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Little is known about the formation pathway of colloidal semiconductor magic‐size clusters (MSCs). Here, the synthesis of the first single‐ensemble ZnSe MSCs, which exhibit a sharp optical absorption singlet peaking at 299 nm, is reported; their formation is independent of Zn and Se precursors used. It is proposed that the formation of MSCs starts with precursor self‐assembly followed by Zn and Se covalent bond formation to result in immediate precursors (IPs) which can transform into the MSCs. It is demonstrated that the IPs in cyclohexane appear transparent in optical absorption, and become visible as MSCs exhibiting one sharp optical absorption peak when a primary amine is added at room temperature. It is shown that when the preparation of the IP is controlled to be within the induction period, which occurs prior to nucleation and growth of conventional quantum dots (QDs), the resulting MSCs can be produced without the complication of the simultaneous coproduction of conventional QDs. The present study reveals the existence of precursor self‐assembly which leads to the formation of colloidal semiconductor MSCs and provides insights into a multistep nucleation process in cluster science. Precursor self‐assembly, with ZnSe as a model system is proposed as a general pathway for the formation of colloidal semiconductor magic‐size clusters (MSCs). The self‐assembly followed by ZnSe bond formation gives rise to the formation of immediate precursors of MSCs prior to formation of conventional quantum dots. ZnSe MSC‐299 forms from reactions of various Zn and Se precursors.

Mechanical interlocking of molecules (catenation) is a nontrivial challenge in modern synthetic chemistry and materials science 1 , 2 . One strategy to achieve catenation is the design of pre-annular molecules that are capable of both efficient cyclization and of pre-organizing another precursor to engage in subsequent interlocking 3 – 9 . This task is particularly difficult when the annular target is composed of a large ensemble of molecules, that is, when it is a supramolecular assembly. However, the construction of such unprecedented assemblies would enable the visualization of nontrivial nanotopologies through microscopy techniques, which would not only satisfy academic curiosity but also pave the way to the development of materials with nanotopology-derived properties. Here we report the synthesis of such a nanotopology using fibrous supramolecular assemblies with intrinsic curvature. Using a solvent-mixing strategy, we kinetically organized a molecule that can elongate into toroids with a radius of about 13 nanometres. Atomic force microscopy on the resulting nanoscale toroids revealed a high percentage of catenation, which is sufficient to yield ‘nanolympiadane’ 10 , a nanoscale catenane composed of five interlocked toroids. Spectroscopic and theoretical studies suggested that this unusually high degree of catenation stems from the secondary nucleation of the precursor molecules around the toroids. By modifying the self-assembly protocol to promote ring closure and secondary nucleation, a maximum catenation number of 22 was confirmed by atomic force microscopy. Nanoscale toroids with a high percentage of poly-catenation and radii of up to about 13 nm are kinetically organized using fibrous supramolecular assemblies with intrinsic curvature and a solvent-mixing strategy.

Vertical phase distribution plays an important role in the quasi-two-dimensional perovskite solar cells. So far, the driving force and how to tailor the vertical distribution of layer numbers have been not discussed. In this work, we report that the vertical distribution of layer numbers in the quasi-two-dimensional perovskite films deposited on a hole-transporting layer is different from that on glass substrate. The vertical distribution could be explained by the sedimentation equilibrium because of the colloidal feature of the perovskite precursors. Acid addition will change the precursors from colloid to solution that therefore changes the vertical distribution. A self-assembly layer is used to modify the acidic surface property of the hole-transporting layer that induces the appearance of desired vertical distribution for charge transport. The quasi-two-dimensional perovskite cells with the surface modification display a higher open-circuit voltage and a higher efficiency comparing to reference quasi-two-dimensional cells. Vertical phase distribution of quasi-two-dimensional perovskite plays vital roles in their optoelectronic properties. Here Liu et al. show that surface modification of the hole-transporting layer is an effective approach to control the vertical phase distribution and optimize the device efficiency.

The sol-gel method is an attractive synthetic approach in the design of advanced catalytic formulations that are based on metal and metal oxide with high degree of structural and compositional homogeneity. Nowadays, though it originated with the hydrolysis and condensation of metal alkoxides, sol-gel chemistry gathers plenty of fascinating strategies to prepare materials from solution state precursors. Low temperature chemistry, reproducibility, and high surface to volume ratios of obtained products are features that add merit to this technology. The development of different and fascinating procedure was fostered by the availability of new molecular precursors, chelating agents and templates, with the great advantage of tailoring the physico-chemical properties of the materials through the manipulation of the synthesis conditions. The aim of this review is to present an overview of the “traditional” sol-gel synthesis of tailored and multifunctional inorganic materials and their application in the main domain of heterogeneous catalysis. One of the main achievements is to stress the versatility of sol-gel preparation by highlighting its advantage over other preparation methods through some specific examples of the synthesis of catalysts.

Designing high‐performance and low‐cost electrocatalysts for oxygen evolution reaction (OER) is critical for the conversion and storage of sustainable energy technologies. Inspired by the biomineralization process, we utilized the phosphorylation sites of collagen molecules to combine with cobalt‐based mononuclear precursors at the molecular level and built a three‐dimensional (3D) porous hierarchical material through a bottom‐up biomimetic self‐assembly strategy to obtain single‐atom catalysts confined on carbonized biomimetic self‐assembled carriers (Co SACs/cBSC) after subsequent high‐temperature annealing. In this strategy, the biomolecule improved the anchoring efficiency of the metal precursor through precise functional groups; meanwhile, the binding‐then‐assembling strategy also effectively suppressed the nonspecific adsorption of metal ions, ultimately preventing atomic agglomeration and achieving strong electronic metal‐support interactions (EMSIs). Experimental characterizations confirm that binding forms between cobalt metal and carbonized self‐assembled substrate (Co–O4–P). Theoretical calculations disclose that the local environment changes significantly tailored the Co d‐band center, and optimized the binding energy of oxygenated intermediates and the energy barrier of oxygen release. As a result, the obtained Co SACs/cBSC catalyst can achieve remarkable OER activity and 24 h durability in 1 M KOH (η10 at 288 mV; Tafel slope of 44 mV dec−1), better than other transition metal‐based catalysts and commercial IrO2. Overall, we presented a self‐assembly strategy to prepare transition metal SACs with strong EMSIs, providing a new avenue for the preparation of efficient catalysts with fine atomic structures. This work inspired by the natural biomineralization process, utilizes the phosphate sites of collagen to anchor mononuclear transition metal precursors at the molecular level and form three‐dimensional porous single‐atom catalysts through bottom‐up biomimetic self‐assembly. The binding‐then‐assembling strategy effectively prevents atomic agglomeration and achieves strong electronic metal‐support interactions, thereby remarkably improving oxygen evolution reaction performance.

Supramolecular assemblies are essential components of living organisms. Cellular scaffolds, such as the cytoskeleton or the cell membrane, are formed via secondary interactions between proteins or lipids and direct biological processes such as metabolism, proliferation and transport. Inspired by nature’s evolution of function through structure formation, a range of synthetic nanomaterials has been developed in the past decade, with the goal of creating non-natural supramolecular assemblies inside living mammalian cells. Given the intricacy of biological pathways and the compartmentalization of the cell, different strategies can be employed to control the assembly formation within the highly crowded, dynamic cellular environment. In this Review, we highlight emerging molecular design concepts aimed at creating precursors that respond to endogenous stimuli to build nanostructures within the cell. We describe the underlying reaction mechanisms that can provide spatial and temporal control over the subcellular formation of synthetic nanostructures. Showcasing recent advances in the development of bioresponsive nanomaterials for intracellular self-assembly, we also discuss their impact on cellular function and the challenges associated with establishing structure–bioactivity relationships, as well as their relevance for the discovery of novel drugs and imaging agents, to address the shortfall of current solutions to pressing health issues. Creating artificial nanostructures inside living cells requires the careful design of molecules that can transform into active monomers within a complex cellular environment. This Review explores the recent development of bioresponsive precursors for the controlled formation of intracellular supramolecular assemblies.

Osteoarthritis (OA), a common degenerative disease, is characterized by high disability and imposes substantial economic impacts on individuals and society. Current clinical treatments remain inadequate for effectively managing OA. Organoids, miniature 3D tissue structures from directed differentiation of stem or progenitor cells, mimic native organ structures and functions. They are useful for drug testing and serve as active grafts for organ repair. However, organoid construction requires extracellular matrix-like 3D scaffolds for cellular growth. Hydrogel microspheres, with tunable physical and chemical properties, show promise in cartilage tissue engineering by replicating the natural microenvironment. Building on prior work on SF-DNA dual-network hydrogels for cartilage regeneration, we developed a novel RGD-SF-DNA hydrogel microsphere (RSD-MS) via a microfluidic system by integrating photopolymerization with self-assembly techniques and then modified with Pep-RGDfKA. The RSD-MSs exhibited uniform size, porous surface, and optimal swelling and degradation properties. In vitro studies demonstrated that RSD-MSs enhanced bone marrow mesenchymal stem cells (BMSCs) proliferation, adhesion, and chondrogenic differentiation. Transcriptomic analysis showed RSD-MSs induced chondrogenesis mainly through integrin-mediated adhesion pathways and glycosaminoglycan biosynthesis. Moreover, in vivo studies showed that seeding BMSCs onto RSD-MSs to create cartilage organoid precursors (COPs) significantly enhanced cartilage regeneration. In conclusion, RSD-MS was an ideal candidate for the construction and long-term cultivation of cartilage organoids, offering an innovative strategy and material choice for cartilage regeneration and tissue engineering. [Display omitted] •RGD-SF-DNA hydrogel microspheres (RSD-MSs) were prepared through photopolymerization and self-assembly.•RSD-MSs up-regulated integrin-mediated cell adhesion and focal adhesion pathways.•Cartilage organoid precursors significantly enhanced cartilage regeneration.•RSD-MS emerged as an ideal candidate for the construction of cartilage organoids.

Protein crystallization is an astounding feat of nature. Even though proteins are large, anisotropic molecules with complex, heterogeneous surfaces, they can spontaneously group into two-and three-dimensional arrays with high precision. And yet, the biggest hurdle in this assembly process, the formation of a nucleus, is still poorly understood. In recent years, the two-step nucleation model has emerged as the consensus on the subject, but it still awaits extensive experimental verification. Here, we set out to reconstruct the nucleation pathway of the candidate protein glucose isomerase (GI), for which there have been indications that it may follow a two-step nucleation pathway under certain conditions. We find that the precursor phase present during the early stages of the reaction process is nanoscopic crystallites that have lattice symmetry equivalent to the mature crystals found at the end of a crystallization experiment. Our observations underscore the need for experimental data at a lattice-resolving resolution on other proteins so that a general picture of protein crystal nucleation can be formed.

N -heterocyclic carbenes (NHCs) have been widely utilized for the formation of self-assembled monolayers (SAMs) on various surfaces. The main methodologies for preparation of NHCs-based SAMs either requires inert atmosphere and strong base for deprotonation of imidazolium precursors or the use of specifically-synthesized precursors such as NHC(H)[HCO 3 ] salts or NHC–CO 2 adducts. Herein, we demonstrate an electrochemical approach for surface-anchoring of NHCs which overcomes the need for dry environment, addition of exogenous strong base or restricting synthetic steps. In the electrochemical deposition, water reduction reaction is used to generate high concentration of hydroxide ions in proximity to a metal electrode. Imidazolium cations were deprotonated by hydroxide ions, leading to carbenes formation that self-assembled on the electrode’s surface. SAMs of NO 2 -functionalized NHCs and dimethyl-benzimidazole were electrochemically deposited on Au films. SAMs of NHCs were also electrochemically deposited on Pt, Pd and Ag films, demonstrating the wide metal scope of this deposition technique. N-heterocyclic carbenes (NHCs) have been widely used for the formation of monolayers but self-assembly methods come with drawbacks such as need for dry environment or using specifically-synthesized precursors. Here, the authors demonstrate an approach for surface-anchoring of NHCs which overcomes these limitations by using electrochemically-assisted deprotonation.

The preparation of topologically nontrivial molecules is often assisted by covalent, supramolecular or coordinative templates that provide spatial pre-organization for all components. Herein, we report a trefoil knot that can be self-assembled efficiently in water without involving additional templates. The direct condensation of three equivalents of a tetraformyl precursor and six equivalents of a chiral diamine produces successfully a [3 + 6] trefoil knot whose intrinsic handedness is dictated by the stereochemical configuration of the diamine linkers. Contrary to the conventional wisdom that imine condensation is not amenable to use in water, the multivalent cooperativity between all the imine bonds within the framework makes this trefoil knot robust in the aqueous environment. Furthermore, the presence of water is proven to be essential for the trefoil knot formation. A topologically trivial macrocycle composed of two tetraformyl and four diamino building blocks is obtained when a similar reaction is performed in organic media, indicating that hydrophobic effect is a major driving force behind the scene. The self-assembly of molecular knots in water is challenging. Here, authors report the self-assembly of a trefoil knot in water via imine condensation, without relying on external templates; the handedness of the trefoil knot is determined by the chirality of the bisamino precursor.