Junling Guo

Engineering Multifunctional Capsules through the Assembly of Metal–Phenolic Networks

Metal-organic coordination materials are of widespread interest because of the coupled benefits of inorganic and organic building blocks. These materials can be assembled into hollow capsules with a range of properties, which include selective permeability, enhanced mechanical/thermal stability, and stimuli-responsiveness. Previous studies have primarily focused on the assembly aspects of metal-coordination capsules; however, the engineering of metal-specific functionality for capsule design has not been explored. A library of functional metal-phenolic network (MPN) capsules prepared from a phenolic ligand (tannic acid) and a range of metals is reported. The properties of the MPN capsules are determined by the coordinated metals, allowing for control over film thickness, disassembly characteristics, and fluorescence behavior. Furthermore, the functional properties of the MPN capsules were tailored for drug delivery, positron emission tomography (PET), magnetic resonance imaging (MRI), and catalysis. The ability to incorporate multiple metals into MPN capsules demonstrates that a diverse range of functional materials can be generated.

pH-Responsive Capsules Engineered from Metal–Phenolic Networks for Anticancer Drug Delivery

A new class of pH-responsive capsules based on metal-phenolic networks (MPNs) for anticancer drug loading, delivery and release is reported. The fabrication of drug-loaded MPN capsules, which is based on the formation of coordination complexes between natural polyphenols and metal ions over a drug-coated template, represents a rapid strategy to engineer robust and versatile drug delivery carriers.

One-step seeding growth of controllable Ag@Ni core–shell nanoparticles on skin collagen fiber with introduction of plant tannin and their application in high-performance microwave absorption

Controllable magnetic Ag@Ni core–shell nanoparticles (NPs) have been designed and constructed on the bayberry tannin (BT) grafted skin collagen fiber (SCF) though a simple one-step route. Due to the mild and naturally occurring reduction ability of BT, when the SCF-BT made contact with the mixture of Ag+/Ni2+ solution, BT was able to preferentially reduce Ag+ into Ag NPs, and subsequently, the formed Ag NPs served as in situ seeds for the over growth of magnetic Ni shell by the reduction of NaBH4. The systematic TEM and EDS analysis confirmed that the as-prepared Ag@Ni NPs on SCF-BT were a typical core–shell structure. Magnetic study of core–shell NPs indicated that their magnetic properties could be tuned by modulating their shell thickness with the change of Ag+/Ni2+ molar ratio. The diameter and size distribution of SCF-supported Ag@Ni core–shell NPs also can be controlled by varying the grafting degree of BT on SCF, as characterized by TEM. A novel and important application of these SCF-supported Ag@Ni core–shell NPs composites is use as high-performance microwave absorption materials in the whole X-band, C-band and some part of S-band with maximum reflection loss (RL) of −51 dB. The further analysis of electromagnetic parameters indicated that the enhancement of dielectric loss properties of SCF-supported Ag@Ni core–shell NPs is introduced by the multiple defective site polarization and interfacial polarization in bimetallic interface. In addition, owing to the combinated magnetic property on the nickel shell, the SCF-supported Ag@Ni core–shell NPs also exhibited a significant eddy current effect and anisotropic energy effect for the microwave absorption. To the best of our knowledge, this is the first time to explore tailoring the magnetic property, electromagnetic property and microwave absorption performance of functional core–shell NPs by tuning their core–shell microstructures. The present work has a significant potential for the development of novel, lightweight, low-cost, flexible and highly efficient microwave absorbing materials.

Modular assembly of superstructures from polyphenol-functionalized building blocks

The organized assembly of particles into superstructures is typically governed by specific molecular interactions or external directing factors associated with the particle building blocks, both of which are particle-dependent. These superstructures are of interest to a variety of fields because of their distinct mechanical, electronic, magnetic and optical properties. Here, we establish a facile route to a diverse range of superstructures based on the polyphenol surface-functionalization of micro- and nanoparticles, nanowires, nanosheets, nanocubes and even cells. This strategy can be used to access a large number of modularly assembled superstructures, including core-satellite, hollow and hierarchically organized supraparticles. Colloidal-probe atomic force microscopy and molecular dynamics simulations provide detailed insights into the role of surface functionalization and how this facilitates superstructure construction. Our work provides a platform for the rapid generation of superstructured assemblies across a wide range of length scales, from nanometres to centimetres.

Ag Nanoparticle/Polydopamine-Coated Inverse Opals as Highly Efficient Catalytic Membranes

Polymeric three-dimensional inverse-opal (IO) structures provide unique structural properties useful for various applications ranging from optics to separation technologies. Despite vast needs for IO functionalization to impart additional chemical properties, this task has been seriously challenged by the intrinsic limitation of polymeric porous materials that do not allow for the easy penetration of waterborne moieties or precursors. To overcome this restriction, we present a robust and straightforward method of employing a dipping-based surface modification with polydopamine (PDA) inside the IO structures, and demonstrate their application to catalytic membranes via synthetic incorporation of Ag nanoparticles. The PDA coating offers simultaneous advantages of achieving the improved hydrophilicity required for the facilitated infiltration of aqueous precursors and successful creation of nucleation sites for a reduction of growth of the Ag nanoparticles. The resulting Ag nanoparticle-incorporated IO structures are utilized as catalytic membranes for the reduction of 4-nitrophenol to its amino derivatives in the presence of NaBH4. Synergistically combined characteristics of high reactivity of Ag nanoparticles along with a greatly enhanced internal surface area of IO structures enable the implementation of remarkably improved catalytic performance, exhibiting a good conversion efficiency greater than 99% while minimizing loss in the membrane permeability.

Boronate-Phenolic Network Capsules with Dual Response to Acidic pH and cis-Diols

Dual-responsive boronate-phenolic network (BPN) capsules are fabricated by the complexation of phenylborate and phenolic materials. The BPN capsules are stable in the presence of competing carbohydrates, but dissociate at acidic pH or in the presence of competing cis-diols at physiological pH. This engineered capsule system provides a platform for a wide range of biological and biomedical applications.

Flow-Based Assembly of Layer-by-Layer Capsules through Tangential Flow Filtration

Layer-by-layer (LbL) assembly on nano- and microparticles is of interest for a range of applications, including catalysis, optics, sensors, and drug delivery. One current limitation is the standard use of manual, centrifugation-based (pellet/resuspension) methods to perform the layering steps, which can make scalable, highly controllable, and automatable production difficult to achieve. Here, we develop a fully flow-based technique using tangential flow filtration (TFF) for LbL assembly on particles. We demonstrate that multilayered particles and capsules with different sizes (from micrometers to submicrometers in diameter) can be assembled on different templates (e.g., silica and calcium carbonate) using several polymers (e.g., poly(allylamine hydrochloride), poly(styrenesulfonate), and poly(diallyldimethylammonium chloride)). The full system only contains fluidic components routinely used (and automated) in industry, such as pumps, tanks, valves, and tubing in addition to the TFF filter modules. Using the TFF LbL system, we also demonstrate the centrifugation-free assembly, including core dissolution, of drug-loaded capsules. The well-controlled, integrated, and automatable nature of the TFF LbL system provides scientific, engineering, and practical processing benefits, making it valuable for research environments and potentially useful for translating LbL assembled particles into diverse applications.

Versatile loading of diverse cargo into functional polymer capsules

Polymer microcapsules are of particular interest for applications including self‐healing coatings, catalysis, bioreactions, sensing, and drug delivery. The primary way that polymer capsules can exhibit functionality relevant to these diverse fields is through the incorporation of functional cargo in the capsule cavity or wall. Diverse functional and therapeutic cargo can be loaded into polymer capsules with ease using polymer‐stabilized calcium carbonate (CaCO3) particles. A variety of examples are demonstrated, including 15 types of cargo, yielding a toolbox with effectively 500+ variations. This process uses no harsh reagents and can take less than 30 min to prepare, load, coat, and form the hollow capsules. For these reasons, it is expected that the technique will play a crucial role across scientific studies in numerous fields.

Fluidized bed layer-by-layer microcapsule formation.

Polymer microcapsules can be used as bioreactors and artificial cells; however, preparation methods for cell-like microcapsules are typically time-consuming, low yielding, and/or involve custom microfluidics. Here, we introduce a rapid (∼30 min per batch, eight layers), scalable (up to 500 mg of templates), and efficient (98% yield) microcapsule preparation technique utilizing a fluidized bed for the layer-by-layer (LbL) assembly of polymers, and we investigate the parameters that govern the formation of robust capsules. Fluidization in water was possible for particles of comparable diameter to mammalian cells (>5 μm), with the experimental flow rates necessary for fluidization matching well with the theoretical values. Important variables for polymer film deposition and capsule formation were the concentration of polymer solution and the molecular weight of the polymer, while the volume of the polymer solution had a negligible impact. In combination, increasing the polymer molecular weight and polymer solution concentration resulted in improved film deposition and the formation of robust microcapsules. The resultant polymer microcapsules had a thickness of ∼5.5 nm per bilayer, which is in close agreement with conventionally prepared (quiescent (nonflow) adsorption/centrifugation/wash) LbL capsules. The technique reported herein provides a new way to rapidly generate microcapsules (approximately 8 times quicker than the conventional means), while being also amenable to scale-up and mass production.

Complex oxide-noble metal conjugated nanoparticles.

Hybrid nanoparticles (NPs) composed of multiple components offer new opportunities for next-generation materials. In this study, a paradigm for the noble metal/ternary complex oxide hybrid NPs is reported by adopting pulsed laser ablation in liquids. As model hybrids, gold-spinel heterodimer (Au-CoFe2O4) and gold-pervoskite heterodimer (Au-SrTiO3) NPs are investigated. This work has demonstrated the diverse playgroup of NP conjugation enlarged by complex oxides.