Enhancement of Fluorescence Emission for Tricolor Quantum Dots Assembled in Polysiloxane toward Solar Spectrum-Simulated White Light-Emitting Devices.

Commercial white light-emitting diodes (LEDs) have the undesirable characteristics of blue-rich emission and low color rendering index (CRI), while the constituent quantum dots (QDs) suffer from aggregation-induced fluorescence quenching and poor stability. Herein, a strategy is developed to assemble tricolor QDs into a polysiloxane matrix using a polymer-mediated hybrid approach whereby the hybrid composite exhibits a significant enhancement of aggregation-dispersed emission, outstanding photostability, high thermal stability, and outstanding fluorescence recovery. Using the as-prepared hybrid fluorescent materials, the fabricated LEDs exhibit solar spectrum-simulated emission with adjustable Commission Internationale de L'Eclairage coordinates, correlated color temperature, and a recorded CRI of 97. Furthermore, they present no ultraviolet emission and weak blue emission, thus indicating an ideal healthy and high-CRI white LED lighting source.

Graphene Oxide (GO) as Stabilizer for Preparing Chirally Helical Polyacetylene/GO Hybrid Microspheres via Suspension Polymerization.

Hybrid materials consisting of polymers and graphene are gathering ever-growing interest. This article reports a novel methodology for preparing chirally helical polyacetylene/graphene hybrid microspheres (MPs) via suspension polymerization in which graphene oxide (GO) or alkynylated GO (MGO) serves as a sole stabilizer. Such polymerizations show remarkable advantages in circumventing the difficulties in usual suspension polymerizations and especially in directly providing clean hybrid MPs. Scanning electron microscopy (SEM), Raman spectra, and electron dispersive spectroscopy indicate that graphene sheets cover the MPs through physical interaction (GO) or covalent bonds (MGO). The hybrid MPs are also characterized by Fourier-transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy, and thermogravimetric analysis. Circular dichroism spectra demonstrate that the polymer chains constituting the MPs adopt predominantly one-handed helices, endowing the MPs with intriguing optical activity. The established strategy opens a new approach for preparing hybrid MPs constructed by acetylenic polymers and GO.

Polymerizable Molecular Silsesquioxane Cage Armored Hybrid Microcapsules with In Situ Shell Functionalization.

We prepared core-shell polymer-silsesquioxane hybrid microcapsules from cage-like methacryloxypropyl silsesquioxanes (CMSQs) and styrene (St). The presence of CMSQ can moderately reduce the interfacial tension between St and water and help to emulsify the monomer prior to polymerization. Dynamic light scattering (DLS) and TEM analysis demonstrated that uniform core-shell latex particles were achieved. The polymer latex particles were subsequently transformed into well-defined hollow nanospheres by removing the polystyrene (PS) core with 1:1 ethanol/cyclohexane. High-resolution TEM and nitrogen adsorption-desorption analysis showed that the final nanospheres possessed hollow cavities and had porous shells; the pore size was approximately 2-3 nm. The nanospheres exhibited large surface areas (up to 486 m2 g-1 ) and preferential adsorption, and they demonstrated the highest reported methylene blue adsorption capacity (95.1 mg g-1 ). Moreover, the uniform distribution of the methacryloyl moiety on the hollow nanospheres endowed them with more potential properties. These results could provide a new benchmark for preparing hollow microspheres by a facile one-step template-free method for various applications.

Fabrication of highly crosslinked and monodispersed silicon-containing polymeric microspheres via photo-initiated polymerization and their application in capillary liquid chromatography.

Although inorganic silica-based and polymeric micron-sized spheres have widely been explored as column packing materials in high performance liquid chromatography (HPLC), they are still suffering the problems of either alkali corrosion of silica or polymer swelling. It is still necessary to search simple approaches for fabrication of monodisperse micron-sized hybrid particles as packing materials in HPLC. A novel kind of silicon-containing polyacrylate microspheres was designed and fabricated via two-step swelling and photo-initiated polymerization approach using 3-(allylpropylsilane) propyl acrylate (TAPA) containing both acrylate and vinyl groups and trimethylolpropane triacrylate (TRIM) as precursors. After carefully optimizing the fabrication conditions, the monodisperse micron-sized microspheres could be acquired as chromatographic packing, exhibiting excellent mechanical stability and reproducibility. Due to existence of electron-rich vinyl groups, three kinds of thiols such as octadecanethiol (ODT), dithiothreitol (DTT) and trimethylolpropane tris(3-mercaptopropionate) (TTMP) were facilely anchored onto the surface of microsphere via photo-initiated thiol-ene click reaction. They were applied in the separation of small molecules by cLC-UV and complex biosamples by cLC-MS/MS. A total of 6691 unique peptides from 1771 unique proteins was identified by ODT-modified microsphere, which was higher than those by unmodified and DTT/TTMP-modified poly(TAPA-co-TRIM) microspheres. It was expected this kind of hybrid microspheres can be further modified and widely applied in chromatographic field, offering great potential in commercialization.

Design of green coating material of combining rigid and flexible properties for the extraction of aminoglycosides residues.

Bio-based and low-cost hybrid polyvinyl alcohol (PVA) and gelatin (Gel) hydrophilic macromolecular complex coated microspheres were prepared based on one-pot process, characterized, and applied as novel sorbent materials for the purification of trace aminoglycosides from complex matrices. PVA acts as a "rigid" component in the hybrid complex to enhance its mechanical properties, while Gel's "flexible" role is to improve the swelling properties of the hybrid complex in water. It is shown that hybrid PVA/Gel-functionalized sorbents are more efficient than the respective PVA or Gel sorbents since the presence of Gel increases the material selectivity for aminoglycosides, which is due to the specific interactions occurring between the targets and amino acid residues in the hybrid materials. Under the optimum conditions, material preparation and pretreatment processes were entirely carried out in single water system without toxic organic solvent. The detection limit (LOD) of spectinomycin, kanamycin, streptomycin and dihydrostreptomycin in honey were 0.811, 0.303, 0.168, 0.045 µg⋅kg-1 respectively. Linearity was obtained in the range of 20 to 2000 ug⋅kg-1, relative recovery yield up to 84.1-111.7% were obtained and matrix effect of all four aminoglycosides was within 100.8-107.6%. Intra-day and inter-day precision under four spiking levels (5, 200, 500 and 1000 ug⋅kg-1) were less than 10.9% (n=6) and 13.6% (n=3) respectively. In addition, the sorbents exhibited excellent reusability even after six recycles. This work demonstrates the potential of bio-based and low-cost hybrid polymer extraction platforms as promising bonded phase alternatives, in which eco-friendly and natural-based polymers can be used to improve the material selectivity and are conducive to the realization of "green chemistry".

Engineering of Naproxen Loaded Polymer Hybrid Enteric Microspheres for Modified Release Tablets: Development, Characterization, in silico Modelling and in vivo Evaluation.

BACKGROUND: Naproxen (NP) is a non-steroidal anti-inflammatory drug with poor aqueous solubility and low oral bioavailability, which may lead to therapeutic failure. NP causes crucial GIT irritation, bleeding, and peptic and duodenal ulcers. PURPOSE OF THE STUDY: This study aimed to engineer and characterize polymer hybrid enteric microspheres using an integrated (experimental and molecular modelling) approach with further development to solid dosage form with modified drug release kinetics and improved bioavailability. MATERIALS AND METHODS: NP loaded polymer hybrid enteric microspheres (PHE-Ms) were fabricated by using a modified solvent evaporation technique coupled with molecular modelling (MM) approach. The PHE-Ms were characterized by particle size, distribution, morphology, crystallinity, EE, drug-polymer compatibility, and DSC. The optimized NP loaded PHE-Ms were further subjected to downstream procedures including tablet dosage form development, stability studies and comparative in vitro-in vivo evaluation. RESULTS: The hydrophobic polymer EUD-L100 and hydrophilic polymer HPMC-E5 delayed and modified drug release at intestinal pH while imparting retardation of NP release at gastric pH to diminish the gastric side effects. The crystallinity of the NP loaded PHE-Ms was established through DSC and P (XRD). The particle size for the developed formulations of PEH-Ms (M1-M5) was in the range from 29.06 ±7.3-74.31 ± 17.7 µm with Span index values of 0.491-0.69, respectively. The produced NP hybrid microspheres demonstrated retarded drug release at pH 1.2 and improved dissolution at pH 6.8. The in vitro drug release patterns were fitted to various release kinetic models and the best-followed model was the Higuchi model with a release exponent "n" value > 0.5. Stability studies at different storage conditions confirmed stability of the NP loaded PHE-Ms based tablets (P<0.05). The molecular modelling (MM) study resulted in adequate binding energy of co-polymer complex SLS-Eudragit-HPMC-Naproxen (-3.9 kcal/mol). In contrast to the NP (unprocessed) and marketed formulations, a significant increase in the Cmax of PHE-MT1 (44.41±4.43) was observed. CONCLUSION: The current study concludes that developing NP loaded PHE-Ms based tablets could effectively reduce GIT consequences with restored therapeutic effects. The modified release pattern could improve the dissolution rate and enhancement of oral bioavailability. The MM study strengthens the polymer-drug relationship in microspheres.

Development of hybrid microspheres for assessment of multiphase processes.

This work presents a new technique for the synthesis of particles satisfying the conditions of several multiphase suspensions. It consists of manufacturing PMMA_La2O3 hybrid microspheres through suspension polymerization first and then submitting the beads to neutron activation. It was found that the fractional mass of the filler La2O3 in the beads can be greater that 60% using this technique. The results and other properties of the particles clearly indicate that the technique is effective to produce particles for several RPT applications.

Preparation and evaluation of BCP-CSD-agarose composite microsphere for bone tissue engineering.

Composite microspheres have been widely investigated over the years in order to achieve a sound scaffold with suitable combinations of biodegradable polymers and bioactive ceramics/glasses for bone tissue engineering. In our present study, composite microspheres were prepared for the first time by agarose (1 wt %) enforcement with combination of biphasic calcium phosphate (BCP; 20 wt %) and calcium sulfate dehydrate (CSD; 20 wt %), and analyzed for use in bone regeneration. The one-step fabrication process revealed spheres of sizes ranging from 50 to 1000 µm of BCP-CSD contents effectively formed by natural solidification of agarose matrix, which is very simple, time and cost-effective, and could allow for large scale production. Furthermore, the BCP-CSD-agarose composite microspheres were tested in in vitro and in vivo for bone-forming properties in order to assess their biocompatibility. The rapid diffusion of Ca 2+ ions from CSD of the composite microspheres through agarose matrix potentially increased interactivity with microenvironment and gave support for cell adhesion and proliferation. Moreover, in vivo result demonstrated that fabricated microspheres promoted neovascularization, stimulated fibroblast cell proliferation, and host cell migration occurred throughout the defects and within microspheres, ultimately guided to new bone formation. The developed composite microspheres with novel approach could have potential for bone regeneration application. © 2019 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 107B: 2263-2272, 2019.

Superparamagnetic hybrid microspheres affecting osteoblasts behaviour.

The present work describes biomimetic hybrid microspheres made of collagen type I-like peptide matrix (RCP) mineralised with Fe2+/Fe3+ doping hydroxyapatite (RCPFeHA) by a bio-inspired process. Superparamagnetic RCPFeHA microspheres are obtained by emulsification of the hybrid slurries in the presence of citrate ions, to achieve a biomimetic surface functionalisation improving the bioactivity and the dispersion ability in cell culture medium. A biological in vitro study correlates the osteoblast cells behaviour to calcium and iron ions released by the hybrid microspheres in culture media mimicking physiological or inflammatory environment, evidencing a clear triggering of cell activity and bio-resorption ability. In presence of the microspheres, the osteoblast cells maintain their typical morphology and no cell damage were detected, whereas also showing up-regulation of osteogenic markers. The ability of the hybrid microspheres to undergo bio-resorption and release bioactive ions in response to different environmental stimuli without harmful effects opens new perspectives in bone regeneration, as magnetically active bone substitute with potential ability of drug carrier and smart response in the presence of inflammatory states.

Synthesis of novel quaternary silica hybrid bioactive microspheres.

PURPOSE: To survey the preparation of novel hybrid microspheres of quaternary silicate glassy composition (SiO2 P2 O5 CaONa2 O) and the prospect of using them as an osteogenic system with enhanced bioactive properties for the development of hydroxyapatite. METHOD: In line with our previous synthetic procedure a two-step process was followed, wherein polystyrene (PS) microspheres were prepared by the emulsifier free-emulsion polymerization method and constituted the core for the sol-gel coating of the silicate inorganic shell. The development of the hybrid microspheres was based on silane and phosphate precursors and was assesses at different ratio of ethanol/water (of 9/1, 4/1, and 2/1, in mL) and at varied ammonia concentration of 4.8-1.0 mL. RESULTS: The hybrid microspheres had an average size ranged between 350 and 550 nm according to SEM, depending on the ethanol/water solution rate and ammonia content. The final microspheres probably exhibited a porous-like structure through the formation of diffused voids along with the low carbon content of the EDX analysis, which could be regulated by the catalyst content. The hybrid microspheres exhibited effective in vitro bioactivity assessed in simulated body fluids (SBF). CONCLUSION: Quaternary hybrid silica microspheres were effectively synthesized. The bioassay evaluation of the final microspheres revealed the rapid in vitro formation of a bone-like apatite layer. The results verify the bioactivity of the microspheres and promote further research of their suitability on regenerative treatment of bone abnormalities. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 106B: 112-120, 2018.

Micro/Mesoporous Fe3O4/Fe-Phthalocyanine Microspheres and Effects of Their Surface Morphology on the Crystallization and Properties of Poly(Arylene Ether Nitrile) Composites.

The surface morphology of nanoparticles significantly affects the final properties and interfacial characteristics of their composites. Thus, investigations on the surface morphology of the nanoparticles is essential to fabricate improved nanoparticle-reinforced composites. Fe3O4/Fe-phthalocyanine (FePc) hybrid microspheres with micro/mesoporous structures were prepared via a solvothermal process and solvent etching method. The surface morphology and compositional distribution were respectively investigated using a scanning electron microscope (SEM) and a transmission electron microscope (TEM) to rule out that FePc monomers have been blended with Fe3O4 to form Fe3O4/FePc hybrid microspheres without serious agglomeration. The surface roughness of Fe3O4/FePc microspheres was investigated by the scanning probe microscope (SPM), and confirmed by the adsorption and desorption isotherms of N2. The effects of the various surface morphologies on the crystallization behavior of crystallizable poly(arylene ether nitrile) (c-PEN) were first employed to confirm the surface characteristics of the resulted microspheres. Results indicated that the etched Fe3O4/FePc microspheres would improve the crystallization degree of c-PEN, due to their much more micro/mesoporous structures than that of original Fe3O4/FePc. Then, Fe3O4/FePc hybrid microspheres reinforced PEN composite films were prepared and their interfacial compatibility was monitored using an SEM. Excellent thermal stability and improved mechanical properties were obtained by combining the etched Fe3O4/FePc and PEN matrix. The excellent surface properties and micro/mesoporous structures make the novel Fe3O4/FePc an excellent candidate of organic/inorganic hybrid fillers and micro/mesoporous materials.

Effective Enrichment and Detection of Trace Polycyclic Aromatic Hydrocarbons in Food Samples based on Magnetic Covalent Organic Framework Hybrid Microspheres.

The present study reported a facile, sensitive, and efficient method for enrichment and determination of trace polycyclic aromatic hydrocarbons (PAHs) in food samples by employing new core-shell nanostructure magnetic covalent organic framework hybrid microspheres (Fe3O4@COF-(TpBD)) as the sorbent followed by HPLC-DAD. Under mild synthetic conditions, the Fe3O4@COF-(TpBD) were prepared with the retention of colloidal nanosize, larger specific surface area, higher porosity, uniform morphology, and supermagnetism. The as-prepared materials showed an excellent adsorption ability for PAHs, and the enrichment efficiency of the Fe3O4@COF-(TpBD) could reach 99.95%. The obtained materials also had fast adsorption kinetics and realized adsorption equilibrium within 12 min. The eluent was further analyzed by HPLC-DAD, and good linearity was observed in the range of 1-100 ng/mL with the linear correlation being above 0.9990. The limits of detection (S/N = 3) and limits of quantitation (S/N = 10) for 15 PAHs were in the range of 0.83-11.7 ng/L and 2.76-39.0 ng/L, respectively. For the application, the obtained materials were employed for the enrichment of trace PAHs in food samples and exhibited superior enrichment capacity and excellent applicability.

A new approach for the one-step synthesis of bioactive PS vs. PMMA silica hybrid microspheres as potential drug delivery systems.

In this work, hybrid microspheres were prepared in a two-step process combining the emulsifier free-emulsion polymerization and the sol-gel coating method. In the first step, polystyrene (St) and poly(methyl methacrylate) (PMMA) microspheres were prepared as sacrificial template and in the second step a silanol shell was fabricated. The functionalized surface of the hybrid microspheres by silane analogs (APTES, TEOS) resulted in enhanced effects. The hollow microspheres were resulted either in an additional step by template dissolution and/or during the coating process. The microspheres' surface interactions and the size distribution were optimized by treatment in simulated body fluids, which resulted in the in vitro prediction of bioactivity. The bioassay test indicated that the induced hydroxyapatite resembled in structure to naturally occurring bone apatite. The drug doxorubicin (DOX) was used as a model entity for the evaluation of drug loading and release. The drug release study was performed in two different pH conditions, at acidic (pH=4.5) close to cancer cell environment and at slightly basic pH (pH=7.4) resembling the orthopedic environment. The results of the present study indicated promising hybrid microspheres for the potential application as drug delivery vehicles, for dual orthopedic functionalities in bone defects, bone inflammation, bone cancer and bone repair.

Graphene functionalized porous Au-paper based electrochemiluminescence device for detection of DNA using luminescent silver nanoparticles coated calcium carbonate/carboxymethyl chitosan hybrid microspheres as labels.

In the paper, a simple and sensitive electrochemiluminescence (ECL) DNA sensor based on graphene-modified porous Au-paper working electrode (GR/Au-PWE) and calcium carbonate/carboxymethyl chitosan (CaCO3/CMC) hybrid microspheres @ luminescent silver nanoparticles (AgNPs) composites was developed. The GR/Au-PWE with excellent conductivity was successfully prepared for the immobilization of capture probe. The CaCO3/CMC hybrid microspheres were prepared by the precipitation of calcium carbonate in an aqueous solution containing CMC. The AgNPs was synthesized by thermal reduction of silver ions in glycine matrix, taking advantage of the solid-state matrix to control the nucleation and migration of reduced silver atoms. The CaCO3/CMC@AgNPs composites exhibited 3.6 times higher ECL intensity than the pure AgNPs-labeled reporter DNA. Taking advantage of dual-amplification effects, the paper-based DNA sensor could detect the target DNA quantitatively, in the range of 4.0×10(-17)-5.0×10(-11) M, with a limit of detection as low as 8.5×10(-18) M, and perform excellent selectivity. The simple, low-cost, sensitive device could be easily applied for point-of-care testing, public health and environmental monitoring in remote regions, developing or developed countries.

Synthesis of organic-inorganic hybrid microspheres and the corresponding mesoporous silica nanoparticles.

Poly(methacrylic acid-co-3-(methacryloxy)propyltrimethoxysilane) (P(MAA-co-MPS)) organic-inorganic hybrid microspheres were prepared by distillation-precipitation copolymerization of MAA and MPS in acetonitrile in absence of any surfactant and additive. The resultant hybrids had a spherical shape when the MPS inorganic precursor was varied from 0% to 60% in the comonomers during the polymerization. The hybrid microspheres can be facilely cross-linked via the hydrolysis of methoxy groups of polyMPS network and further self-condensation of the hydroxyl groups of silanols. As a result, the hybrid microspheres were facilely converted to mesoporous silica particles via the removal of the organic component through calcination. The narrow dispersed mesoporous silica had a high surface area of 554.2 m(2)/g as well as the average pore size of 8 nm and pore volume of 0.24 cm(3)/g. The corresponding microspheres were characterized by TEM, FT-IR, TGA, and nitrogen sorption-desorption.