Synthesis of Polymer Brushes on Tannic Acid-Coated Copper Particles and Surface Co-Assembly.

The synthesis of polymer brushes on inorganic particles is an effective approach to surface modification. The polymer brushes on the surface endow the substrates with new surface properties. However, the lack of functional groups and the difficulty of surface modification have made it difficult to develop an effective method for the synthesis of polymer brushes on metal surfaces. Herein, a simple and versatile strategy for synthesizing polymer brushes on copper particles is reported. Tannic acid (TA) molecules are adsorbed onto the surfaces of copper particles, forming TA coatings. Quaternized poly(2-(dimethylamino)ethyl methacrylate)-block-polystyrene (qPDMAEMA-b-PS) block copolymer (BCP) chains are grafted on the TA coatings through hydrogen bonding and electrostatic interaction, and PS brushes are grafted on the copper particles. The effects of TA concentration on the adsorption of TA and PS brush synthesis are discussed. The PS brushes are able to form surface nanostructures on the copper particles through co-assembly with PDMAEMA-b-PS BCP chains. The effect of BCP concentration on the surface nanostructures is investigated. It is reasonable to expect that polymer brushes and surface nanostructures can be synthesized on different metal surfaces by using the TA-coating approach reported in this paper.

Polyethylenimine Inclusion to Develop Aqueous Alginate-Based Core-Shell Capsules for Biomedical Applications.

Aqueous core-shell structures can serve as an efficient approach that allows cells to generate 3D spheroids with in vivo-like cell-to-cell contacts. Here, a novel strategy for fabricating liquid-core-shell capsules is proposed by inverse gelation of alginate (ALG) and layer-by-layer (LbL) coating. We hypothesized that the unique properties of polyethylenimine (PEI) could be utilized to overcome the low structural stability and the limited cell recognition motifs of ALG. In the next step, alginate dialdehyde (ADA) enabled the Schiff-base reaction with free amine groups of PEI to reduce its possible toxic effects. Scanning electron microscopy and light microscopy images proved the formation of spherical hollow capsules with outer diameters of 3.0 ± 0.1 mm for ALG, 3.2 ± 0.1 mm for ALG/PEI, and 4.0 ± 0.2 mm for ALG/PEI/ADA capsules. The effective modulus increased by 3-fold and 5-fold when comparing ALG/PEI/ADA and ALG/PEI to ALG capsules, respectively. Moreover, PEI-coated capsules showed potential antibacterial properties against both Staphylococcus aureus and Escherichia coli, with an apparent inhibition zone. The cell viability results showed that all capsules were cytocompatible (above 75.5%). Cells could proliferate and form spheroids when encapsulated within the ALG/PEI/ADA capsules. Monitoring the spheroid thickness over 5 days of incubation indicated an increasing trend from 39.50 µm after 1 day to 66.86 µm after 5 days. The proposed encapsulation protocol represents a new in vitro platform for developing 3D cell cultivation and can be adapted to fulfill the requirements of various biomedical applications.

Enhancing Enzyme Activity Using Hydrophilic Hollow Layered Double Hydroxides as Encapsulation Carriers.

Enzyme immobilization enables the fabrication of flexible and powerful biocatalytic systems that can meet the needs of green and efficient development in various fields. However, restricted electron and mass transfer during enzymatic reactions and disruption of the enzyme structure during encapsulation limit the wide application of the immobilized enzyme systems. Herein, we report an encapsulation strategy based on hollow-shell-layered double hydroxides (LDHs; ZnCo-LDH) for green and nondestructive enzyme immobilization. Benefiting from the protective and enzyme-friendly microenvironment provided by the hydrophilic hollow structure of ZnCo-LDH, the encapsulated enzyme maintains a nearly natural enzyme biostructure and enhanced stability. Notably, mesoporous ZnCo-LDH with excellent electrical properties considerably facilitates electron and mass transport during enzymatic reactions, exhibiting 5.56 times the catalytic efficiency of free enzymes or traditional enzyme encapsulation systems. The current study broadens the family of encapsulated carriers and alleviates the trade-off between enzyme stability and catalytic activity in the encapsulated state, presenting a promising avenue for the industrial application of the enzyme.

Encapsulating soluble active species into hollow crystalline porous capsules beyond integration of homogeneous and heterogeneous catalysis.

Homogeneous molecular catalysts and heterogeneous catalysts possess complementary strengths, and are of great importance in laboratory/commercial procedures. While various porous hosts, such as polymers, carbons, silica, metal oxides and zeolites, have been used in an attempt to heterogenize homogeneous catalysts, realizing the integration of both functions at the expense of discounting their respective advantages, it remains a significant challenge to truly combine their intrinsic strengths in a single catalyst without compromise. Here, we describe a general template-assisted approach to incorporating soluble molecular catalysts into the hollow porous capsule, which prevents their leaching due to the absence of large intergranular space. In the resultant yolk (soluble)-shell (crystalline) capsules, the soluble yolks can perform their intrinsic activity in a mimetic homogeneous environment, and the crystalline porous shells endow the former with selective permeability, substrate enrichment, size-selective and heterogeneous cascade catalysis, beyond the integration of the respective advantages of homogeneous and heterogeneous catalysts.

Synthesis of Polydopamine Hollow Capsules via a Polydopamine Mediated Silica Water Dissolution Process and Its Application for Enzyme Encapsulation.

Herein, we present a systematic study on the preparation of polydopamine (PDA) hollow capsules by templating silica particles which were subsequently removed by a PDA mediated water dissolution process without using any harsh chemical treatment. It was found that the time required for silica removal varied depending on the PDA coating and dissolution conditions. Factors that could influence the core removal process including the PDA thickness and coating temperature, silica calcination duration and the availability of water were then examined in detail. Additionally, catalase was used as a model enzyme to be encapsulated into PDA hollow capsules and its bio-functionality was found to remain active. The bioactivity test results also indicated that the as-synthesized PDA capsules possessed a porous structure, which allows the penetration of small molecules such as H2O2. This study offers a better insight into silica dissolution process that mediated by PDA and contributes to the development of an eco-friendly approach for the fabrication of hollow capsules that have promising applications in drug delivery systems.

Photo-Cross-Linked Dual-Responsive Hollow Capsules Mimicking Cell Membrane for Controllable Cargo Post-Encapsulation and Release.

Multifunctional and responsive hollow capsules are ideal candidates to establish highly sophisticated compartments mimicking cell membranes for controllable bio-inspired functions. For this purpose pH and temperature dual-responsive and photo-cross-linked hollow capsules, based on silica-templated layer-by-layer approach by using poly(N-isopropyl acrylamide)-block-polymethacrylate) and polyallylamine, have been prepared to use them for the subsequent and easily available post-encapsulation process of protein-like macromolecules at room temperature and pH 7.4 and their controllable release triggered by stimuli. The uptake and release properties of the hollow capsules for cargos are highly affected by changes in the external stimuli temperature (25, 37, or 45 °C) and internal stimuli pH of the phosphate-containing buffer solution (5.5 or 7.4), by the degree of photo-cross-linking, and the size of cargo. The photo-cross-linked and dual stimuli-responsive hollow capsules with different membrane permeability can be considered as attractive material for mimicking cell functions triggered by controllable uptake and release of different up to 11 nm sized biomolecules.

Coating Strategies Using Layer-by-layer Deposition for Cell Encapsulation.

The layer-by-layer (LbL) deposition technique is widely used to develop multilayered films based on the directed assembly of complementary materials. In the last decade, thin multilayers prepared by LbL deposition have been applied in biological fields, namely, for cellular encapsulation, due to their versatile processing and tunable properties. Their use was suggested as an alternative approach to overcome the drawbacks of bulk hydrogels, for endocrine cells transplantation or tissue engineering approaches, as effective cytoprotective agents, or as a way to control cell division. Nanostructured multilayered materials are currently used in the nanomodification of the surfaces of single cells and cell aggregates, and are also suitable as coatings for cell-laden hydrogels or other biomaterials, which may later be transformed to highly permeable hollow capsules. In this Focus Review, we discuss the applications of LbL cell encapsulation in distinct fields, including cell therapy, regenerative medicine, and biotechnological applications. Insights regarding practical aspects required to employ LbL for cell encapsulation are also provided.

A simple way to prepare Pd/Fe3O4/polypyrrole hollow capsules and their applications in catalysis.

Preparation of catalysts with good catalytic activity and high stability, together with magnetic separation property, in a simple way is highly desirable. In this paper, we reported a novel strategy to construct magnetic recyclable hollow capsules with Pd and Fe3O4 nanoparticles embedded in polypyrrole (PPy) shell via only two steps: first, synthesization of Pd nanoparticles, preparation of Fe3O4 nanoparticles, and formation of PPy shell were finished in one-step on the surface of polystyrene (PS) nanospheres; then, the PS core was selectively removed by tetrahydrofuran. The Pd/Fe3O4/PPy hollow capsules exhibited good catalytic property in reduction of 4-nitrophenol with NaBH4 as reducing agent, and the reaction rate constants were calculated through pseudo-first-order reaction equation. Due to incorporation of Fe3O4 nanoparticles, the catalysts could be quickly separated from the reaction solution by magnet and reused without obvious catalytic loss. Besides catalytic property and reusability, their stability was also examined by HNO3 etching experiment. Compared with bare Pd and Fe3O4 nanoparticles, the stability of both Pd and Fe3O4 nanoparticles in hollow capsules was largely improved owing to the protection of PPy shell. The good catalytic performance, ease of separation, high stability and especially a simple preparation procedure, made Pd/Fe3O4/PPy hollow capsules highly promising candidates for diverse applications.