Preparation and characterization of novel semi‐interpenetrating 2‐hydroxyethyl methacrylate‐g‐chitosan copolymeric microspheres for sustained release of indomethacin

A novel semi‐interpenetrating (semi‐IPN) graft copolymer of 2‐hydroxyethyl methacrylate (HEMA) with chitosan (CS) has been prepared in the form of microspheres, using water‐in‐oil (W/O) emulsion technique. Microspheres were characterized by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and X‐ray diffractometry (X‐RD) to confirm the crosslinking and polymorphism of indomethacin (IDM). The X‐RD and DSC techniques indicated a molecular‐level dispersion of IDM in the IPN matrix. Scanning electron micrographs (SEM) taken at the cross section of the microspheres have shown rough surfaces around the microspheres. The sustained release characteristics of the matrices for IDM, an anti‐inflammatory drug, were investigated in pH 7.4 media. Particle size and size distribution of the microspheres were studied by laser light diffraction particle size analyzer. The drug was released in a sustained manner for up to 12 h. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Preparation and characterization of chitosan–zeolite composites

Double crosslinked chitosan–zeolite (CZ-2) and noncrosslinked chitosan–zeolite (CZ-0) composites were prepared and characterized by using Fourier transform infrared (FTIR) spectrometer, surface area analyzer, scanning electron microscope coupled with energy dispersive X-ray (SEM-EDX) spectrometer, thermogravimetric analyzer (TGA), X-ray diffraction analyzer (XRD) and carbon, hydrogen, nitrogen (CHN) analyzer. After crosslinking, CZ-2 showed a reduction in surface area and CHN content in comparison to chitosan, zeolite, and CZ-0. Crosslinking resulted in improved stability of CZ-2 in distilled water, acetic acid and NaOH as CZ-2 recorded the lowest percentage of swelling. XRD diffractograms confirmed the formation of composites as there was a marked difference in the peak intensity at 2θ = 19.8°. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Swelling characterizations of chitosan and polyacrylonitrile semi‐interpenetrating polymer network hydrogels

Temperature‐ and pH‐responsive semi‐interpenetrating polymer network (semi‐IPN) hydrogels constructed with chitosan and polyacrylonitrile (PAN) were studied. The characterizations of semi‐IPN hydrogels were investigated using Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). IPN hydrogels exhibited a relatively high swelling ratio, 23.31%–145.20% at room temperature. The swelling ratio of hydrogels depends on pH and temperature. DSC was used to determine the amount of free water in IPN hydrogels. The amount of free water increased with increasing chitosan content in the semi‐IPN hydrogels. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2011–2015, 2003     

Synthesis and swelling properties of pH‐sensitive hydrogels based on chitosan and poly(methacrylic acid) semi‐interpenetrating polymer network

A novel semi‐interpenetrating polymer network (semi‐IPN) hydrogel composed of chitosan and poly(methacrylic acid) was synthesized using formaldehyde as a crosslinker. The amount of crosslinker was searched and optimized. The structure of the hydogel was investigated by Fourier transform infrared (FTIR) spectroscopy. The spectrum shows that a structure of polyelectrolyte complex exists in the hydrogel. The effects of pH, ionic strength, and inorganic salt on the swelling behaviors of the hydrogel were studied. The results indicate the hydrogel has excellent pH sensitivity in the range of pH 1.40 to 4.50, pH reversible response between pH 1.80 and 6.80, and ionic strength reversible response between ionic strength 0.2 and 2.0M. The results also show that the hydrogel has a bit higher swelling capacity in a mix solution of calcium chloride (CaCl₂) and hydrochloric acid (HCl) solution than in a mix solution of sodium chloride (NaCl) and HCl. These results were further confirmed through morphological change measured by scanning electron microscope (SEM). © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1720–1726, 2005     

Preparation,characterization, and drug‐release properties of pH/temperature‐responsive poly(N‐isopropylacrylamide)/chitosan semi‐IPN hydrogel particles

Novel poly(N‐isopropylacrylamide) (PNIPAAm)/chitosan (CS) semi‐interpenetrating polymer network hydrogel particles were prepared by inverse suspension polymerization. The prepared particles were sensitive to both temperature and pH, and they had good reversibility in solution at different temperatures and pH values. The swelling ratios of PNIPAAm/CS hydrogel particles decreased slightly with the addition of CS, which did not shift the lower critical solution temperature. The drug‐release behavior of the particles was investigated using cyclic adenosine 3′,5′‐monophosphate (cAMP) as a model drug. The release of cAMP from the hydrogel particles was affected by temperature, pH, and the CS content in the particles. These results showed that semi‐IPN hydrogel particles appeared to be of great promise in pH‐ and temperature‐sensitive oral drug release. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of semi‐interpenetrating networks based on poly(dimethylsiloxane) and poly(vinyl alcohol)

Semi‐interpenetrating networks (Semi‐IPNs) with different compositions were prepared from poly(dimethylsiloxane) (PDMS), tetraethylorthosilicate (TEOS), and poly(vinyl alcohol) (PVA) by the sol‐gel process in this study. The characterization of the PDMS/PVA semi‐IPN was carried out using Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and swelling measurements. The presence of PVA domains dispersed in the PDMS network disrupted the network and allowed PDMS to crystallize, as observed by the crystallization and melting peaks in the DSC analyses. Because of the presence of hydrophilic (? OH) and hydrophobic (Si? (CH₃)₂) domains, there was an appropriate hydrophylic/hydrophobic balance in the semi‐IPNs prepared, which led to a maximum equilibrium water content of ～ 14 wt % without a loss in the ability to swell less polar solvents. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

AZF工艺与高塔熔体造粒工艺生产尿基复合肥的优缺点

介绍AZF工艺与高塔熔体造粒工艺生产复合肥的过程,从原料调节控制、成本、产品养分等方面进行了比较,认为高塔熔体工艺综合成本较高,新建高塔熔体复合肥项目应慎重。     

Preparation and characterization of poly(ethylene glycol) crosslinked chitosan films

Poly(ethylene glycol) (PEG) crosslinked chitosan films with various PEG to chitosan ratio and PEG molecular weight were successfully prepared via the epoxy‐amine reaction between chitosan and PEG‐epoxy. The thermal and mechanical properties and swelling behavior were studied for the PEG crosslinked chitosan films. The mechanical strength of chitosan films were greatly enforced by the introduction of PEG‐epoxy, achieving an elongation of about 80%. It was found that the crosslinked chitosan films form hydrogel in water, achieving a swelling ratio higher than 20 times of original weight. The swelling behavior of chitosan films relied greatly on the molecular weight of the crosslinker PEG‐epoxy and the weight percent of PEG‐epoxy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Preparation and Swelling Study of a pH-Dependent Interpolymeric Hydrogel Based on Chitosan for Controlled Drug Release

Novel pH-dependent, biodegradable interpolymeric network (IPN) hydrogels were prepared for controlled drug release investigations. The IPN hydrogels were prepared by irradiation of solutions of N-acryloyglycine (NAGly), polyethylene glycol diacrylate (PEGDA) mixed with chitosan, in the presence of a lower amount of glutaraldehyde as the crosslinker and using 2,2-dimethoxy-2-phenyl acetophenone as the photo-initiator. The equilibrium swelling studies were carried out for the gels at 37°C in buffer solutions of pH 2.1 and 7.4 (simulated gastric and intestinal fluids, respectively). 5-Fluorouracil (5-FU) was entrapped, as a model therapeutic agent, in the hydrogels and equilibrium-swelling studies were carried out for the drug-entrapped gels at 37°C. The in-vitro release profiles of the drug were established at 37°C in pH 2.1 and 7.4.     

Coupled reaction and solvent extraction process to form Li2CO3: Mechanism and product characterization

A coupled reaction and solvent extraction process to produce Li₂CO₃ from LiCl and CO₂ is proposed. The aqueous reaction occurs with difficulty and is not spontaneous at 298 K. To ensure the continuous reaction between LiCl and CO₂ to produce Li₂CO₃, it is necessary to remove HCl. Experiments conducted in an open reactor at room‐temperature showed that the product sample was pure Li₂CO₃ with a particle‐size distribution in two regions and a larger number of small crystals. The large and small crystals were obtained by radial growth in the free aqueous phase and in water‐in‐oil structures with growth space constraints, respectively. Factors influencing the particle‐size distribution and Li₂CO₃ morphology were investigated. A short reaction time, large phase ratio (O/A), low–temperature, and surfactant addition (TritonX‐100) can increase the number of small particle crystals and reduce the number and volume of large particle crystals. © 2013 American Institute of Chemical Engineers AIChE J, 60: 282–288, 2014     

Effect of cationic surfactant on homogenization and polymerization of methyl methacrylate miniemulsion modified by chitosan

Homogenization of monomer droplets and polymerization of methyl methacrylate (MMA) miniemulsion, stabilized by a combination of cationic surfactants including different amounts of n‐hexadecyltrimethylammonium chloride (HTMA) and chitosan 100, were investigated. With increasing HTMA concentration or decreasing concentration of chitosan 100, the required ultrasonication time for the miniemulsion to reach a critically stabilized state is reduced. After polymerization, for higher HTMA concentrations, droplet nucleation dominates because of higher surface coverage of HTMA on the droplets. However, for lower HTMA concentrations, the size distributions (SDs) of final latex particles are different from those of the droplets. Because surface coverage of HTMA on the droplets is lower in this condition, both droplet nucleation and homogeneous and/or micellar nucleation occur simultaneously in the miniemulsion polymerization. On increasing the concentration of chitosan 100 in the system, the SD of the final latex particles is far different from that of the droplets. This is due to a decrease of the effective surface coverage of chitosan 100 and HTMA on the droplets. Consequently, the opportunity of collision coalescence of the droplets increases, and MMA molecules can diffuse out more easily into the aqueous phase. Droplet nucleation is, therefore, no longer the major source for the latex particles. Copyright © 2006 Society of Chemical Industry     

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     

Semi‐interpenetrating polymer network hydrogels based on aspen hemicellulose and chitosan: Effect of crosslinking sequence on hydrogel properties

Semi‐interpenetrating network hydrogel films were prepared using hemicellulose and chemically crosslinked chitosan. Hemicellulose was extracted from aspen by using a novel alkaline treatment and characterized by HPSEC, and consisted of a mixture of high and low molecular weight polymeric fractions. HPLC analysis of the acid hydrolysate of the hemicellulose showed that its major constituent sugar was xylose. X‐ray analysis showed that the relative crystallinity of hydrogels increased with increasing hemicellulose content up to 31.3%. Strong intermolecular interactions between chitosan and hemicellulose were evidenced by FT‐IR analysis. Quantitative analysis of free amino groups showed that hemicellulose could interrupt the chemical crosslinking of chitosan macromolecules. Mechanical testing and swelling experiments were used to define the effective network crosslink density and average molecular weight between crosslinks. Swelling ratios increased with increasing hemicellulose content and mainly consisted of H‐bonded bound water. Results revealed that by altering the hydrogel preparation steps and hemicellulose content, crosslink density and swelling behavior of semi‐IPN hydrogels could be controlled without deteriorating their mechanical properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

高塔复合肥加强冷却、筛分与粉尘回收的综合技术

介绍一套高塔复合肥装置加强冷却、筛分与粉尘回收的综合技术，可有效解决高塔复合肥生产中存在的产品热结块、易粉化以及工作环境粉尘大等问题。     

Rheological characterization of chitosan matrices: Influence of biopolymer concentration

Viscoelastic properties of chitosan (CH), chitosan‐poly(ethylene glycol) 400 (CH‐PEG), and chitosan‐poly(ethylene glycol) 400 with glyoxal as crosslinking agent (CH‐PEG‐Gly) systems were studied to analyze the effect of chitosan concentration (from 0.83 to 1.67%). Dynamic moduli increase as chitosan concentration increases for all systems. For CH and CH‐PEG systems the loss modulus (G″) is greater than the storage modulus (G′) with predominance of the viscous over the elastic behavior. This corresponds to the characteristic behavior of solutions (nonstructured systems). The presence of PEG 400 induces a complementary reinforcement of the mechanical properties of the system. Except for the lowest chitosan concentration, when glyoxal was added to the CH‐PEG systems, a gelled matrix was obtained. In this case, G′ is greater than G″, and practically independent of frequency. This behavior is typical of three‐dimensional networks and indicates true gel formation, showing clear elastic behavior (tan δ < 1). In creep and recovery analysis, CH‐PEG‐Gly systems exhibited distinct regions that were mathematically modeled using Burger's model. This analysis shows that the CH‐PEG‐Gly matrices (from 1.25 to 1.67%) recover almost totally (100%). Therefore, these matrices could be useful as systems for the development of films for topical hydrophilic drug delivery, and the levels of the residual viscosity (η₀) or the complex viscosity (η*) could be used to control drug release. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

对乙酰氨基苯甲酰壳聚糖的制备和应用性能研究

在乙酸体系中,通过对乙酰氨基苯甲酰氯与壳聚糖在超声波振荡下反应制得一种新型的壳聚糖衍生物,采用紫外光谱、红外光谱、元素分析法对目标产物进行了结构表征。结果表明,m(壳聚糖)∶m(对乙酰氨基苯甲酸)为1∶2时,壳聚糖衍生物取代度为0.23;红外光谱显示在1 734.98 cm-1处出现C=O的吸收;壳聚糖衍生物溶液在273 nm处有较大的紫外吸收峰;壳聚糖衍生物还具有较好的表面活性和溶解性能。     

Preparation of uniform hollow polystyrene particles with large voids by a glass‐membrane emulsification technique and a subsequent suspension polymerization

Hollow polymer particles with large voids were prepared with styrene (St) as the main component and in the presence of a small amount of N,N′‐dimethylaminoethyl methacrylate (DMAEMA) via a glass‐membrane emulsification technique and a subsequent suspension polymerization. A mixture of the monomer, hexadecane (HD), and N,N′‐azobis(2,4‐dimethylvaleronitrile) as an initiator was used as a dispersed phase (oil phase). By the careful pushing of the dispersed phase through the pores of the glass membrane into the aqueous phase, an emulsion of fairly monodisperse monomer droplets was formed. Then, the polymerization was performed by temperature being elevated to 70°C. The aqueous phase (continuous phase) contained poly(N‐vinyl pyrrolidone) as a stabilizer, sodium lauryl sulfate as a surfactant, Na₂SO₄ as an electrolyte, and sodium nitrite (NaNO₂) as a water‐soluble inhibitor. Results related to the effects of the HD content, DMAEMA, and the composition of the comonomer, including the crosslinker and flexible segment, on the features of the hollow particles were investigated. When the content of DMAEMA was higher than 1.0 wt % based on the total monomer, small, secondary particles were generated in the aqueous phase, but the generation was effectively prevented when DMAEMA was limited to 0.5 wt %. Hollow particles, with an average diameter of around 7 μm, were obtained with an St–DMAEMA system. The void size of the hollow particles was controlled by the HD content. When the HD content was lower (<25 wt % based on the oil phase), unbroken hollow particles were easily obtained. However, they tended to break into halves after drying when the HD content was increased to 50 wt %. A soft segment, lauryl acrylate, and a crosslinker, ethylene glycol dimethacrylate, were added to overcome this problem. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 244–251, 2003     

Preparation and characterization of glutaraldehyde crosslinked chitosan nanofiltration membrane

In this article, we prepare chitosan (CS) membrane on polyacrylonitrile (PAN) ultrafiltration membrane, and utilize the protonated amine group (? NH₃⁺) on the CS to retain γ‐aminobutyric acid (GABA) in a solution with a pH condition below the amino acid isoelectric point, so as to separate the amino acid from a mixture with sodium acetate that simulates the amino acid fermentation broth. To improve the acid resistance of the composite membrane, we chelate the amine groups on the CS by copper sulfate first, then crosslink the hydroxyl groups in glutaraldehyde solution, and remove the copper ion in hydrochloric acid finally to release the amine groups. This crosslinked CS/PAN composite membrane achieves 95% GABA rejection in pH 4.69 solution under the operation pressure of 0.2 MPa, while over 90% of the sodium acetate permeates the membrane. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and characterization of a novel thermosensitive hydrogel based on chitosan and gelatin blends

In this study, a novel injectable in situ gelling thermosensitive hydrogel system based on chitosan and gelatin blends was designed and investigated. The addition of gelatin provides the correct buffering and other physicochemical conditions including control of hydrophobic interactions and hydrogen bonding, which are necessary to retain chitosan in solution at neutral pH near 4°C and furthermore to allow gel formation upon heating to body temperature. The chitosan/gelatin hydrogels were studied by FTIR, swelling, and rheological analysis. The rheological analysis evidenced the endothermic gelation of chitosan/gelatin solutions, which indicated their gelation temperatures and reflected the effect of gelatin concentration on the thermosensitive properties of gels. The morphology of this system was examined with laser scanning confocal microscopy and scanning electron microscopy. The images indicated that the gels were quite heterogeneous and porous. The investigation of these gels as vehicles for delivering bovine serum albumin as a model drug of protein showed that the system could sustain the release of the protein drug. These results show that chitosan/gelatin solutions can form gels rapidly at body temperature and have promising perspective for their use in local and sustained delivery of protein drug. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

高塔复合肥熔体造粒工艺粒度成因机理及影响造粒的各种因素

我国现有高塔熔体工艺生产尿基、硝基复合肥,成品粒度波动较大,常有大块肥、扁平粒、细粉的产生,生产过程较难控制。分析高塔熔体造粒工艺成粒机理,原料物性、配方、操作条件对造粒的影响;介绍根据成品粒度的状况及观察喷头造粒情况如何进行生产控制的经验,以生产内外在质优的复合肥。