Janus Nanoparticle Coupled Double-Network Hydrogel.

For double network (DN) hydrogels, their performance can be tuned by adjusting the interaction between their two networks. A novel DN hydrogel toughening approach is proposed by employing Janus nanoparticles (JNs) as crosslinkers to gain a conjoined-network hydrogel. First, a kind of JNs modified by amino groups and quaternary ammonium salt is synthesized, named R3 N+ -JN-NH2 . The DN hydrogel is fabricated based on ionic coordination between calcium chloride (CaCl2 ) and sodium alginate (Alg), as well as covalent (benzoic imine) between glycol chitosan (GC) and benzaldehyde-capped poly(ethylene oxide) (BzCHO-PEO-BzCHO). Based on the same covalent and ionic dynamic crosslinking mechanism, the added R3 N+ -JN-NH2 interacts with two networks to promote crosslinking to form a dually crosslinked structure. The R3 N+ -JN-NH2 effectively provides more energy dissipation, and the hydrogel with conjoined networks shows better compression resistance.

Semi-IPNs Reinforced with Silica Janus Nanoparticles and Their Stress Sensing with Mechanoluminescent Probe.

A series of nanocomposite elastomers are prepared by dispersing surface-modified silica Janus nanoparticles into semi-interpenetrating network (Semi-IPN) of polyurethane/polyethyl methacrylate. Benefiting from the hierarchically crosslinked structures that consist of physical interlocking mediated by hydrogen-bond-rich silica Janus nanoparticles and permanent crosslinking by Semi-IPN, these elastomers exhibit excellent mechanical properties. Moreover, the Janus nanosheet is found more effective in strengthening and toughening the Semi-IPN, in comparison to Janus hollow sphere. Since 1,2-dioxetane is covalently embedded in these elastomers as a mechanoluminescent stress probe, stress transfer between the polymer and Janus nanoparticles and the toughening mechanism can be illuminated, which offer exciting opportunities to study the failure process of complex polymer nanocomposites with high spatial and temporal resolution.

Stabilizing Polymeric Interface by Janus Nanosheet.

A strategy is proposed to stabilize the polymeric interface by using the irregular Janus nanosheet (JNS). The poly(vinylidene fluoride) (PVDF)/poly(l-lactic acid) (PLLA) at 60/40 (wt/wt) with a bi-continuous structure is selected as the model melt blend, and the PMMA/epoxy JNS is synthesized and used as the compatibilizer. The JNS is preferentially located at the interface. The interfacial coverage by the JNS reaches a saturated state forming the interconnected jamming structure at 0.5 wt% of the JNS. The interface is thus stabilized which is well preserved after annealing at high temperature. After selectively etching PLLA, the robust PVDF porous material is derived with the JNS armored at the pore skeleton surface. The porous material provides a universal scaffold to achieve stable functional materials after filling the pores.

Particle Mold Synthesis of Block Copolymer Janus Nanomaterials.

A particle mold synthesis of 2D Janus nanomaterials is proposed by crosslinking of copolymer self-assembled monolayers confined within the mold domains. Onto the silica (SiO2 ) particle surface, mold domains with functional groups such as imidazole are generated. The model copolymer of polyacrylic acid-block-polystyrene (PAA-b-PS) can be preferentially absorbed onto the domains via electrostatic interactions, forming a self-assembled monolayer. In a cosolvent such as tetrahydrofuran (THF), the crosslinking occurs within the whole of the PAA side. A Janus disc is thus achieved after detachment from the particle upon breaking the specific interaction. In a poor solvent, the crosslinking slowly occurs from the periphery, giving Janus nanorings. The rings evolve into discs with further crosslinking. The mold particles can be recycled to synthesize the same 2D Janus materials.

Construction of Injectable Double-Network Hydrogels for Cell Delivery.

Herein we present a unique method of using dynamic cross-links, which are dynamic covalent bonding and ionic interaction, for the construction of injectable double-network (DN) hydrogels, with the objective of cell delivery for cartilage repair. Glycol chitosan and dibenzaldhyde capped poly(ethylene oxide) formed the first network, while calcium alginate formed the second one, and in the resultant DN hydrogel, either of the networks could be selectively removed. The moduli of the DN hydrogel were significantly improved compared to that of the parent single-network hydrogels and were tunable by changing the chemical components. In situ 3D cell encapsulation could be easily performed by mixing cell suspension to the polymer solutions and transferred through a syringe needle before sol-gel transition. Cell proliferation and mediated differentiation of mouse chondrogenic cells were achieved in the DN hydrogel extracellular matrix.

Shaping functional nano-objects by 3D confined supramolecular assembly.

Nano-objects are generated through 3D confined supramolecular assembly, followed by a sequential disintegration by rupturing the hydrogen bonding. The shape of the nano-objects is tunable, ranging from nano-disc, nano-cup, to nano-toroid. The nano-objects are pH-responsive. Functional materials for example inorganic or metal nanoparticles are easily complexed onto the external surface, to extend both composition and microstructure of the nano-objects.

Poly(lactic acid)/Poly(butylene succinate) (PLA/PBS) Layered Composite Gas Barrier Membranes by Anisotropic Janus Nanosheets Compartibilizers.

Poly(lactic acid) (PLA), one of the most promising biodegradable polymer products, has achieved wide applications for its relatively good mechanical properties and moderate degradability. Here we report an environment-friendly filler, the organic-inorganic composite Janus nanosheets (PLA/PBS JNs), which can jam at the interface of the PLA/PBS blend with a low threshold as the compatibilizer and can simultaneously toughen the composites and improve the gas barrier performance due to better interfacial interaction and tortuous path effect. With 0.3 wt % of PLA/PBS JNs added, the tensile strength and elongation at break of the PLA/PBS blend can be improved by 37% and 224%, respectively. After a further hot-pressing process, the barrier performance of the PLA/PBS composite membranes can be significantly enhanced since PLA, PLA/PBS JNs, and PBS are arranged in a nearly lamellar structure with oxygen permeability of 0.63 × 10-15 cm3 cm·cm-2 s-1 Pa-1 with only 0.5 wt % of PLA/PBS JNs.

Janus Nanoparticles for Improved Dentin Bonding.

The amphiphilic monomer 2-hydroxyethyl methacrylate (HEMA) is widely used in dental adhesives as a priming component, especially for dentin bonding. It behaves as a compatibilizer between hydrophilic and hydrophobic components and stabilizes the multicomponent adhesive system. However, there are several drawbacks associated with using HEMA, such as water retention within the adhesive layer, hydrolysis in oral environments, and cytotoxicity. These drawbacks lead to the failure of tooth restoration and represent a heavy medical burden. Thus, it is imperative to find a new compatibilizer to substitute for HEMA. Because of their superior compatibilization capabilities as functional solid surfactants, amphiphilic Janus particles are chosen as candidates for an alternative to HEMA in dental adhesives. Reactive amphiphilic Janus nanoparticles are synthesized by selectively etching and modifying at the interface of a Pickering emulsion. This approach could be extended to the synthesis of a series of other Janus nanoparticles. The Janus nanoparticles were verified to be better for the reduction of the phase separation and stabilization of dentin adhesives than HEMA. It is also demonstrated that these reactive Janus nanoparticles can strongly enhance the dentin bonding interface without cytotoxicity. It is clearly illustrated by this study that Janus nanoparticles may be promising materials to substitute for HEMA in dental adhesives.

Suppressing inflammation and enhancing osteogenesis using novel CS-EC@Ca microcapsules.

The aim of this study was to investigate the suppression of inflammation and enhancement of osteogenesis using chitosan-coated calcium hydroxide-loaded microcapsules (CS-EC@Ca microcapsules) in vivo. Circular defects were created in the mandibular bones of rabbits and filled with Ca(OH)2 , Bio-oss, or CS-EC@Ca microcapsules, and rabbits without drug implantation served as the controls. Lipopolysaccharides were injected in situ daily in all groups for 7 days. Mandibular bones were investigated at 4 and 12 weeks after surgery using micro-CT, histological observations, and real-time PCR analysis. At the postoperation, there was more substantial nascent bone in the microcapsule and Bio-oss groups than in the control group. The recovery of the rabbits in the Ca(OH)2 group was slower than the control group, as determined using micro-CT and histological staining. Osteocalcin and collagen type I production was not significantly different between the microcapsule and Bio-oss groups (p > 0.05), but the expression levels of the two molecules were significantly increased compared to the control and Ca(OH)2 groups at postoperation (p < 0.05). The mRNA transcript levels of inflammatory factors in the microcapsule group had the most reduced expression of IL-6 and TNF-α (p < 0.05). The microcapsules significantly reduced inflammation and promoted osteogenesis in this rabbit model of inflammatory bone destruction. Our findings indicate that CS-EC@Ca microcapsules hold potential for use in apical periodontitis treatment. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 106A: 3222-3230, 2018.

Chlorhexidine-Loaded Amorphous Calcium Phosphate Nanoparticles for Inhibiting Degradation and Inducing Mineralization of Type I Collagen.

A major shortcoming of contemporary dentin adhesives is their limited durability. Exposed collagen fibrils within the bonding interface are degraded by matrix metalloproteinases (MMPs), resulting in aging of the resin-dentin bond. In this study, chlorhexidine-loaded amorphous calcium phosphate (ACP) nanoparticles were synthesized to induce the mineralization of collagen fibrils. The nanoparticles sustainably released chlorhexidine to inhibit MMPs during mineralization. Three types of ACP nanoparticles were prepared: N-ACP containing no chlorhexidine, C-ACP containing chlorhexidine acetate, and G-ACP containing chlorhexidine gluconate, which had a higher drug-loading than C-ACP. Scanning and transmission electron microscopy indicated that the synthesized nanoparticles had diameters of less than 100 nm. Some had diameters of less than 40 nm, which was smaller than the width of gap zones in the collagen fibrils. Energy dispersive X-ray spectroscopy, Fourier-transform infrared spectroscopy, and high performance liquid chromatography confirmed the presence of chlorhexidine in the nanoparticles. X-ray diffraction confirmed that the nanoparticles were amorphous. The drug loading was 0.11% for C-ACP and 0.53% for G-ACP. In vitro release profiles indicated that chlorhexidine was released sustainably via first-order kinetics. Released chlorhexidine inhibited the degradation of collagen in human dentine powder, and its effect lasted longer than that of pure chlorhexidine of the same concentration. The ACP could induce the mineralization of self-assembled type I collagen fibrils. The chlorhexidine-loaded ACP nanoparticles sustainably released chlorhexidine and ACP under appropriate conditions. This is useful for inhibiting degradation and inducing the mineralization of dentine collagen fibrils.

Stability and phase behavior of acrylamide-based emulsions before and after polymerization.

The stability and phase behavior of acrylamide-based emulsions, prepared with surfactants consisting of lipophilic Span80 and hydrophilic OP10, before or after polymerization were investigated. The research results indicated that the phase separation behavior of the W/O-type emulsions is related to the toluene/water ratio. When the water volume fraction was larger, the phase separation mechanism was mainly a penetration of aqueous molecules from the dispersed-phase droplets. When the water volume fraction was smaller, the phase separation mechanism was mainly a sedimentation of the separated aqueous droplets. At a fixed toluene/water ratio, the emulsion stability and the emulsion type are related not only to the ratio of the two surfactants but also to the acrylamide concentration, and the effect of increasing acrylamide concentration on the character of the emulsions is similar to that of increasing OP10 mass fraction (increasing HLB value), which determines the corresponding relationship between acrylamide concentration and HLB value in the most stable emulsion system. To obtain the most stable emulsion at a fixed acrylamide concentration, the emulsion with higher acrylamide concentration needs a lower HLB value for the emulsion systems.

Chitosan-decorated calcium hydroxide microcapsules with pH-triggered release for endodontic applications.

The treatment of apical periodontitis (AP) remains challenging because traditional root canal therapy (RCT) outcomes are limited by the complexity of the root canal system, drug toxicity, and host immune factors. It is necessary to develop methods to prepare controlled drug release vehicles with improved biocompatibility for treatment of AP. Herein, calcium hydroxide microcapsules with chitosan and ethylcellulose coated (CS-EC@Ca(OH)2 microcapsules) were prepared and the presence of hydrogen bonding between shell materials was observed by FT-IR. Through release assessment and biological assays, we showed that the microcapsules had enhanced controlled-release performance and biocompatibility. In particular, drug release from the microcapsules was pH-triggered. The cumulative release of drugs in pH 5.0 buffer was 8-fold higher than that in pH 7.0 buffer. Furthermore, the microcapsules exhibited prolonged antibacterial activity against refractory strains of Enterococcus faecalis. Additionally, the CS-EC@Ca(OH)2 microcapsules reduced inflammation and promoted osteogenesis, which could be beneficial for the healing of AP with bone defects. Therefore, CS-EC@Ca(OH)2 microcapsules improve the innate properties of Ca(OH)2 and hold potential for AP treatment.

A Novel Composite PMMA-based Bone Cement with Reduced Potential for Thermal Necrosis.

Percutaneous vertebroplasty (VP) and balloon kyphoplasty (BKP) are now widely used to treat patients who suffer painful vertebral compression fractures. In each of these treatments, a bone cement paste is injected into the fractured vertebral body/bodies, and the cement of choice is a poly(methyl methacrylate) (PMMA) bone cement. One drawback of this cement is the very high exothermic temperature, which, it has been suggested, causes thermal necrosis of surrounding tissue. In the present work, we prepared novel composite PMMA bone cement where microcapsules containing a phase change material (paraffin) (PCMc) were mixed with the powder of the cement. A PCM absorbs generated heat and, as such, its presence in the cement may lead to reduction in thermal necrosis. We determined a number of properties of the composite cement. Compared to the values for a control cement (a commercially available PMMA cement used in VP and BKP), each composite cement was found to have significantly lower maximum exothermic temperature, increased setting time, significantly lower compressive strength, significantly lower compressive modulus, comparable biocompatibility, and significantly smaller thermal necrosis zone. Composite cement containing 20% PCMc may be suitable for use in VP and BKP and thus deserves further evaluation.

Rational design and synthesis of Janus composites.

Janus composites with two different components divided on the same object have gained growing interest in many fields, such as solid emulsion stabilizers, sensors, optical probes and self-propellers. Over the past twenty years, various synthesis methods have been developed including Pickering emulsion interfacial modification, block copolymer self-assembly, microfluidics, electro co-jetting, and swelling emulsion polymerization. Anisotropic shape and asymmetric spatial distribution of compositions and functionalities determine their unique performances. Rational design and large scale synthesis of functional Janus materials are crucial for the systematical characterization of performance and exploitation of practical applications.

Influence of calcium hydroxide-loaded microcapsules on osteoprotegerin and receptor activator of nuclear factor kappa B ligand activity.

INTRODUCTION: Calcium hydroxide (Ca[OH]2) microcapsules were synthesized to allow controlled release of Ca(OH)2. The aim of this study was to evaluate the influence of Ca(OH)2 microcapsules on osteoprotegerin (OPG) activity, receptor activator of nuclear factor kappa B ligand (RANKL) activity, and the OPG/RANKL ratio compared with pure Ca(OH)2 powder and Vitapex (Neo Dental Chemical Products Co Ltd, Tokyo, Japan). METHODS: One formula of Ca(OH)2 microcapsules was evaluated, and pure Ca(OH)2 powder was used as a control. A commonly used Ca(OH)2 medication containing an oily vehicle (Vitapex) was also evaluated, and the in vitro release profile of Vitapex was studied. The human osteosarcoma cell line MG63 was used to evaluate the influence of Ca(OH)2 microcapsules, pure Ca(OH)2 powder, and Vitapex on OPG and RANKL activity. The relative messenger RNA (mRNA) expression of OPG and RANKL was determined by real-time polymerase chain reaction. The protein expression of OPG and RANKL in supernatants was measured using enzyme-linked immunosorbent assay. RESULTS: Vitapex prolonged the release of Ca(OH)2 compared with pure Ca(OH)2 powder, and the release rate of Vitapex was faster than that of the microcapsules. The OPG/RANKL ratio in the microcapsules group was up-regulated at both the mRNA and protein levels compared with the negative control group and the pure Ca(OH)2 powder group. The ratio in the Vitapex group was lower than the microcapsule group both at the mRNA and protein levels. CONCLUSIONS: Ca(OH)2 microcapsules increased the expression of OPG although they did not increase the expression of RANKL compared with pure Ca(OH)2 powder and Vitapex. This increase in expression led to an increase in the OPG/RANKL ratio and eventual inhibition of osteoclast activity.

The biological performance of calcium hydroxide-loaded microcapsules.

INTRODUCTION: Calcium hydroxide (Ca[OH]2) microcapsules were synthesized for use in controlled release. The aim of this study was to evaluate the cytotoxicity, antibacterial properties, and influence on gene expression of bone-related markers of 2 different formulas of Ca(OH)2 microcapsules. METHODS: Two formulas of Ca(OH)2 microcapsules (A and B) were evaluated, and pure Ca(OH)2 powder was used as a positive control. The shell material of formula A was pure EC, and the PLA/EC blend of 1:1 was used as the shell material for formula B. The MG63 cells/Cell Counting Kit-8 (Dojindo, Kumamoto, Japan) were used to evaluate the cytotoxicity, and the colony-forming units of Enterococcus faecalis were monitored for the antibacterial effect. The relative messenger RNA expression of collagen I and osteocalcin was determined by real-time polymerase chain reaction. RESULTS: Both formulas of the Ca(OH)2 microcapsules showed no cytotoxicity in MG63 cells; however, the Ca(OH)2 positive control did exhibit cytotoxicity. The antibacterial effect of the 2 microcapsule formulas lasted longer than the positive control, and formula A lasted longer than formula B. For both Ca(OH)2 microcapsule formulas, the relative messenger RNA expression of collagen I and osteocalcin was prolonged and up-regulated. The time effects of the influence on messenger RNA expression of collagen I and osteocalcin were different between the 2 microcapsule formulas. CONCLUSIONS: Ca(OH)2 microcapsules had prolonged antibacterial activity and prolonged the up-regulation of bone-related markers with reduced cytotoxicity.

Polymer nanotubes toward gelating organic chemicals.

Crosslinked polymer nanotubes are large scale synthesized. The method is based on fast cationic polymerization using immiscible initiator nanodroplets. Nanoporous network processed from the nanotubes is superhydrophobic, which can absorb all the tested organic chemicals forming robust gels. The nanotubes are promising in the collection of spilled organic chemicals, detoxification and water treatment.

Synthesis and characterization of biodegradable microcapsules for the controlled delivery of calcium hydroxide.

This study aimed to synthesize and characterize biodegradable microcapsules based on poly(lactic acid) (PLA) and ethylcellulose (EC) for a controlled delivery of calcium hydroxide. Phase separation technique was adopted to synthesize calcium hydroxide-loaded PLA/EC microcapsules. Four PLA/EC blends (4/1, 1/1, 1/4, pure EC) were used as shell materials and the input ratio of calcium hydroxide to shell polymer was 4:1 for all microcapsules. The morphology and composition were studied using SEM-EDS and TEM. Particle size distribution, glass-transition temperature, drug loading, and encapsulation efficiency were characterized. In vitro release of the microcapsules was evaluated using a pH microelectrode and an auto-biochemistry analyzer. SEM images of microcapsules showed uniform spherical structures with smooth surfaces. Core-shell, hetero-structures were confirmed using TEM. The presence of calcium in the microcapsules was verified with EDS. Pure calcium hydroxide was 160 nm in diameter and the particle size of the microcapsules ranged between 500 nm and 4 µm. With an increase of PLA in PLA/EC blend, the size of microcapsules increased accordingly. Encapsulation efficiency of these microcapsules was higher than 57% and drug loading was higher than 80%, which were not significantly different among four microcapsules. Pure calcium hydroxide powder was used as a control and 90% was released within 48 h, while release of calcium hydroxide from microcapsules took between 168 and 456 h, depending on the PLA/EC ratio. Compared with calcium hydroxide powder, the calcium hydroxide-loaded microcapsules showed a sustained and prolonged release, which could be controlled via the regulation of the PLA/EC ratio.