Core-shell Particles Research Articles

Growth of metal nanoparticles in hydrocarbon atmosphere of arc discharge

A direct current (DC) arc discharge is a widely used method for large-scale production of metal nanoparticles, core–shell particles, and carbon nanotubes. Here, the growth of iron nanoparticles is explored in a modified DC arc discharge. Iron particles are produced by the evaporation of an anode, made from low-carbon steel. Methane admixture into argon gas serves as a carbon source. Electron microscopy and elemental analysis suggest that methane and/or products of its decomposition adhere to iron clusters forming a carbon shell, which inhibits iron particle growth until its full encapsulation, at which point the iron core growth is ceased. Experimental observations are explained using an aerosol growth model. The results demonstrate the path to manipulate metal particle size in a hydrocarbon arc environment.

Impact-dispersed Fe–Fe1−xS core–shell particles in Chang’e-5 lunar soil impact glass

Lunar soil undergoes space weathering and accumulates optically active opaque particles (OAOpq) of different sizes, resulting in a darkening or red shift of the reflectance spectrum. The surfaces of weakly weathered objects exhibit spectral characteristics of strong weathering; these mechanisms are still unclear. The causes of OAOpq in lunar soil are complex, especially for submicrometer particles, which account for the largest mass proportion. We found ubiquitous impact-dispersed Fe–Fe1-xS core–shell particles in Chang’e-5 lunar soil impact glass and splatter. The crystal structure, particle size distribution, and chemical composition of OAOpq in the impact glass indicate that these OAOpq consist of sulfides or metals from multiple sources. Thermodynamic evidence, diffusion behavior, and particle dispersion characteristics indicate that impact dispersion is the most likely formation mechanism of these OAOpq. The proposed impact dispersion provides a reason for the large number of OAOpq and the limited products for in situ reactions. This process explains why lunar soil with a low degree of weathering exhibits substantial spectral modification properties. The results provide insights into space weathering of the lunar surface and also imply that impact-dispersed OAOpq may be the primary modification type on asteroid surfaces. The unique chemical properties of Fe–Fe1-xS OAOpq also indicate that the lunar regolith has the potential for resource utilization.

Enhanced photocatalytic performance of coaxially electrospun titania nanofibers comprising yolk-shell particles

The present paper reports the fabrication of novel types of hybrid fibrous photocatalysts by combining block copolymer (BCP) templating, sol–gel processing, and coaxial electrospinning techniques. Coaxial electrospinning produces core–shell nanofibers (NFs), which are converted into hollow porous TiO2 NFs using an oxidative calcination step. Hybrid BCP micelles comprising a single plasmonic nanoparticle (NP) in their core and thereof derived silica-coated core–shell particles are utilized as precursors to generate yolk-shell type particulate inclusions in photocatalytically active NFs. The catalytic and photocatalytic activity of calcined NFs comprising different types of yolk-shell particles is systematically investigated and compared. Interestingly, calcined NFs comprising silica-coated yolk-shells demonstrate enhanced catalytic and photocatalytic performance despite the presence of silica shell separating plasmonic NP from the TiO2 matrix. Electromagnetic simulations indicate that this enhancement is caused by a localized surface plasmon resonance and a confinement effect in silica-coated yolk-shells embedded in porous TiO2 NFs. Utilization of the coaxially electrospun TiO2 NFs in combination with yolk-shells comprising plasmonic NPs reveals to be a potent method for the photocatalytic decomposition of numerous pollutants. It is worth noting that this study stands as the first occurrence of combining yolk-shells (Au@void@SiO2) with porous electrospun NFs (TiO2) for photocatalytic purposes and gaining an understanding of plasmon and confinement effects for photocatalytic performance. This approach represents a promising route for fabricating highly active and up-scalable fibrous photocatalytic systems.

Co-axial electrosprayed RAD001-loaded polycaprolactone/polyvinyl alcohol core–shell particles for treating pediatric brain tumours

Core-shell particles composed of polycaprolactone/polyvinyl alcohol (PCL/PVA) with pH sensitive properties were successfully fabricated by co-axial electrospraying in which PVA and PCL formed the shell and core layers respectively. The core–shell structure was confirmed by FTIR, DSC and SEM analysis. No chemical interaction between PVA and PCL core–shell were observed in the FTIR analysis. The RAD001 loaded core–shell particles showed a sustained and pH dependent drug release and was assayed via our previously developed HPLC method. After indirect treatment of the PF-A cells with the core–shell particles for 24 h and 5 days a decrease in cell viability was observed. Additionally, a comparison was made with our previously developed nanoparticles containing 2 %PVA-14 %SOL®-0.6 % RAD001, for the cell viability study on ependymoma. Our findings show that optimised core–shell particles exerted a significant effect for the 24 h and 5 day treatment however further studies are required to ensure toxicity of the control core–shell particles with no drug is reduced. In comparison, the 2 %PVA-14 %SOL®-0.6 %RAD001 uniaxial electrosprayed nanoparticles also exerted a toxicity effect decreasing cell viability with no toxicity observed for the control nanoparticles as well. Such pH-sensitive core–shell particles, which can degrade effectively in either acidic or neutral condition, have great potential for application in the biomedical field.

Improving the intestinal lipidome coverage in a gnotobiotic mouse model using UHPLC-MS-based approach through optimization of mobile phase modifiers and column selection

Lipidomics is focusing on the screening of lipid species in complex mixtures using mass spectrometry-based approaches. In this work, we aim to enhance the intestinal lipidome coverage within the Oligo-Mouse-Microbiota (OMM12) colonized mouse model by testing eight mobile phase conditions on five reversed-phase columns. Our selected mobile phase modifiers included two ammonium salts, two concentrations, and the addition of respective acids at 0.1 %. We compared two columns with hybrid surface technology, two with ethylene bridged hybrid technology and one with core–shell particles. Best performance was attained for standards and intestinal lipidome, using either ammonium formate or acetate in ESI(+) or ammonium acetate in ESI(−) for all column technologies. Notably, a concentration of 5 mM ammonium salt showed optimal results for both modes, while the addition of acids had a negligible effect on lipid ionization efficiency. The HST BEH C18 column improved peak width and tailing factor parameters compared to other technologies. We achieved the highest lipid count in colon and ileum content, including ceramides, phosphatidylethanolamines and phosphatidylcholines, when using 5 mM ammonium acetate in ESI(−). Conversely, in ESI(+) 5 mM ammonium formate demonstrated superior coverage for diacylglycerols and triacylglycerols.

Hybrid films loaded with 5-fluorouracil and Reglan for synergistic treatment of colon cancer via asynchronous dual-drug delivery

Combination therapy with oral administration of several active ingredients is a popular clinical treatment for cancer. However, the traditional method has poor convenience, less safety, and low efficiency for patients. The combination of traditional pharmaceutical techniques and advanced material conversion methods can provide new solutions to this issue. In this research, a new kind of hybrid film was created via coaxial electrospraying, followed by a casting process. The films were composed of Reglan and 5-fluorouracil (5-FU)-loaded cellulose acetate (CA) core-shell particles in a polyvinylpyrrolidone (PVP) film matrix. Microscopic observations of these films demonstrated a solid cross section loaded with core-shell particles. X-ray diffraction and Fourier-transform infrared tests verified that the Reglan and 5-FU loaded in the films showed amorphous states and fine compatibilities with the polymeric matrices, i.e., PVP and CA, respectively. In vitro dissolution tests indicated that the films were able to provide the desired asynchronous dual-drug delivery, fast release of Reglan, and sustained release of 5-FU. The controlled release mechanisms were shown to be an erosion mechanism for Reglan and a typical Fickian diffusion mechanism for 5-FU. The protocols reported herein pioneer a new approach for fabricating biomaterials loaded with multiple drugs, each with its own controlled release behavior, for synergistic cancer treatment.

Single atoms/metal nanoparticles-decorated hollow carbon spheres as oxygen reduction catalyst for zinc-air batteries

Non-platinum electrocatalyst development for improving the oxygen reduction reaction (ORR) is critical in electrochemical energy conversion applications such as zinc-air batteries (ZABs). Herein, we developed dual Fe-Co single atoms and Co nanoparticles embedded N-doped hollow carbon (Fe-Co/N-HCS-x) catalysts via the carbonization of polypyrrole (PPy)@zeolitic imidazolate framework (ZIF) core–shell particles, with various PPy concentrations. PPy serves as a secondary nitrogen source that enhances nitrogen amount and promotes metal dispersion to increase active sites density. The Fe-Co/N-HCS-x catalysts with optimized PPy concentration control demonstrated improved ORR performance in alkaline media, with a half-wave potential (E1/2) of 0.921 V and an onset potential (Eonset) of 1.019 V. Fe-Co/N-HCS-x also exhibited high ZABs performance, with a power density of 244.6 mW cm−2 and an operating time of more than 100 h. Our research contributes to the development of optimized active sites for ORR, which can be applied to new electrochemical storage and conversion systems.

Microstructure, cracking susceptibility and abrasive wear resistance of core-shell ceramic particles reinforced laser cladding coatings

In this study, the typical core-shell ceramic particles were synthesized in-situ in the Fe-based composite coating using the laser cladding technology. The core-shell ceramic particles were composed of a pure TiC core and a (Ti,Nb,W)C multiple carbide shell, exhibiting fine cubic morphologies with particle sizes ranging from 0.5 μm to 1.0 μm rather than coarse dendritic morphologies. These core-shell ceramic particles were uniformly distributed in the entire coating with no obvious gradient distribution from the upper to the bottom. With the formation of the core-shell ceramic particles, the clad coating showed a more stable microhardness distribution along the depth direction and a lower cracking susceptibility than the original coating, and its average microhardness value (about 410 HV0.5) was only about 64 % of that of the original coating (about 640 HV0.5). Besides, the introduction of the core-shell ceramic particles caused the clad coating to possess the excellent abrasive wear resistance, which was approximately 10 times higher than that of the original coating. This significant improvement was attributed to the outstanding dispersion strengthening effect provided by the core-shell ceramic particles.

Enhanced mechanical properties of alumina ceramics: Role of nanoscale C@Al2O3 core-shell particle

The introduction of pores to improve the toughness of alumina ceramics is considered to be a feasible strategy by using the inhibitory effect of pores on crack propagation. However, the mechanical properties of alumina ceramics are often reduced due to the uncontrollable pore shape. In this work, the nano-scale C@Al2O3 core-shell particles were fabricated and introduced into the alumina powder treated by dielectric barrier discharge plasma-assisted milling, and the alumina ceramics with closed pores of regular shape (approximate sphere) and small size (<1 μm) were prepared. Since the approximate spherical pore structure and small pore size eliminate the adverse effects of stress concentration, and the deflection and pinning effect of closed pores on cracks, the flexural strength and fracture toughness of the prepared samples were improved, increasing by 12.6 % and 18.8 % respectively.

Lightweight, flexible, and antimicrobial X-ray shielding composites with liquid metal-derived bismuth-tin core-shell particles

The extensive use of low-energy X-rays in clinical diagnostics increased radiation exposure, growing concerns for the health of patients and healthcare professionals. Lead has long served as a traditional material for radiation shielding owing to its high density and atomic number; however, concerns have arisen due to its toxicity and substantial weight. In this study, we developed flexible and wearable radiation protection materials by employing a layered structure comprising liquid metal-derived bismuth-tin (BiSn) core-shell particles embedded in a thermoplastic polyurethane (TPU) matrix. The structural and mechanical properties of the TPU-BiSn composites were thoroughly investigated. The use of liquid metal particles (LMPs) resulted in outstanding flexibility (retained the flexibility of TPU matrix), while their oxide shell strengthened the composites significantly (∼15 % enhancement in the tensile strength at break point). The TPU-BiSn composites exhibited promising X-ray attenuation properties. X-ray attenuation efficiency surpassed 99 % for 5 mm thick composite sheets, suitable for mammographic diagnostics in the energy range of 20–30 kVp. Increasing particle loading improved shielding efficiency for higher energy ranges (40–90 kVp), with predictions extending to 90–120 kVp, demonstrating their suitability for composites that comply with ASTM standards for radiation attenuation gloves. In addition, the composite sheets displayed contact-active antimicrobial properties, rendering them appealing for various healthcare applications. Given the availability of materials and the feasibility of production, these composites hold significant potential for practical implementation in real-world applications.

Encapsulation of Cadmium-Free InP-based Quantum Dots in Cross-Linked Core-Shell Microparticles via Coaxial Electrospraying.

Quantum dots (QDs) are inorganic semiconductornanocrystalscapable of emitting light. The current major challenge lies in theuseofheavy metals, which are known to be highly toxic to humans and pose significant environmental risks. Researchers have turned to indium (In) as a promising option for more environmentally benign QDs, specifically indium phosphide (InP). A significant obstacle remains in sustaining the long-term photostability of InP-based QDs when exposed to the environment. To tackle this, electrospraying is used in this work to protect indium phosphide/zinc selenide/zinc sulfide (InP/ZnSe/ZnS) QDs by embedding them within polymer core-shell microparticles of poly[(lauryl methacrylate)-co-(ethylene glycol dimethacrylate)]/poly(methyl methacrylate)(poly(LMA-co-EGDMA)/PMMA). During the flight of droplets, the liquid monomer core of LMA and EGDMA with QDs is encapsulated by the solid shell of PMMA formed due to solvent evaporation, resulting in a liquid-core/solid-shell particle structure. After that, the captured core of monomers is polymerized into a cross-linked polymer with the embedded QDs via a thermal initiation. They demonstrate how a successful core-shell particle formation is achieved to produce structures for initially liquid monomer systems via coaxial electrospraying that are used for cross-linked polymers, which are of major interest for the encapsulation of InP-based QDs for generally improved photostability over pristineQDs.

Formation of metastable phases during spark plasma sintering of Fe@Au core–shell particles

ABSTRACT The present work reports the formation of Fe-Au metastable alloys by galvanic replacement, pressureless spark plasma sintering (SPS) and acid treatment. The reaction of partial galvanic replacement between micrometer-sized iron particles and HAuCl4 solution allowed synthesising core–shell Fe@Au particles. When the Fe@Au particles were treated in HCl solution, iron was selectively dissolved and hollow Au particles were formed. Pressureless SPS of the Fe@Au core–shell particles led to the formation of a metastable intermetallic phase, FeAu3, and a supersaturated solid solution, Au(Fe). The latter was resistant to HCl solution; at the same time, the FeAu3 phase decomposed during HCl treatment to form a porous gold structure. This work shows that a combination of galvanic replacement, SPS and acid treatment can be used for the preparation of metastable Fe-Au alloys with different phase compositions and particle morphologies.

Toward coupling across inorganic/organic hybrid interfaces: polyaniline-coated gold nanoparticles with 4-aminothiophenol as gold-anchoring moieties

AbstractThe chemical binding between metal nanoparticles and (semi-)conductive polymer layers is essential to control the (opto-)electronic properties of such hybrid materials. Current approaches that achieve a conjugated binding of organic (semi-)conductive ligands to metal nanoparticles demonstrated promising functional properties, but are based on tedious multi-step organic synthesis to incorporate the required binding moieties at the chain ends of targeted macromolecular species. Herein, we explore the pre-functionalization of gold nanoparticles with p-aminothiophenol and subsequent surfactant-assisted formation of a poly(aniline) (PANI) shell as a means to access gold/PANI core–shell-type nanoparticles with enhanced conductive properties. Controlled surface deposition of these hybrid nanoparticles is achieved via template-assisted self-assembly. For these surface-deposited nanoparticles, charge transport properties are characterized at the nanoscale by conductive atomic force microscopy measurements and show a significant conductivity increase of our core–shell particles as compared to reference particles formed by conventional surfactant-assisted PANI-shell formation. Graphical Abstract

Effect of in-situ activated core-shell particles on fatigue behavior of carbon fiber reinforced thermoplastic composites

In this unique study, the effect of adding core-shell particles (CSPs) on fatigue performance of carbon-fiber reinforced PA6 (CF-PA6) laminates is investigated. The thermoplastic laminates were prepared using compression molding and were reinforced at ply interfaces with 2 wt% and 4 wt% CSPs of the polymer mass. A manual method was used to disperse CSPs using a sieve and carefully selected process parameters. The cyclic tests were conducted and assessed, considering S–N curve, stiffness degradation, and energy dissipation. Consequently, the fatigue life of modified composites improved respectively by eight and four times when 2 wt% and 4 wt% CSPs were used. The results showed that an optimal improvement was achieved with a 2 wt% CSPs. The fatigue strength coefficient and fatigue strength exponent of CF-PA6 composites improved by 22.13 % and 9.85 %, respectively. The findings have the potential to establish a new frontier in thermoplastic research and would help designers to enhance the fatigue properties of thermoplastic laminates in specific elastic tailoring structures.

Investigation of swelling degree of polypropylene beads with monomers and blowing agents

AbstractThe swelling step of polymer particles or beads with blowing agents and monomers is one of the factors that directly affect the performance properties of expandable core–shell particles, including morphology, composition, and expansion degree. In this regard, the present work investigated the effect of swelling agents on polypropylene (PP) beads. Swelling agents were used to perform swelling tests in both bulk and suspension media at different temperatures and stirring rates. Additionally, a mass transfer model was implemented to predict the swelling degree at the analyzed experimental conditions. The obtained results indicated the important effect of temperature on swelling in both bulk and suspension tests. Among the investigated swelling agents, higher rates of PP beads swelling were observed when styrene was employed (~80 wt%), when compared to methyl methacrylate (~20 wt%), vinyl acetate (~9 wt%), and acrylonitrile (~6 wt%). Moreover, it seems that the stirring rate does not exert a considerable influence on the swelling rates, indicating that swelling is controlled by thermodynamic constraints and particle properties. Finally, experimental results showed that the final saturation concentration of the swelling agent can be reached before 1 hour of swelling, indicating that the swelling kinetics can be much faster than the polymerization kinetics.Highlights The effects of non‐conventional swelling agents on PP were investigated. The swelling presented a fast dynamic behavior. The swelling dynamics was controlled by the solubility of the swelling agent. The highest swelling degree was obtained with styrene.

Development of Perfluoro Decalin/Fluorinated Polyimide Core-Shell Microparticles via SPG Membrane Emulsification Using Methyl Perfluoropropyl Ether Cosolvent.

Red blood cell-inspired perfluorocarbon-encapsulated core-shell particles have been developed for biomedical applications. Although the use of perfluorodecalin (FDC) is expected for core-shell particles owing to its high oxygen solubility, the low solubility of FDC in any organic solvent, owing to its fluorous properties, prevents its use in core-shell particles. In this study, a new cosolvent system composed of dichloromethane (DCM) and heptafluoropropyl methyl ether (HFPME) was found to dissolve both FDC and fluorinated polyimide (FPI) based on a systematic study using a phase diagram, achieving a homogeneous disperse phase for emulsification composed of oxygen-permeable FPI and oxygen-soluble FDC. Using this novel cosolvent system and Shirasu porous glass (SPG) membrane emulsification, FDC-encapsulated FPI shell microparticles were successfully prepared for the first time. In addition to oxygenation, demonstrated using hypoxia-responsive HeLa cells, the fabricated core-shell microparticles exhibited monodispersity, excellent stability, biocompatibility, and oxygen capacity.

Modeling hyperthermia-based prostate cancer treatment in the presence of core-shell nanoparticles and large blood vessels under different ultrasound sonication patterns

The use of nanoparticles, as enhancing agents to transform ultrasound energy into heat for tumor destruction, is a promising approach to improve the efficacy of thermal-based cancer therapies. This study aimed to evaluate the effectiveness of core-shell type nanoparticles and the heat loss due to blood flow in large vessels under different patterns of ultrasound sonication in the hyperthermia-based treatment of the prostate cancer. For this purpose, the ultrasound attenuation coefficient in the prostate tumor embedded with nanoparticles was calculated using a scattering theory that was developed for core-shell type particles. Using the attenuation coefficient and the linear pressure wave equation, the acoustic power dissipated per unit volume of a three-dimensional (3D) model of the prostate tumor and its surrounding tissues was calculated. By simultaneous solving the bioheat, the convective energy, the continuity, the Navier-Stokes, and the thermal dose equations, the temperature and thermal dose distribution were computed in the model. The attenuation coefficient of the tumor showed a decreasing trend with increasing the thickness of the silica shell coating the magnetite or titania core. The capability of nanoparticles to enhance heat production in the medium was directly, and the blood flow heat loss was inversely, related to the degree of focus of the ultrasound beam. The thermal response of the tumor was influenced by its size and geometry, as well as the acoustic intensity. Titania nanoparticles were more efficient than the magnetite nanoparticles in ultrasound attenuation and heat production in the medium. Our findings can be useful in understanding the factors affecting the hyperthermia-based treatment of the prostate cancer using a combination of ultrasound and nanoparticles.

Calcium Alginate Core–Shell Liquid Beads Encapsulated with Microalgae for Wastewater Treatment

Liquid beads are core–shell particles with a liquid core and a solid shell. Calcium alginate liquid beads have been emerging as a promising platform for cell encapsulation. These beads have demonstrated their capability of encapsulating and culturing a wide range of human cells for tissue engineering. However, a significant research gap remains in the application of alginate liquid beads for encapsulating photosynthetic microorganisms. Herein, fast‐growing microalgae strain Chlorella vulgaris is encapsulated into calcium alginate liquid beads to facilitate the removal of nutrients from wastewater, minimizing the risk of eutrophication. Liquid bead‐microalgae systems are prepared, using different calcium ion concentrations as crosslinking ions. It has been thoroughly characterized for their morphologies, cell growth patterns, nutrient removal capabilities, and overall stability throughout the wastewater treatment process, with upflow anaerobic sludge blanket effluent as the wastewater model. The results indicate that the liquid bead‐microalgae system with the highest calcium ion concentration (5%) performs more efficiently, exhibiting a well‐formed crosslinking structure, leading to rapid cell growth with the highest cell density and the most effective removal of nutrients. The findings from this study provide valuable insights for future optimization and upscaling efforts in wastewater treatment systems based on calcium alginate liquid beads.

Recyclable Polymer Composites with a Wrinkled Core-Shell Structure for Highly Efficient EMI Shielding and Low Reflection.

Green electromagnetic interference (EMI) shielding materials not only require high shielding effectiveness (SE) and low reflection but also need to be recyclable after damage; however, it is challenging to strike a balance in practice. Here, a polyacrylamide (PAM) composite composed of numerous chemically cross-linked PAM@carbon nanotube (cPAM@CNT) core-shell particles featuring rich wrinkled microstructures was prepared using an adsorption-drying-shrinking strategy. The wrinkled microstructures enable the incident electromagnetic waves (EMWs) to undergo attenuation within the composites, achieving an average EMI SE of 67.5 dB in the X band. Due to the hygroscopicity of hydrophobically associated PAM (hPAM, an adhesive for cPAM@CNTs core-shell particles), the average EMI SE of the composites further increased to 83.2 dB after exposure to 91% relative humidity for 24 h, with only a 2.7 dB low reflection. Additionally, the composites also demonstrated excellent Joule heating, photothermal performance, and recyclability, which exhibit substantial promise for advanced EMI shielding applications.

Development of a rapid HPLC-fluorescence method for monitoring warfarin metabolites formation: In vitro studies for evaluating the effect of piperine on warfarin metabolism and plasma coagulation

Warfarin, a widely prescribed anticoagulant, is highly effective for various coagulation disorders. However, its efficacy is limited by a narrow therapeutic index and frequent drug interactions, especially those involving metabolism by Cytochrome P450 (CYP450) enzymes. Piperine, found in black and long pepper, possesses blood-thinning properties and has been observed to inhibit CYP3A and CYP2C enzymes linked to warfarin metabolism. This study investigated the effect of piperine on warfarin metabolism in liver microsomes using a rapid and sensitive HPLC-Fluorescence method. The use of PFP (pentafluorophenyl) column with core shell particles provided the selectivity and resolution to resolve warfarin and its 4-, 6-, 7-, and 10-hydroxy metabolites in addition to the internal standard naproxen in less than 3 min. This is the fastest analytical assay for warfarin and its major metabolites reported to date, making it ideal for metabolic studies. The applicability of the method was demonstrated by monitoring the metabolism of S-warfarin in human and rat liver microsomes, and evaluating the inhibitory effect of piperine on metabolite formation. The results showed that piperine inhibited the formation of the major metabolite, 7-hydroxywarfarin, with half-maximal inhibitory concentration (IC50) 14.2 μM and 3.2 μM in human and rat liver microsomes, respectively. Furthermore, coagulation studies in vitro using rat plasma showed that piperine does not affect prothrombin time (PT) and activated partial thromboplastin time (aPTT). This study suggested that piperine may present a potential drug interaction with warfarin at the metabolism level, but has no direct effect on the activation of the extrinsic or intrinsic coagulation cascades. Further clinical investigation is therefore required, as piperine may increase the bioavailability of warfarin, thus increasing risk of serious adverse events in patients.