Magnetic Nanoparticle Chains in Gelatin Ferrogels: Bioinspiration from Magnetotactic Bacteria

Inspired by chains of ferrimagnetic nanocrystals (NCs) in magnetotactic bacteria (MTB), the synthesis and detailed characterization of ferrimagnetic magnetite NC chain‐like assemblies is reported. An easy green synthesis route in a thermoreversible gelatin hydrogel matrix is used. The structure of these magnetite chains prepared with and without gelatin is characterized by means of transmission electron microscopy, including electron tomography (ET). These structures indeed bear resemblance to the magnetite assemblies found in MTB, known for their mechanical flexibility and outstanding magnetic properties and known to crystallographically align their magnetite NCs along the strongest <111> magnetization easy axis. Using electron holography (EH) and angular dependent magnetic measurements, the magnetic interaction between the NCs and the generation of a magnetically anisotropic material can be shown. The electro‐ and magnetostatic modeling demonstrates that in order to precisely determine the magnetization (by means of EH) inside chain‐like NCs assemblies, their exact shape, arrangement and stray‐fields have to be considered (ideally obtained using ET).     

Tuning Magnetic Property and Autophagic Response for Self‐Assembled Ni–Co Alloy Nanocrystals

Induction of autophagy is a common response of cells upon exposure to nanomaterials and represents both a safety concern and an application niche for engineered nanomaterials. Herein, it is reported that the magnetic property and the autophagy‐inducing activity for Ni–Co alloy nanocrystal (NC) assemblies can be differentially “tuned” through altering the material composition. A series of Ni–Co alloy NC assemblies, composed of nanoparticles (NPs) with a size of about 30 nm, can be quickly synthesized under microwave irradiation in aqueous solution. A controllable self‐assembling effect is observed due to the strong magnetic moment of NPs and external magnetic field. Interestingly, the saturation magnetization (Ms) shows a ‘roller coaster’ effect with varying component molar ratio, while the autophagy‐inducing activity and toxicity of these alloy NCs presents an elevated tendency with the increase of nickel component. The autophagic response partly contributes to the observed cellular toxicity of the NC assemblies, as inhibition of autophagy partially but significantly reduces toxicity. Therefore, through tuning the composition of the alloy, optimal Ni–Co NCs satisfying the needs of different applications such as diagnostic imaging (maximum magnetization and low autophagic response) or magnetically‐directed cancer cell killing (maximum autophagic response and sufficient magnetization) may be designed and developed.     

Copper(I) Phosphide Nanocrystals for In Situ Self‐Generation Magnetic Resonance Imaging‐Guided Photothermal‐Enhanced Chemodynamic Synergetic Therapy Resisting Deep‐Seated Tumor

Fe‐based Fenton agents can generate highly reactive and toxic hydroxyl radicals (·OH) in the tumor microenvironment (TME) for chemodynamic therapy (CDT) with high specificity. However, the strict condition (lower pH environment: 3–4) of the highly efficient Fenton reaction limits its practical application in the clinic. Development of new CDT agents more suitable for TME is significant and challenging. A highly efficient Cu(I)‐based CDT agent, copper(I) phosphide nanocrystals (CP NCs), which is more adaptable to the pH value of TME than Fe‐based agents, thereby producing more ·OH to trigger the apoptosis of cancer cells, is prepared. Moreover, the excess glutathione (GSH) in TME can reduce the Cu(II) produced by a Fenton‐like reaction to Cu(I), further increasing the generation rate of ·OH and relieving tumor antioxidant ability. Furthermore, owing to their strong absorption in the NIR II region, CP NCs exhibit an excellent photothermal conversion effect, which can further improve the Fenton reaction. What is more, CP NCs can act as in situ self‐generation magnetic resonance imaging (MRI) agents owing to the generation of paramagnetic Cu(II) in response to excess H₂O₂ in the TME. These properties may open up the exploration of copper‐based materials in clinical application of self‐generation imaging‐guided synergetic treatment.     

Directed Self‐Assembly as a Route to Ferromagnetic and Superparamagnetic Nanoparticle Arrays

Block co‐polymer patterns are attractive candidates for nanoparticle assemblies. Directed self‐assembly of block co‐polymers in particular allows for long range ordering of the patterns, making them interesting scaffolds for the organization of magnetic particles. Here, a method to tune the channel width of polymer‐derived trenches via atomic layer deposition (ALD) of alumina is reported. The alumnia coating provides a much more thermally robust pattern that is stable up to 250 °C. Using these patterns, magnetic coupling in both ferromagnetic and superparamagnetic nanocrystal chains is achieved.     

DNA Origami‐Guided Assembly of the Roundest 60–100 nm Gold Nanospheres into Plasmonic Metamolecules

DNA origami can provide programmed information to guide the self‐assembly of gold nanospheres (Au NSs) into higher‐order supracolloids. Molecularly precise and truly 2D/3D integration of Au NSs is possible using DNA origami‐enabled assembly, and the resulting assemblies have potential applications in plasmonics and metamaterials. However, the relatively small size (<60 nm) and randomly faceted Au NSs that have been used thus far in DNA origami‐enabled assembly have limited their nanophotonic applications. Here, the robust self‐assembly of the 60–100 nm roundest Au NSs into metamolecular assemblies using 3D DNA origami is described. These Au NSs are successfully conjugated with DNA oligonucleotides and are therefore stable at high salt concentrations even without backfilling using organic ligands. The roundest Au NSs are successfully assembled into supracolloidal metamolecules and chains via 3D DNA origami. These plasmonic metamolecules and chains display strong electric and unnatural magnetic resonances that can be deterministically controlled.     

Self-Assemblies of Fe3O4 Nanocrystals: Toward Nanoscale Precision of Photothermal Effects in the Tumor Microenvironment

Fe₃O₄ nanocrystals are self-assembled into two different conformations: colloidosome and supraball that confer them with distinct properties determining their photo-induced heating capacities. These self-assemblies are assessed for photothermal therapy, an adjuvant strategy for tumor therapy. The tumor microenvironment is a heterogeneous ecosystem including immune cells and the extracellular matrix. The interactions between photothermal therapy agents and the different components of the tumor microenvironment determine the outcome of this therapy. In this study, the fate of both colloidosomes and supraballs within the tumor microenvironment in comparison to their Fe₃O₄ nanocrystal building blocks is revealed. This study highlights how these two hybrid self-assemblies target different compartments of the tumor microenvironment and trigger local photothermal damages that are inaccessible for isolated nanocrystals and not predicted by global temperature measurements.     

Soft Nanotubes with a Hydrophobic Channel Hybridized with Au Nanoparticles: Photothermal Dispersion/Aggregation Control of C60 in Water

Simple glycolipid N‐alkaroyl‐β‐D‐glucopyranosylamine 1(n) selectively self‐assembles into sheets in water, nanotubes in alcohols, and helical nanocoils in toluene. All self‐assemblies consist of bilayer membranes in which 1(n) packed in an interdigitated fashion. The outer surface of the sheet is covered with the hydrophilic glucose headgroup of 1(n), whereas those of the nanotube and helical nanocoil are covered with the hydrophobic alkyl‐chain tail of 1(n). Heat treatment of the nanotube in the presence of water induces a rearrangement of the molecular packing of the outermost surface that allows the nanotube to become an effective nanocontainer for the dispersion of fullerene (C60) in water, a result of the ability of the hydrophilic outer surface of the nanotube and the hydrophobic nanochannel to encapsulate C60. The nanotube also exhibits photothermal characteristics after being hybridized with Au nanoparticles (AuNPs). The photothermal effect of the AuNPs allows the nanotube to unfold its tubular morphology and leads to compulsive release of the encapsulated C60 to the bulk water. Application of other nanotubes with similar photostimulated transformation ability should facilitate control of the dispersion/aggregation of other carbon nanomaterials, functional aromatic compounds, and drugs with low solubility in water.     

Self‐Healing Graphene Oxide Based Functional Architectures Triggered by Moisture

Self‐healing materials are capable of spontaneously repairing themselves at damaging sites without additional adhesives. They are important functional materials with wide applications in actuators, shape memorizing materials, smart coatings, and medical treatments, etc. Herein, this study reports the self‐healing of graphene oxide (GO) functional architectures and devices with the assistance of moisture. These GO architectures can completely restore their mechanical‐performance (e.g., compressibility, flexibility, and strength) after healing their broken sites using a little amount of water moisture. On the basis of this effective moisture‐triggered self‐healing process, this study develops GO smart actuators (e.g., bendable actuator, biomimetic walker, rotatable fiber motor) and sensors with self‐healing ability. This work provides a new pathway for the development of self‐healing materials for their applications in multidimensional spaces and functional devices.     

Magnetically Enhanced Mechanical Stability and Super‐Size Effects in Self‐Assembled Superstructures of Nanocubes

Artificial materials from the self‐assembly of magnetic nanoparticles exhibit extraordinary collective properties; however, to date, the contribution of nanoscale magnetism to the mechanical properties of this class of materials is overlooked. Here, through a combination of Monte Carlo simulations and experimental magnetic measurements, this contribution is shown to be important in self‐assembled superstructures of magnetite nanocubes. By simulating the relaxation of interacting macrospins in the superstructure systems, the relationship between nanoscale magnetism, nanoparticle arrangement, superstructure size, and mechanical stability is established. For all considered systems, a significant enhancement in cohesive energy per nanocube (up to 45%), and thus in mechanical stability, is uncovered from the consideration of magnetism. Magnetic measurements fully support the simulations and confirm the strongly interacting character of the nanocube assembly. The studies also reveal a novel super‐size effect, whereby mechanically destabilization occurs through a decrease in cohesive energy per nanocube as the overall size (number of particles) of the system decreases. The discovery of this effect opens up new possibilities in size‐controlled tuning of superstructure properties, thus contributing to the design of next‐generation self‐assembled materials with simultaneous enhancement of magnetic and mechanical properties.     

Silicon‐Based Self‐Assemblies for High Volumetric Capacity Li‐Ion Batteries via Effective Stress Management

Silicon nanoparticles (Si NPs) have been considered as promising anode materials for next‐generation lithium‐ion batteries, but the practical issues such as mechanical structure instability and low volumetric energy density limit their development. At present, the functional energy‐storing architectures based on Si NPs building blocks have been proposed to solve the adverse effects of nanostructures, but designing ideal functional architectures with excellent electrochemical performance is still a significant challenge. This study shows that the effective stress evolution management is applied for self‐assembled functional architectures via cross‐scale simulation and the simulated stress evolution can be a guide to design a scalable self‐assembled hierarchical Si@TiO₂@C (SA‐SiTC) based on core–shell Si@TiO₂ nanoscale building blocks. It is found that the carbon filler and TiO₂ layer can effectively reduce the risk of cracking during (de)lithiation, ensuring the stability of the mechanical structure of SA‐SiTC. The SA‐SiTC electrode shows long cycling stability (842.6 mAh g^?1 after 1000 cycles at 2 A g^?1), high volumetric capacity (174 mAh cm^?3), high initial Coulombic efficiency (80.9%), and stable solid‐electrolyte interphase (SEI) layer. This work provides insight into the development of the structural stable Si‐based anodes with long cycle life and high volumetric energy density for practical energy applications.     

Embedding Perovskite Nanocrystals into a Polymer Matrix for Tunable Luminescence Probes in Cell Imaging

Lead halide perovskite nanocrystals (NCs) with bright luminescence and broad spectral tunability are good candidates as smart probes for bioimaging, but suffer from hydrolysis even when exposed to atmosphere moisture. In this paper, a strategy is demonstrated by embedding CsPbX₃ (X = Cl, Br, I) NCs into microhemispheres (MHSs) of polystyrene matrix to prepare “water‐resistant” NCs@MHSs hybrids as multicolor multiplexed optical coding agents. First, a facile room‐temperature solution self‐assembly approach to highly luminescent colloidal CsPbX₃ NCs is developed by injecting a stock solution of CsX?PbX₂ in N ,N ‐dimethylformamide into dichloromethane. Polyvinyl pyrrolidone (PVP) is chosen as the capping ligand, which is physically adsorbed and wrapped on the surface of perovskite NCs to form a protective layer. The PVP protective layer not only leads to composition‐tunable CsPbX₃ NCs with high quantum yields and narrow emission linewidths of 12–34 nm but also acts as an interfacial layer, making perovskite NCs compatible with polystyrene polymers and facilitating the next step to embed CsPbX₃ NCs into polymer MHSs. CsPbX₃ NCs@MHSs are demonstrated as multicolor luminescence probes in live cells with high stability and nontoxicity. Using ten intensity levels and seven‐color NCs@MHSs that show non‐overlapping spectra, it will be possible to individually tag about ten million cells.     

TpyCo2+‐Based Coordination Polymers by Water‐Induced Gelling Trigged Efficient Oxygen Evolution Reaction

Though the use of conventional self‐assembled architectures in functional applications involving advanced energy chemistries is an important research area, it remains largely unexplored. The self‐assembly of the threefold and sixfold‐symmetric terpyridines (tpy) with Co(II) salts results in a novel morphological and structural characteristics, regardless of the nature of the self‐assembled fragments. Herein, such metallopolymers are achieved by one‐pot synthesis in CH₃OH/CHCl₃ (v/v = 5:1) mixture ambient. It is found, for the first time, that Co‐containing polymers can be well dispersed in deionized water to form gel‐like self‐assemblies that consist of a highly interconnected 3D network and exhibit enhanced electrical conductivity and thus are attractive as electrocatalysts. As expected, the optimized Co‐based polymeric structures exhibit a low overpotential of 320 mV at 10 mA cm^?2 and high stability over 2000 cycles toward oxygen evolution reaction (OER), surpassing commercial RuO₂/C, single‐site Co catalysts, polymer, and metal–organic framework‐based OER catalysts reported to date. X‐ray absorption spectroscopy and density functional theory calculations reveal that the tpy‐Co²⁺ (3N‐Co or tpy‐Co²⁺) configurations act as highly active sites. Importantly, this work demonstrates the functional application of the self‐assembled metallopolymers as electrocatalysts for energy conversion.     

Bioinspired Reversibly Cross‐linked Hydrogels Comprising Polypeptide Micelles Exhibit Enhanced Mechanical Properties

Noncovalently cross‐linked networks are attractive hydrogel platforms because of their facile fabrication, dynamic behavior, and biocompatibility. The majority of noncovalently cross‐linked hydrogels, however, exhibits poor mechanical properties, which significantly limit their utility in load bearing applications. To address this limitation, hydrogels are presented composed of micelles created from genetically engineered, amphiphilic, elastin‐like polypeptides that contain a relatively large hydrophobic block and a hydrophilic terminus that can be cross‐linked through metal ion coordination. To create the hydrogels, heat is firstly used to trigger the self‐assembly of the polypeptides into monodisperse micelles that display transition metal coordination motifs on their coronae, and subsequently cross‐link the micelles by adding zinc ions. These hydrogels exhibit hierarchical structure, are stable over a large temperature range, and exhibit tunable stiffness, self‐healing, and fatigue resistance. Gels with polypeptide concentration of 10%, w/v, and higher show storage moduli of ≈1 MPa from frequency sweep tests and exhibit self‐healing within minutes. These reversibly cross‐linked, hierarchical hydrogels with enhanced mechanical properties have potential utility in a variety of biomedical applications.     

Significant Enhancement of Proton Transport in Bioinspired Peptide Fibrils by Single Acidic or Basic Amino Acid Mutation

Bioinspired materials are extremely suitable for the development of biocompatible and environmentally friendly functional materials. Peptide‐based assemblies are remarkably attractive for such tasks, since they provide a simple way to fuse together functional and structural protein motifs in artificial materials. Motivated by this idea, it is shown here that the introduction of a single acidic, or basic, amino acid into the side chain of a heptameric self‐assembling peptide increases proton conduction in the resulting fibers by two orders of magnitude. This self‐doping effect is much more pronounced than the effect induced by the peptide's acidic and basic termini groups. Furthermore, the self‐doping process is found to be significantly more effective for acidic side chains than for basic ones due to both much more effective self‐doping process, resulting in an order of magnitude larger concentration of charge carriers for the acidic assemblies, and higher mobility of the formed charge carriers – almost threefolds in this case. This work facilitates the realization of unique bioinspired self‐assembled proton conducting materials that may find uses in the emerging bioprotonic technology. The presented design flexibility and, in particular, the ability to introduce both proton and proton holes further extend the usefulness of these materials.     

Robust Self‐Healing Host–Guest Gels from Magnetocaloric Radical Polymerization

Given the increasing environmental and energy issues, materials with the ability to repair themselves following damage are highly desirable because this self‐healing property can prolong the lifespan of materials and reduce replacement costs. Host–guest assemblies are a powerful approach to create supramolecular materials with versatile functions. Here, a new mode of radical polymerization is demonstrated which is achieved via magnetocaloric effect to fabricate novel host–guest supramolecular gels within 5 min. The resulting gels can repair themselves spontaneously when damaged, without the assistance of any external stimuli, and possess great mechanical strength. Moreover, the Fe₃O₄‐doped supramolecular gels show accelerated self‐healing (from 24 h to 3 h) under an applied magnetic field, which is attributed to the synergy between host–guest healing and a magnetocaloric effect. This strategy might open a promising avenue for accelerating the use of host–guest assemblies to rapidly build robust materials.     

Magneto‐Thermal Metrics Can Mirror the Long‐Term Intracellular Fate of Magneto‐Plasmonic Nanohybrids and Reveal the Remarkable Shielding Effect of Gold

Multifunctional nanoparticles such as magneto‐plasmonic nanohybrids are rising theranostic agents. However, little is yet known of their fate within the cellular environment. In order to reach an understanding of their biotransformations, reliable metrics for tracking and quantification of such materials properties during their intracellular journey are needed. In this study, their long‐term (one month) intracellular fate is followed within stem‐cell spheroids used as tissue replicas. A set of magnetic (magnetization) and thermal (magnetic hyperthermia, photothermia) metrics is implemented to provide reliable insightsinto the intracellular status. It shows that biodegradation is modulated by the morphology and thickness of the gold shell. First a massive dissolution of the iron oxide core (nanoflower‐like) is observed, starting with dissociation of the multigrain structure. Second, it is demonstrated that an uninterrupted gold shell can preserve the magnetic core and properties (particularly magnetic hyperthermia). In addition to the magnetic and thermal metrics, intracellular high‐resolution chemical nanocartography evidences the gradual degradation of the magnetic cores. It also shows different transformation scenarios, from the release of small gold seeds when the magnetic core is dissolved (interesting for long‐term elimination) to the protection of the magnetic core (interesting for long‐term therapeutic applicability).     

Supramolecular Nanostructuring of Silver Surfaces via Self‐Assembly of [60]Fullerene and Porphyrin Modules

Recent achievements in our laboratory toward the “bottom‐up” fabrication of addressable multicomponent molecular entities obtained by self‐assembly of C₆₀ and porphyrins on Ag(100) and Ag(111) surfaces are described. Scanning tunneling microscopy (STM) studies on ad‐layers constituting monomeric and triply linked porphyrin modules showed that the molecules self‐organize into ordered supramolecular assemblies, the ordering of which is controlled by the porphyrin chemical structure, the metal substrate, and the surface coverage. Specifically, the successful preparation of unprecedented two‐dimensional porphyrin‐based assemblies featuring regular pores on Ag(111) surfaces has been achieved. Subsequent co‐deposition of C₆₀ molecules on top of the porphyrin monolayers results in selective self‐organization into ordered molecular hybrid bilayers, the organization of which is driven by both fullerene coverage and porphyrin structure. In all‐ordered fullerene–porphyrin assemblies, the C₆₀ guests organize, unusually, into long chains and/or two‐dimensional arrays. Furthermore, sublimation of C₆₀ on top of the porous porphyrin network reveals the selective long‐range inclusion of the fullerene guests within the hosting cavities. The observed mode of the C₆₀ self‐assembly originates from a delicate equilibrium between substrate–molecule and molecule–molecule interactions involving charge‐transfer processes and conformational reorganizations as a consequence of the structural adaptation of the fullerene–porphyrin bilayer.     

MnO Nanocrystals: A Platform for Integration of MRI and Genuine Autophagy Induction for Chemotherapy

Herein, a kind of novel monocomponent hydrophilic and paramagnetic manganese(II) oxide nanocrystal is prepared in polar solution by a one‐pot microwave‐assisted synthesis. This kind of nanocrystal can be taken up efficiently to serve as an excellent T₁ magnetic resonance imaging (MRI) contrast agent with an enhanced r₁ value of 0.81 mM^?1 s^?1. The key to the success of this method is that no additional capping agents are required for coating onto the surface via ligand exchange, facilitating research of their intrinsic biological activities. Furthermore, multiple lines of convincing evidence are presented to prove that MnO nanocrystals (NCs) elicit p53‐activation‐independent and authentic functional autophagy via inducing autophagosome formation. Notably, there are very few reports so far of the autophagy phenomenon induced by magnetic nanocrystals. Moreover, these results offer an indication for cancer therapy that MnO NCs combined with doxorubicin at a nontoxic concentration can have a definite synergistic effect, which is mediated through the genuine autophagy induction, on killing cancer cells in vitro and in vivo.     

Surfactant‐Assisted Emulsion Self‐Assembly of Nanoparticles into Hollow Vesicle‐Like Structures and 2D Plates

The emulsion‐based self‐assembly of nanoparticles into low‐dimensional superparticles of hollow vesicle‐like assemblies is reported. Evaporation of the oil phase at relatively low temperatures from nanoparticle‐containing oil‐in‐water emulsion droplets leads to the formation of stable and uniform sub‐micrometer vesicle‐like assembly structures in water. This result is in contrast with those from many previously reported emulsion‐based self‐assembly methods, which produce solid spherical assemblies. It is found that extra surfactants in both the oil and water phases play a key role in stabilizing nanoscale emulsion droplets and capturing hollow assembly structures. Systematic investigation into what controls the morphology in emulsion self‐assembly is carried out, and the approach is extended to fabricate more complex rattle‐like structures and 2D plates. These results demonstrate that the emulsion‐based assembly is not limited to typical thermodynamic spherical assembly structures and can be used to fabricate various types of interesting low‐dimensional assembly structures.