the biodegradation process. [ABSTRACT FROM AUTHOR]

The low toughness under the tension of cement and concrete materials has been a long‐standing issue for decades and it has become increasingly urgent to address in modern society due to the growing demand for the development of high‐performance and sustainable constructions. Manipulating calcium silicate hydrate (C‐S‐H), the main hydration product of Portland cement, which determines the mechanical properties of cementitious materials, is an attractive method for improving their toughness following a bottom‐up approach. Inspired by the microstructure of nacre, a high energy absorption C‐S‐H‐based composite with a highly ordered structure is fabricated by a designed ternary building block, in which exfoliated montmorillonite provides a template for the nucleation and growth of C‐S‐H generating the "brick", and polyvinyl alcohol acts as a "mortar" binding all the building blocks together. With the hierarchical toughening strategy explored here, the obtained C‐S‐H composite achieves a remarkable energy absorption of 16.2 ± 2.6 MJ m−3, which surprisingly outperforms the ultra‐high toughness cementitious materials by a factor of 20–60 and is even higher than that of natural nacre and other nacre‐like composites. These findings not only provide valuable insights into enhancing the toughness of cementitious materials but also open possibilities for broadening potential applications of C‐S‐H. [ABSTRACT FROM AUTHOR]

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