Hierarchical etching-assembly engineering of Fe-based composite microspheres with balanced magnetic-dielectric synergy towards ultrahigh electromagnetic wave absorption.

Hierarchical engineering of magnetic-dielectric composite microspheres has attracted increasing attention owing to its potential to enhance electromagnetic wave absorption (EMA) through magnetic-dielectric synergy. However, optimizing magnetic-dielectric balance in composite microspheres at the nanoscale remains a formidable task due to their limited component optimization and microstructural regulation. Herein, a novel approach is proposed to modify conventional carbonyl iron powder (CIP) microspheres via synergistic etching-assembly strategy. By applying a polydopamine coating, successive tannic acid (TA) etching-assembly, and pyrolysis, hierarchical iron@carbon-1/N-doped carbon (Fe@C-1/NC) composite microspheres are obtained. This overcomes the drawbacks of CIP microspheres, including their high density and poor impedance matching, which hinder EMA performance. Hierarchical carbon layer engineering can introduce abundant dipole centers, heterogeneous interfaces, and conductive networks to induce dielectric loss, while magnetic components contribute to magnetic resonance and eddy current loss, as demonstrated by the results. Accordingly, Fe@C-1/NC composite microspheres demonstrate a minimum reflection loss (RLmin) of -70.7 dB and an effective absorption bandwidth of 3.75 GHz at a matching thickness of 2.3 mm. Generally, this work paves the way towards CIP engineering to provide guidance to the future exploration of hierarchical magnetic-dielectric EMA materials.

Iodine-Doped Hollow Carbon Nanocages without Templates Strategy for Boosting Zinc-Ion Storage by Nucleophilicity.

Zn-ion hybrid supercapacitors (ZHCs) combining merits of battery-type and capacitive electrodes are considered to be a prospective candidate in energy storage systems. Tailor-made carbon cathodes with high zincophilicity and abundant physi/chemisorption sites are critical but it remains a great challenge to achieve both features by a sustainable means. Herein, a hydrogen-bonding interaction-guided self-assembly strategy is presented to prepare iodine-doped carbon nanocages without templates for boosting zinc-ion storage by nucleophilicity. The biomass ellagic acid contains extensional hydroxy and acyloxy groups with electron-donating ability, which interact with melamine and ammonium iodide to form organic supermolecules. The organic supermolecules further self-assemble into a nanocage-like structure with cavities under hydrothermal processes via hydrogen-bonding and π-π stacking. The carbon nanocages as ZHCs cathodes enable the high approachability of zincophilic sites and low ion migration resistance resulting from the interconnected conductive network and nanoscale architecture. The experimental analyses and theoretical simulations reveal the pivotal role of iodine dopants. The I5-/I3- doping anions in carbon cathodes have a nucleophilicity to preferentially adsorb the Zn2+ cation by the formation of C+-I5--Zn2+ and C+-I3--Zn2+. Of these, the C+-I3- shows stronger bonding with Zn2+ than C+-I5-. As a result, the iodine-doped carbon nanocages produced via this template-free strategy deliver a high capacity of 134.2 mAh/g at 1 A/g and a maximum energy and power density of 114.1 Wh/kg and 42.5 kW/kg.

Polymer self-assembly guided heterogeneous structure engineering towards high-performance low-frequency electromagnetic wave absorption.

Magnetic-dielectric synergy is currently regarded as among the most effective approaches to achieve low-frequency electromagnetic wave absorption (EMA). However, designing and fabricating EMA materials with tunable magnetic-dielectric balance towards high-performance low-frequency EMA remains challenging. Herein, a polymer self-assembly guided heterogeneous structure engineering strategy is proposed to fabricate hierarchical magnetic-dielectric nanocomposite. Polymer assemblies not only can be employed as intermediates to encapsulate metal-organic frameworks and load metal hydroxide, but also that they play a crucial role for the in-situ formation of polycrystalline FeCo/Co composite nanoparticles. As a result, the minimum reflection loss (RLmin) can reach -59.61 dB at 5.4 GHz (4.8 mm) with a 20 wt% filler loading, while the effective absorption bandwidth (EAB, RLmin ≤ -10 dB) is 2.16 GHz, exhibiting excellent low-frequency EMA performance. Systematic investigations demonstrate that hierarchical mesoporous carbon matrix that supports FeCo/Co composite nanoparticles is beneficial for optimizing impedance matching and increasing attenuation capacity. In general, this study opens up new prospects for developing magnetic-dielectric EMA materials using a polymer self-assembly guided heterogeneous structure engineering strategy, which may receive significant attention in future research.

Hierarchical engineering of Large-caliber carbon Nanotube/Mesoporous Carbon/Fe3C nanoparticle hybrid nanocomposite towards Ultra-lightweight electromagnetic microwave absorber.

The rational regulation of the magnetic-dielectric composition and microstructures of the absorber is considered an important approach to optimize both the impedance matching and the electromagnetic microwave attenuation ability. Along these lines, a novel architecture-controlled large-caliber carbon nanotube/mesoporous carbon/Fe3C nanoparticle-based hybrid nanocomposites (CNT/C/Fe3C), which were derived from the CNT/polyimide (PI) assemblies anchoring ferric oxide hydrate nanoprecipitates, are presented in this work. The proposed configurations were prepared by applying a cooperative co-assembly strategy and high-temperature pyrolysis procedure for the development of an ultra-lightweight electromagnetic microwave absorber. The employed hierarchically tubular heterogeneous architecture is composed of a highly graphited CNT supporting skeleton, polyimide assemblies-converted carbon interlayer with mesopores, and uniformly distributed magnetic Fe3C nanoparticles. This unique hierarchical structure can not only induce multiple reflection and scattering effects of the incident electromagnetic microwave but also trigger dipole/interfacial polarization, ferromagnetic resonance and eddy current loss that are beneficial for the synergistic dielectric and magnetic loss. Moreover, the large-caliber CNT and mesoporous carbon interlayer can endow the as-prepared absorber with lightweight characteristics. Hence, the proposed CNT/C-EDA/Fe3C-900 hybrid nanocomposite exhibits a minimum reflection loss (RL) of -48.4 dB at a matching thickness of 3.2 mm, and the effective absorption bandwidth (RL ≤ -10 dB) almost covers the whole X-band only with a 5 wt% filler loading. Undoubtedly, these encouraging outcomes will promote the development of hierarchical engineering techniques of novel magnetic-dielectric nanocomposite absorbers.

Light-Switchable Polymer Adhesive Based on Photoinduced Reversible Solid-to-Liquid Transitions.

The development of switchable adhesives for reversible bonding and debonding can overcome the problems associated with conventional adhesives in separating, recycling, and repairing glued surfaces. Here, a photoresponsive azobenzene-containing polymer (azopolymer) is developed for photocontrolled adhesion. The azopolymer P1 (poly(6-(4-(p-tolyldiazenyl)phenoxy)hexyl acrylate)) exhibits photoinduced reversible solid-to-liquid transitions due to trans-cis photoisomerization. Trans P1 is a solid that glues two substrates with a stiffness comparable to that of conventional adhesives. UV light induces trans-to-cis isomerization, liquefies P1, weakens the adhesion, and facilitates the separation of glued substrates. Conversely, visible light induces cis-to-trans isomerization, solidifies P1, and enhances the adhesion. P1 enables photocontrolled reversible adhesion for various substrates with different wettability, chemical compositions, and surface roughness. P1 can also be implemented in both dry and wet environments. Light can control the adhesion process with high spatiotemporal resolution when using P1 as a switchable adhesive. Photoinduced reversible solid-to-liquid transitions represent a strategy for materials recycling and automated production processes that require reversible bonding and debonding.

Hyperbranched Polymers with Controllable Topologies for Drug Delivery.

Hyperbranched polymers (HPs) have widely been used for drug delivery owing to their highly branched topology, which endows the HPs with a large amount of intramolecular cavities for drug encapsulation and terminal groups for drug conjugation. Additionally, one-pot, large-scale preparations enable the easy fabrication of HPs for biomedical applications. This review provides an overview of the synthesis of HPs and their application for drug delivery. First, we introduce a diversity of methods for the synthesis of HPs with controllable topologies. Subsequently, we discuss drug encapsulation and drug conjugation by using HPs. Finally, we highlight the use of HPs with controllable topologies for promising drug delivery.

Intramolecular Copper-Containing Hyperbranched Polytriazole Assemblies for Label-Free Cellular Bioimaging and Redox-Triggered Copper Complex Delivery.

Intramolecular Cu-containing amphiphilic hyperbranched polytriazoles are purposefully designed and synthesized via a Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction, and are self-assembled into spherical assemblies. Based on the metal coordination ability of triazole groups, the copper catalyst can be intramolecularly coordinated with triazole groups in the CuAAC, producing the copper-triazole coordination polyprodrugs. Unexpectedly, the amphiphilic hyperbranched polytriaozle assemblies can also be applied as fluorescent nanoprobes with aggregation-induced emission enhancement. The cellular uptake verifies their functional application for cellular bioimaging. Furthermore, the results of cell viability indicate that the mPEG-hb-S-S-PTAs assemblies are effective copper delivery systems for cancer therapy by releasing the anticancer copper-triazole coordination complexes. Therefore, the amphiphilic hyperbranched polytriazoles may have very promising applications in complex copper delivery and label-free cellular bioimaging.

An Unconventional Polymerization Route to Hydrophilic Fluorescent Organic Nanoparticles for Multicolor Cellular Bioimaging.

We demonstrated an unconventional polymerization route to synthesize hydrophilic fluorescent organic nanoparticles (FONs) for multicolor cellular bioimaging in this contribution. The route benefits from our unexpected discovery of a rapid polymerization reaction between 1,6-hexanediol dipropiolate and 2,4,6-triazide-1,3,5-triazine under the catalysis of N,N,N',N'',N''-pentamethyldiethylenetriamine (PMDETA). Interestingly, the 2,4,6-triazide-1,3,5-triazine and PMDETA system can also induce rapid free radical polymerization at room temperature. The as-prepared FONs exhibited promising water solubility and stability with an average diameter of 20 nm. The excitation wavelength-dependent fluorescent properties endow the FONs with blue, yellow, and red fluorescent emission under UV, blue, and green excitation, respectively. The cytotoxicity of FONs was investigated by using a Cell Counting Kit (CCK-8) assay, which indicated good biocompatiblity. More importantly, the cell uptake experiment verified the FONs were excellent fluorescent nanoprobes for multicolor cellular bioimaging. Therefore, this unconventional route provides a novel fabrication strategy of highly hydrophilic FONs for biomedical applications.

Noninvasive photothermal cancer therapy nanoplatforms via integrating nanomaterials and functional polymers.

In the cutting-edge field of cancer therapy, noninvasive photothermal therapy (PTT) has received great attention because it is considered to overcome the drawbacks of conventional surgery, radiotherapy and chemotherapy of severe body injuries and side effects on the immune system. The construction of PTT therapeutic and theranostic nanoplatforms is the key issue in achieving tumor targeting, imaging and therapy in a synergetic manner. In this review, we focus on the recent advances in constructing PTT therapeutic and theranostic nanoplatforms by integrating nanomaterials and functional polymers. The noninvasive photothermal cancer therapy mechanism and achievement strategies of PTT therapeutic and theranostic nanoplatforms are presented as well as the innovative construction strategies and perspectives for the future. Owing to their high tumor ablation efficiency, biological availability and low- or non-toxicity, PTT therapeutic and theranostic nanoplatforms are promising and emerging in medicine and clinical applications.