Adipose-derived mesenchymal stem cell-incorporated PLLA porous microspheres for cartilage regeneration

Background:In facial plastic surgery,patients with nasal deformity are often treated by rib cartilage transplantation.In recent years,cartilage tissue engineering has developed as an alternative to complex surgery for patients with minor nasal defects via injection of nasal filler material.In this study,we prepared an injectable nasal filler material containing poly-L-l actic acid(PLLA)porous microspheres(PMs),hyaluronic acid(HA)and adipose-derived mesenchymal stem cells(ADMSCs).Methods:We seeded ADMSCs into as-prepared PLLA PMs using our newly invented centrifugation perfusion technique.Then,HA was mixed with ADMSC-i ncorporated PLLA PMs to form a hydrophilic and injectable cell delivery system(ADMSCincorporated PMH).Results:We evaluated the biocompatibility of PMH in vitro and in vivo.PMH has good injectability and provides a favorable environment for the proliferation and chondrogenic differentiation of ADMSCs.In vivo experiments,we observed that PMH has good biocompatibility and cartilage regeneration ability.Conclusion:In this study,a injectable cell delivery system was successfully constructed.We believe that PMH has potential application in cartilage tissue engineering,especially in nasal cartilage regeneration.

Porous Microspheres Comprising CoSe2 Nanorods Coated with N-Doped Graphitic C and Polydopamine-Derived C as Anodes for Long-Lived Na-Ion Batteries

Metal–organic framework-templated nitrogen-doped graphitic carbon(NGC)and polydopaminederived carbon(PDA-derived C)-double coated one-dimensional CoSe_(2) nanorods supported highly porous threedimensional microspheres are introduced as anodes for excellent Na-ion batteries,particularly with long-lived cycle under carbonate-based electrolyte system.The microspheres uniformly composed of ZIF-67 polyhedrons and polystyrene nanobeads(φ=40 nm)are synthesized using the facile spray pyrolysis technique,followed by the selenization process(P-CoSe_(2)@NGC NR).Further,the PDA-derived C-coated microspheres are obtained using a solution-based coating approach and the subsequent carbonization process(P-CoSe_(2)@PDA-C NR).The rational synthesis approach benefited from the synergistic effects of dual carbon coating,resulting in a highly conductive and porous nanostructure that could facilitate rapid diffusion of charge species along with efficient electrolyte infiltration and effectively channelize the volume stress.Consequently,the prepared nanostructure exhibits extraordinary electrochemical performance,particularly the ultra-long cycle life stability.For instance,the advanced anode has a discharge capacity of 291(1000th cycle,average capacity decay of 0.017%)and 142 mAh g^(-1)(5000th cycle,average capacity decay of 0.011%)at a current density of 0.5 and 2.0 A g^(-1),respectively.

Synthesis and Characterization of Suspension Polymerized Styrene-Divinylbenzene Porous Microsphere Using as Slow-Release-Active Carrier

Functional porous microspheres used for the slow release carrier of actives in cosmetics or pharmaceuticals were prepared by modified suspension polymerization of styrene （ST） with divinylbenzene （DVB） in the presence of toluene, cyclohexanol and heptane as porogenic diluents. The use of ultrasonic dispersion decreases the beads＇ size and improves the uniformity. The effects of the porogen mixture, DVB content and solvent extraction on the surface performance of the synthesized beads were studied. The microspheres were characterized by scanning electron microscopy （SEM） and BET surface area determination. It was found that a great proportion of the non-solvating porogen increases the pore diameter and the specific surface area. High DVB concentration also results in the great specific surface area and porosity. When the ratio of toluene/cyclohexanol is 1：2, DVB content is at the range of 40%-60% and methylene chloride was used as extractant, the beads with good spherical shape and pore size were obtained. The prepared porous microspheres were applied as active carriers and showed satisfactory slow release effect. Over 10h constantly sustained release was observed in vitro releasing test for hydroquinone-loaded microspheres. Great surface area promoted high concentration of released hydroquinone.

MoSe2 porous microspheres comprising monolayer flakes with high electrocatalytic activity

A facile colloidal route to synthesize MoSe2 porous microspheres with diameters of 400-600 nm made up of MoSe2 monolayer flakes （-0.7 nm in thickness） is reported. The solvents trioctylamine （TOA） and oleylamine （OAM） are found to play important roles in the formation of MoSe2 microspheres, whereby TOA determines the three-dimensional （3D） microspherical morphology and OAM directs the formation of MoSes monolayer flakes. The robust 3D MoSe2 microspheres exhibit remarkable activity and durability for the electrocatalytic hydrogen evolution reaction （HER） in acid, maintaining a small onset overpotential of -77 mV and keeping a small overpotential of 100 mV for a current density of 5 mA/cm2 after 1,000 cycles. In addition, similar 3D WSe2 microspheres can also be prepared by using this method. We expect this facile colloidal route could further be expanded to synthesize other porous structures which will find applications in fields such as in energy storage, catalysis, and sensing.

Bioinspired porous microspheres for sustained hypoxic exosomes release and vascularized bone regeneration

Exosomes derived from mesenchymal stem cells(MSCs)have demonstrated regenerative potential for cell-free bone tissue engineering,nevertheless,certain challenges,including the confined therapeutic potency of exosomes and ineffective delivery method,are still persisted.Here,we confirmed that hypoxic precondition could induce enhanced secretion of exosomes from stem cells from human exfoliated deciduous teeth(SHEDs)via comprehensive proteomics analysis,and the corresponding hypoxic exosomes(H-Exo)exhibited superior potential in promoting cellular angiogenesis and osteogenesis via the significant up-regulation in focal adhesion,VEGF signaling pathway,and thyroid hormone synthesis.Then,we developed a platform technology enabling the effective delivery of hypoxic exosomes with sustained release kinetics to irregular-shaped bone defects via injection.This platform is based on a simple adsorbing technique,where exosomes are adsorbed onto the surface of injectable porous poly(lactide-co-glycolide)(PLGA)microspheres with bioinspired polydopamine(PDA)coating(PMS-PDA microspheres).The PMS-PDA microspheres could effectively adsorb exosomes,show sustained release of H-Exo for 21 days with high bioactivity,and induce vascularized bone regeneration in 5-mm rat calvarial defect.These findings indicate that the hypoxic precondition and PMS-PDA porous microsphere-based exosome delivery are efficient in inducing tissue regeneration,hence facilitating the clinical translation of exosome-based therapy.

Hierarchical porous MgBO_2(OH) microspheres: Hydrothermal synthesis,thermal decomposition, and application as adsorbents for Congo red removal

A facile eco-friendly hydrothermal route （180 ℃, 12.0 h） has been developed for the first time to the uniform hierarchical porous MgBO2（OH） microspheres without the aid of any organic additive, surfactant or template, by using the abundant MgCl2·6H2O, H3BO3 and NaOH as the raw materials. The as-obtained porous microspheres exhibit a specific surface area of 94.752 mg·g-1, pore volume of 0.814 cm3.g-1, and ca. 84.0% of which have a diameter of 2.25-3.40 μm. The thermal decomposition of the porous MgBO2（OH） microspheres （650 ℃, 2.5 ℃. min-l） leads to the porous Mg2B2O5 rnicrospheres with well-retained morphology. When utilized as the adsorbents for the removal of CR from mimic waste water, the present porous MgBO2（OH） microspheres exhibit satisfactory adsorption capacity, with the maximum adsorption capacity qm of 309.1 mg-g-1, much higher than that derived from most of the referenced adsorbents. This opens a new window for the facile green hydrothermal synthesis of the hierarchical porous MgBO2（OH） microspheres, and extends the potential application of the 3D hierarchical porous metal borates as high-efficiency adsorbents for organic dyes removal.

Surface Treatment and Biomimetic Mineralization of Porous Microspheres Fabricated by Calcium Gluconate-g-Poly(D,L-lactide)

Porous hybrid microspheres were fabricated by the synthesized calcium gluconate-g-poly（D,L-lactide） （CG-g- PDLLA） composites. These hybrid microspheres were treated with an alkaline solution for different period of time to control the amount of generated carboxylate groups and remained CG on the surface. The microspheres were then incubated in a supersaturated simulated body fluid （1.5 SBF） solution for different time to investigate their biomimetic mineralization behavior. The depositions were found to have a fine cluster morphology, a similar crystal structure and chemical structure to natural hydroxyapatite, and a medium Ca/P of approximately 1.30. The effect of surface treating time on the structure and mineralization behavior of these microspheres has been discussed in detail. The results indicate that the nucleation and growth of apatite on the surface are influenced by the induced carboxylate groups and the remained CG. The hybrid CG-g- PDLLA microspheres have the potential as a novel alternative in bone tissue engineering.

Study on Preparation of Porous ZnO Microspheres and Photocatalytic Performance

This paper introduces the method of porous ZnO microspheres by sodium citrate assisted hydrothermal synthesis with a mild, economy： first, basic synthesis globose precursor of Zinc Carbonate Hydroxide, then followed by thermal decompose the precursor to obtain porous Zinc Oxide microspheres. The morphology and structure of the precursor and synthesized porous microspheres were characterize by a series of methods, and did a series of experiments by changing dosage and reaction time of the sodium citrate and urea, finally the paper discussed the formation mechanism of porous ZnO microspheres.

Hollow TiO2-x porous microspheres composed of wellcrystalline nanocrystals for high-performance lithiumion batteries

Hollow TiO2-x porous microspheres consisted of numerous well-crystalline nanocrystals with superior structural integrity and robust hollow interior were synthesized by a facile sol-gel template-assisted approach and two-step carbonprotected calcination method, together with hydrogenation treatment. They exhibit a uniform diameter of -470 nm with a thin porous wall shell of -50 nm in thickness. The Brunauer-Emmett-Teller （BET） surface area and pore volume are -19 m2/g and 0.07 crnB/g, respectively. These hollow TiOR_x porous microspheres demonstrated excellent lithium storage performance with stable capacity retention for over 300 cycles （a high capacity of 151 mAh/g can be obtained up to 300 cycles at I C, retaining 81.6% of the initial capacity of 185 mAh/g） and enhanced rate capability even up to 10 C （222, 192, 121, and 92.1 mAh/g at current rates of 0.5, 1, 5, and 10 C, respectively）. The intrinsic increased conductivity of the hydrogenated TiO2 microspheres and their robust hollow structure benefidal for lithium ion-electron diffusion and mitigating the structural strain synergistically contribute to the remarkable improvements in their cycling stability and rate performance.

Noble metal-like behavior of plasmonic Bi particles deposited on reduced TiO2 microspheres for efficient full solar spectrum photocatalytic oxygen evolution

Herein, novel plasmonic Bi metal in situ deposited in reduced Ti O2 microspheres(Bi@R-Ti O2) are fabricated via a bimetallic MOF-derived synthesized strategy by adjusting the synthesizing temperature. Different characterization techniques, including XRD, SEM, TEM, XPS, DRS, PL, EIS, and photocurrent generation, are performed to investigate the structural and optical properties of the as-prepared samples. The results indicate that the Bi particles are generated inside and outside of reduced Ti O2 microspheres via the reduction of Ti4+ and Bi3+ by ethylene glycol. When the annealing temperature is controlled at 300 o C, the corresponding Bi@R-Ti O2-300 sample with an appropriate amount of Bi nanoparticles exhibits the highest full solar spectrum photocatalytic oxygen evolution activity(4728.709 μmol h–1 g–1), which is 5.9 and 9.5 times higher than that of pure Ti O2 and Bi-Ti bimetal organic frameworks(Bi-Ti-MOFs). Several reasons are suggested for the above results:(1) Bi metal behaves as an "electron acceptor" to accelerate the charge carrier transfer from Ti O2 to Bi;(2) The surface plasmon resonance effect of loaded metallic Bi particles can enhance the visible and NIR light absorption capacity;(3) The generation of Ti3+ further narrows the band gap of TiO2.

Porous carbon microspheres assembled by defective nitrogen and sulfur co-doped nanosheets as anode materials for lithium-/sodium-ion batteries

Carbon-based anode materials are widely used in various battery energy storage systems due to their low cost,wide source,high conductivity and easy morphology control.However,current commercially available anode materials as active materials for lithium-/sodium-ion batteries generally suffer from large volume changes and poor rate performance.In response,we synthesized defect-rich N,S co-doped two dimensional(2D)nanosheet-assembled porous carbon microspheres(N,S-PCS)via simple hydrothermal,carbonization and etching process based on the principle of Schiff base reaction.The N,S-PCS structure is thus constructed by removing Fe7S8 nanoparticles from the carbon skeleton to form porous microspheres with N,S doping.Therefore,the micromorphology characteristic,pore structure and electroconductivity of carbon materials are effectively optimized via heteroatom doping and surface engineering.As expected,the prepared N,S-PCS electrodes exhibit excellent electrochemical performance in both lithium-ion and sodium-ion batteries.For lithium-ion batteries,it achieves reversible capacities of 1045 and 237 mAh g^(-1) at 0.1 and 20 A g^(-1),respectively.For sodium-ion batteries,it shows good cycling stability with a capacity of 157 mAh g^(-1) after 500 cycles at 1 A g^(-1).Experimental and theoretical calculation results confirm that the N,S co-doping strategies help to improve the structural stability,shorten the ion diffusion paths,and promote the reaction kinetics,thus achieving excellent electrochemical performance.This work is instructive for the practical application of nonmetal doping functionalized porous carbon structures for metal-ion batteries.

Multispectral ErBO_(3)@ATO porous composite microspheres with laser and electromagnetic wave compatible absorption

The high-speed advances in electromagnetic(EM)wave and laser detection technology have accelerated the innovation of absorbing materials toward specific multi-band compatibility.It is difficult to achieve dual absorption of EM waves and near-infrared lasers by absorbing materials in a single frequency band;the design of high-performance laser-EM wave multi-band compatible absorbing materials is imminent.Herein,ErBO_(3)@ATO(erbium borate/antimony-doped tin oxide)porous composite microspheres with an average size of 15-20μm are produced solvothermal method and self-assembly,which exhibit excellent laser-EM wave compatible absorption.The porous structure on the surface of ErBO_(3)microspheres provides heterogeneous nucleation sites for ATO particle deposition.The minimum reflectivity of the composite for1.06 and 1.54μm lasers is 9.59%and 4.79%,which is0.57%and 3.78%lower than those of pure ATO particles,respectively.The composites containing 70 wt%porous ErBO_(3)@ATO reveal the minimum reflection loss(RL)value of-31.6 dB,and an effective absorption band width reaches 2.08 GHz at 2.5 mm thickness.The mechanism of near-infrared laser and EM wave compatible absorption is the synergistic effect of the energy level transition of ErBO_(3)and the dielectric loss of ATO,coupled with the large surface area and porous structure of the micro spheres.Therefore,the designed porous ErBO_(3)@ATO composite microspheres can be an attractive choice for lasers and EM wave high-quality compatible absorption.

Fabrication of magnesium-doped porous polylactic acid microsphere for bone regeneration

Biodegradable polymer microspheres that can be used as drug carriers are of great importance in biomedical applications,however,there are still challenges in controllable preparation of microsphere surface morphology and improvement of bioactivity.In this paper,firstly,poly(L-lactic acid)(PLLA)was synthesised by ring-opening polymerisation under anhydrous anaerobic conditions and further combined with the emulsion method,biodegradable PLLA microspheres(PM)with sizes ranging from 60-100μm and with good sphericity were prepared.In addition,to further improve the surface morphology of PLLA microspheres and enhance their bioactivity,functionalised porous PLLA microspheres loaded with magnesium oxide(MgO)/magnesium carbonate(MgCO_(3))(PMg)were also prepared by the emulsion method.The results showed that the loading of MgO/MgCO_(3)resulted in the formation of a porous structure on the surface of the microspheres(PMg)and the dissolved Mg^(2+)could be released slowly during the degradation of microspheres.In vitro cellular experiments demonstrated the good biocompatibility of PM and PMg,while the released Mg^(2+)further enhanced the anti-inflammatory effect and osteogenic activity of PMg.Functionalised PMg not only show promise for controlled preparation of drug carriers,but also have translational potential for bone regeneration.

MoSe_(2)/TiO_(2)heterostructure integrated in N-doped carbon nanosheets assembled porous core-shell microspheres for enhanced sodium storage

Engineering the structure and composition of electrode materials is one of the essential means for achieving excellent electrochemical performance.The rational design of Na+host materials is still a massive challenge for sodium ion batteries(SIBs).Herein,MoSe_(2)/TiO_(2)heterostructure is integrated with N-doped carbon nanosheets to assemble into hierarchical flowerlike porous core-shell microspheres(MoSe_(2)/TiO_(2)@N-C),which is firstly reported by room-temperature stirring coupled with vulcanization treatment.The cavity of the core-shell structure could provide enough storage space for Na+and alleviate the volume expansion during charge/discharge processes.The apertures between nanosheets provide a guarantee for the rapid penetration of electrolyte to enhance the utilization rate of electrode materials.Furthermore,building heterostructures by combining different phase structures can facilitate electron transfer and accelerate reaction kinetics.Benefiting from the synergistic contributions of structure and composition,MoSe_(2)/TiO_(2)@N-C as SIBs anode material shows better reversible capacities of 302.5 mAh·g^(-1)at 1 A·g^(-1)for 400 cycles and 217.4 mAh·g^(-1)at 4 A·g^(-1)for 900 cycles.Strikingly,the reversible capacities can be restored entirely to the initial level after a high current density cycle.

Fabrication of three-dimensional porous La-doped SrTiO3 microspheres with enhanced visible light catalytic activity for Cr（VI） reduction

In recent years, much effort has been focused on the development of the photocatalysts with high performance under visible light irradiation. In this paper, three-dimensional porous La-doped SrTiO3 （LST） micro- spheres were prepared by a modified sol-gel method, in which the agarose gel/SrCO3 microsphere and La2O3 were employed as the template and the La resource, respectively. The as-prepared LST microspheres exhibit a porous structure with a diameter of about 10 μm and a surface pore size of about 100 nm. The La element was doped into the crystal lattice of SrTiO3 by the substitution of La^3＋ for Sr^2＋. Therefore, the absorption edge of LST samples shifts toward the visible light region, and their photocatalytic activity for the Cr（VI） reduction is enhanced under visible light. Among all LST samples, LST-0.5 （the La^3＋ doping content is 0.5 wt-%） exhibited the highest visible-light photocatalytic activity, which can reduce 84% Cr（VI） within 100 rain. This LST materials may become a promising photocatalyst for the facile treatment of waste- water containing poisonous heavy metal ions.

Preparation of PLGA Microspheres with Different Porous Morphologies

Poly（D,L-lactide-co-glycolide）（PLGA） microspheres were prepared by emulsion solvent evaporation method. The influences of inner aqueous phase, organic solvent, PLGA concentration on the morphology of microspheres were studied. The results showed that addition of porogen or surfactants to the inner aqueous phase, types of organic solvents and polymer concentration affected greatly the microsphere morphology. When dichloromethane was adopted as organic solvent, microspheres with porous structure were produced. When ethyl acetate served as organic solvent, two different morphologies were obtained. One was hollow microspheres with thin porous shell under a lower PLGA concentration, another was erythrocyte-like microspheres under a higher PLGA concentration. Three types of microspheres including porous, hollow core with thin porous shell（denoted by hollow in brief） and solid structures were finally selected for in vitro drug release tests. Bovine serum albumin（BSA） was chosen as model drug and encapsulated within the microspheres. The BSA encapsulation efficiency of porous, hollow and solid microspheres was respectively 90.4%, 79.8% and 0. And the ultimate accumulative release was respectively 74.5%, 58.9% and 0. The release rate of porous microspheres was much slower than that of hollow microspheres. The experiment results indicated that microspheres with different porous structures showed great potentials in controlling drug release behavior.

Preparation of Porous Polylactide Microspheres and Their Application in Tissue Engineering

In this study, porous polylactide（PLA） microspheres with different structures were prepared through the multiple emulsion solvent evaporation method. By changing organic solvents（ethyl acetate and chloroform） and adding effervescent salt NH4 HCO3 in the inner water phase, microspheres with porous capsular, matrix, microcapsular and multivesicular structures were prepared. The protein encapsulation and release, and the cell growth behavior of porous microspheres were further explored. Under the same inner water phase, microspheres prepared with chloroform had higher protein encapsulation efficiency and less protein release rate as compared with those prepared with ethyl acetate. Cell experiments showed that the relatively rough surface of microspheres prepared with chloroform was more favorable for the cell growth in comparison with the smooth surface of microspheres prepared with ethyl acetate. This study shows a simple and effective method to control the protein release and cell growth behaviors of polymer microspheres by tuning their porous structure.

Preparation of porous polyimide microspheres by thermal degradation of block copolymers

A new preparation method has been developed for thermally stable porous polyimide microspheres. Porous polyimide microspheres were prepared using trib]ock copolymers that consisted of a thermally stable polyimide derived from pyromellitic dianhydride/4,4＇-oxydianiline as the continuous phase and a thermally labile polyether as the dispersed phase. Spheres of copolymers were generated in a nonaqueous emulsion and then gradually heated to complete the imidization to form a microphase-separated structure. Subsequently, thermal treatment at a slightly reduced pressure removed the labile blocks and produced pores. Under suitable decomposition conditions, the pore size of the porous polyimide was in the range of 200-400nm.

Synergic effects of Cu_xO electron transfer co-catalyst and valence band edge control over TiO_2 for efficient visible-light photocatalysis

Bandgap engineering by doping and co‐catalyst loading are two primary approaches to designing efficient photocatalysts by promoting visible‐light absorption and charge separation,respectively.Shifting of the TiO2conduction band edge is frequently applied to increase visible‐light absorption but also lowers the reductive properties of photo‐excited electrons.Herein,we report a visible‐light‐driven photocatalyst based on valance band edge control induced by oxygen excess defects and modification with a CuxO electron transfer co‐catalyst.The CuxO grafted oxygen‐rich TiO2microspheres were prepared by ultrasonic spray pyrolysis of the peroxotitanate precursor followed by a wet chemical impregnated treatment.We found that oxygen excess defects in TiO2shifted the valence band maximum upward and improved the visible‐light absorption.The CuxO grafted onto the surface acted as a co‐catalyst that efficiently reduced oxygen molecules to active intermediates(i.e.,O2??radial and H2O2),thus consuming the photo‐generated electrons.Consequently,the CuxO grafted oxygen‐rich TiO2microspheres achieved a photocatalytic activity respectively8.6,13.0and11.0as times high as those of oxygen‐rich TiO2,normal TiO2and CuxO grafted TiO2,for degradation of gaseous acetaldehyde under visible‐light irradiation.Our results suggest that high visible‐light photocatalytic efficiency can be achieved by combining oxygen excess defects to improve visible‐light absorption together with a CuxO electron transfer co‐catalyst.These findings provide a new approach to developing efficient heterojunction photocatalysts.

Adipose-derived stem cell/FGF19-loaded microfluidic hydrogel microspheres for synergistic restoration of critical ischemic limb

The efficacy of stem cell therapy is substantially compromised due to low cell survival rate and poor local retention post-delivery. These issues drastically limit the application of stem cells for ischemic limb therapy, which requires effective blood perfusion and skeletal muscle regeneration. Herein, based on microfluidic technology, an integrated stem cell and cytokine co-delivery system designed for functional ischemic limb salvage was constructed by first incorporating the myogenic cytokine, fibroblast growth factor 19 (FGF19), into microspheres composed of methacrylate gelatin (GelMA). Then adipose-derived stem cells (ADSCs) were highly absorbed into the porous structure of the microspheres, overcoming the insufficient loading efficiency and activities by conventional encapsulation strategy. The fabricated ADSCs/FGF19@μsphere system demonstrated a uniform size of about 180 μm and a highly porous structure with pore sizes between 20 and 40 μm. The resultant system allowed high doses of ADSCs to be precisely engrafted in the lesion and to survive, and achieved sustained FGF19 release in the ischemic region to facilitate myoblast recruitment and differentiation and myofibrils growth. Furthermore, the combination of ADSCs and FGF19 exhibited a positive synergistic effect which substantially improved the therapeutic benefit of angiogenesis and myogenesis, both in vitro and in vivo. In summary, a stem cell and cytokine co-delivery system with the properties of easy preparation and minimal invasiveness was designed to ensure highly efficient cell delivery, sustained cytokine release, and ultimately realizes effective treatment of ischemic limb regeneration.