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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.

T‐cell acute lymphoblastic leukemia (T‐ALL) is a highly aggressive hematologic malignancy with limited targeted therapies. CD28, a costimulatory receptor aberrantly overexpressed on T‐ALL cells, presents a promising underexplored therapeutic target. In this study, we developed an enzyme‐responsive self‐assembling peptide, SAp‐CD28, designed to target CD28 and undergo receptor‐mediated self‐assembly in the tumor microenvironment. Upon dephosphorylation by overexpressed phosphatases, SAp‐CD28 transitions from an α‐helix to a β‐sheet/β‐turn rich structure, facilitating the formation of nanooligomers that engage CD28 and activate cytotoxic pathways. Transcriptomic and biochemical analyses reveal that SAp‐CD28 induces a profound dysregulation of CD28 downstream signaling, characterized by the suppression of the PLCγ and Akt pathways. These signaling perturbations lead to oxidative stress and disruption of intracellular calcium homeostasis, resulting in calcium overload, calpain activation, and cytoskeletal collapse. Besides, confocal imaging suggested that the peptide self‐assembly can enter the nucleus and disrupt it. In Jurkat xenograft models, SAp‐CD28 demonstrated potent antitumor activity, and its combination with cytarabine resulted in near‐complete tumor suppression, highlighting its potential for T‐ALL treatment. This work introduces a CD28‐targeted, enzyme‐activated nanotherapeutic strategy that synergizes biochemical and mechanical mechanisms to selectively eliminate T‐ALL cells. This multi‐mechanistic tumor‐killing strategy can also be extended to inspire therapeutic approaches for other diseases. We developed the enzyme‐responsive peptide SAp‐CD28 to selectively target CD28‐overexpressing T‐ALL cells. Following phosphatase‐mediated activation, SAp‐CD28 undergoes conformational switching and nanooligomerization, resulting in the disruption of CD28 downstream signaling. This includes suppression of the PLCγ and Akt pathways, triggering oxidative stress, calcium overload, cytoskeletal collapse, and necrotic cell death. In vivo, SAp‐CD28 effectively inhibited Jurkat xenograft growth and tumor inhibition.

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.

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.

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.

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.

L1 0 -FePt-type bit-patterned media has provided a promising alternative for ultrahigh-density magnetic recording systems in the current digital era, but rapid fabrication of magnetic patterns with hyperfine bit islands is still challenging, especially with the target for miniaturization and scalable production simultaneously. Herein, Fe,Pt-containing block copolymers were utilized as single-source precursors for solution-processable patterning and subsequent generation of the demanding magnetic FePt dots by in situ pyrolysis. High-throughput nanoimprint lithography was initially employed to fabricate the predefined bit cells precisely, and then the intrinsic self-assembly of phase-separated block copolymers further drove the formation of accurate bit islands. Benefiting from the synergistic effect of top-down lithographic approach and bottom-up self-assembly, the customizable patterns could be achieved for large-scale mass production in targeted areas, but high-density isolated dots could also be accurately aligned along the patterned features after subsequent self-assembly. This reliable strategy would provide a good avenue to precisely construct ultrahigh-density magnetic data storage devices.

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.

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.