Fabrication of Hydroxyapatite Hollow Microspheres by the Composite‐Hydroxide Approach

Hydroxyapatite (HAp) hollow microspheres with hierarchically porous structure and nanorice‐like architecture units were synthesized by the composite‐hydroxide approach. NH₄H₂PO₄ was first reacted with hydroxides to form a hydroxide‐insoluble M₃PO₄ (the term M represents either Na or K). The diffusing M₃PO₄ at the liquid–solid interface then reacted with the Ca(OH)₂, forming insoluble HAp hollow spheres by Kirkendall process. Results show that when reaction time is increased from 3 to 12 h, the average diameter of the microspheres increased from 2.64 to 4.16 μm. In addition, the size homogeneity of the hollow microspheres was improved gradually due to Ostwald ripening. The prepared hollow microspheres were treated by ultrasound, and nanorice‐like component units with a large mass of mesopores (<10 nm) were displayed. These prepared HAp hollow microspheres might be expected to apply to ion adsorption and drug delivery.     

The Role of MgAl2O4 Powder Packing on Phase Stability of Hydroxyapatite During Sintering

MgAl₂O₄ (spinel) was utilized as a packing powder in the sintering of hydroxyapatite (HAp) and the composite of HAp/3 mol% Y₂O₃‐stabilized tetragonal zirconia (3Y‐TZP). The influence of spinel on phase stability of HAp was investigated using X‐ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy, and electron probe microanalysis (EPMA) to reveal the reaction in the vicinity of the interface between HAp and spinel. When covered with spinel powder, decomposition temperatures for both HAp monolith and HAp in the composite were raised from 1360°C to 1470°C and from 930°C to 1280°C, respectively. SEM images supported the role of spinel on retardation of the decomposition, showing a dense cross section of the monolith after sintering for 2 h at 1400°C with the spinel as opposed to a porous feature without the covering. XRD results indicated that the increase in the decomposition temperatures was accompanied by a decrease in the a‐axis dimension of the hexagonal structure of HAp, probably as a result of the substitution of F^? for OH^?. EPMA revealed that negligible reaction occurred between HAp and spinel even at 1500°C, but the Ca²⁺ in HAp diffused about 20 μm into 3Y‐TZP to form a cubic zirconia solid solution at 1275°C, resulting in the decomposition. The involvement of F^? ion in the contraction of a‐axis parameter and the consequent phase stability were manifested by an increase in the Raman band of the symmetric stretching of the P–O bonds at 962.3 cm^?1 and the appearance of a band for fluoroapatite at 3538 cm^?1.     

Chitosan and chitosan/β‐cyclodextrin microspheres as sustained‐release drug carriers

The main aim of this study was to compare two microspheres, chitosan (CTS) and CTS/β‐cyclodextrin (β‐CD), made by spray‐drying, as pulmonary sustained drug‐delivery carriers. Theophylline (TH) was used as a model drug. The characteristics of the microspheres and in vitro release were studied. The yield of CTS/β‐CD microspheres was 46.1%, which was higher than that of the CTS microspheres (36.5%). The drug loads of the CTS and CTS/β‐CD microspheres were 22.7 and 21.1%, respectively, whereas the encapsulation efficiencies were 90.7 and 91.4%, respectively. The distribution of 50% [(diameter) d (0.5)] of the CTS microspheres was below 6.49 μm and that of the CTS/β‐CD microspheres was below 4.90 μm. Scanning electron microscopy showed that both microspheres yielded a spherical shape with smooth or wrinkled surfaces. Fourier transform infrared spectroscopy demonstrated that the carbonyl group of TH formed hydrogen bonds with the amide group of CTS and the hydroxyl group of β‐CD. The swelling ability of the two microspheres was more than three times their weight, and their humidity rates attained equilibrium within 24 h. The ciliary beat movement times of CTS and CTS/β‐CD microspheres were 493.00 and 512.33 min, respectively, which indicated that the two microspheres effectively reduced the ciliotoxicity and possessed better adaptability. In vitro release of TH from CTS/β‐CD microspheres was slower than that from CTS microspheres at pH 6.8 and provided a sustained release of 72.0% within 12 h. The results suggest that CTS/β‐CD microspheres are a promising carrier for sustained release for pulmonary delivery. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1183–1190, 2007     

Mineralization of hydroxyapatite crystallites on zein microspheres

Bioinspired mineralization process has been extended to the formation of bonelike hydroxyapatite (HAp) coatings on biodegradable polymer substrates. HAp‐coated zein microspheres were prepared through phase separation procedure, followed by incubation in modified simulated body fluids (mSBF). The morphologies of mineralized zein microspheres with different diameters and incubation time were investigated by scanning electron microscopy (SEM). The nature of the deposited mineral phase was characterized by energy‐dispersive spectroscopy (EDS) and wide‐angle X‐ray diffraction (XRD). The results showed that as the average diameter of zein microspheres increased to 1.13 μm, randomly oriented minerals were observed on the surface of microspheres. Two characteristic HAp diffraction reflections 002 and 211 centered at 2θ of 25.6° and 32.0° were ascertained on the XRD patterns of the mineralized microspheres. Incubation of zein microspheres with larger diameters in mSBF led to nucleation and growth of minerals on the surface. Even larger number of minerals were deposited and a porous structure of platelike HAp crystals was obtained after incubation for 21 days. The novel zein/HAp microspheres may have a wide variety of potential applications in bone regeneration and tissue engineering. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Eggshell derived hydroxyapatite microspheres for chromatographic applications by a novel dissolution - precipitation method

Hydroxyapatite ((Ca₁₀(PO₄)₆(OH)₂, HAp) based chromatography matrix has attracted great interest in the field of protein separation. However, researchers have been trying to combat the growing costs associated with the HAp matrix. In the present investigation, we utilized a cheap biological waste material, viz. eggshells, for the development of hydroxyapatite (HAp) resins and evaluated them for protein purification. Initially, the calcite of the eggshell carbonate was converted into metastable vaterite microspheres. The HAp microspheres (ECHAp) were then prepared from eggshell carbonate microspheres using a novel dissolution-precipitation process. Synthetic source calcium carbonate was also used to prepare HAp microspheres (CHAp) for comparison. The purity and morphology of the apatite microspheres were characterized using X-ray diffraction (XRD) method, Fourier Transform Infrared spectroscopy (FTIR), Scanning Electron Microscopy (SEM), and laser diffraction particle analysis. Although both the apatites have similar morphology, the ECHAp has a larger surface area of 33.8 m² g^?1 compared to CHAp of 17.27 m² g^?1 by surface area analysis method. A commercial HAp matrix (CHT) with similar properties was also studied for comparison. All the apatite microspheres were found to have a similar protein binding capacity for bovine serum albumin (BSA). But ECHAp showed better protein separation for BSA and lysozyme mixture compared to CHAp and CHT matrices. The ECHAp matrix was also found to be highly stable over 20 purification cycles. Hence, the eggshell waste seems to have the potential for HAp matrix by a novel carbonate route with ease of preparation and also an economical packing material for chromatographic purification of biomolecules.     

Fabrication and structural regulation of PLLA porous microspheres via phase inversion emulsion and thermally induced phase separation techniques

In this work, a facile, scalable technique was developed to produce biodegradable porous microspheres by combining an oil‐in‐oil (O/O) surfactant‐free phase inversion emulsion technique with thermally induced phase separation (TIPS) method. The effects of PLLA concentration, stirring speed, macromolecule weight, and organic solvents on the size and microstructure of microspheres were investigated by scanning electron microscopy (SEM). The results revealed a highly porous structured microsphere with controllable sizes and morphologies by tuning the synthesis conditions. The typical resulting PLLA microspheres consist of nanoscale topographic structured surface and highly microporous interior. The coarse nanotopography and microcellular inner structure lead to a high drug loading capacity up to 60% for the PLLA microspheres from THF. The cumulative release percentage of the ibuprofen could reach 80% for drug‐loaded microspheres with different microstructures. The fabricated PLLA microspheres would have potential applications in the field of drug delivery and tissue engineering. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44885.     

Temperature-Sensitive Microspheres for Controlled Release of Enalprilmaleate

Poly(N′-isopropylacrylamide-co–methacryl amide) has been prepared by free-radical emulsion polymerization. The copolymer was transformed into thermoresponsive microspheres by chemical crosslinking with N′, N′ Methylenebis-acrylamide (NNMBA). Enalpril maleate (ENAM), an anti-hypertensive drug, was successfully loaded into these microspheres during in-situ polymerization. DSC and X-RD analysis of the drug-loaded and plain microspheres have confirmed partial dispersion of ENAM in the microspheres. SEM confirmed the spherical nature of the particles with a mean particle size of 100 µm. Drug release profiles of these microspheres exhibited a prolonged release of ENAM for more than 12 h.     

Synthesis and characterisation of gelatin–nano hydroxyapatite composite scaffolds for bone tissue engineering

Abstract

Gelatin–hydroxyapatite (HAp) nanocomposites have been prepared by particulate leaching technique using glutaraldehyde (GTA) as cross-linking agent for polymer. The porosity in the scaffolds was controlled using sodium chloride as porogen agent. Microstructural investigation by scanning electron microscopy (SEM), revealed the formation of a well interconnected porous scaffold with pore size in the range of 100–200 μm. X-ray diffraction and Fourier transform infrared spectroscopy were used to confirm the formation of crystalline HAp as well the presence of both constituents in the composite samples. The bioactivity of the samples was evaluated by conducting MTT (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide) assay and cell adhesion tests. The results suggest that the use of GTA in excess of 0˙25% can be detrimental to cell survival. Cell attachment on the nanocomposite scaffold was verified by microscopic analysis.     

Advanced antistatic/anticorrosion coatings prepared from polystyrene composites incorporating dodecylbenzenesulfonic acid‐doped SiO2@polyaniline core–shell microspheres

We present the preparation of advanced antistatic and anticorrosion coatings of polystyrene (PS) incorporating a suitable amount of dodecylbenzenesulfonic acid (DBSA)‐doped SiO₂@polyaniline (SP) core–shell microspheres. First, aniline‐anchored SiO₂ (AS) microspheres that were about 850 nm in diameter were synthesized using the conventional base‐catalyzed sol–gel process with tetraethyl orthosilicate in the presence of N‐[3‐(trimethoxysilyl)propyl]aniline. SP core–shell microspheres were then synthesized by chemical oxidative polymerization of aniline monomers with ammonium persulfate as an oxidizing agent in the presence of the AS microspheres. The polyaniline shell thickness of the as‐prepared core–shell microspheres was estimated to be about 120 nm. The AS and SP microspheres were further characterized using Fourier transform infrared spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy. The as‐synthesized DBSA‐doped SP core–shell microspheres were then blended into PS using N‐methyl‐2‐pyrrolidone as solvent and then cast onto a cold–rolled steel (CRS) electrode to obtain antistatic and anticorrosion coatings with a thickness of about 10 µm. The corrosion protection efficiency of the as‐prepared coating materials on the CRS electrode was investigated using a series of systematic electrochemical measurements under saline conditions. The enhanced corrosion protection ability of the PS/SP composite coatings may be attributed to the formation of a dense passive metal oxide layer induced by the redox catalytic effect of the polyaniline shell of the as‐synthesized core–shell microspheres, as evidenced by electron spectroscopy for chemical analysis and SEM observations. Moreover, the PS composite coating containing 10 wt% of the SP core–shell microspheres showed an electrical resistance of about 3.65 × 10⁹Ω cm^?2, which meets the requirements for antistatic applications. Copyright © 2012 Society of Chemical Industry     

Polyoxymethylene‐homopolymer/hydroxyapatite nanocomposites for biomedical applications

In this article, new polyoxymethylene (POM)/hydroxyapatite (HAp) nanocomposites for bone long‐term implants have been obtained and characterized by using FTIR, WAXD, SEM, TG, DSC, tensile tests, and in vitro evaluation. Characteristic bands both for extended chain crystals (ECC) and folded chain crystals (FCC) were observed in FTIR profiles for both pure POM and POM in POM/HAp nanocomposites. From WAXD analysis it has been found that the addition of HAp does not change the hexagonal system of POM in POM/HAp nanocomposites. Moreover, degree of crystallinity of POM increases with an increase of HAp content up to 1.0% and next decreases with an increase HAp content. It indicates that HAp nanoparticles up to 1.0% content act as effective nucleating sites. Mechanical tests revealed that Young's modulus increases, whereby, elongation at break and tensile strength decrease with increasing hydroxyapatite concentration. Results of in vitro investigations show that an increase of HAp content in POM nanocomposites facilitates formation of apatite layer on the sample surface and improves in vitro stability POM/HAp nanocomposites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of supercritical CO2 on three‐dimensional colloid arrays of PS‐MA–EGDMA

Using emulsifier‐free emulsion polymerization method, monodispersed crosslinked poly(styrene‐co‐methacrylic acid‐co‐ethylene glycol dimethacrylate) colloid microspheres were synthesized. The microspheres were treated in supercritical carbon dioxide (SCCO₂) after they have self‐assembled into ordered three‐dimensional (3D) colloid arrays. The CO₂ absorbed into the polymer microspheres enhances chain segments mobility and reduces the glass transition temperature (T_g) of polymer, which induce the microspheres coalesce at the relatively low temperature. The coalescence degree of microspheres was studied by varying the experimental temperature, pressure, and exposure time in SCCO₂. The results were shown by scanning electron microscopy (SEM). Further, the lattice spacing of the assembled 3D colloid microspheres was calculated from the SEM images. It was illustrated that the coalescence degree enhanced with the increase of CO₂ pressure; however, this tendency became weak when CO₂ pressure reached a certain value. Extending exposure time in SCCO₂ or elevating temperature can also increase coalescence degree, and the effect of temperature is more significant. It is believed that these results will make sense when the polymer microspheres are considered to be used as templates in SCCO₂; meanwhile, it raises a new method about tuning the final morphology of the stabilized colloidal crystals and porous materials via controlling the coalescence degree with the assistance of SCCO₂. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The single-step synthesis of thiol-functionalized phosphazene-based polymeric microspheres as drug carrier

ABSTRACT

Herein, new microspheres were successfully fabricated from pentaerythritol tetrakis(3-mercaptopropionate) as model monomer and hexachlorocyclotriphosphazene as crosslinker using a single-step via precipitation polymerization method. Trimethoprim was chosen as the model antibiotic drug for drug release and antimicrobial activity studies. The percent of drug loading and drug entrapment efficiency of the microspheres was calculated to be 0.85% and 42.2%. According to correlation coefficients, the release kinetic was found to be Higuchi kinetic model and the release mechanism was non-Fickian model for microspheres. The drug-loaded microspheres exhibited excellent bacterial inhibition against gram-positive (Staphylococcus aureus and Bacillus subtilis) and gram-negative (Escherichia coli) bacteria.     

Preparation and evaluation of cellulose acetate butyrate and poly(ethylene oxide) blend microspheres for gastroretentive floating delivery of repaglinide

In this study, hollow microspheres of cellulose acetate butyrate (CAB) and poly(ethylene oxide) (PEO) were prepared by emulsion–solvent evaporation method. Repaglinide was successfully encapsulated into floating microspheres. Various formulations were prepared by varying the ratio of CAB and PEO, drug loading and concentration of poly(vinyl alcohol) (PVA) solution. Encapsulation of the drug up to 95% was achieved. The microspheres tend to float over the simulated gastric media for more than 10 h. The micromeritic properties of microspheres reveal the excellent flow and good packing properties. The % buoyancy of microspheres was found to be up to 87. SEM showed that microspheres have many pores on their surfaces. Particle size ranges from 159 to 601 μm. DSC and X‐RD revealed the amorphous dispersion in the polymer matrix. In vitro release experiments were performed in simulated gastric fluid. In vitro release studies indicated the dependence of release rate on the extent of drug loading and the amount of PEO in the microspheres; slow release was extended up to 12 h. The release data were fitted to an empirical equation to compute the diffusional exponent (n), which indicated that the release mechanism followed the non‐Fickian trend. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Nano‐hydroxyapatite (HAp) and hydroxyapatite/platinum (HAp/Pt) core shell nanorods: Development,structural study,and their catalytic activity

The development of a new kind of material that is a nanostructured catalytic material with an environmentally benign nature that can be used for alternative energy has acquired significance in recent years. In this context, the use of heterogeneous catalysts for the transesterification of vegetable oils has gained prominence due to their eco‐friendly and reusable nature. Hence in the present study, pure hydroxyapatite (HAp) and hydroxyapatite/platinum (HAp/Pt) nanostructured particles have been prepared successfully through a facile chemical method without templates and surfactants and their catalytic activity investigated for transesterification of natural vegetable oil to bioenergy (biodiesel). The textural and structural features of pure HAp and HAp/Pt were investigated using various characterization techniques such as x‐ray diffraction, Fourier transform infrared (FTIR) and Raman spectroscopy, field emission scanning electron microscopy (FESEM), and transmission electron microscopy (TEM). The elements present in the prepared nanostructures were confirmed through energy dispersive spectroscopy (EDS) and x‐ray photoelectron spectroscopy (XPS) techniques. The XPS analysis also confirms the metallic nature of the platinum in HAp/Pt. The specific surface area and porous nature of the prepared nanostructured catalysts were studied using the N₂ physisorption Brunauer‐Emmett‐Teller‐Barrett‐Joyner‐Halenda (BET‐BJH) method. The catalytic activity of the pure HAp nanoparticles and HAp/Pt core shell nanorods with the Simarouba glauca plant seed oil was investigated. The obtained results indicate that the pristine HAp nanoparticles and HAp/Pt core shell nanorods (NRs) show 91.4% and 87.1% fatty acid methyl ester (FAME) conversion, respectively, potentially offering environmental benign biocatalysts for biofuel production from natural feed stock.     

Structural and biological properties of novel Vanadium and Strontium co-doped HAp for tissue engineering applications

The development of novel bioactive materials with improved physical and biological properties is crucial for advancing tissue engineering applications. In this study, we synthesized a Vanadium and Strontium co-doped hydroxyapatite (V–Sr:HAp) nanoparticle intending to enhance the performance of pure HAp. The V–Sr:HAp nanoparticles were synthesized using a microwave-assisted reflux condensation method, and their structural and chemical characteristics were investigated using X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). The morphology and elemental composition of the nanoparticles were examined through scanning electron microscopy (SEM) and energy-dispersive X-ray analysis (EDX). The XRD analysis confirmed the presence of characteristic peaks of HAp in each sample. SEM images revealed well-connected and highly agglomerated small sphere-like morphology in both pure HAp and V–Sr:HAp nanoparticles. The Vickers hardness test demonstrated the improved mechanical strength in V–Sr:HAp compared to pure HAp. Antibacterial efficacy was evaluated using an agar diffusion test, which showed enhanced antibacterial activity in the co-doped HAp samples against S. aureus and P. aeruginosa. Moreover, the Ca–P deposition rate on the surface of the co-doped HAp samples during biomineralization was higher. Hemolysis assay results have indicated compatibility of both pure HAp and V–Sr:HAp with human blood (<5% lysis). The results of cell viability tests demonstrate that the V and Sr co-doped HAp samples do not exhibit any cytotoxic effects and instead promote cell proliferation. Overall, the incorporation of V and Sr metal ions into HAp presents a promising bio-functional tool for tissue engineering applications, offering improved mechanical and antibacterial properties.     

Composition,structure and mechanical properties of the titanium surface after induction heat treatment followed by modification with hydroxyapatite nanoparticles

Coatings of titania (TiO₂) and "titania–hydroxyapatite" were prepared by oxidation of commercially pure titanium VT1-00 using induction heat treatment (IHT), followed by modification with colloidal hydroxyapatite (HAp) nanoparticles. The IHT treatment was performed at temperatures within 600–1200 °C for 300 s. According to the results of scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive X-ray fluorescent analysis (EDX), nanoindentation and in vitro testing, titania coatings of high morphological heterogeneity, and high mechanical properties and biocompatibility were formed on the titanium surface after IHT. The coatings were found to consist of nano- and submicron crystals of oval, needle-like, plate and prismatic shapes. A subsequent modification with HAp nanoparticles of the coated titanium substrate leads to accelerated formation of mechanically strong oxidebioceramic composite coatings. It was established that the porous oxide coatings modified with nanoparticles of HAp that were formed at temperatures from 800 to 1000 °C and holding for at least 30 s had a high biocompatibility.     

Europium-doped amorphous calcium phosphate porous nanospheres: preparation and application as luminescent drug carriers

Calcium phosphate is the most important inorganic constituent of biological tissues, and synthetic calcium phosphate has been widely used as biomaterials. In this study, a facile method has been developed for the fabrication of amorphous calcium phosphate (ACP)/polylactide-block-monomethoxy(polyethyleneglycol) hybrid nanoparticles and ACP porous nanospheres. Europium-doping is performed to enable photoluminescence (PL) function of ACP porous nanospheres. A high specific surface area of the europium-doped ACP (Eu³⁺:ACP) porous nanospheres is achieved (126.7 m²/g). PL properties of Eu³⁺:ACP porous nanospheres are investigated, and the most intense peak at 612 nm is observed at 5 mol% Eu³⁺ doping. In vitro cytotoxicity experiments indicate that the as-prepared Eu³⁺:ACP porous nanospheres are biocompatible. In vitro drug release experiments indicate that the ibuprofen-loaded Eu³⁺:ACP porous nanospheres show a slow and sustained drug release in simulated body fluid. We have found that the cumulative amount of released drug has a linear relationship with the natural logarithm of release time (ln(t)). The Eu³⁺:ACP porous nanospheres are bioactive, and can transform to hydroxyapatite during drug release. The PL properties of drug-loaded nanocarriers before and after drug release are also investigated.     

Fabrication,drug delivery kinetics and cell viability assay of PLGA-coated vancomycin-loaded silicate porous microspheres

Porous ceramic microspheres are a desirable substance for bone tissue reconstruction and delivery applications. This study focuses on Mg–Ca silicate microspheres encapsulated in biodegradable poly (lactic-co-glycolic acid) (PLGA) to serve as a biocompatible carrier for the controlled release of vancomycin hydrochloride. In this regard, diopside (MgCaSi₂O₆), bredigite (MgCa₇Si₄O₁₆), and akermanite (MgCa₂Si₂O₇) powders were synthesized by sol-gel and subsequent calcination methods. Then, porous akermanite, diopside and bredigite microspheres of 700–1000 μm in diameter were fabricated by using carbon porogen, droplet extrusion and sintering, then loaded with the drug and eventually coated with PLGA. The bare microspheres showed a considerable burst release mode of the drug into a physiological medium, whereas PLGA coating of the microspheres reduced the burst release level. To investigate effective mechanisms governing in the drug release from the carriers, the contribution of burst, degradation, and diffusion was analyzed by the sequential quadratic programming algorithm method. It was found that the relative contribution of diffusion to bioresorption is ranked as diopside > akermanite > bredigite, whereas PLGA coating dominates the diffusion mechanism. The dental pulp stem cells cytocompatibility MTT assay of the microspheres also showed that the drug loading deteriorates but PLGA coating improves the cell biocompatibility significantly. Comparatively, the biocompatibility of the PLGA-coated microspheres was ranked as akermanite > diopside > bredigite, as a result of a compromise between the release of the constituting ions of the ceramic carriers and vancomycin molecules. It was eventually concluded that PLGA-coated Mg–Ca silicate microspheres are promising candidates for drug-delivery bone tissue engineering and dental bone grafting applications.     

Synthesis,characterization, and drug‐release behavior of amphiphilic quaternary ammonium chitosan derivatives

A new type of amphiphilic quaternary ammonium chitosan derivative, 2‐N‐carboxymethyl‐6‐O‐diethylaminoethyl chitosan (DEAE–CMC), was synthesized through a two‐step Schiff base reaction process and applied to drug delivery. In the first step, benzaldehyde was used as a protective agent for the incorporation of diethylaminoethyl groups to form the intermediate (6‐O‐diethylaminoethyl chitosan). On the other hand, NaBH₄ was used as a reducing agent to reduce the Schiff base, which was generated by glyoxylic acid, for the further incorporation of carboxymethyl groups to produce DEAE–CMC. The structure, thermal properties, surface morphology, and diameter distribution of the resulting chitosan graft copolymers were characterized by Fourier transform infrared spectroscopy, ¹H‐NMR, thermogravimetric analysis, differential scanning calorimetry, X‐ray powder diffraction, scanning electron microscopy, and laser particle size analysis. Benefiting from the amphiphilic structure, DEAE–CMC was able to be formed into microspheres in aqueous solution with an average diameter of 4.52 ± 1.21 μm. An in vitro evaluation of these microspheres demonstrated their efficient controlled release behavior of a drug. The accumulated release ratio of vitamin B₁₂ loaded DEAE–CMC microspheres were up to 93%, and the duration was up to 15 h. The grafted polymers of DEAE–CMC were found to be blood‐compatible, and no cytotoxic effect was shown in human SiHa cells in an MTT [3‐(4, 5‐dimethyl‐thiazol‐2‐yl)‐2, 5‐diphenyltetrazolium bromide] cytotoxicity assay. These results indicate that the DEAE–CMC microspheres could be used as safe, promising drug‐delivery systems. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39890.     

Preparation of porous and hollow Mn2O3 microspheres and their adsorption studies on heavy metal ions from aqueous solutions

Mn₂O₃ microspheres are prepared and used as adsorbent for removal of heavy metal ions. Morphology and structure of Mn₂O₃ microspheres are analyzed by SEM, TEM, XRD, XPS and N₂ sorption technique. Effects of adsorbent concentration, ion concentration and agitation time on adsorption behavior are investigated. Adsorption isotherm and kinetics are also studied. The results show Mn₂O₃ microspheres have well-developed porous and hollow structure, demonstrating good potential on removal of heavy metal ions. Adsorption data fit better with Freundlich isotherms than Langmuir isotherms. Kinetic studies indicate adsorption behavior is described by pseudo-second-order kinetic model, and intra-particle diffusion plays a significant role.