Research Progress on the Preparation of Inorganic/Natural Materials Composite Microspheres

Microspheres are a new type of drug carrier with great potential for development and application.Natural polymers have good biocompatibility,biodegradability,and are easily dispersed in living organisms,making them suitable for preparing microspheres.Inorganic materials(mainly inorganic minerals)have excellent mechanical properties and are inexpensive and easy to obtain.Through the coupling and hybridization of natural polymers and inorganic materials,they can complement each other's advantages and synergistically enhance efficiency,resulting in many excellent physical and chemical properties.Inorganic materials/natural polymer composite microspheres can be prepared by modifying natural polymers with inorganic materials through various methods such as emulsification crosslinking,solution mixing,in-situ synthesis,extrusion,etc.The application of inorganic materials/natural polymer composite microspheres in drug delivery systems has significant sustained-release effects,is safe and non-toxic,and the cost of carrier materials is relatively low,which has certain significance for the development of new drug carriers.This article reviews the recent research on the preparation,drug loading and release properties of inorganic material/natural polymer composite microspheres,analyzes the advantages and disadvantages of commonly used preparation methods,and looks forward to the development direction of composite microspheres.

Preparation and characterization of composite microspheres of nano zinc ferrite/poly(D,L-lactide-co-alanine)

Magnetic nano zinc ferrite fliuds were synthesized using an improved liquid phase chemical method, which would be used to replace tradditional iron oxides magnetic material. A novel copolymer （PLAA） with D, L-lactide （D, L-LA） and alanine was synthesized using stannous octoate as initiator. Magnetic polymer microspheres were fabricated with nano zinc ferrite fluid coated with alanine modified poly lactide. These as-prepared zinc ferrite fluids, modified poly lactide and magnetic composites, were characterized with X-ray diffraction diffractometer, FT-IR spectrometer, nuclear magnetic resonance spectrometer, scanning electron microscope, transmission electron microscope, vibrating sample magnetometer, and thermogravimetric analyzer. The results demonstrate that the as-prepared zinc ferrite is spinel type of ZnFe2O4 nano crystals with particle size of 20-45 nm and magnetization of 32×10^-3 A.m2. Alanine is copolymerized with lactide, and the prepared composite magnetic microsphere is coated with the modified polylactide, with mass fraction of 45.5% of PLA, particle size ranging from 80-300 nm, and magnetization of 10.6×10^-3 A·m^2, which suggests ZnFe2O4 enjoys a stable magnetization after being coated by polymer.

Preparation of Dysprosium Ferrite/Polyacrylamide Magnetic Composite Microsphere and Its Characterization

Using the technique of microemulsion polymerization with nano-reactor, dysprosium ferrite/polyacrylamide magnetic composite microsphere was prepared by one-step method in a single inverse microemulsion. The structure, average particle size, morphology of composite microsphere were characterized by FTIR, XRD, TEM and TGA. The magnetic responsibility of composite microsphere was also investigated. The results indicate that the magnetic composite microsphere possess high magnetic responsibility and suspension stability.

Research on properties of hollow glass microspheres/epoxy resin composites applied in deep rock in-situ temperature-preserved coring

Deep petroleum resources are in a high-temperature environment.However,the traditional deep rock coring method has no temperature preserved measures and ignores the effect of temperature on rock porosity and permeability,which will lead to the distortion of the petroleum resources reserves assessment.Therefore,the hollow glass microspheres/epoxy resin(HGM/EP)composites were innovatively proposed as temperature preserved materials for in-situ temperature-preserved coring(ITP-Coring),and the physical,mechanical,and temperature preserved properties were evaluated.The results indicated that:As the HGM content increased,the density and mechanical properties of the composites gradually decreased,while the water absorption was deficient without hydrostatic pressure.For composites with 50 vol%HGM,when the hydrostatic pressure reached 60 MPa,the water absorption was above 30.19%,and the physical and mechanical properties of composites were weakened.When the hydrostatic pressure was lower than 40 MPa,the mechanical properties and thermal conductivity of composites were almost unchanged.Therefore,the composites with 50 vol%HGM can be used for ITPCoring operations in deep environments with the highest hydrostatic pressure of 40 MPa.Finally,to further understand the temperature preserved performance of composites in practical applications,the temperature preserved properties were measured.An unsteady-state heat transfer model was established based on the test results,then the theoretical change of the core temperature during the coring process was obtained.The above tests results can provide a research basis for deep rock in-situ temperature preserved corer and support accurate assessment of deep petroleum reserves.

Preparation and Properties of Guiqi Polysaccharides/Chitosan/Alginate Composite Hydrogel Microspheres

A series of the Guiqi polysaccharides/chitosan/alginate composite hydrogel microspheres(GPcM)with different particle sizes were prepared with Guiqi polysaccharides(GP),chitosan(CS)and sodium alginate(Alg).The optimum preparation process was also determined by single factor and orthogonal experiment analysis.The GPcM were characterized by fourier transform infrared spectroscopy(FT-IR),scanning electron microscope(SEM),drug loading efficiency test(LE),encapsulation efficiency test(EE)and in vitro release study.The results showed that the Guiqi polysaccharides chitosan hydrogel(GPCH)and sodium alginate hydrogel(SAH)formed a crossover system in GPcM.The GPcM have a uniform particle size ranging from 395.1μm to 841.5μm.The drug loading efficiency and encapsulation efficiency of the GPcM were 56.3%and 72.6%,respectively.The bovine serum albumin(BSA)loaded in the GPcM released slowly within 180 h.The results suggested that the GPcM may have potential application value in drug sustained and controlled release system.

UV-Vis and Surface Photovoltage Spectra of Fe_2O_3/Polystyrene Composite Microspheres

Fe_2O_3 sol with the particle diameter of 3-5 nm was flocculated by the addition of SDS, and the flocculate formed was redispersed by the further addition of that surfactant. Thus the surfactant bilayer was formed on the surface of Fe_2O_3. The emulsion polymerization of styrene(St) adsolubilized on the surfactant adsorbed bilayer was carried out by initiator potassium persulfate(KPS). The UV-Vis and surface photovoltage spectra(SPS) indicate that the Fe_2O_3 particles were encapsulated in polystyrene(PSt) successfully.

Crystal phase control and ignition properties of HNS/CL-20 composite microspheres prepared by microfluidics combined with emulsification techniques

Improved controllability and energy density of ignition agents are of great significance for the devel-opment of energetic composite materials.In this study,droplet microfluidics and emulsification tech-niques were combined to prepare HNS/CL-20 composite microspheres with polyglycidyl azide polymer(GAP)as the binder.The influence of binder content on the morphology of microspheres was investi-gated,and the microspheres were characterized and tested for particle size,crystal structure,thermal decomposition,dispersibility,mechanical sensitivity,combustion behavior and detonation performance.The results showed that microspheres prepared with a binder content of 3%had higher sphericity and particle size uniformity.The microspheres retained the crystal structure of both HNS and CL-20(ε-type).Compared with raw HNS,the microspheres had higher apparent activation energy,better safety per-formance,and good dispersibility.The ignition experiments and detonation performance tests show that HNS/CL-20 composite microspheres have excellent ignition performance,obvious combustion flame,and significant energy release effects,which are expected to achieve high energy and high-speed response of the igniter,thus improving the ignition reliability in special environments or systems.

Design and Fabrication of Superparamaganitic Hybrid Microspheres for Protein Immobilization

Superparamagnetic poly（styrene）-co-poly（2-acrylanmido-2-methyl propanesulfonic acid） （PSt-co-PAMPS） and poly（methylmethacrylate）-co-poly（glycidyl methacrylate） （PMMA-co-PGMA） microspheres with mean size of 170 nm were prepared by emulsion polymerization in the presence of oleic acid-coated Fe3O4 nanoparticles. The structures, morphologies, diameter and diameter distribution of the as-prepared microspheres were identified by Fourier transform infrared spectroscopy （FT-IR） and transmission electron microscopy （TEM）. The saturation magnetizations of PSt-co-PAMPS and PMMA-co-PGMA microspheres are 21.94 and 25.07 emu/g, respectively. The as-synthesized magnetic microspheres were used for immobilization of Bovine serum albumin （BSA） by physical interaction and covalent interaction respectively. The equilibrium amount of BSA immobilized onto PMMA-co-PGMA microspheres was 86.48 mg/g microspheres in 90 min, while on PSt-co-PAMPS microspheres was 59.62 mg/g microspheres in 120 min.

Hierarchically electrospraying a PLGA@chitosan sphere-in-sphere composite microsphere for multi-drug-controlled release

Sequential administration and controlled release of different drugs are of vital importance for regulating cellular behaviors and tissue regeneration,which usually demands appropriate carriers like microspheres(MS)to control drugs releases.Electrospray has been proven an effective technique to prepare MS with uniform particle size and high drug-loading rate.In this study,we applied electrospray to simply and hierarchically fabricate sphere-in-sphere composite microspheres,with smaller poly(lactic-co-glycolic acid)MS(~8-10 lm in diameter)embedded in a larger chitosan MS(~250-300 lm in diameter).The scanning electron microscopy images revealed highly uniform MS that can be accurately controlled by adjusting the nozzle diameter or voltage.Two kinds of model drugs,bovine serum albumin and chlorhexidine acetate,were encapsulated in the microspheres.The fluorescence-labeled rhodamine-fluoresceine isothiocyanate(Rho-FITC)and ultraviolet(UV)spectrophotometry results suggested that loaded drugs got excellent distribution in microspheres,as well as sustained,slow release in vitro.In addition,far-UV circular dichroism and matrixassisted laser desorption/ionization time-of-flight mass spectrometry(MALDI-TOF-MS)results indicated original secondary structure and molecular weight of drugs after electrospraying.Generally speaking,our research proposed a modified hierarchically electrospraying technique to prepare sphere-in-sphere composite MS with two different drugs loaded,which could be applied in sequential,multi-modality therapy.

PREPARATION OF COMPOSITE MAGNETIC MICROSPHERES BY REACTIVE BLENDING

A novel method for preparation of polymer-based magnetic microspheres was proposed by utilizing melt reactive blending, which was based on selective location of Fe3O4 nanoparticles in PA6 domains of polystyrene （PS）/polyamide 6 （PA6） immiscible blends. The morphology of PA6/Fe3O4 composite magnetic mierospheres was studied by scanning electronic microscopy （SEM）. The composite magnetic mierospheres were spherical with a diameter range of 0.5-8 μm; the diameter was sharply decreased with a very narrow distribution by adding terminal maleic anhydride fimctionalized polystyrenes （FPS） for reactive blending. Transmission electron microscopy （TEM） and thermogravimetry analysis （TGA） results showed that most of Fe3O4 was located in the PA6 microspheres. Magnetization data revealed the magnetite content of PA6/Fe3O4 microspheres was about 32 wt% and the saturation magnetization could be up to 17.2 AmE/kg.

Rational construction of densely packed Si/MXene composite microspheres enables favorable sodium storage

The fast and reversible sodiation/desodiation of anode materials remains an indelible yet fascinating target.Herein, a class of the densely packed Si/MXene composite microspheres is constructed and prepared, taking advantages of the synergistic effects of the activated Si nanoparticles and conductive flower-like MXene microspheres with ample ion-diffusion pathways. Consequently,the intrinsic MXene nanosheets with intelligently regulated interlayer spacing can accommodate the volume change induced strain during cycling, and the strong interaction between the Si and MXene matrix greatly contributes to the robust structural stability. As expected, the Si/MXene composite architecture exhibits boosted sodium storage performance, in terms of an inspiring reversible capacity of 751 mAh·g^(-1)at 0.1 A·g^(-1), remarkable long-term cycling stability of 376 mAh·g^(-1)at 0.1 A·g^(-1) over 500 cycles, and outstanding rate capability(after one consecutive current density changing from 0.1 to 2.0 A·g^(-1), a large capacity of 275 mAh·g^(-1) is regained after suddenly returning the initial current density back to 0.1 A·g^(-1) and in the subsequent 200 cycles this composite architecture anode still delivers a capacity of 332 mAh·g^(-1)). The kinetics analysis indicates superior pseudocapacitive property, high electronic conductivity, and favorable sodium-ion adsorption and diffusion capability,confirming fast sodium storage performance. Impressively, ex-situ X-ray diffraction and selected area electron diffraction characterizations corroborate the formation of NaSi;as the main sodiation products during the reversible evolutions of cycled proceeding with sodium-ion insertion. This work sheds light on the elaborate design of silicon-based nanostructured anodes towards advanced high-performance sodium-ion batteries.

Fabrication of polymeric-Laponite composite hollow microspheres via LBL assembly

Hollow structure microspheres with composite polymeric-Laponite shells were prepared by electrostatic self-assembly of Laponite on the polymeric hollow microspheres in this work.The multilayer hydrophilic core/hydrophobic shell polymer latex particles containing carboxyl groups inside were first synthesized via seeded emulsion polymerization,followed by alkali treatment,generating polymeric hollow microspheres.Then,polyethyleneimine（PEI） and Laponite were alternately electrostatic adsorbed on the prepared polymeric hollow microspheres to form polymeric-Laponite composite hollow microspheres.It was indicated that the morphology of alkali-treated microspheres could be tuned through simply altering the dosage of alkali used in the post-treatment process.Along with the increasing of the coating layers,the zeta potential of microspheres absorbed PEI or Laponite approximately tended to be constant respectively,and the thickness of Laponite layer around the hollow microspheres increased clearly,getting more uniform and homogenous.Furthermore,the corresponding polymeric-Laponite hollow microspheres showed high pressure resistance ability compared to the polymeric hollow microspheres.

Hierarchical coupling effect in hollow Ni/NiFe2O4-CNTs microsphere via spray-drying for enhanced oxygen evolution electrocatalysis

Design and fabrication of cost-effective transition metal and their oxides-based nanocomposites are of paramount significance for metal-air batteries and water-splitting.However,the traditional optimized designs for nanostructure are complicated,low-efficient and underperform for wide-scale applications.Herein,a novel hierarchical framework of hollow Ni/NiFe2O4-CNTs compositemicrosphere forcibly-assembled by zero-dimensional(OD)Ni/NiFo204 nanoparticle(<16 nm)and one-dimensional(1D)self-supporting CNTs was fabricated successfully.Benefitted from the unique nanostructure,such monohybrids can achieve remarkable oxygen evolution reaction(OER)performance in alkaline media with a low overpotential and superior durability,which exceeds most of the commercial catalysts based on IrO/RuO2 or other non-noble metal nanomaterials.The enhanced OER performance of Ni/NiFe2OA-CNTs composite is mainly ascribed to the increased catalytic activity and the optimized conductivity induced by the effects of strong hierarchical coupling and charge transfers between CNTs and Ni/NiFe204 nanoparticles.These effects are greatly boosted by the polarized heterojunction interfaces confirmed by electron holography.The density functional theory(DFT)calculation indicates the epitaxial Ni further enriches the intrinsic electrons contents of NiFe204 and thus accelerates absorption/desorption kinetics of OER intermediates.This work hereby paves a facile route to construct the hollow composite microsphere with excellent OER electrocatalytic activity based on non-noble metal oxide/CNTs.

Synthesis and morphology control of raspberry-like poly(ethylene terephthalate)/polyacrylonitrile microspheres

The fabrication of raspberry-like poly（ethylene terephthalate）/polyacrylonitrile（PET/PAN） microspheres by g-ray radiation-induced polymerization of acrylonitrile on micron-sized PET microspheres were first reported in this work. A PET emulsion was firstly prepared by dispersing a PET solution with 1,1,2,2-tetrachloroethane/phenol mixture as the solvent into an aqueous solution of sodium dodecyl sulfate.Then, PET microspheres were formed by precipitating the PET emulsion droplets from ethanol. The influence of the PET solvent and the weight ratio of ethanol to PET emulsion on the morphology of the PET microspheres had been investigated. After the surface of the prepared PET microspheres was grafted with poly（acrylic acid）, the grafting polymerization of AN also had been successfully initiated by g-ray radiation to form PAN microspheres with a size of about 100 nm on the PET microspheres. This work provides a new method to fabricate micron-sized PET microspheres, and further expands the functionalization of PET and its application fields.