Spontaneous patterning and nanoparticle encapsulation in carboxymethylcellulose/alginate/dextran hydrogels and sponges

Novel polysaccharide sponges containing a network of capillaries and pore structures have been prepared by freeze drying of Ca²⁺ ion cross-linked sodium carboxymethylcellulose/sodium alginate hydrogels with or without addition of dextran. The iontropic gels consisted of capillaries, 5 to 40 µm in width, which comprised small pores, 1–25 µm in size. Gold, Fe₃O₄ or TiO₂ nanoparticles were encapsulated in the patterned gels and the mechanical strength of the resulting sponges investigated.     

The production of volvox spheres and their potential application in multi-drugs encapsulation and release

Volvox sphere is a bio-mimicking concept of an innovative biomaterial structure of a sphere that contains smaller microspheres which then encapsulate chemicals, drugs and/or cells. The volvox spheres were produced via a high-voltage electrostatic field system, using alginate as the primary material. Encapsulated materials tested in this study include staining dyes, nuclear fast red and trypan blue, and model drugs, bovine serum albumin (BSA) and cytochrome c (CytC). The external morphology of the volvox spheres was observed via electron microscopy whereas the internal structure of the volvox spheres was observed via an optical microscope with the aid of the staining dyes, since alginate is colorless and transparent. The diameter of the microspheres was about 200 to 300 μm, whereas the diameter of the volvox spheres was about 1500 μm. Volvox spheres were durable, retaining about 95% of their mass after 4 weeks. Factors affecting entrapment efficiency, such as temperature and concentration of the bivalent cross-linker, were compared followed by a 7-day in vitro release study. The encapsulation efficiency of CytC within the microspheres was higher at cold (~ 4 °C) and warm (~ 50 °C) temperatures whereas temperature has no obvious effect on the BSA encapsulation. High crosslinking concentration (25% w/v) of calcium chloride has resulted higher entrapment efficiency for BSA but not for CytC. Furthermore, volvox spheres showed a different release pattern of BSA and CytC when compared to microspheres encapsulating BSA and CytC. Despite the fact that the mechanisms behind remain unclear and further investigation is required, this study demonstrates the potential of the volvox spheres for drug delivery.     

Interphase coordination design in carbamate-siloxane/vaterite composite microparticles towards tuning ion-releasing properties

Siloxane-containing vaterite (SiV) microparticles were prepared with controlling the degree of aminopropyl-functionalization in the siloxane; they are aiming for applications as bone regenerative devices. The aim of this work was to evaluate the structure at siloxane/vaterite interphase and to control the solubility of particles by the structural tuning of siloxane. The particles were spherical with average diameters of 1.1–1.4 μm. Differential infrared spectrometry revealed the transformation of aminopropyl terminals in the siloxane into carbamate (NH-COO^?) groups. Moreover, the vaterite crystallites in the particles were slightly oriented towards the (0 0 1) plane. These results describe the interphase structure, with the carbamate groups coordinating on the Ca²⁺ ion face in the (0 0 1) plane of neighbouring vaterite. Upon soaking in buffer solution, the particles exhibited a rapid initial release of Ca²⁺ ions within 30 min and of soluble silica within 2 h. The vaterite in this particle survived for more than 6 h. The chemical stability of the siloxane was enhanced by incorporating tetraethoxysilane-derived siloxane with fractions of 24 mol% or 50 mol%. This enhancement controlled the initial release of not only soluble silica but also Ca²⁺ ions.     

A general approach to monodisperse perovskite microspheres

BaTiO₃, PbTiO₃, SrTiO₃, and Pb(Zr,Ti)O₃ microspheres with uniform size and narrow size distribution have been successfully synthesized by a novel hydrothermal and annealing approach. In this approach, the chemical reaction and crystallization process of the ABO₃ perovskite oxides were separated in two steps. Spherical particles containing the B-site ions were obtained first via a controlled hydrolysis and aging process. Then, during hydrothermal treatment, the A-site ions were incorporated in situ into the microspheres to form amorphous perovskite microspheres. The particles were further crystallized with preserved spherical morphology under subsequent annealing treatment. The BET surface areas of the TiO₂ gel particles, the amorphous PbTiO₃ and the as-annealed PbTiO₃ microspheres were 245.7 m²/g, 41.67 m²/g and 4.53 m²/g, respectively, showing a significant change of the surface feature in the preparation process. This approach also allowed the microspheres diameters to be manipulated from 100 nm to 1500 nm in a controlled manner. Most of the microspheres were composed by closely packed nano-sized particles. Furthermore, the Pb(Zr,Ti)O₃ microspheres with an average diameter of 200 nm exhibited single crystal features, indicating highly oriented growth in the crystallization process. The microspheres were very stable, and still maintained spherical shape after higher temperature calcination.     

Microstructure and microwave absorption properties of Fe3O4/dextran/SnO2 multilayer microspheres

Fe₃O₄/dextran/SnO₂ multilayer microspheres have been successfully designed and synthesized by solvothermal and hydrothermal reactions. Dextran worked as a linker between Fe₃O₄ core and SnO₂ shell. It can not only prevent the oxidation of Fe₃O₄ but also be carbonize to another absorber carbon black. The as-synthesized microspheres were about 320 nm in size and well-defined in shape. The maximum reflection loss of Fe₃O₄/dextran/SnO₂ microspheres and paraffin wax composites could reach 20.26 dB at 4.72 GHz, and the bandwidth with a reflection loss less than ? 10 dB was 4.86 GHz with 4 mm in thickness. The excellent microwave absorption properties of the composites were attributed to the special multilayer structures of Fe₃O₄/dextran/SnO₂ microspheres and the effective complementarity between dielectric loss and magnetic loss.     

Encapsulation of superparamagnetic iron oxide nanoparticles in poly-(lactide-co-glycolic acid) microspheres for biomedical applications

Magnetic microspheres were prepared using a single step coaxial electrohydrodynamic atomization technique at ambient temperature and pressure, with poly(lactic-co-glycolic acid) as the coating and iron oxide (Fe₃O₄) nanoparticles dispersed in polyethylene glycol as the encapsulated material. The morphology and particle size distributions of the prepared magnetic microspheres were investigated by scanning electron microscopy. The particles were spherical with mean diameters ranging from ~ 2 μm to 18 μm, depending on the combination of processing parameters (flow rate and applied voltage). Analysis by infrared spectroscopy and focused ion-beam sectioning confirmed incorporation of iron oxide nanoparticles into the microspheres and the prepared samples were shown to be responsive to an applied magnetic field. This study demonstrates a convenient method for the preparation of nanoparticle loaded microspheres, which could be used potentially as transverse relaxation contrast agents in magnetic resonance imaging, as well as for magnetically guided drug delivery.     

Fabrication of (Ca + Yb)- and (Ca + Sr)-stabilized α-SiAlON by combustion synthesis

In this paper, (Ca + Yb)- and (Ca + Sr)-stabilized α-SiAlON powders were fabricated by combustion synthesis. The influence of Ca²⁺ incorporation on the phase composition and grain morphology of combustion products was discussed. The experimental results showed that with the incorporation of Ca²⁺ well-developed rod-like (Ca + Yb) α-SiAlON crystals could be produced. It was also found that, when only Sr²⁺ was used as stabilizing cation, the reaction product was (α + β)-SiAlON composite, in which β-SiAlON was the predominant phase and the relative content of α-SiAlON was low. With the incorporation of Ca²⁺, however, both the relative content and the lattice parameters of α-SiAlON were clearly increased. These results indicated that the incorporation of Ca²⁺ could assist Sr²⁺ into the α-SiAlON lattice structure.     

A novel red phosphor Na2Ca4Mg2Si4O15:Eu3+ for plasma display panels

A novel red emitting phosphor, Eu³⁺-doped Na₂Ca₄Mg₂Si₄O₁₅, was prepared by the solid-state reaction. X-ray powder diffraction (XRD) analysis confirmed the formation of Na₂Ca₄Mg₂Si₄O₁₅:Eu³⁺. Field-emission scanning electron-microscopy (FE-SEM) observation indicated a narrow size-distribution of about 300 nm for the particles with spherical shape. Upon excitation with vacuum ultraviolet (VUV) and near UV light, the phosphor showed strong red-emission lines at around 611 and 617 nm, respectively, corresponding to the forced electric dipole ⁵D₀ → ⁷F₂ transition of Eu³⁺, and the highest PL intensity at 617 nm was found at a content of about 8 mol% Eu³⁺. The optical properties study suggests that it is a potential candidate for plasma display panels (PDPs) application.     

Influence of temperature, [Ca2+], Ca/P ratio and ultrasonic power on the crystallinity and morphology of hydroxyapatite nanoparticles prepared with a novel ultrasonic precipitation method

Nanocrystalline hydroxyapatite was prepared by a precipitation method with the aid of ultrasonic irradiation using Ca(NO₃)₂ and NH₄H₂PO₄ as source material and carbamide (NH₂CONH₂) as precipitator. The influence of Ca/P molar ratio, precipitation temperature, concentration of Ca²⁺ ([Ca²⁺]) and ultrasonic power on the crystallinity of the nanopowder were systematically investigated by XRD analysis. The size of the as-prepared particles was analyzed using TEM and XRD methods. The results revealed that the monophase hydroxyapatite could be obtained at the following technological conditions: [Ca²⁺] = 0.01–0.1 mol/L, ultrasonic power = 300 W, Ca/P (mol) = 1.2–2.5 and T = 313–353 K. In addition, the acicular and spherical particles could be prepared at different ultrasonic powers of 300 and 200 W, respectively.     

Pulsed laser deposition of hydroxyapatite on nanostructured titanium towards drug eluting implants

Titania nanotubes grown on titanium substrates by electrochemical anodization in glycerol–ammonium fluoride–water system were used to develop efficient drug carrying implants upon coating hydroxyapatite (HA) ceramic. The nanostructured surfaces achieved by anodization were caped with HA crystallites by pulsed laser deposition. The implant substrates were studied for their drug carrying capacity using gentamicin as a model. The nano-tubular surface with HA coating had better drug loading capacity of about 800 μg/cm² gentamicin while the bare anodized substrate carried less than 660 μg/cm². The HA coating alone stored as low as 68 μg/cm² and released the drug within the initial burst period itself. The ceramic coated anodized substrates were found to be more efficient in controlled delivery for longer than 160 h with a drug release of 0.5 μg/cm² even towards the end. The substrate with nanostructuring alone delivered the whole drug within 140 h. This study proposes the application of laser deposition of HA over nanostructured titanium, which proves to be promising towards controlled drug eluting bioceramic coated metallic prostheses.     

Preparation of alginate–CaCl2 microspheres as resveratrol carriers

Resveratrol-loaded calcium alginate microspheres for prolonged drug release were prepared by ionic gelation of alginate with calcium chloride (CaCl₂). Further, resveratrol-loaded calcium alginate microspheres were developed using two concentrations of alginate (0.5 and 1 % w/v) and CaCl₂ (0.5 and 1 M) and an encapsulator equipped with a 300-μm nozzle. The mean particle size of the microspheres was between 175.52 and 244.03 μm, and an encapsulation efficiency (EE) of over 95 % was observed. FTIR spectroscopy indicated a polyelectrolyte interaction between alginate and CaCl₂; alginate microsphere thermograms were analyzed by differential scanning calorimetry. X-ray diffraction shows the crystalline change of microspheres by cross linking. The release profiles and EE increased depending on the CaCl₂ concentration, and a slow initial burst release was observed on freeze-dried microspheres. These results indicate that resveratrol-loaded calcium alginate microspheres can be used as a potential resveratrol delivery system in the food industry.     

Synthesis and luminescence properties of monodisperse SiO2@SiO2:Eu3+ microspheres

Monodisperse core–shell structured SiO₂@SiO₂:Eu³⁺ microspheres were synthesized in a seeded growth way. In that way, a thin shell of Eu³⁺-doped silica was grown on the prepared monodisperse silica colloids. The samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectrometry (EDX), X-ray diffraction (XRD), Fourier transform infrared spectrum (FT-IR), thermal analysis (TGA-DSC) and photoluminescence (PL) spectroscopy. The results reveal that the SiO₂ spheres have been successfully coated by SiO₂:Eu³⁺ phosphors and the obtained SiO₂@SiO₂:Eu³⁺ particles have perfect spherical shape with narrow size distribution. Additionally, the monodisperse SiO₂@SiO₂:Eu³⁺ microspheres exhibit considerably strong photoluminescence (PL) of Eu³⁺ under the excitation of 393 nm compared with the SiO₂:Eu³⁺ samples with polydispersed or irregular shapes and sizes obtained by base-catalyzed Stöber method. Furthermore, the PL intensity increases with the increasing of Eu³⁺ concentration in SiO₂ microspheres shell, and concentration quenching occurs when Eu³⁺ concentration exceeds 5.0 mol%.     

Photochemical and complexation studies for new fluorescent and colored chelator

The photo-induced intramolecular proton (or hydrogen atom) transfer (ESIPT) and metal binding properties of Oxa-ester were studied in methanol solution. The dissociation constant between Oxa-ester and the metal ion was highly dependent with the metal ion and was determined by Hill plots or iterative least squares fitting to be 447 mM, 14.9 μM, and 290 nM for Ca²⁺, Zn²⁺, and Cu²⁺, respectively, in methanol. The fluorescence intensity of Oxa-ester greatly increased with increasing concentration of Zn²⁺, while the fluorescence intensity decreased with the addition of Ca²⁺ and Cu²⁺. Transient absorption spectroscopy revealed that Oxa-ester underwent ESIPT to give Z-NH isomer in the excited state in benzene, while Oxa did not undergo ESIPT probably due to the hydrogen bonding with solvent water.     

Lovastatin release from polycaprolactone coated β-tricalcium phosphate: Effects of pH,concentration and drug–polymer interactions

The approach of local drug delivery from polymeric coating is currently getting significant attention for both soft and hard tissue engineering applications for sustained and controlled release. The chemistry of the polymer and the drug, and their interactions influence the release kinetics to a great extent. Here, we examine lovastatin release behaviour from polycaprolactone (PCL) coating on β-tricalcium phosphate (β-TCP). Lovastatin was incorporated into biodegradable water insoluble PCL coating. A burst and uncontrolled lovastatin release was observed from bare β-TCP, whereas controlled and sustained release was observed from PCL coating. A higher lovastatin release was observed pH 7.4 as compared to pH 5.0. Effect of PCL concentration on lovastatin release was opposite at pH 7.4 and 5.0. At pH 5.0 lovastatin release was decreased with increasing PCL concentration, whereas release was increased with increasing PCL concentration at pH 7.4. High Ca^2 + ion concentration due to high solubility of β-TCP and degradation of PCL coating were observed at pH 5.0 compared to no detectable Ca^2 + ion release and visible degradation of PCL coating at pH 7.4. The hydrophilic–hydrophobic and hydrophobic–hydrophobic interactions between lovastatin and PCL were found to be the key factors controlling the diffusion dominated release kinetics of lovastatin from PCL coating over dissolution and degradation processes. Understanding the lovastatin release chemistry from PCL will be beneficial for designing drug delivery devices from polymeric coating or scaffolds.     

Experimental composite guidance conduits for peripheral nerve repair: An evaluation of ion release

Poly (lactide-co-glycolide) (PLGA) — Pluronic F127 — glass composites have demonstrated excellent potential, from the perspective of controlled mechanical properties and cytocompatibility, for peripheral nerve regeneration. In addition to controlling the mechanical properties and cytotoxicity for such composite devices, the glass component may mediate specific responses upon implantation via degradation in the physiological environment and release of constituent elements. However, research focused on quantifying the release levels of such therapeutic ions from these experimental medical devices has been limited. To redress the balance, this paper explores the ion release profiles for Si⁴⁺, Ca²⁺, Na⁺, Zn²⁺, and Ce⁴⁺ from experimental composite nerve guidance conduits (CNGC) comprising PLGA (at 12.5, and 20 wt.%), F127 (at 0, 2.5 and 5 wt.%) and various loadings of Si–Ca–Na–Zn–Ce glass (at 20 and 40 wt.%) for incubation periods of up to 28 days. The concentration of each ion, at various time points, was determined using Inductively Coupled Plasma–Atomic Emission Spectrometry (Perkin Elmer Optima 3000). It was observed that the Si⁴⁺, Na⁺, Ca²⁺, Zn²⁺ release from CNGCs in this study ranged from 0.22 to 6.477 ppm, 2.307 to 3.277 ppm, 40 to 119 ppm, and 45 to 51 ppm, respectively. The Ce⁴⁺ concentrations were under the minimum detection limits for the ICP instrument utilized. The results indicate that the ion release levels may be appropriate to mediate therapeutic effects with respect to peripheral nerve regeneration. The data generated in this paper provides requisite evidence to optimize composition for pre-clinical evaluation of the experimental composite.     

Preparation of carbon aerogel microspheres by a simple-injection emulsification method

Carbon aerogel microspheres were successfully prepared using a simple-injection emulsification method, employing sol–gel polycondensation of a resorcinol–formaldehyde solution containing sodium carbonate as a catalyst. This process was followed by solvent exchange using acetone, supercritical drying with carbon dioxide and carbonization in a nitrogen atmosphere. The effect of curing time before starting injection, injection rate and agitation rate of continuous phase on the particle size and the porous properties of the carbon aerogel microspheres was investigated. Adsorption of phenol by using the prepared carbon aerogel microspheres was also examined. The diameter of carbon aerogel microspheres was controlled in the range of 20–55 μm by varying injection rate and agitation rate. The mean diameter of carbon aerogel microspheres decreased with increasing the injection rate and the agitation rate, whereas their mean diameter was independent of the curing time. The BET surface area and total pore volume of carbon aerogel microspheres increased with increasing the curing time. In contrast, their BET surface area and total pore volume decreased with increasing the injection rate and the agitation rate. The BET surface area, total pore volume, mesopore volume and micropore volume of the carbon aerogel microspheres with a mean diameter of 45 μm were 903 m²/g, 0.60 cm³/g, 0.31 cm³/g and 0.27 cm³/g, respectively. The phenol-adsorption capacity of these carbon aerogel microspheres was 29.3 mg phenol/g adsorbent.     

Preparation of grafted microspheres CPVA-g-PSSS and studies on their drug-carrying and colon-specific drug delivery properties

Sodium 4-styrene sulfonate (SSS) was graft-polymerized on the surfaces of crosslinked polyvinyl alcohol (CPVA) microspheres in a manner of surface-initiated graft-polymerization by using cerium salt-hydroxyl group redox initiation system, obtaining the grafted microspheres CPVA-g-PSSS. The chemical structure and physicochemical characters of CPVA-g-PSSS microspheres were fully characterized with infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and zeta potential determination. The aim of this work is to constitute a novel colon-specific drug delivery system via molecular design by using CPVA-g-PSSS microspheres as the drug-carrying material and by taking metronidazole (MTZ) as the model drug. The drug-carrying ability and mechanism of the grafted microspheres CPVA-g-PSSS for MTZ were investigated. Finally, in-vitro release tests for the drug-carrying microspheres were conducted. The experimental results show that in an acidic medium, the grafted microspheres CPVA-g-PSSS exhibit strong adsorption ability for MTZ by driving of electrostatic interaction, and have an adsorption capacity of 112 mg/g, displaying the high efficiency of drug-carrying. The in-vitro release behavior of the drug-carried microspheres is highly pH-sensitive. In the medium of pH = 1, the drug-carrying microspheres do not release the drug, whereas in the medium of pH = 7.4, a sudden delivery phenomenon of the drug will occur, displaying an excellent colon-specific drug delivery behavior.     

In vitro study of vancomycin release and osteoblast-like cell growth on structured calcium phosphate-collagen

A drug delivery vehicle consisting of spherical calcium phosphate-collagen particles covered by flower-like (SFCaPCol) blossoms composed of nanorod building blocks and their cellular response is studied. The spherical structure was achieved by a combination of sonication and freeze-drying. The SFCaPCol blossoms have a high surface area of approximately 280 m²g^? 1. The blossom-like formation having a high surface area allows a drug loading efficiency of 77.82%. The release profile for one drug, vancomycin (VCM), shows long term sustained release in simulated body fluid (SBF), in a phosphate buffer saline (PBS, pH 7.4) solution and in culture media over 2 weeks with a cumulative release ~ 53%, 75% and 50%, respectively, over the first 7 days. The biocompatibility of the VCM-loaded SFCaPCol scaffold was determined by in vitro cell adhesion and proliferation tests of rat osteoblast-like UMR-106 cells. MTT tests indicated that UMR-106 cells were viable after exposure to the VCM loaded SFCaPCol, meaning that the scaffold (the flower-like blossoms) did not impair the cell's viability. The density of cells on the substrate was seen to increase with increasing cultured time.     

Fabrication and evaluation of a sustained-release chitosan-based scaffold embedded with PLGA microspheres

Nutrient depletion within three-dimensional (3D) scaffolds is one of the major hurdles in the use of this technology to grow cells for applications in tissue engineering. In order to help in addressing it, we herein propose to use the controlled release of encapsulated nutrients within polymer microspheres into chitosan-based 3D scaffolds, wherein the microspheres are embedded. This method has allowed maintaining a stable concentration of nutrients within the scaffolds over the long term. The polymer microspheres were prepared using multiple emulsions (w/o/w), in which bovine serum albumin (BSA) and poly (lactic-co-glycolic) acid (PLGA) were regarded as the protein pattern and the exoperidium material, respectively. These were then mixed with a chitosan solution in order to form the scaffolds by cryo-desiccation. The release of BSA, entrapped within the embedded microspheres, was monitored with time using a BCA kit. The morphology and structure of the PLGA microspheres containing BSA before and after embedding within the scaffold were observed under a scanning electron microscope (SEM). These had a round shape with diameters in the range of 27–55 μm, whereas the chitosan-based scaffolds had a uniform porous structure with the microspheres uniformly dispersed within their 3D structure and without any morphological change. In addition, the porosity, water absorption and degradation rate at 37 °C in an aqueous environment of 1% chitosan-based scaffolds were (92.99 ± 2.51) %, (89.66 ± 0.66) % and (73.77 ± 3.21) %, respectively. The studies of BSA release from the embedded microspheres have shown a sustained and cumulative tendency with little initial burst, with (20.24 ± 0.83) % of the initial amount released after 168 h (an average rate of 0.12%/h). The protein concentration within the chitosan-based scaffolds after 168 h was found to be (11.44 ± 1.81) × 10^? 2 mg/mL. This novel chitosan-based scaffold embedded with PLGA microspheres has proven to be a promising technique for the development of new and improved tissue engineering scaffolds.     

Polyvinylpyrrolidone (PVP)-assisted hydrothermal synthesis of luminescent YVO4:Eu3+ microspheres

Spherical YVO₄:Eu³⁺ microstructures were hydrothermally synthesized by the reaction of NH₄VO₃, Y₂O₃, and Eu₂O₃ at 180 °C for 24 h with the assistance of polyvinylpyrrolidone (PVP) as a surfactant. The resulting products were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and photoluminescence (PL) spectroscopy. The experimental results showed that ball-like YVO₄:Eu³⁺ microspheres with a diameter of about 4–5 μm, corresponding to the SEM observations, formed at 180 °C for 24 h using 0.2 g PVP with the molecular weight of 20,000 g mol^?1. The amount of PVP and the reaction time of hydrothermal processing were found to play a key role in the formation of YVO₄:Eu³⁺ microspheres. It has been observed that the relative luminescence intensities of the as-synthesized samples increased with increasing hydrothermal reaction times due mainly to the increase of crystallinity.