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The path to minimal life involves a series of stages that can be understood in terms of incremental, stepwise additions of complexity ranging from simple solutions of organic compounds to systems of encapsulated polymers capable of capturing nutrients and energy to grow and reproduce. This brief review will describe the initial stages that lead to populations of protocells capable of undergoing selection and evolution. The stages incorporate knowledge of chemical and physical properties of organic compounds, self-assembly of membranous compartments, non-enzymatic polymerization of amino acids and nucleotides followed by encapsulation of polymers to produce protocell populations. The results are based on laboratory simulations related to cyclic hydrothermal conditions on the prebiotic Earth. The final portion of the review looks ahead to what remains to be discovered about this process in order to understand the evolutionary path to minimal life.

An active droplet system, programmed to repeatedly move autonomously at a specific velocity in a well-defined direction, is demonstrated. Coulombic energy is stored in oversaturated interfacial assemblies of charged nanoparticle-surfactants by an applied DC electric field and can be released on demand. Spontaneous emulsification is suppressed by an increase in the stiffness of the oversaturated assemblies. Rapidly removing the field releases the stored energy in an explosive event that propels the droplet, where thousands of charged microdroplets are ballistically ejected from the surface of the parent droplet. The ejection is made directional by a symmetry breaking of the interfacial assembly, and the combined interaction force of the microdroplet plume on one side of the droplet propels the droplet distances tens of times its size, making the droplet active. The propulsion is autonomous, repeatable, and agnostic to the chemical composition of the nanoparticles. The symmetry-breaking in the nanoparticle assembly controls the microdroplet velocity and direction of propulsion. This mechanism of droplet propulsion will advance soft micro-robotics, establishes a new type of active matter, and introduces new vehicles for compartmentalized delivery.

Compartments are a fundamental feature of life, based variously on lipid membranes, protein shells, or biopolymer phase separation. Here, this combines self-assembling bacterial microcompartment (BMC) shell proteins and liquid-liquid phase separation (LLPS) to develop new forms of compartmentalization. It is found that BMC shell proteins assemble at the liquid-liquid interfaces between either 1) the dextran-rich droplets and PEG-rich continuous phase of a poly(ethyleneglycol)(PEG)/dextran aqueous two-phase system, or 2) the polypeptide-rich coacervate droplets and continuous dilute phase of a polylysine/polyaspartate complex coacervate system. Interfacial protein assemblies in the coacervate system are sensitive to the ratio of cationic to anionic polypeptides, consistent with electrostatically-driven assembly. In both systems, interfacial protein assembly competes with aggregation, with protein concentration and polycation availability impacting coating. These two LLPS systems are then combined to form a three-phase system wherein coacervate droplets are contained within dextran-rich phase droplets. Interfacial localization of BMC hexameric shell proteins is tunable in a three-phase system by changing the polyelectrolyte charge ratio. The tens-of-micron scale BMC shell protein-coated droplets introduced here can accommodate bioactive cargo such as enzymes or RNA and represent a new synthetic cell strategy for organizing biomimetic functionality.

Self-assembly of colloidal nanocrystals (NCs) into superlattices (SLs) is an appealing strategy to design hierarchically organized materials with promising functionalities. Mechanistic studies are still needed to uncover the design principles for SL self-assembly, but such studies have been difficult to perform due to the fast time and short length scales of NC systems. To address this challenge, we developed an apparatus to directly measure the evolving phases in situ and in real time of an electrostatically stabilized Au NC solution before, during, and after it is quenched to form SLs using small-angle X-ray scattering. By developing a quantitative model, we fit the time-dependent scattering patterns to obtain the phase diagram of the system and the kinetics of the colloidal and SL phases as a function of varying quench conditions. The extracted phase diagram is consistent with particles whose interactions are short in range relative to their diameter. We find the degree of SL order is primarily determined by fast (subsecond) initial nucleation and growth kinetics, while coarsening at later times depends nonmonotonically on the driving force for self-assembly. We validate these results by direct comparison with simulations and use them to suggest dynamic design principles to optimize the crystallinity within a finite time window. The combination of this measurement methodology, quantitative analysis, and simulation should be generalizable to elucidate and better control the microscopic self-assembly pathways of a wide range of bottom-up assembled systems and architectures.

It is unclear how severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) infection leads to the strong but ineffective inflammatory response that characterizes severe Coronavirus disease 2019 (COVID-19), with amplified immune activation in diverse cell types, including cells without angiotensin-converting enzyme 2 receptors necessary for infection. Proteolytic degradation of SARS-CoV-2 virions is a milestone in host viral clearance, but the impact of remnant viral peptide fragments from high viral loads is not known. Here, we examine the inflammatory capacity of fragmented viral components from the perspective of supramolecular self-organization in the infected host environment. Interestingly, a machine learning analysis to SARS-CoV-2 proteome reveals sequence motifs that mimic host antimicrobial peptides (xenoAMPs), especially highly cationic human cathelicidin LL-37 capable of augmenting inflammation. Such xenoAMPs are strongly enriched in SARS-CoV-2 relative to low-pathogenicity coronaviruses. Moreover, xenoAMPs from SARS-CoV-2 but not low-pathogenicity homologs assemble double-stranded RNA (dsRNA) into nanocrystalline complexes with lattice constants commensurate with the steric size of Toll-like receptor (TLR)-3 and therefore capable of multivalent binding. Such complexes amplify cytokine secretion in diverse uninfected cell types in culture (epithelial cells, endothelial cells, keratinocytes, monocytes, and macrophages), similar to cathelicidins role in rheumatoid arthritis and lupus. The induced transcriptome matches well with the global gene expression pattern in COVID-19, despite using

Artificial light harvesting, a process that involves converting sunlight into chemical potential energy, is considered to be a promising part of the overall solution to address urgent global energy challenges. Conjugated polyelectrolyte complexes (CPECs) are particularly attractive for this purpose due to their extended electronic states, tunable assembly thermodynamics, and sensitivity to their local environment. Importantly, ionically assembled complexes of conjugated polyelectrolytes can act as efficient donor-acceptor pairs for electronic energy transfer (EET). However, to be of use in material applications, we must understand how modifying the chemical structure of the CPE backbone alters the EET rate beyond spectral overlap considerations. In this report we investigate the dependence of the EET efficiency and rate on the electronic structure and excitonic wave function of the CPE backbone. To do so, we synthesized a series of alternating copolymers where the electronic states are systematically altered by introducing comonomers with electron withdrawing and electron-rich character while keeping the linear ionic charge density nearly fixed. We find evidence that the excitonic coupling may be significantly affected by the exciton delocalization radius, in accordance with analytical models based on the line-dipole approximation and quantum chemistry calculations. Our results imply that care should be taken when selecting CPE components for optimal CPEC EET. These results have implications for using CPECs as key components in water-based light-harvesting materials, either as standalone assemblies or as adsorbates on nanoparticles and thin films.

For over 60 years, cyclophanes have inspired the design of novel molecular architectures of different sizes and geometries, unleashing significant advances in supramolecular chemistry and also in biomedical and materials sciences. Reported cyclophanes are countless and more complex molecular structures continue to be spawned. Herein, the study classifies cyclophanes into different families to emphasize and feature their structure‐properties relationships. While neutral cyclophanes have attracted more attention owing to their solid‐state physical properties, water‐soluble anionic cyclophanes have been explored predominantly in drug delivery. In the broad family of cationic cyclophanes, viologen‐based cyclophanes (VBCs) are widely investigated for designing molecular interlocked molecules (MIMs), molecular switches, and machines owing to their unique electrochemical properties. Despite decades of ground‐breaking research in academia, controlling the cationic cyclophanes and MIMs solid‐state structures is still a limiting factor when it comes to introducing them into functional materials. Here, the study draws attention to some current challenges in cyclophane chemistry from a materials sciences perspective and highlights processes that, if overcome, would lead to cyclophanes producing transformational materials. It is envisioned that zwitterionic VBCs can have a seminal impact on host–guest chemistry, MIMs, molecular machines, and supramolecular tessellations, which can pave the way toward next‐generation technologies. [ABSTRACT FROM AUTHOR]

This work reports the synthesis and self‐assembly of perylene diimide (PDI)‐containing macrocycles designed for facile and high‐throughput production of shape‐persistent, macrocyclic organic electronic materials. Specifically, utilizing dynamic covalent chemistry (DCvC), this work showcases ditopic thiols can be utilized as building blocks toward 3D materials with defined porosity, low‐lying unoccupied molecular orbitals, and intrinsic fluorescence. The PDI disulfide‐linked macrocycles are generated in a single step from the thiolic building block to yield dimeric through pentameric assemblies in overall 95% combined yield; moreover, following self‐assembly, the disulfide ensemble is sulfur extruded to the more kinetically stable thioether in 79% combined yield. The modular design suggests these methods can be used to easily self‐assemble other electronically active precursors for utility in porous macrocyclic materials where stepwise pathways may be laborious and/or low yielding. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Kagome lattices have garnered significant attention due to their promising applications in catalysis, electronics, and magnetics. Although many efforts have been paid to the design and synthesis of Kagome lattices, there is a limited focus on constructing this lattice by multiple interaction forces. In this work, we employ 2,7‐dibromo‐carbazole as precursors to successfully fabricate the two‐dimensional self‐assembly Kagome lattices stabled by multiple interaction forces on Au(111) substrate. Using low‐temperature scanning tunneling microscopy, non‐contact atomic force microscopy and density functional theory calculation, we visualize and identify the four interaction forces within Kagome lattices: Au—N coordination bonds, Au—H hydrogen bonds, Br—Br halogen bonds, and Br—H hydrogen bonds, respectively. This study provides a basic understanding for designing and constructing more complex Kagome lattices. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Polycatenane gels have attracted extensive attention due to their high degree of freedom and mobility. However, the syntheses of poly[2]catenane gels reported to date all rely on the polymer as the backbone. Herein, we prepared poly[2]catenane gels based on entirely sequential assembly of small molecules. Monomer M1 with two unclosed rings was first prepared, which self‐assembled to form supramolecular polymers (SPs) via hydrogen bonding and π‐π interactions. Upon adding small molecule monomers M2 and M3 with aldehyde groups, ring closing of SPs occurred because the amino groups in the SPs reacted with M2 to form imine bonds. In addition, M3, which had twice the number of aldehyde groups as M2, enabled SPs to ring‐close, causing the proceeding of crosslinking process at the same time. Thus linear SPs were transformed into poly[2]catenane gel networks. Due to the presence of hydrogen bonds in the poly[2]catenane gel, the gel also possessed stimulus responsiveness and self‐healing properties. [ABSTRACT FROM AUTHOR]

[Display omitted] Since the chiral emission of excited states is observed on carbon dots (CDs), exploration towards the design and synthesis of chiral CDs nanomaterials with circularly polarized luminescence (CPL) properties has been at a brisk pace. In this regard, the "host and guest" co-assembly strategy based on the combination of CDs and chiral templates has been of unique interest recently for its convenient operation, multicolor tunable CPL, and wide application of prepared CDs-composited materials in optoelectronic devices and information encryption. However, the existing chiral templates that match perfectly with chiral CDs exhibiting optical activity both in ground and excited states are rather scarce. In this work, we synthesize the chiral CDs that could induce the spontaneous supramolecular self-assembly of N-(9-fluorenylmethox-ycarbonyl) (Fmoc)-protected glutamic acid to form chiral hydrogels with helical nanostructure. The co-assembled hydrogels show powerful chiral template function, which not only enable chiral CDs with a luminescence dissymmetry factor (g lum) up to 10-2, but also have universal chiral transfer to inserted dye molecules, realizing full-color CPL and Förster resonance energy transfer (FRET) CPL as well as the distinction between left and right circularly polarized light. This CPL-active template based on chiral CDs enriches the design scenario of chiral functionalized nanomaterials. [ABSTRACT FROM AUTHOR]

The evaporation-induced self-assembly process of amphiphilic molecules (4POSS-DL-POM) in a mixed acetone/ n -decane solution is investigated using small-angle X-ray scattering. A series of scattering data analysis methods is employed to elucidate the structural evolution of heterocluster 4POSS-DL-POM from a fractal network to compact nanoclusters, followed by the formation of core–shell nanoclusters, and ultimately to hcp superlattice structure. [Display omitted] Self-assembly of nanoclusters (NCs) is an effective synthetic method for preparing functionalized nanomaterials. However, the assembly process and mechanisms in solutions still remain ambiguous owing to the limited strategies to monitor intermediate assembled states. Herein, the self-assembly process of amphiphilic molecule 4POSS-DL-POM (consisting of four polyhedral oligomeric silsesquioxanes, a dendritic linker, and one polyoxometalate) by evaporation of acetone in a mixed acetone/ n -decane solution is monitored by time-resolved synchrotron small-angle X-ray scattering (SAXS). Scattering data assessments, including Kratky analysis, pair distance distribution function, and model fitting, track the self-assembly process of 4POSS-DL-POM from a fractal network to compact NCs, then to core–shell NCs, and finally to superlattice structure. The calculated average aggregation number of a core–shell NC is 11 according to the parameters obtained from core-shell model fitting, in agreement with electron microscopy. The fundamental understanding of the self-assembly dynamics from heterocluster into NCs provides principles to control building block shape and guide target aggregation, which can further promote the design and construction of highly ordered cluster-assembled functional nanomaterials. [ABSTRACT FROM AUTHOR]

Lung‐on‐chips (LoCs) are advanced microsystems designed to culture pulmonary cells under physiologically relevant conditions, including air–liquid interface, cell stretch, and shear stress. As the most promising preclinical models, the LoCs are aimed to reduce and ultimately replace conventional ineffective animal studies. Biomimetic and functional LoCs lead to more translational preclinical studies that effectively address unmet needs across therapeutic areas. A variety of cell‐ and scaffold‐based techniques are employed to establish biomimetic pulmonary cell models that closely resemble their in vivo counterparts, which is a challenging yet critical aspect of LoCs. Herein, the challenges encountered in biomimetic LoCs are discussed, and the future perspectives toward higher biomimicry using advanced biofabrication approaches are explored. [ABSTRACT FROM AUTHOR]

Two new structural motifs within the class of heteroleptic PdnAnBn assemblies, namely syn‐cis‐Pd3A3B3 bowls and bowl‐ (syn) or saddle‐ (anti) shaped cis‐Pd4A4B4 rings are introduced. All of the ten examples share a common longer fluorenone‐based bis‐monodentate ligand, equipped with meta‐pyridine donor groups. The ring size (3‐ vs. 4‐membered) and conformational preference (bowl vs. saddle) are controlled by the choice of the shorter ligand. These carry para‐pyridine donors, different aromatic backbones (benzene, thiophene or selenophene) and either no or small or bulky endohedral substituents, serving to control the nuclearity of the heteroleptic rings through different effects (ligand angle, charge distribution or backbone bulk). Moreover, the luminescence of the fluorenone ligand is conserved in the formed architectures. Emission intensity as well as host–guest properties vary depending on the inward‐pointing functions. All Pd3A3B3 assemblies are shown to bind chiral guest BINOL bis‐sulfonate which imparts its chirality to the entire host–guest complex. This results in a guest‐induced circular dichroism (CD) and circularly polarized luminescence (CPL) with dissymmetry factor glum up to 10−3. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Polycatenane gels have attracted extensive attention due to their high degree of freedom and mobility. However, the syntheses of poly[2]catenane gels reported to date all rely on the polymer as the backbone. Herein, we prepared poly[2]catenane gels based on entirely sequential assembly of small molecules. Monomer M1 with two unclosed rings was first prepared, which self‐assembled to form supramolecular polymers (SPs) via hydrogen bonding and π‐π interactions. Upon adding small molecule monomers M2 and M3 with aldehyde groups, ring closing of SPs occurred because the amino groups in the SPs reacted with M2 to form imine bonds. In addition, M3, which had twice the number of aldehyde groups as M2, enabled SPs to ring‐close, causing the proceeding of crosslinking process at the same time. Thus linear SPs were transformed into poly[2]catenane gel networks. Due to the presence of hydrogen bonds in the poly[2]catenane gel, the gel also possessed stimulus responsiveness and self‐healing properties. [ABSTRACT FROM AUTHOR]

Interface‐stabilizing polymers are frequently used in commercial applications to provide long‐lasting dispersions of colloids in liquid media. Dispersing high concentrations of pigments in aqueous solution can be particularly challenging. Here, we present a novel, fully hydrophilic dispersing agent system for carbon black (CB) pigments based on partially hydrolyzed poly(N‐vinylamides). These highly water‐soluble polymers adsorb onto CB through specific interactions between the polymer and surface‐bound moieties, rather than the hydrophobic effect. They participate in hydrogen bonding, ion–dipole interactions and can be partially positively charged to engage in ion pair formation, providing strong surface affinity. Dispersants are synthesized using free radical copolymerization of N‐vinylform‐ and ‐acetamide, acidic hydrolysis, and subsequent PEGylation. Molecular water solubility of the synthesized polymers is confirmed by using fluorescence spectroscopy. Highly concentrated CB dispersions are prepared in acidic, neutral, and basic media, which we identify to strongly affect the interactions between polymer and CB. The stability of CB dispersions is analyzed using ultracentrifugation and thermogravimetric analysis. The presented polymers are able to provide significantly more stable dispersions than a commercial reference product, showcasing the suitability of poly(N‐vinylamines) as potent CB dispersing agents. [ABSTRACT FROM AUTHOR]

Bis‐dioxolene ligands 1–5, linked by m‐dioxyarylene spacers were synthesized. Such ligands are considered as potential building blocks for coordination‐driven design of cage‐like units by self‐assembly mechanism. The peculiarity of new species is in presence of additional functional group in the linker such as pyridinyl (1), ester (2–3), and carboxyl (4–5) that add the possibilities for ordering modes during the design of coordination polymers. Di‐o‐quinones 1–2 were synthesized by reaction of 4‐chloro‐3,6‐di‐tert‐butyl‐o‐quinone (4‐Cl‐3,6‐Q) with pyridine‐3,5‐diol and methyl 3,5‐dixydroxybenzoate, respectively, in presence of base. The preparation of di‐o‐quinone 5 turned to be a multistage process where di‐catechols 3–4 were isolated as intermediates. [ABSTRACT FROM AUTHOR]

Achieving both high redox activity and rapid ion transport is a critical and pervasive challenge in electrochemical energy storage applications. This challenge is significantly magnified when using large‐sized charge carriers, such as the sustainable ammonium ion (NH4+). A self‐assembled MXene/n‐type conjugated polyelectrolyte (CPE) superlattice‐like heterostructure that enables redox‐active, fast, and reversible ammonium storage is reported. The superlattice‐like structure persists as the CPE:MXene ratio increases, accompanied by a linear increase in the interlayer spacing of MXene flakes and a greater overlap of CPEs. Concurrently, the redox activity per unit of CPE unexpectedly intensifies, a phenomenon that can be explained by the enhanced de‐solvation of ammonium due to the increased volume of 3 Å‐sized pores, as indicated by molecular dynamic simulations. At the maximum CPE mass loading (MXene:CPE ratio = 2:1), the heterostructure demonstrates the strongest polymeric redox activity with a high ammonium storage capacity of 126.1 C g−1 and a superior rate capability at 10 A g−1. This work unveils an effective strategy for designing tunable superlattice‐like heterostructures to enhance redox activity and achieve rapid charge transfer for ions beyond lithium. [ABSTRACT FROM AUTHOR]

Artificial light‐harvesting systems (LHSs) are of growing interest for their potential in energy capture and conversion, but achieving efficient fluorescence in aqueous environments remains challenging. In this study, a novel tetraphenylethylene (TPE) derivative, TPEN, is synthesized and co‐assembled with poly(sodium 4‐styrenesulfonate) (PSS) to enhance its fluorescence via electrostatic interactions. The resulting PSS⊃TPEN network significantly increased blue emission, which is further harnessed by an energy‐matched dye, 4,7‐di(2‐thienyl)benzo[2,1,3]thiadiazole (DBT), to produce an efficient LHS with yellow emission. Moreover, this system is successfully applied to develop color‐tunable light‐emitting diode (LED) devices. The findings demonstrate a cost‐effective and environmentally friendly approach to designing tunable luminescent materials, with promising potential for future advancements in energy‐efficient lighting technologies. [ABSTRACT FROM AUTHOR]

Self‐assembly has proven to be one of the effective methods for the formation of nanoscale therapeutics without the need to use nanodelivery systems. Such minimal models of supramolecular systems formed from amphiphilic photosensitizers (PS) have recently emerged as a new class of photoactive systems, providing unique and in some cases superior activities. Although the mechanism of photogenerated reactive oxygen species (ROS) in such systems is studied and to a certain extent understood, there are very limited studies investigating the influence of intricate environmental factors, including those occurring in the cellular environment, on the self‐assembly and thus the activity of the system. Understanding the optimal conditions for the formation of active PS aggregates is an important area of research in the field of photodynamic therapy (PDT), as it is directly linked to the optimal treatment dose. In this study, we describe the synthesis, self‐assembly properties, photophysical characterization, and photobiological efficacy of structurally closely related low‐symmetry phthalocyanine derivatives. Studying the decay behavior of the PS fluorescence lifetime in the presence of molecular crowders and different bacterial strains, we found that certain derivatives exhibited adaptive behavior and change in activity, while others demonstrated non‐adaptive characteristics. [ABSTRACT FROM AUTHOR]

Self‐assembly is an effective approach to construct complicated structures. Polyrotaxanes (PRs) as one of the typical polymer types with complex structure, own interlocked structures and dynamic components, in which it results in unique characteristics and functions. Currently, the synthesis of which involves covalent reactions to hinder the development of polyrotaxanes. Herein, we employed supramolecular interactions as well as dynamic covalent bonds to synthesize PRs by sequential self‐assembly. First, we prepared M1 possessing two diamine structures and M2 of a bisammonium salt with two dibenzylammonium (DBA) units modified by two stoppers at its ends, then M1 and M2 self‐assembled into supramolecular polymers stemming from hydrogen bonding of [N+−H ⋅ ⋅ ⋅ O] under high concentrations. After adding 2,6‐pyridinedicarboxaldehyde (M3), the imine bond formation enabled the generation of macrocycles, transforming supramolecular polymers into PRs. Besides, the solution of polyrotaxanes was applied as the adhesive for diverse hard and soft materials. This strategy provides an important approach for synthesizing PRs, accelerating the advances of mechanically interlocked polymers. [ABSTRACT FROM AUTHOR]

Organic luminescence materials makes the molecule more enthusiastic in wide variety of applications. The luminescent organic materials are in a attraction of the researchers, and the Aggregation‐Induced Emission (AIE) is attributed to the occurrence that particular chromophores (typically fluorophores) display very low or nearly no emission in the monomolecular soluble state but become highly emissive when forming aggregates in solution or in solid state. This phenomenon is relatively abnormal when compared with many other traditional fluorophores. AIE research suppresses aggregation‐caused quenching (ACQ). Nevertheless, the carbon dots (CDs) and quantum dots have shown to have tyical florescence properties, therefore, recent years many researchers have also attracted for their developments. The CDs, luminescent, and AIE materials are not only used in biomedical applications and organic light‐emitting diodes but also in sensing, self‐assembly, and other areas. One should introduce promising material to a designed framework that exhibits AIE characteristics to ensure moral results in AIE. Amongest, AIE‐active tetraphenylethylene (TPE) is attractive fluorophores due to its easy synthesis strategy. This review article discusses the synthesis properties of TPE, CDs, and luminescent materials with a broad range of applications. We have outlined linear, branched‐shaped supramolecular, and hybrid macromolecules due to its potential in the future. [ABSTRACT FROM AUTHOR]

Four new Ni16 molecular wheels with the general formula [L4Ni16(RCOO)16(H2O)x(MeOH)12‐x] (where H4L=1,4‐bis((E)‐((2'‐hydroxybenzyl)imino)methyl)‐2,3‐naphthalenediol, and R=H or Me) have been isolated and structurally characterised. Complexes C1−C3 (R=Me) were formed using nickel (II) acetate and presented as polymorphs with the same formulation of charged components. The same wheel‐like architecture was observed in C4 (R=H), which was prepared using nickel (II) formate, demonstrating the potential for further versatility of the system. In contrast to similar four‐fold symmetric Ni(II) wheel clusters, measurements of the static magnetic properties of C1 indicated the presence of dominant antiferromagnetic interactions and an S=0 ground state. [ABSTRACT FROM AUTHOR]

Gallium (Ga), a low‐melting‐point liquid metal with soft, metallic, and biocompatible properties, offers many possibilities. However, the potential of composites that integrate Ga with biomacromolecules, combining their biocompatibility, elasticity, and conductivity, has not been thoroughly explored, which is a gap for advancing these composites in various applications. In parallel and independently, protein self‐assembled l.,;3bhnanofibrils have attracted great interest as building blocks for functional biomaterials. Here, composites of Ga droplets and nanofibrils are presented, self‐assembled from plant proteins of soy protein isolate (SPI). It is evidenced that in these composites self‐assembled SPI nanofibrils can effectively reduce the oxidation of Ga droplets. It is observed that the composites of β‐sheet nanofibrils and Ga droplets offer mechanical properties similar to only fibrils‐based films. Films of 32 wt% Ga in SPI showed enhanced electrical conductivity and well‐structured nanofibrils with multifunctional potential in gas‐sensing and electronically controlled antibacterial applications. It is illustrated that the 32 wt% Ga in SPI composite offered the best sensing performance for a diatomic molecule, CO, and electro‐stimulation of this composite effectively reduced bacterial growth. The Ga in SPI composite, combining the advantages of protein nanofibrils and Ga droplets, offers great potential in future biomedical applications. [ABSTRACT FROM AUTHOR]

Bagworm silk proteins, which contain crystalline structures with large β‐nanocrystal sizes, are ideal candidates for biosynthetic high‐performance fibers. However, the extremely high glycine content and greater molecular weight limit their heterologous expression efficiency and further application exploration. Here, a multi‐module assembly strategy is developed to engineer novel chimeric structural proteins by incorporating the mechanical functional domains of bagworm silk proteins with the C‐terminal self‐assembly domains of spider silk proteins. By selecting a single repetitive unit of the functional region of bagworm silk proteins, the challenge of low heterologous expression efficiency is successfully addressed. Furthermore, the content and ordering of β‐sheet structure are enhanced in the chimeric proteins through the alignment mediated by the spider silk C‐terminal domain and ligation facilitated by split inteins, resulting in a remarkable Young's modulus of ≈15 GPa. This surpasses many artificial protein fibers, synthetic polymer fibers, and even natural spider silk. Notably, these protein fibers are drawn into surgical sutures and demonstrate superior wound healing effects compared to clinical suture in a skin wound model. This research presents a novel strategy for developing high‐performance protein fibers, which will expand the scope of their mechanically demanding applications. [ABSTRACT FROM AUTHOR]

The realization of persistent luminescence and in particular circularly polarized luminescence (CPL) of organic radicals remains a challenge due to their sensitivity to oxygen at ambient conditions and elusive excited state chirality control. Here, it is reported that UV‐irradiation on a supramolecular gel from a chiral triarylamine derivative, TPA‐Ala, led to the formation of luminescent radicals with bright CPL. TPA‐Ala can form an organogel in chloroform with blue emission and supramolecular chirality as demonstrated by both CD and CPL signals. Upon UV 365 nm irradiation, an emission color change from blue to cyan is observed due to the formation of photo‐induced radicals. Interestingly, it is found that the supramolecular gel radicals showed stable luminescence with a lifetime ≈ 10 days in dark environments and inverted CPL, which represents a scarce example with persistent CPL from doublet‐state due to oxygen isolation ability of the gel network. Furthermore, doping a guest dye, Rhodamine B (RhB), into the supramolecular gel (RhB/TPA‐Ala = 30% in molar ratio) successfully obtained a transient white‐light CPL through the superposition of photo‐induced radical and guest dye emissions. This work provides a useful methodology for the fabrication of radical‐based CPL materials via a supramolecular assembly approach. [ABSTRACT FROM AUTHOR]

Here we designed enantiomeric lipid‐mimetic glutamic acid derivatives (L/D‐UG) and investigated their self‐assembled chiral nanostructures' interaction with the protein adsorption as well as the osteogenesis. It was found that L or D‐UG molecules can self‐assemble into vesicle bilayers and two‐dimensional (2D) nanocrystals via a kinetic and thermodynamic control, respectively. These chiral vesicles and 2D crystals showed differentiated adsorption of proteins, determined by their curvature and chirality. Specifically, fibronectin constituted by L‐amino acids adsorbed preferentially on L‐UG 2D crystal in a semi‐random pattern and L‐2D nanocrystal show as the most effective structures to promote bone regeneration. The controlled vesicle and 2D crystal assemblies with different chirality and curvature helps to clarify their determine roles in protein adsorption and osteogenesis. [ABSTRACT FROM AUTHOR]

One of the central focuses in self‐assembly is precisely controlling the self‐assembly pathway so that the target molecules can be produced exclusively. Trans‐1,2‐cyclohexanediamine contains two amino units that form a 60° angle when projected on a plane. This angle naturally favors the formation of triangular products in most cases when trans‐1,2‐cyclohexanediamine is used as a bisamino building block in the synthesis of macrocycles and tubes. Here, we synthesized a slightly bent tetraformyl precursor bearing a central dibenzothiophene moiety, whose 3,7‐positions are functionalized with two m‐phthalaldehyde units. We observed that combining this tetraformyl building block with trans‐1,2‐cyclohexanediamine yielded a quadrangular tube when the concentrations of the precursors were relatively high. Both experimental measurements and theoretical calculations indicate that the formation of this unlikely occurring quadrangular product was driven by the intramolecular C−H⋅⋅⋅π interactions between the dibenzothiophene building blocks within the tube framework. This driving force, however, was disturbed in the triangular tube, a smaller counterpart whose formation was considered previously much more thermodynamically favored. These results improved our fundamental understanding on how to create those products whose syntheses are considered difficult or impossible, by modulating the intramolecular driving forces. [ABSTRACT FROM AUTHOR]

The anode is the key material that constrains the performance of solid oxide electrolysis cells (SOECs). Here, we have developed self-assembled Sm 0.5 Sr 0.5 CoO 3-δ -Ce 0.8 Sm 0.2 O 2-δ (SSC-SDC) composite by the co-synthesis strategy and studied its electrochemical performance as the anode for SOECs. The surface and interface properties of the self-assembled SSC-SDC composite were systematically studied. The SDC lattice expansion and the SSC lattice contraction of the SSC-SDC composite have been shown by XRD analysis, ascribed to the strong cation interdiffusion during the self-assembly process. The self-assembled SSC-SDC also exhibits superior oxygen evolution activity and displays a larger oxygen desorption peak than the physically mixed SSC&SDC. A higher proportion of adsorbed oxygen species on the surface of the self-assembled SSC-SDC than the physically mixed SSC&SDC also have been shown by XPS results. The cell with the self-assembled SSC-SDC as anode exhibits ca. 2.1 times higher current density than the physically mixed SSC&SDC as anode. Meanwhile, the polarization resistance of the cell with self-assembled SSC-SDC as the anode is 0.0957 Ω cm2, which is only 40 % of that observed in the cell where SSC and SDC are physically mixed as the anode. This novel self-assembly strategy shows great potential for preparing high-performance oxygen electrodes. [ABSTRACT FROM AUTHOR]

Giant tetrahedral molecules have sparked significant interest in the past decade due to their unique and diverse supramolecular nanostructures. The longer and bulkier peripheral substituents create deep molecular concavities and thus contribute to the different self‐assembly behaviors compared to the conventional small tetrahedral molecules. In this study, a molecular giant tetrahedra, TetraNDI, was synthesized to investigate the important roles of the molecular concavities in the self‐assembly mechanism. Single‐crystal structural characterizations indicate that the TetraNDI takes its trigonal concavities to form 1D supramolecular columns, and its tetragonal concavities to reach close inter‐columnar packing. The difficulty in occupying the concavities leads to the path‐dependent phase behaviors of the giant tetrahedra. It is also found that the remaining molecular concavities in the supramolecular scaffolds affect the CO2 affinity of TetraNDI. With an understanding of the packing principles of molecular giant tetrahedra, the structure‐property relationships could be better evaluated in the future and might broaden the horizon of porous materials. [ABSTRACT FROM AUTHOR]

Miniaturization of organic afterglow materials has shown promising application in biomedical and other areas. Current technologies, such as nanoprecipitation, mechanical treatment, and emulsion polymerization, lack the capability of facile control on the morphology and dimension of the miniaturized organic afterglow materials. Here we report the fabrication of organic afterglow nanostructures via block copolymer self‐assembly at room temperature. The fabrication is based on two‐component design strategy where hydrophobic luminescent emitters with small rate constants of phosphorescence decay or reverse intersystem crossing are designed as the first component. Amphiphilic block copolymers that can form spherical core‐shell micelles and worm‐like micelles with glassy hydrophobic cores are used as the second component. Upon addition of water into a dimethylformamide solution that contains the two components, the amphiphilic block copolymers self‐assemble into well‐defined nanostructures and accommodate the hydrophobic luminescent emitters in nanostructure's hydrophobic cores. After switching to pure water by dialysis, room‐temperature afterglow nanostructures have been obtained because of the excellent protection of organic triplets by the glassy hydrophobic cores. The afterglow nanostructures exhibit intriguing afterglow mechanism modulated by the types of luminescent emitters, controlled dimensions and morphologies by the structural parameters of the block copolymers. [ABSTRACT FROM AUTHOR]

Conventional chemotherapeutic agents are limited by their lack of targeting and penetration and their short retention time, and chemotherapy might induce an immune suppressive environment. Peptide self‐assembly can result in a specific morphology, and the resulting morphological changes are stimuli responsive to the external environment, which is important for drug permeation and retention of encapsulated chemotherapeutic agents. In this study, a polypeptide (Pep1) containing the peptide sequences PLGLAG and RGD that is responsive to matrix metalloproteinase 2 (MMP‐2) was successfully developed. Pep1 underwent a morphological transformation from a spherical structure to aggregates with a high aspect ratio in response to MMP‐2 induction. This drug delivery system (DI/Pep1) can transport doxorubicin (DOX) and indomethacin (IND) simultaneously to target tumor cells for subsequent drug release while extending drug retention within tumor cells, which increases immunogenic cell death and facilitates the immunotherapeutic effect of CD4+ T cells. Ultimately, DI/Pep1 attenuated tumor‐associated inflammation, enhanced the body's immune response, and inhibited breast cancer growth by combining the actions of DOX and IND. Our research offers an approach to hopefully enhance the effectiveness of cancer treatment. [ABSTRACT FROM AUTHOR]

Water-in-oil microemulsions, as stable colloidal dispersions from quasi-ternary mixtures, have been used in diverse applications, including nanoreactors for confined chemical processes. Their use as soft templates not only includes nanomaterial synthesis but also the interfacial assembly of nanoparticles in hybrid nanostructures. Especially the hierarchical arrangement of different types of nanoparticles over a surface in filament networks constitutes an interesting bottom-up strategy for facile and tunable film coating. Herein, we demonstrate the versatility of this surface assembly from microemulsion dispersions. Transmission and Scanning Electron Microscopy, in addition to UV–Vis Transmittance Spectroscopy, proved the assembly tunability after solvent evaporation under different conditions: the nanostructured films can be formed over different surfaces, using different compositions of liquid phases, as well as with the incorporation of different nanoparticle materials while keeping equivalent surface functionalization. This offers the possibility of adapting different components and conditions for coating tuning on a larger scale with simple procedures. [ABSTRACT FROM AUTHOR]

Supramolecules are considered a promising approach for molecular logic gates due to their inherent dynamic responsiveness driven by non‐covalent forces. However, the lack of input sequence dependence in these logic gates may lead to misinterpretation of outputs, compromising their reliability. This study proposes an efficient universal supramolecular Förster resonance energy transfer (FRET) platform for logic gates with self‐locking features. Specifically, well‐designed naphthalene‐based monomers serve as energy donors, while dyes such as eosin Y (EY), rhodamine B (RhB), and sulforhodamine 101 (SR101), spanning from yellow to red, are employed as energy acceptors. Leveraging large exciton migration rates (1.21 × 1014 to 1.36 × 1014 L mol−1 s−1) between donor and acceptors, FRET processes are effectively facilitated. Building upon this framework, supramolecular logic gates with self‐locking features are successfully constructed. Notably, in these logic gates, even with the correct truth table, any deviation in the order of inputs can lead to alterations in the original outputs. [ABSTRACT FROM AUTHOR]

Several bacterial strains have developed resistance against commercial antibiotics, and interestingly, supramolecular nanomaterials have shown considerable advantages for antibacterial applications. However, the main challenges in adopting nanotechnology for antibacterial studies are random aggregation, compromised toxicity, multi-step preparation approaches, and unclear structure-function properties. Herein, we designed the amphiphilic tripeptide that acts as a reducing and capping agent for silver metal to form silver-peptide colloidal nanohybrids with the mild assistance of UV light (254 nm) through the photochemical reduction method. The nanohybrids are characterized by different spectroscopic and microscopic techniques, and non-covalent molecular interactions between metal and peptide building blocks confirm their central role in the formation of nanohybrids. The tripeptide is biocompatible and can reduce the toxicity of silver ions (Ag+) by reducing to Ag0. These colloidal nanohybrids showed antibacterial activity against gram-negative and gram-positive bacterial strains, and the possible mechanism of killing bacterial cells could be membrane disruption. This synthetic strategy is facile and green, which helps avoid using toxic chemicals or reagents and complicated methods for colloidal nanohybrid preparation for biomedical applications. [ABSTRACT FROM AUTHOR]

Exine, this complex sporopollenin-containing and highly variable among taxa envelope of the male gametophyte, consists of two layers, ectexine and endexine. We traced in detail the pollen wall development in Lysimachia vulgaris (Primulaceae), with emphasis on driving forces and critical ontogenetic time. By observation on the sequence of the emergent patterns and by analysis of their substructure with TEM, we intended to clarify the obvious and not-obvious ways of exine construction and to find out the common features in pattern development in other representatives in living nature. The ectexine and endexine ontogeny follows the main stages observed in many other species: first, the appearance of microspore plasma membrane invaginations with isotropic contents within, changed later to anisotropic state; then successive appearance of spherical, rod-like, and lamellate units in the periplasmic space. The lamellate endexine appears unusually early in the exine development. All these elements and their aggregations are manifestation of well-known physical phenomena: phase separation and micellar self-assembly. A consideration of similar surface patterns in very remote taxa suggests the participation in their development of some general nature phenomena as the lows of space-filling operations. [ABSTRACT FROM AUTHOR]

While reaction-diffusion processes are utilized in multiple scientific fields, these phenomena have seen limited practical application in the polymer industry. Although self-regulating processes driven by parallel reaction and diffusion can lead to patterned structures, most polymeric products with repeating subunits are still prepared by methods that require complex and expensive instrumentation. A notable, high-added-value example is surgical mesh, which is often manufactured by weaving or knitting. In our present work, we demonstrate how the polymer and the biomedical industry can benefit from the pattern-forming capabilities of reaction-diffusion. We would like to propose a self-regulating method that facilitates the creation of surgical meshes from biocompatible polymers. Since the control of the process assumes a thorough understanding of the underlying phenomena, the theoretical background, as well as a mathematical model that can accurately describe the empirical data, is also introduced and explained. Our method offers the benefits of conventional techniques while introducing additional advantages not attainable with them. Most importantly, the method proposed in this paper enables the rapid creation of meshes with an average pore size that can be adjusted easily and tailored to fit the intended area of application. [ABSTRACT FROM AUTHOR]

BACKGROUND: Sturgeon cartilage type II collagen peptides (SHCPs) can self‐assemble and be used to prepare collagen peptide assemblies. Self‐assembled peptides have great potential for applications in the food industry. In the present study, self‐assembled peptides were prepared from sturgeon cartilage and then characterized. RESULTS: The SHCPs self‐assembled and formed collagen peptide assemblies. After response surface experiment optimization, the optimal enzyme digestion process comprised 43.1 °C, 3.37 h and 0.96% enzyme addition, and the peptide yield was 78.46%. Physicochemical analysis showed that the SHCPs were amphiphilic, with an average molecular weight of 1081 Da, and were rich in hydrophobic amino acids. Peptide sequence identification showed that the peptides of SHCPs with polar amino acids followed by hydrophobic amino acids could be self‐assembled through hydrogen bonding and hydrophobic interaction. Through turbidity experiments, Fourier transform infrared spectroscopy and scanning electron microscopy, we demonstrated that SHCPs can self‐assemble into reticular and tubular structures under specific conditions. Furthermore, both the SHCPs‐Ca and SHCPs‐Mg assemblies were stabilized within a pH range consistent with that of the human gastrointestinal tract. CONCLUSION: The present study provides a simple and safe method for preparing novel self‐assembled peptide materials from sturgeon by‐products, providing a scientific basis for the exploitation of sturgeon cartilage and potentially reducing resource wastage. © 2024 Society of Chemical Industry. [ABSTRACT FROM AUTHOR]

This study delineates the novel revelation that traditional Chinese medicine polysaccharides facilitate and expedite the intramolecular conformational alterations within filipin proteins, culminating in amplified β-fold content and self-assembly proclivity to generate hydrogels. Augmentation of assembly kinetics was achieved by pH or ethanol supplementation. The resultant self-assembled hydrogels exhibited homogenous pore size distribution, registering porosities consistently surpassing 95 ± 2.3%, effectively accommodating pharmaceutical payloads. Noteworthy characteristics included low water loss rates spanning between 15% and 25%, exceptional swelling behavior, a storage modulus (G') ranging from 68 to 283 Pa, and discernible mechanical robustness. Insights into the self-assembly mechanism were preliminarily explained via Fourier infrared, Raman spectroscopy and X-ray diffraction spectroscopy analyses. In-depth examinations, encompassing in-vitro release, degradation and biocompatibility, corroborated the hydrogel's capacity for smooth drug release, sustained stability, absence of cytotoxicity and favorable biocompatibility. In conclusion, the self-assembled filipin protein hydrogels preserved polysaccharide activity to a heightened extent and enhanced drug adaptability by reducing the overall formulation volume. This innovation, we suggest, holds significant promise for applications in sustained drug release and in the realm of tissue engineering materials. [ABSTRACT FROM AUTHOR]

Proteolysis targeting chimeras (PROTACs) have recently emerged as promising therapeutic agents for cancer therapy. However, their clinical application is considerably hindered by the poor membrane permeability and insufficient tumor distribution of PROTACs. Here we proposed a nanoengineered targeting strategy to construct a self-assembled affibody-PROTAC conjugate nanomedicine (APCN) for tumor-specific delivery of PROTACs. As proof of concept, a hydrophobic PROTAC MZ1 (a bromodomain-containing protein 4 degrader) was selected to couple with a hydrophilic affibody ZHER2:342 (an affinity protein of human epidermal growth factor receptor 2, HER2) via a smart linker containing disulfide bond to form an amphiphilic ZHER2:342-MZ1 conjugate. It spontaneously self-assembled into nanoparticles (ZHER2:342-MZ1 APCN) in water. Upon the excellent targeting property of ZHER2:342 and HER2 receptor-mediated endocytosis, ZHER2:342-MZ1 APCN was accumulated in tumor sites and internalized by cancer cells effectively in vitro. Under the intracellular high level of glutathione (GSH), ZHER2:342-MZ1 APCN released MZ1 to specifically degrade bromodomain-containing protein 4 (BRD4) and subsequently induced BRD4 deficiency-mediated apoptosis of cancer cells. By the tail-vein injection, ZHER2:342-MZ1 APCN showed the outstanding tumor-specific targeting ability, drug accumulation capacity, enhanced BRD4 degradation and antitumor efficacy in vivo for an HER2-positive SKOV-3 tumor model. Such an affibody mediated nanoengineered strategy would facilitate the application of PROTACs for targeted cancer therapy. [ABSTRACT FROM AUTHOR]

Self‐repairing catalysts are useful for achieving alkaline water electrolyzers with long lifetimes under intermittent operation. However, rational methodologies for designing self‐repairing catalysts have not yet been established. Herein, hybrid cobalt hydroxide nanosheets (Co‐ns), with a high deposition (repairing) rate, and β‐FeOOH nanorods (Fe‐nr), with high oxygen evolution reaction (OER) ability, are electrostatically self‐assembled into composite catalysts. This strategy is developed to integrate multifunctionality in self‐repairing catalysts. Positively charged Co‐ns and negatively charged Fe‐nr form uniform composites when dispersed in an electrolyte. These composites are electrochemically deposited on a nickel electrode by electrolysis at 800 mA cm−2. Co‐ns form a conductive mesoporous assembly of CoOOH nanosheets as a support. Fe‐nr are then distributed on the CoOOH nanosheets as active sites for the OER. Because of the high deposition rate of Co‐ns, the amount of Fe‐nr deposited increases 22 times compared to when Fe‐nr is deposited alone, and the OER current density increases 14 times compared to that of Co‐ns alone. The composite self‐repair catalyst shows the highest activity and durability under an accelerated durability test (ADT), and its degradation rate decreases from 84 μV cycle−1 (Fe‐nr only) to 60 μV cycle−1 (composite catalyst) under ADT conditions without repair. [ABSTRACT FROM AUTHOR]

The possibility of introducing various functionalities on peptides with relative ease allows them to be used for molecular applications. However, oligopeptides prepared entirely from proteinogenic amino acids seldom assemble as ordered structures on surfaces. Therefore, sidechain modifications of peptides that can increase the intermolecular interactions without altering the constitution of a given peptide become an attractive route to self‐assembling them on surfaces. We find that replacing phenylalanine residues with unusual amino acids that have phenylcarbonyl sidechains in oligopeptides increases the formation of ordered self‐assembly on a highly ordered pyrolytic graphite surface. Peptides containing the modified amino acids provided extended long‐range ordered assemblies, while the analogous peptides containing phenylalanine residues failed to form long‐range assemblies. X‐ray crystallographic analysis of the bulk structures of these peptides and the analogous peptides containing phenylalanine residues reveal that such modifications do not alter the secondary structure in crystals. It also reveals that the secondary hydrogen bonding interaction through phenylcarbonyl sidechains facilitates extended growth of the peptides on graphite. [ABSTRACT FROM AUTHOR]

Self‐assembled peptides are used for diverse applications in the biomedical and technological fields. The morphology and function of the assembled systems are dictated by the peptide sequence and length. In this work, a supramolecular catalyst was obtained upon self‐assembly of the diphenylalanine peptide conjugated to a triphenylphosphine Au(I) complex in acetonitrile. The assembled molecules were characterized by spectroscopic techniques and by scanning electron microscopy. The activity of the catalyst was tested on two substrates in cyclization reactions. The morphology and the dimensions of the assembled systems vary depending on the presence of a carboxyl versus an amide C‐terminal end. The catalyst efficiently promotes intramolecular cyclization reactions. Results obtained encourage the use of self‐assembled peptides for the obtainment of new and efficient catalysts. [ABSTRACT FROM AUTHOR]

Nanostructures formed by self-assembly of semiconductor nanoparticles have unique properties that make them useful in various fields. In particular, cadmium telluride is being actively studied in the field of solar cells on the strengths of its long-term stability and low cost. In this study cadmium telluride nanoparticles were synthesized into nanowires in the dark and their evolutionary process was investigated. Thioglycolic acid was selected from among several thiol-based stabilizers. A ratio of 1.4:1 (thioglycolic acid to cadmium ion) was used rather than the traditional 2.4:1 ratio. In this study, nanowires were prepared by self-assembly of nanoparticles and the process of forming straight nanowires was observed. Synthesized nanowires were observed by using a scanning electron microscope and a transmission electron microscope, and the synthesized nanostructures were characterized. The wavelength of photoluminescence was converted from 549.9 nm to 553.3 nm as nanoparticles transformed into nanowires in an aqueous solution. The nanowire solution did not precipitate even after 60 days. The suggested synthetic procedure thus provides a viable pathway for the fabrication of nanomaterials. [ABSTRACT FROM AUTHOR]

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The wide-spreading of multidrug resistance poses a significant threat to human and animal health. Although antimicrobial peptides (AMPs) show great potential application, their instability has severely limited their clinical application. Here, self-assembled AMPs composed of multiple modules based on the principle of associating natural marine peptide N6 with ß-sheet-forming peptide were designed. It is noteworthy that one of the designed peptides, FFN could self-assemble into nanoparticles at 35.46 µM and achieve a dynamic transformation from nanoparticles to nanofibers in the presence of bacteria, resulting in a significant increase in stability in trypsin and tissues by 1.72–57.5 times compared to that of N6. Additionally, FFN exhibits a broad spectrum of antibacterial activity against multidrug-resistant (MDR) gram-positive (G+) and gram-negative (G−) bacteria with Minimum inhibitory concentrations (MICs) as low as 2 µM by membrane destruction and complemented by nanofiber capture. In vivo mouse mastitis infection model further confirmed the therapeutic potential and promising biosafety of the self-assembled peptide FFN, which can effectively alleviate mastitis caused by MDR Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus), and eliminate pathogenic bacteria. In conclusion, the design of peptide-based nanomaterials presents a novel approach for the delivery and clinical translation of AMPs, promoting their application in medicine and animal husbandry. [ABSTRACT FROM AUTHOR]

Bioactive peptides play crucial roles in the biomedicine fields including cancer therapy and regenerative medicine due to their favorable biocompatibility, low immunogenicity, and excellent biological activity. However, their low stability greatly limits their clinical application. Herein, a novel bioactive peptide delivery strategy is reported that utilizes triphen[3]arene polyvalent‐conjugated bioactive peptides to induce self‐assembly and form nanofibers to enhance the in vivo stability and bioactivity of bioactive peptides. Specifically, a water‐soluble triphen[3]arene (WTP3(YRSRK)6, Comp. 2) containing six FGF‐mimicking peptides, primarily comprising two components: triphen[3]arene serves as a skeleton molecule and an assembly motif with multiple customizable sites, while YRSRK is a pentapeptide with fibroblast growth factor 2 (FGF‐2) biological activity. Despite the presence of the inhibitor dexamethasone (Dex), Comp. 2 continued to enhance cell proliferation by 15% and rescued 17% of cells from apoptosis. The administration of Comp. 2 resulted in improved restoration of skeletal muscle atrophy and functional damage in mice. The mean grip strength increased by 42%, and the calf muscle volume increased by 17%. This innovative approach of utilizing macrocycle polyvalent conjugated bioactive peptides offers a universal method for enabling bioactive peptides to produce sustained and efficient biological effects, potentially advancing the development of promising peptide‐based nanomedicines. [ABSTRACT FROM AUTHOR]

N‐substituted pyridino‐based congeners of Ebselen, named here as Pyrselen, incorporating proximal Se and N atoms, undergo dimerization in solution and the solid state through a dual donor‐acceptor arrangement of chalcogen bonding sites. Dimerization constants were measured within the 5–50 M−1 range. Computational studies on the dimers depict a notable charge‐transfer contribution to the association, validating Pyrselen as an effective scaffold for designing chalcogen‐bonding‐based recognition motifs. [ABSTRACT FROM AUTHOR]

Nanocarriers are essential for targeted and enhanced drug delivery. However, the use of toxic solvent and the complex of chemical functionalization have seriously limited their clinical translation. Here, a one‐step strategy is developed to direct the self‐assembly of biocompatible core‐shell nanocapsules with tunable surface functionality by microfluidics. Upon rapid mixing and solvent exchange of ethanol with water in a microfluidic device, drug, oil, polymer, and polymer‐PEG‐function co‐precipitate and self‐assemble into core‐shell nanocapsules with desired surface functionality as driven by energy minimization. The prepared PCL‐PEG‐FA core‐shell nanocapsules demonstrate a high encapsulation efficiency and loading capacity and exhibit excellent tumor‐targeting drug delivery performances both in vitro and in vivo via the binding of functional group on the nanocapsule surface with corresponding receptor on the tumor cell membrane. The immune activation in the tumor microenvironment is investigated in detail by flow cytometry and multiplex immunohistochemistry staining to reveal the underlying mechanism for enhanced anti‐tumor performances. The developed strategy is green, facile, versatile, scalable and offers a promising platform for the design of advanced nanocarriers with hierarchical structure and desired function for enhanced drug delivery. [ABSTRACT FROM AUTHOR]

Biofilm‐associated infections pose complex challenges that require addressing the multifaceted requirements of biofilm disruption, bacterial killing, and immunomodulation. In this study, microenvironment‐adaptive metallo‐polymeric nanodecoys (MPNs) are synthesized through one‐pot subcomponent coordination in aqueous solution, effectively eradicating bacterial biofilms and modulating immune response. Within the acidic microenvironment of biofilms, the positively charged MPNs demonstrated the ability to interact with and eliminate bacteria while facilitating a Fenton‐like reaction for efficient eradication of bacterial biofilms. As the local microenvironment shifted from a neutral to a basic state during subsequent tissue healing processes, the MPNs adaptively harness the multiple properties to bind pathogen‐associated molecular patterns, scavenge reactive oxygen species, thereby modulating the immune response, alleviating inflammation, and promoting tissue healing. This study presents an efficient strategy for preparing enzyme‐mimicking materials that closely resemble natural metalloenzymes, and the MPNs offer an efficient alternative to current antibiotic treatments for biofilm‐associated infections. [ABSTRACT FROM AUTHOR]