Inorganic Microparticles Research Articles

Zeolite-Loaded Hydrogels as Wound pH-Modulating Dressings for Diabetic Wound Healing.

Wound pH has emerged as a promising therapeutic target in diabetic foot ulcers (DFU). Here, we aimed to develop a microparticle-loaded hydrogel for pH modulation in wound fluid. In a screen of polymeric and inorganic microparticles, zeolites were identified as pH-modulating microparticles. Zeolites were encapsulated in a calcium cross-linked alginate hydrogel, a biocompatible matrix clinically used as a wound dressing. This hydrogel potently neutralized hydroxide ions in serum-containing simulated wound fluid. These findings encourage a further development of this pH-modulating device as a molecular therapeutic system for DFUs.

Multilayer Hydrogel Microcubes: Effects of Templating Particle Morphology on Cubic Hydrogel Properties

AbstractNon‐spherical stimuli‐responsive polymeric particles have shown critical importance in therapeutic delivery. Herein, pH‐responsive poly(methacrylic acid) (PMAA) cubic hydrogel microparticles are synthesized by crosslinking PMAA layers within PMAA/poly(N‐vinylpyrrolidone) hydrogen‐bonded multilayers templated on porous inorganic microparticles. This study investigates the effects of template porosity and surface morphology on the PMAA multilayer hydrogel microcube properties. It is found that the hydrogel structure depends on the template's calcination time and temperature. The pH‐triggered PMAA hydrogel cube swelling depends on the hydrogel's internal architecture, either hollow capsule‐like or non‐hollow continuous hydrogels. The loading efficiency of the doxorubicin (DOX) drug inside the microcubes is analyzed by high‐performance liquid chromatography (HPLC), and shows the dependenceof the drug uptake on the network structure and morphology controlled by the template porosity. Varying the template calcination from low (300 °C) to high (1000 °C) temperature results in a 2.5‐fold greater DOX encapsulation by the hydrogel cubes. The effects of hydrogel surface charge on the DOX loading and release are also studied using zeta‐potential measurements. This work provides insight into the effect of structural composition, network morphology, and pH‐induced swelling of the cubical hydrogels and may advance the development of stimuli‐responsive vehicles for targeted anticancer drug delivery.

Omniphobic coatings based on functional acrylic polymer

Omniphobic coatings were prepared on flat surfaces using a functional acrylic polymer and common micron sized inorganic particles by a simple spray application technique. This coating comprises of a blend of functional acrylic polysiloxane polymer and liquid epoxy resin as a primer base coat followed by spray application of a mixture of organosilanes and inorganic microparticles. The microparticles are fillers commonly used in the paint and coating industry. The resulting surface has the desired surface energy and surface morphology to enable liquid repellency with contact angles of ∼150° for water and 142° for diiodomethane with a roll off angle of <5°. Scanning Electron Microscopic (SEM) and Atomic Force Microscopy (AFM) analysis were performed to study surface morphology. This coating can be applied on large areas and can be cured under ambient conditions. This omniphobic coating is robust, free of nanoparticles and can be used for potential applications in the field of self-cleaning coatings, anti-microbial coatings, and easy cleaning coatings.

Controlling Surface of Rods With Entrained Particle as Asperities

Abstract Changing the surface properties (i.e., roughness or friction) can be instrumental for many applications but can be a complex and resource-intensive process. In this paper, we demonstrate a novel process of controlling the friction of a continuous rod by delivering inorganic microparticles. A standardized continuous particle transfer protocol has been developed in our laboratory for depositing particles from a liquid carrier system (LCS) to the cylindrical rod substrate. The particle transfer process can produce controllable and tunable surface properties. Polymeric binder is used to deliver the particles as asperities over the rod substrate and by controlling their size, shape, and distribution, the coefficient of friction of the rod is determined. Tabletop experiments are designed and performed to measure the friction coefficient following the Capstan equation. The entrained particles on the substrate will create size- and shape-based asperities, which will alter the surface morphology toward the desired direction. Both oblique and direct quantitative measurements are performed at different particles and binder concentrations. A systematic variation in the friction coefficient is observed and reported in the result section. It is observed from the capstan experiment that adding only 1% irregular shaped particles in the suspension changes the friction coefficient of the rods by almost 115%. The proposed friction control technique is a simple scale-up, low-cost, low-waste, and low-energy manufacturing method for controlling the surface morphology.

Preliminary Evidence of Differentially Induced Immune Responses by Microparticle-adsorbed LPS in Patients with Crohn's Disease.

Inorganic microparticles are ubiquitous in the modern Western diet present as food additives and are actively scavenged by microfold (M) cells overlying human intestinal lymphoid aggregates. In Crohn's disease (CD), inflammation is caused by the inability of the intestinal mucosa to sustain tolerance to gut luminal factors including bacteria and their by-products. Having large, highly charged surface areas dietary particles can avidly bind biomolecules such as lipopolysaccharide (LPS). The aim of this paper was to examine whether the dietary particle, titanium dioxide (TiO2), modified cellular immune responses to LPS differently in peripheral blood mononuclear cells (PBMC) from CD patients compared with healthy controls. Our data showed that LPS-associated particles predominantly stimulated release of IL-1β and induced concurrent cell death in peripheral monocytes following particle uptake in both health and disease. In addition, IL-1β release was increased more in CD patients compared with controls following particle stimulation. In conclusion, LPS adsorption to dietary particulates provides a mechanism for stimulation of phagocytic mononuclear cells and may cause aggravation of mucosal immune responses in inflammatory conditions of the bowel such as CD, irritable bowel syndrome, and autism spectrum disorder and schizophrenia associated gastrointestinal conditions, by immune priming mediated through increased production of pro-inflammatory cytokines.

MODIFICATION OF ASPERGILLUS NIGER ATCC 11414 GROWTH FOR THE ENHANCEMENT OF PROTEASE PRODUCTION BY THE EFFECT OF NATURAL MICROPARTICLES

Even though fungal proteases under interest, bulk fungal growth during the productions decreases the overall mass transfer and consequently the yield. In this study, instead of inorganic microparticles, various organic microparticles were used in the production medium to prevent bulky fungal growth and increase the homogeneity. Results showed that all microparticle additions did not only increased the maximum enzyme activity but also decreased the required time to reach the highest value. Among organic microparticle addition productions, the highest protease activity was reported as 100,76 U/ml in walnut shells added flasks, which was approximately 1,4 fold higher compared to highest activity obtained in the control production. It was also reported that microparticle addition increased the homogeneity but also resulted in higher viscosity due to hyphae type growth. Additionally, evaluation of various storage temperatures showed that produced enzyme lost only its 7% activity at 4oC at the end of 25 days.

Systematic Variation of Friction of Rods

Abstract The mechanical response of a knot tied in elastic rods strongly depends on the frictional force due to rod–rod contact. The behavior of a knot can be qualitatively different based on the frictional coefficient of the elastic rod. Systematic variation of friction during rod–rod contact is a crucial component of any experimental design to uncover the underlying ingredients behind the mechanics of knots. In this paper, we demonstrate a novel process of controlling the friction of a continuous rod by adhering non-spherical inorganic micro-particles. Polymeric binder is used to deliver the particles as asperities over the rod substrate and by controlling their size and distribution the coefficient of friction of the rod is determined. In parallel, numerical simulations with the discrete elastic rods algorithm are used to reproduce the experimental observations. Tabletop experiments are performed where overhand knots with a variety of unknotting numbers are pulled tight. The force–extension curve of these experiments shows that the proposed process can successfully tune the friction between rods.

Plastic and natural inorganic microparticles do not differ in their effects on adult mussels (Mytilidae) from different geographic regions

Microplastics are ubiquitous in the marine environment and studies on their effects on benthic filter feeders at least partly revealed a negative influence. However, it is still unclear whether the effects of microplastics differ from those of natural suspended microparticles, which constitute a common stressor in many coastal environments. We present a series of experiments that compared the effects of six-week exposures of marine mussels to two types of natural particles (red clay and diatom shells) to two types of plastic particles (Polymethyl Methacrylate and Polyvinyl Chloride). Mussels of the family Mytilidae from temperate regions (Japan, Chile, Tasmania) through subtropical (Israel) to tropical environments (Cabo Verde) were exposed to concentrations of 1.5 mg/L, 15 mg/L and 150 mg/L of the respective microparticles. At the end of this period, we found significant effects of suspended particles on respiration rate, byssus production and condition index of the animals. There was no significant effect on clearance rate and survival. Surprisingly, we observed only small differences between the effects of the different types of particles, which suggests that the mussels were generally equally robust towards exposure to variable concentrations of suspended solids regardless of whether they were natural or plastic. We conclude, that microplastics and suspended solids elicit similar effects on the tested response variables, and that both types of microparticles mainly cause acute responses rather than more persistent carry-over effects.

Design and characterisation of calcium carbonate microspheres for anticancer drug delivery

The development of delivery systems providing prolonged release of antitumor drugs represents one of the challenges in designing and optimization of novel tools for cancer therapy. The employment of spherical inorganic microparticles, in particular, calcium carbonate vaterite microspheres, as microcarriers appears promising because of their porous, matrix structure, biocompatibility, and biodegradability. Here, we summarize the results of the development of the approaches to synthesis of calcium carbonate vaterite microspheres with narrowed size distribution and microencapsulation of low-molecular-weight anticancer drugs, such as doxorubicin hydrochloride into obtained microspheres. Supplementing the reaction mixture with a thickener defines fabrication of homogeneous vaterite microparticles with a spherical shape and an average size of 2 to 3 μm. Synthesised microspheres ensure prolonged release of doxorubicin at physiological pH values and can be used as a delivery system and as a structural component for development of a theranostic platform for tumour treatment and diagnosis.

Stabilization of Aqueous Dispersions of Inorganic Microparticles Under Mechanical Activation

The stability of aqueous dispersed systems of TiO2 and Fe2O3 microparticles in the presence of a water-soluble polymer - ethylhydroxyethylcellulose (EHEC) - has been studied under the condition of using two methods of mechanoactivation of the pigment surface - processing them in a disintegrator and in an ultrasonic field. It is shown that in the absence of a polymer stabilizer, an intense effect on aqueous dispersed systems of pigments leads to rapid coagulation of particles. In the presence of EHEC, a small stabilizing effect is observed, which is significantly enhanced when processing dispersed systems in a disintegrator and in an ultrasonic field. In this case, the stability of dispersed systems depends little on the method of mechanoactivation of their surface, but significantly depends on the duration of the intense exposure.

Continuous Flow Reactors from Microfluidic Compartmentalization of Enzymes within Inorganic Microparticles.

Compartmentalization and selective transport of molecular species are key aspects of chemical transformations inside the cell. In an artificial setting, the immobilization of a wide range of enzymes onto surfaces is commonly used for controlling their functionality but such approaches can restrict their efficacy and expose them to degrading environmental conditions, thus reducing their activity. Here, we employ an approach based on droplet microfluidics to generate enzyme-containing microparticles that feature an inorganic silica shell that forms a semipermeable barrier. We show that this porous shell permits selective diffusion of the substrate and product while protecting the enzymes from degradation by proteinases and maintaining their functionality over multiple reaction cycles. We illustrate the power of this approach by synthesizing microparticles that can be employed to detect glucose levels through simultaneous encapsulation of two distinct enzymes that form a controlled reaction cascade. These results demonstrate a robust, accessible, and modular approach for the formation of microparticles containing active but protected enzymes for molecular sensing applications and potential novel diagnostic platforms.

Hyperspectral Imaging as a Tool to Study Optical Anisotropy in Lanthanide-Based Molecular Single Crystals.

In this work, we describe a protocol for a novel application of hyperspectral imaging (HSI) in the analysis of luminescent lanthanide (Ln3+)-based molecular single crystals. As representative example, we chose a single crystal of the heterodinuclear Ln-based complex [TbEu(bpm)(tfaa)6] (bpm=2,2'-bipyrimidine, tfaa- =1,1,1-trifluoroacetylacetonate) exhibiting bright visible emission under UV excitation. HSI is an emerging technique that combines 2-dimensional spatial imaging of a luminescent structure with spectral information from each pixel of the obtained image. Specifically, HSI on single crystals of the [Tb-Eu] complex provided local spectral information unveiling variation of the luminescence intensity at different points along the studied crystals. These changes were attributed to the optical anisotropy present in the crystal, which results from the different molecular packing of Ln3+ ions in each one of the directions of the crystal structure. The HSI herein described is an example of the suitability of such technique for spectro-spatial investigations of molecular materials. Yet, importantly, this protocol can be easily extended for other types of luminescent materials (such as micron-sized molecular crystals, inorganic microparticles, nanoparticles in biological tissues, or labelled cells, among others), opening many possibilities for deeper investigation of structure-property relationships. Ultimately, such investigations will provide knowledge to be leveraged into the engineering of advanced materials for a wide range of applications from bioimaging to technological applications, such as waveguides or optoelectronic devices.

High-performance ceramic/epoxy composite adhesives enabled by rational ceramic bandgaps

High over-all properties, including low dielectric loss, high breakdown strength, high mechanical shock strength, high thermal conductivity and high weight stability, are very difficult to simultaneously achieve in electrical-insulation applicable cured potting-adhesive materials. To deal with this challenge, in this work, we have designed and fabricated a series of epoxy based composite potting-adhesives filled with low-cost and high-performance inorganic micro-particles including alpha-silica, alpha-alumina and alpha-SiC. Combination employment of high-molecular-weight and low-molecular-weight epoxy resins as matrices has been made. Heat-induced curing or crosslink of resin matrices has been carried out. Large band gap of silica filler has endowed the cured composite with high breakdown strength and ageing breakdown strength, and meanwhile relatively high deformation trait of silica has led to high shock strength of cured composite. Silica filler has been found to be superior to other two fillers, namely, optimal over-all properties such as dielectric, breakdown, mechanical and thermal features have been obtained in silica filled cured composite. High breakdown strength of ~48 MV m−1 and shock strength of ~9950 J m−2 have been achieved in silica loaded composite. This work might open up the way for large-scale fabrication of promising epoxy-based hybrid potting-adhesives.

Study on non-bioparticles and Staphylococcus aureus by dielectrophoresis.

This article demonstrated a chip device with alternating current (AC) dielectrophoresis (DEP) for separation of non-biological micro-particle and bacteria mixtures. The DEP separation was achieved by a pair of metal electrodes with the shape of radal-interdigital to generate a localized non-uniform AC electric field. The electric field and DEP force were firstly investigated by finite element methods (FEM). The mixed microparticles such as different scaled polystyrene (PS) beads, PS beads with inorganic micro-particles (e.g., ZnO and silica beads) and non-bioparticles with bacterial Staphylococcus aureus (S. aureus) were successfully separated at DEP-on-a-chip by an AC electric field of 20 kHz, 10 kHz and 1 MHz, respectively. The results indicated that DEP trapping can be considered as a potential candidate method for investigating the separation of biological mixtures, and may well prove to have a great impact on in situ monitoring of environmental and/or biological samples by DEP-on-a-chip.

Scalable and cost-effective generation of osteogenic micro-tissues through the incorporation of inorganic microparticles within mesenchymal stem cell spheroids

Mesenchymal stem cells (MSCs) are considered primary candidates for treating complex bone defects in cell-based therapy and tissue engineering. Compared with monolayer cultures, spheroid cultures of MSCs (mesenspheres) are favorable due to their increased potential for differentiation, extracellular matrix (ECM) synthesis, paracrine activity, and in vivo engraftment. Here, we present a strategy for the incorporation of microparticles for the fabrication of osteogenic micro-tissues from mesenspheres in a cost-effective and scalable manner. A facile method was developed to synthesize mineral microparticles with cell-sized spherical shape, biphasic calcium phosphate composition (hydroxyapatite and β-tricalcium phosphate), and a microporous structure. Calcium phosphate microparticles (CMPs) were incorporated within the mesenspheres through mixing with the single cells during cell aggregation. Interestingly, the osteogenic genes were upregulated significantly (collagen type 1 (Col 1) 30-fold, osteopontin (OPN) 10-fold, and osteocalcin (OCN) 3-fold) after 14 days of culture with the incorporated CMPs, while no significant upregulation was observed with the incorporation of gelatin microparticles. The porous structure of the CMPs was exploited for loading and sustained release of an angiogenic small molecule. Dimethyloxaloylglycine (DMOG) was loaded efficiently onto the CMPs (loading efficiency: 65.32 ± 6%) and showed a sustained release profile over 12 days. Upon incorporation of the DMOG-loaded CMPs (DCMPs) within the mesenspheres, a similar osteogenic differentiation and an upregulation in angiogenic genes (VEGF 5-fold and kinase insert domain (KDR) 2-fold) were observed after 14 days of culture. These trends were also observed in immunostaining analysis. To evaluate scalable production of the osteogenic micro-tissues, the incorporation of microparticles was performed during cell aggregation in a spinner flask. The DCMPs were efficiently incorporated and directed the mesenspheres toward osteogenesis and angiogenesis. Finally, the DCMP mesenspheres were loaded within a three-dimensional printed cell trapper and transplanted into a critical-sized defect in a rat model. Computed tomography and histological analysis showed significant bone formation with blood vessel reconstruction after 8 weeks in this group. Taken together, we provide a scalable and cost-effective approach for fabrication of osteogenic micro-tissues, as building blocks of macro-tissues, that can address the large amounts of cells required for cell-based therapies.

Adsorption and fractionation of Pt, Pd and Rh onto inorganic microparticles and the effects of macromolecular organic compounds in seawater

Adsorption and fractionation of Pt, Pd and Rh (defined here as platinum group elements, PGEs) onto the representative inorganic microparticles, including Fe2O3, MnO2, CaCO3, SiO2, Al2O3 and kaolinite in seawater were investigated. The effects of macromolecular organic compounds (MOCs) as the representatives of organic matter, including humic acids (HA), bovine serum albumin (BSA) and carrageenan, on the adsorption were also studied considering that organic matter is ubiquitous in seawater and indispensable to marine biogeochemical cycles. In the absence of MOCs, the representative mineral particles Fe2O3 and MnO2 had the strongest interaction with PGEs. The adsorption of PGEs onto the representative biogenic particles SiO2 and CaCO3 and lithogenic particles Al2O3 and kaolinite was similar or weaker than onto the mineral particles. MOCs inhibited the interaction between PGEs and the particles except for Pt and Pd onto the biogenic particles in artificial seawater. This impediment may be closely related to the interaction between particles, MOCs and elements. The partition coefficient (log Kd) of Pt was similar (∼4.0) in the presence of MOCs, indicating that the complexation between Pt and MOCs was less important than hydrolysis or adsorption onto the acid oxide particle surface. Rh tended to fractionate onto the mineral and lithogenic particles in the presence of HA and carrageenan, while Pd was more likely to fractionate onto the biogenic particles. However, BSA enhanced the fractionation tendency of Pd onto the mineral particles. The results indicate that the adsorption behavior of Pd onto inorganic particles was significantly affected by the composition or the type of MOCs. Hence, the interaction between PGEs and inorganic particles may be greatly affected by the macromolecular organic matter in the ocean.

Anisotropic Hybrid Hydrogels with Superior Mechanical Properties Reminiscent of Tendons or Ligaments

AbstractMimicking the hierarchically anisotropic structure and excellent mechanical properties of natural tissues, such as tendons and ligaments, using biomaterials is challenging. Despite recent achievements with anisotropic hydrogels, limitations remain because of difficulties in achieving both structural and mechanical characteristics simultaneously. A simple approach for fabricating hybrid hydrogels with a hierarchically anisotropic structure and superior mechanical properties that are reminiscent of tendons or ligaments is proposed. Alginate–polyacrylamide double‐network (DN) hydrogels incorporated with high aspect ratio mesoporous silica microparticles are stretched and fixed via subsequent drying and ionic crosslinking to achieve multiscale structures composed of an anisotropically aligned polymer network embedded with aligned microparticles. The mechanical properties of hydrogels can be further controlled by the degree of stretching, quantities, and functional groups of inorganic microparticles, and types of crosslinking cations. The subsequent reswelling results in a high water content (&gt;80%) similar to that of natural tendons while high strength, modulus, and toughness are maintained. The optimized anisotropic hybrid hydrogel exhibits a tensile modulus of 7.2 MPa, strength of 1.3 MPa, and toughness of 1.4 MJ m−3 even in the swollen state, which is 451‐, 27‐, and 2.2 times higher than that observed in the non‐swollen tough DN hydrogel. This study suggests a new strategy for fabricating anisotropic hydrogels with superior mechanical properties to develop new biomaterials for artificial tendons or ligaments.

Bio-hybrid inorganic microparticles derived from CO2 for highly efficient and selective removal of antibiotics

BackgroundAntibiotics, which are the most important medication in human history, have brought global concerns due to their potential risk to human health and environment by accelerating the development of drug-resistant bacteria, and accumulating in the food chain system. Among antibiotics, oxytetracycline (OTC) is widely used in aquaculture, and its potential risk of toxicity to human by bioaccumulation has been reported. Therefore, the effective removal of OTC is highly needed.ResultsIn this study, we report bio-hybrid inorganic microparticles (apt-mag-SiCC) for efficient capturing and facile magnet-based separation of oxytetracycline (OTC). These bio-hybrid inorganic microparticles are composed of magnetic separable silica coated calcium carbonate microparticles (mag-SiCC) derived from CO2, conjugated with oxytetracycline binding aptamers (OBA). These bio-hybrid inorganic microparticles were successfully synthesized, based on the characterization data obtained by SEM, FT-IR, EDAX, BET, and CLSM. About 6 μm sized bio-hybrid inorganic microparticles showed low non-specific adsorption to OTC and other molecules, and the selective capturing towards to the OTC in both buffer and tap water. Moreover, these bio-hybrid mineral microparticles were found to be stable, even after the repeated usages, maintaining the initial capturing efficiency.ConclusionUsing the newly synthesized bio-hybrid inorganic microparticles, we could successfully capture OTC by facile magnet-based separation. With advantages of theses bio-hybrid inorganic microparticles such as easy fabrication, low-price, and environmental friendliness, this novel material could be utilized in the drinking water treatment, in vitro medicinal diagnostics, or in vitro removal of antibiotics lining out from the blood (blood purification).

Ca:Mg:Zn:CO3 and Ca:Mg:CO3—tri- and bi-elemental carbonate microparticles for novel injectable self-gelling hydrogel–microparticle composites for tissue regeneration

Injectable composites for tissue regeneration can be developed by dispersion of inorganic microparticles and cells in a hydrogel phase. In this study, multifunctional carbonate microparticles containing different amounts of calcium, magnesium and zinc were mixed with solutions of gellan gum (GG), an anionic polysaccharide, to form injectable hydrogel–microparticle composites, containing Zn, Ca and Mg. Zn and Ca were incorporated into microparticle preparations to a greater extent than Mg. Microparticle groups were heterogeneous and contained microparticles of differing shape and elemental composition. Zn-rich microparticles were ‘star shaped’ and appeared to consist of small crystallites, while Zn-poor, Ca- and Mg-rich microparticles were irregular in shape and appeared to contain lager crystallites. Zn-free microparticle groups exhibited the best cytocompatibility and, unexpectedly, Zn-free composites showed the highest antibacterial activity towards methicilin-resistant Staphylococcus aureus. Composites containing Zn-free microparticles were cytocompatible and therefore appear most suitable for applications as an injectable biomaterial. This study proves the principle of creating bi- and tri-elemental microparticles to induce the gelation of GG to create injectable hydrogel–microparticle composites.

Ultrasonic atomization based fabrication of bio-inspired micro-nano-binary particles for superhydrophobic composite coatings with lotus/petal effect

Abstract To mimic a superhydrophobic surface as found in nature, micro-nano binary surface structures with specific chemical properties are required. This type of special binary structure was usually realized by introduction of hierarchical inorganic microparticles; however, existing preparation methods are usually complex and difficult for scalable manufacture. In order to solve this problem, a facile ultrasonic atomization-based spray drying method has been developed in the present study for producing hierarchical silica microparticles for eventual fabrication of superhydrophobic coatings with either a lotus or petal effect depending on the required application. 3-aminopropyl-triethoxysilane (APTES) was used as a modifier for enhancing the binding between the silica nanoparticles. The hierarchical silica microparticles exhibited an diameter of around 10 μm and proper nano-roughness to realize a superhydrophobic effect. The prepared hierarchical silica microparticles/epoxy coating achieved a very high water contact angle up to 161° and a sliding angle as low as 5°. Both lotus and petal effects were achieved. Mechanical properties of the composite coating have also been enhanced by virtue of the modifiers. The interactions between –NH2 groups from the APTES modifier and –OH groups from the silica led to a strong adhesive force with water molecules, while the introduction –F groups to the silica could reduce this affinity and result in a smaller sliding angle.