Formation Of Core-shell Particles Research Articles

Core-shell particle formation via Co-assembly of AB diblock copolymers and nanoparticles in 3D soft confinement.

Core-shell particle formation via co-assembly of AB diblock copolymers and nanoparticles in 3D soft confinement was studied using a simulated annealing method. Several sequences of soft confinement-induced core-shell particles were predicted as functions of the volume fraction of the nanoparticle to core-shell particles, the incompatibility between blocks, the volume fractions of A-blocks, the chain length of AB diblocks, the eccentricity of the nanoparticle, and the initial concentration of copolymers. Simulation results demonstrate that those factors are able to tune the morphology of the core-shell particles precisely. Calculated data indicate that the copolymer chain was located between a hard confinement wall composed of the nanoparticle and a soft confinement wall composed of solvents, and the arrangement direction of the copolymer chains was in a competitive equilibrium between the two. We anticipate that this work will be helpful and instructive for the preparation of polymer shells with different structures and shapes, as well as the study of self-assembly morphology of copolymers in a complex confinement systems.

Transformation of alumina-supported Pt-Au alloyed nanoparticles into core-shell Pt@Au structures during high-temperature treatment

A series of alumina-supported bimetallic AuPt catalysts was prepared by decomposition of a double complex salt containing simultaneously gold and platinum. The decomposition was performed in both the reductive and oxidative atmospheres. Monometallic Au/γ-Al2O3 and Pt/γ-Al2O3 catalysts were used as reference samples. Physicochemical characterization of the catalysts has revealed that despite the preparation route and total metal loading, the alloyed nanoparticles are being formed with close values of the average particle size and similar particle size distribution, while the composition and the structure of the particles differ significantly. Thermal aging of the catalysts at 600 and 800 °C leads to redistribution of metals in the alloyed particles and formation of core-shell Pt@Au nanostructures, which results in significant deactivation of the catalysts concerning a model reaction of CO oxidation. The formation of core-shell particles in the case of high-loaded samples was found to prevent the agglomeration process at elevated temperatures.

Creating a composite material ZnO-Bi2O3 with a core-shell structure for varistor ceramics

This paper discusses use of the plasma dynamic synthesis to obtain ZnO-Bi2O3 composite powder. This method allows to get the main ZnO material with the formation of core-shell particles. Sintering of ceramics from this material was carried out using spark plasma sintering facility. Use of this sintering method provides obtaining a fine-grained structure of ZnO (average grain size of 1.3 μm). Comparison of the current-voltage characteristics of ceramics from commercial and plasma dynamic materials showed promise of using a ZnO- Bi2O3 composite with a core-shell structure.

A novel dressing for the combined delivery of platelet lysate and vancomycin hydrochloride to chronic skin ulcers: Hyaluronic acid particles in alginate matrices

The aim of the present work was to develop a medication allowing for the combined delivery of platelet lysate (PL) and an anti-infective model drug, vancomycin hydrochloride (VCM), to chronic skin ulcers. A simple method was set up for the preparation of hyaluronic acid (HA) core-shell particles, loaded with PL and coated with calcium alginate, embedded in a VCM containing alginate matrix. Two different CaCl2 concentrations were investigated to allow for HA/PL core-shell particle formation. The resulting dressings were characterized for mechanical and hydration properties and tested in vitro (on fibroblasts) and ex-vivo (on skin biopsies) for biological activity. They were found of sufficient mechanical strength to withstand packaging and handling stress and able to absorb a high amount of wound exudate and to form a protective gel on the lesion area. The CaCl2 concentration used for shell formation did not affect VCM release from the alginate matrix, but strongly modified the release of PGFAB (chosen as representative of growth factors present in PL) from HA particles. In vitro and ex vivo tests provided sufficient proof of concept of the ability of dressings to improve skin ulcers healing.

Air stable copper-silver core-shell submicron particles: Synthesis and conductive ink formulation

We report on the synthesis of copper-silver core-shell (Cu@Ag) particles with about 1μm-diameter Cu core coated with a thin (∼20nm) silver shell, for application in printed electronics as low cost conductive ink. The process is based on using the environmentally friendly sodium formaldehyde sulfoxylate dehydrate as a reducing agent for copper ions and two types of polymeric stabilizers (nonionic PVP and anionic PAA). The formation of core-shell particles is followed by transmetallation reaction on the surface of the Cu particles, where copper atoms function as the reducer for silver ions. Characterization of the submicron particles by SEM, EDS and XRD confirm the core-shell structure. The resulting Cu@Ag particles enable overcoming a major challenge in copper ink, their rapid oxidation in air. It was found that ink formulations based on propylene glycol as the liquid vehicle and containing a silicone based wetting agent possesses the optimal characteristics (wetting, sintering) for printing on a glass substrate. To obtain conductive metallic structures, thermal sintering of metallic patterns was used. The Cu@Ag coating are stable to oxidation for at least 6 months at room temperature, and also during sintering process which is carried out at temperatures up to 250°C. The conductivity of Cu@Ag coatings after sintering at 250°C was high, 16% of that for bulk copper.

Formation of Core-Shell Particles by Interfacial Radical Polymerization Initiated by a Glucose Oxidase-Mediated Redox System.

A unique design paradigm to form core–shell particles based on interfacial radical polymerization is described. The interfacial initiation system is comprised of an enzymatic reaction between glucose and glucose oxidase (GOx) to generate hydrogen peroxide, which, in the presence of iron (Fe2+), generates hydroxyl radicals that initiate polymerization. Shell formation on prefabricated polymeric cores is achieved by localizing the initiation reaction to the interface of the core and a surrounding aqueous monomer formulation into which it is immersed. The interfacially confined initiation reaction is accomplished by incorporating one or more of the initiating species in the particle core and the remainder of the complementary initiating components in the surrounding media such that interactions and the resulting initiation reaction occur at the interface. This work is focused on engineering the reaction behavior and mass transport processes to promote interfacially confined polymerization, controlling the rate of shell formation, and manipulating the structure of the core–shell particle. Specifically, incorporating GOx in the precursor solution used to fabricate cores ranging from 100 to 200 μm, and the remainder of the complementary initiating components and monomer in the bulk solution prior to interfacial polymerization yielded shells whose average thickness was 20 μm after 4 min of immersion and at a bulk iron concentration of 12.5 mM. When the locations of glucose and GOx are interchanged, the average thickness of the shell was 15 or 100 μm for bulk iron concentrations of 45 and 12.5 mM, respectively. The initial locations of glucose and GOx also determine the degree of interpenetration of the core and the shell. Specifically, for a bulk iron concentration of 45 mM, the thickness of the interpenetrating layer averaged 12 μm when GOx was initially within the core, whereas no interpenetrating layer was observed when glucose was incorporated in the core. The polymeric shell formed by this technique is also demonstrated to be self-supporting following core degradation. This behavior is accomplished by fabricating the particle core hydrogel from monomers possessing degradable groups that can be irreversibly cleaved by light exposure following shell formation. When the coated particle was exposed to light, the shell remained intact while the core degraded as evidenced by a dramatic change in diffusion coefficient of fluorescent beads immobilized within the core.

Particle stability in polymer-assisted reverse colorimetric DNA assays

"Reverse" colorimetric DNA detection by the formation of core-shell particles upon DNA hybridization is described. Specifically, the assay is based on a strategy to covalently link polymer reaction initiators to suspended nanoparticles upon DNA hybridization. These initiators then prompt polymer chain growth to form a thick polymer shell outside of particles, acting as the physical barrier to keep Au particles apart. Particles without DNA hybridization aggregate, accompanied by a pronounced solution color change from red to blue. The focus of this report is to address reaction kinetics of two co-occurring processes: polymer growth and particle aggregation during the reverse colorimetric DNA assay. The results show that Cu ions used as the polymerization catalyst bind strongly to the bases in DNA molecules, resulting in crosslinking of DNA-attached gold nanoparticles and their subsequent precipitation. Both Cu-ion-assisted particle aggregation and polymer growth are found to depend strongly on Cu ion concentration, salt concentration, and reaction temperature. Under the optimized conditions, faster polymer chain growth on the surface overcomes particle aggregation and preserves particle stability via steric stabilization.

Preparation of Well-Defined Core−Shell Particles by Cu2+-Mediated Graft Copolymerization of Methyl Methacrylate from Bovine Serum Albumin

Small well-defined core-shell poly(methyl methacrylate)-bovine serum albumin (PMMA-BSA) particles have been prepared in a direct one-step graft copolymerization of MMA from BSA at 75 degrees C in water with a trace amount of Cu2+ (5 microM). Initially, BSA generates free radicals and acts as a multifunctional macroinitiator, which leads to the formation of an amphiphilic PMMA-BSA grafting copolymer. Such formed copolymer chains act as a polymeric stabilizer to promote further emulsion polymerization of MMA inside, resulting in surfactant-free stable core-shell particles, confirmed by a transmission electron microscopic (TEM) analysis. The PMMA-BSA copolymers as well as PMMA homopolymer inside the particles were isolated by Soxhlet extraction and characterized by Fourier transform infrared spectroscopy (FT-IR) and thermogravimetry (TG). The highest grafting efficiency was approximately 80%. Effects of the reaction temperature, the MMA/BSA ratio, and the concentrations of Cu2+ and BSA on such core-shell particle formation have been systematically studied. Due to their inert PMMA core and biocompatible BSA shell, these small polymer particles are potentially useful in biomedical applications.

Seed polymerization of tetraethyl ortho-silicate in the presence of rod-like colloidal particles of anionic palygorskite and cationic ?-FeO(OH)

Kinetic analyses were made of the seed polymerization of tetraethyl ortho-silicate (TEOS) in the presence of rod-like colloidal particles of palygorskite and cationic β-FeO(OH) by turbidity and dynamic light-scattering measurements. Transmission electron microscopic measurements supported the formation of core-shell particles. The seed polymerization of TEOS took place exclusively on the surfaces of palygorskite. The main cause of the observation is due to the fact that the main component of palygorskite is SiO2 and the affinity between palygorskite and TEOS is high, though the electrostatic repulsion between them is not favorable for shell formation. The shell formation of silica on a β-FeO(OH) particle also proceeded. The electrostatic attraction forces between the anionic polar TEOS monomers and cationic β-FeO(OH) particles played an important role in shell formation. These results are consistent with a polymerization mechanism consisting of the formation of small preliminary particles followed by their coalescence on the surfaces of the seeds to give the final large particles coated with silica layers.

Suspension, emulsion, and dispersion polymerization: A methodological survey

A methodological description of heterogeneous polymerization processes, including suspension, emulsion, dispersion, and precipitation polymerization is presented. The discussion focuses on the initial state of the polymerization mixture, mechanism of particle formation, and the shape and size of polymer particles produced in different heterogeneous polymerization systems. The dependence of particle size and morphology on manufacturing parameters such as emulsifier, stabilizer, reactor design, and stirring speed is discussed. Special topics, including emulsifier-free (soapless) emulsion polymerization, seeded ponymerization, and the formation of core-shell particles are also briefly covered.

Ternary composites of polypropylene/elastomer/calcium carbonate: effect of functionalized components on phase structure and mechanical properties

Investigated ternary composites assume two phase structures: (i) ethylene-propylene elastomer (EPR) and filler are dispersed separately in polypropylene (PP) matrix; (ii) EPR encapsulates filler particles, thus forming a low-modulus interlayer between the filler and PP. Formation of these phase structures is promoted by acid-base interactions when functionalized PP or functionalized EPR is added. PP functionalized with maleic anhydride or acrylic acid enhances the interfacial adhesion between matrix and filler, which prevents dewetting of filler particles and thus accounts for higher yield stress and alteration in failure mechanism. Alternatively, the addition of 5 to 20 vol% of an analogously functionalized EPR results in extensive filler encapsulation, i.e. formation of core-shell particles. The functionalized elastomers have lower molecular mobility manifested in smaller dissipative capacity and higher glass transition temperature. Thus, it seems advisable to combine functionalized species with a standard EPR to ensure good interfacial adhesion and high molecular mobility of the interlayer. Simple model calculations indicate that virtually complete encapsulation of filler can be achieved. Composites with core-shell particles have lower yield stress and higher impact strength than composites with functionalized matrix. These two mechanical properties were found to be inversely proportional in all series of tested composites. However, core-shell particles are apparently less effective impact modifiers than elastomer inclusions, presumably because of improper size (predestined by the size of filler cores) and/or shell modulus.