可降解自乳化聚氨酯微球的合成及性能研究

将预聚-扩链-中和-乳化法联合运用,一步合成出自乳化聚氨酯微球。研究了自乳化聚氨酯微球的合成条件。包括二异氰酸酯单体种类对微球形态的影响;异佛尔酮二异氰酸酯（IPDI）和聚丙二醇（PPG）单体配比对乳化效果的影响;乳化时间对微球形态的影响;反应温度、聚合时间和搅拌速度等对微球合成的影响。并以可降解的聚乳酸（PLA）取代部分PPG合成出可降解的自乳化聚氨酯微球,对其在磷酸缓冲液中的降解性进行了研究。通过IR及SEM对自乳化聚氨酯微球进行了表征,找出了合成稳定、均匀和形态好的自乳化聚氨酯微球的最佳条件。     

可降解聚氨酯材料发展现状与趋势

介绍了可降解聚氨酯材料的概念与意义,并按时间顺序和技术发展程度,对近年来可降解聚氨酯材料经历的与天然物质共混、改性后共混、与天然物质共聚、分子链设计等几个合成阶段的发展历程作了详细介绍,综述了降解机理及表征方法方面的研究进展,并对可降解聚氨酯材料的发展前景作了评述.     

Sustained release of antibiotic from polyurethane coated implant materials

Implant associated infections are of increasing importance. To minimize the risks of implant-associated infections recent biomedical strategies have led to the modification of the medical device surfaces. The modifications are in the terms of increasing surface biocompatibility and decreasing bacterial adherence, which can be achieved by applying a coating of biocompatible polymer onto the said surfaces. Entrapping anti-infective agents in a polymer matrix provides an approach to kill bacteria and combat the possibility of any residual infection. We have prepared a biodegradable polyester urethane coat for implant materials, which have the property to accommodate antibiotics within itself. These polyurethane coating materials were characterized by FTIR spectroscopy, swelling property in SBF, gravimetric analysis, drug release, and biocompatibility study. Drug release rates, bacterial colonization and morphological features were also evaluated to predict and understand the antimicrobial activity of these delivery systems. Drug release characteristics were investigated and the physico-chemical mechanisms of the delivery were discussed. Results suggest that the polyester urethane can be used as an implant coating material and can be used as a matrix for the sustained delivery of anti-infective agent.     

Sustained release of antibiotic from polyurethane coated implant materials

Implant associated infections are of increasing importance. To minimize the risks of implant-associated infections recent biomedical strategies have led to the modification of the medical device surfaces. The modifications are in the terms of increasing surface biocompatibility and decreasing bacterial adherence, which can be achieved by applying a coating of biocompatible polymer onto the said surfaces. Entrapping anti-infective agents in a polymer matrix provides an approach to kill bacteria and combat the possibility of any residual infection. We have prepared a biodegradable polyester urethane coat for implant materials, which have the property to accommodate antibiotics within itself. These polyurethane coating materials were characterized by FTIR spectroscopy, swelling property in SBF, gravimetric analysis, drug release, and biocompatibility study. Drug release rates, bacterial colonization and morphological features were also evaluated to predict and understand the antimicrobial activity of these delivery systems. Drug release characteristics were investigated and the physico-chemical mechanisms of the delivery were discussed. Results suggest that the polyester urethane can be used as an implant coating material and can be used as a matrix for the sustained delivery of anti-infective agent.     

Controlled release of heparin from blended polyurethane and silk fibroin film

Polyurethane was blended with silk fibroin and heparin to prepare a heparin-releasing system. The release rate and the percentage of the cumulative amount of the released heparin can be controlled by the loading amount of heparin in the film, the composition ratio of silk fibroin to polyurethane, and the thickness of the film. The slower and more sustained release of heparin can be obtained by increasing the film thickness, the loading amount of heparin and the content of silk fibroin in the film. Thus the high bioactivity and long lasting antithrombogenicity of the raw heparin can be maintained for the blended film. The coagulation time tests showed that the composite film had good blood compatibility.     

Design, synthesis and properties of a degradable polyurethane scaffold for meniscus regeneration

Longitudinal lesions in menisci are among the most frequent orthopedic problems of the knee. Repair by simple techniques is only limited to the vascular part of the meniscus. For repair of the avascular part of the meniscus a scaffold, which will assist the body in the formation of new meniscus cell tissue, might be applicable. In this study a biomedical segmented polyurethane with poly(epsilon-caprolactone) as soft segment and 1,4-butanediisocyanate and 1,4-butanediol as uniform hard segments has been synthesised. The material has a micro phase separated morphology and excellent mechanical properties. A porous scaffold was prepared via a combination of liquid-liquid phase separation and salt leaching. The foams prepared combined a very high interconnectivity and porosity with the desired compression modulus. After six months of implantation in the knees of beagles full ingrowth with cells was obtained and it was found that meniscus like tissue had been formed in the scaffold. Moreover, compression behaviour appeared to be comparable to native meniscus tissue.     

Effect of water-soluble polymers on the physical stability of aqueous polymeric dispersions and their implications on the drug release from coated pellets

Purpose: To investigate the physical stability and drug release-related properties of the aqueous polymer dispersions Kollicoat® SR 30 D and Aquacoat® ECD (an ethylcellulose-based dispersion) in the presence water-soluble polymers (pore formers) with special attention to the potential flocculation of the polymer dispersions. Methods: A precise characterization of the flocculation phenomena in undiluted samples was monitored with turbidimetric measurements using the Turbiscan Lab-Expert. Theophylline or propranolol HCl drug-layered pellets were coated with Kollicoat® SR 30 D and Aquacoat® ECD by the addition of water-soluble polymers polyvinyl pyrrolidone (Kollidon® 30 and 90 F), polyvinyl alcohol–polyethylene glycol graft copolymer (Kollicoat® IR), and hydroxypropyl methylcellulose (Pharmacoat® 603 or 606) in a fluidized bed coater Glatt GPCG-1 and drug release was performed according to UPS paddle method. Results: Stable dispersions were obtained with both Kollicoat® SR 30 D (a polyvinyl acetate-based dispersion) and Aquacoat® ECD with up to 50% hydrophilic pore formers polyvinyl alcohol-polyethylene glycol graft copolymer (Kollicoat® IR) and polyvinyl pyrrolidone (Kollidon® 30). In general, Kollicoat® SR 30 D was more stable against flocculation than Aquacoat® ECD. Stable dispersions were also obtained with higher amounts of water-soluble polymer or by reducing the concentration of the polymer dispersion. Flocculated dispersions resulted in porous films and, thus, in a sharp increase in drug release. Conclusions: Kollicoat® SR 30 D was more resistant to flocculation upon addition of water-soluble polymers than Aquacoat® ECD. The continuous adjustment of drug release from Kollicoat® SR 30-coated pellets was possible with Kollicoat® IR amounts over a broad range.     

Effect of iron on the solubility of hydrogen in tantalum

Pressure-composition-isotherms for Ta–Fe–H systems have been investigated in the temperature range 673–873 K. Tantalum–iron alloys (Ta–xFe, x = 0, 1.6 and 3.2 atom  % Fe) were prepared by arc melting using high purity elements. The equilibrium solid solubility of hydrogen in the alloys decreases with an increase of iron content. Thermodynamic parameters of the solution process—the Gibb’s free energy, enthalpy, and entropy, for each of the solutions have been calculated. The relative partial molar enthalpy becomes less negative with increase in iron content, whereas the entropy values are nearly constant for these alloys. The solubility changes were explained on the basis of change in lattice strain energy of tantalum due to iron addition.     

Effect of hydroxypropyl-beta-cyclodextrin on the solubility of an antibacterial isoxazolyl-naphthoquinone

The complexation of 2-hydroxy-N-(3,4-dimethyl-5-isoxazolyl)-1,4-naphthoquinone-4-imine (I) with a highly soluble cyclodextrin, hydroxypropyl-β-cyclodextrin (HP-β-CD) was studied in aqueous media by solubility methods. I is an antibacterial and trypanocidal agent that is undergoing preclinical testing. Unfortunately, I exhibits low water solubility, and it is therefore difficult to prepare the solutions for biological tests. I inclusion took place with 1:1 stoichiometry. The stability constants of the I complexes calculated from the slope and the intercept of the phase solubility diagrams are larger in the less ionized form, whereas greater overall solubility is obtained in basic media.     

Effect of grain-boundaries on the solubility of copper in silicon

Solubility studies of copper in high-purity vapour-grown polycrystalline silicon have given direct evidence for strong solute-atom/grain-boundary interactions in this system. The interaction energy between copper-atoms and grain-boundaries was ascribed to chemical bonding and was determined to be –1.47±0.04 eV. Since the grain-structure of the vapour-grown material was found to be very complex, a precise determination of the actual grain-boundary solubility was not possible. A theoretical calculation based on enthalpic considerations (neglecting changes in thermal entropy) estimated the ratio of the grain-boundary solubility to the single-crystal solubility to be 4×10⁶at 700° C.Extracted from the Ph.D. thesis of R. C. Dorward, McMaster University (1967).     

Effect of polysorbates on atenolol release from film-coated tablets

The effects of different concentrations of various polysorbates on the release rate of atenolol from film-coated tablets were evaluated. The release profile of atenolol showed that increasing the concentration of polysorbate resulted in an increase in the release rate of atenolol. The type of polysorbate had less effect on the release rate of atenolol. This study revealed that the release kinetic of atenolol from these film-coated tablets was a function of polysorbate concentration. Correlation coefficients of kinetic models could not solely determine the suitability of the models; the sum of the least square of differences also should be calculated when different kinetic models have similar correlation coefficients.     

Controlled release of triamcinolone acetonide from polyurethane implantable devices: application for inhibition of inflammatory-angiogenesis

The purpose of this study was to develop triamcinolone acetonide-loaded polyurethane implants (TA PU implants) for the local treatment of different pathologies including arthritis, ocular and neuroinflammatory disorders. The TA PU implants were characterized by FTIR, SAXS and WAXS. The in vitro and in vivo release of TA from the PU implants was evaluated. The efficacy of TA PU implants in suppressing inflammatory-angiogenesis in a murine sponge model was demonstrated. FTIR results revealed no chemical interactions between polymer and drug. SAXS results indicated that the incorporation of the drug did not disturb the polymer morphology. WAXS showed that the crystalline nature of the TA was preserved after incorporation into the PU. The TA released from the PU implants efficiently inhibited the inflammatory-angiogenesis induced by sponge discs in an experimental animal model. Finally, TA PU implants could be used as local drug delivery systems because of their controlled delivery of TA.     

A controlled release of antibiotics from calcium phosphate-coated poly(lactic-co-glycolic acid) particles and their in vitro efficacy against Staphylococcus aureus biofilm

Ceramic-polymer hybrid particles, intended for osteomyelitis treatment, were fabricated by preparing poly(lactic-co-glycolic acid) particles through an emulsion solvent evaporation technique, followed by calcium phosphate (CaP) coating via a surface adsorption-nucleation method. The presence of CaP coating on the surface of the particles was confirmed by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. Subsequently, two antibiotics for treating bone infection, nafcillin (hydrophilic) and levofloxacin (amphiphilic), were loaded into these hybrid particles and their in vitro drug release studies were investigated. The CaP coating was shown to reduce burst release, while providing sustained release of the antibiotics for up to 4 weeks. In vitro bacterial study against Staphylococcus aureus demonstrated the capability of these antibiotic-loaded hybrid particles to inhibit biofilm formation as well as deteriorate established biofilm, making this hybrid system a potential candidate for further investigation for osteomyelitis treatment.     

Effect of pH on the in vitro corrosion rate of magnesium degradable implant material

Magnesium (Mg) has been recently advocated as a potential metallic material for degradable bone plates. The corrosion behavior of Mg in body fluids at different pH values, however, has not been fully studied. The pH value of the body fluid at the location of bone fracture changes during the course of recovery, and study of the effect of pH on the corrosion rate of Mg provides important information in the development and design of Mg implants. In the present study, the corrosion behavior of Mg in Hanks' solution (a simulated body fluid) at pH value ranging from 5.5 to 8.0 was studied via monitoring the rate of hydrogen gas evolution. The experimental results show that the pH value has very large effect on the corrosion rate in Hanks' solution within the range 5.5 to 8.0. The corrosion rate (penetration rate) at pH 5.5 exceeds 800 μm per day, which is extremely high. On the other hand, it drops to about 6 μm and 3 μm per day at pH 7.4 and 8.0, respectively. The corrosion behavior of Mg at different pH values was also studied using electrochemical methods, including potentiodynamic polarization measurement and electrochemical impedance spectroscopy (EIS).     

New co-processed MCC-based excipient for fast release of low solubility drugs from pellets prepared by extrusion-spheronization

In this study, a new co-processed excipient composed of microcrystalline cellulose (MCC), sorbitol, chitosan and Eudragit® E, easily obtained by wet massing, to increase the dissolution rate of active ingredients of low water solubility from pellets prepared by extrusion–spheronization is evaluated. Indomethacin, nifedipine, furosemide, ibuprofen, prednisolone and hydrochlorothiazide are used as model drugs of different solubility. All pellet formulations evaluated showed adequate morphological, flow and mechanical properties. Pellets prepared with the co-processed excipient show a higher drug dissolution rate than those prepared with MCC and even higher than the pure drug powder. The fast drug dissolution and the complete disintegration (<3?min) of the pellets can be explained by the great porosity of the formulations, the high solubility of the sorbitol, the disintegrant capacity of the chitosan and the distribution of the Eudragit® E polymer particles in-between the other components of the co-processed mixture. In conclusion, this new co-processed excipient is very suitable to increase the dissolution rate of poorly soluble drugs from pellets prepared by extrusion–spheronization. Moreover, the drug release rate can be estimated from the Ln of the drug solubility in acidic medium.     

Effect of temperature on the release of hexadecane from soil by thermal treatment

A natural organic soil (2.5% of total organic carbon) was artificially contaminated with hexadecane, and thermally treated under an inert medium up to different final temperatures (150-800 degrees C) for 30 min to simulate ex situ thermal process conditions. The experiments were conducted using a complete organic soil, instead of the clays or isolated soil fractions that are commonly used. Neat and contaminated samples were separately heated to understand the impact of the soil itself and the contaminant in the release of volatiles. The soil quality as well as the quality and amount of volatile compounds generated during the process were monitored. More than 80-88% of the initial hexadecane content in the soil matrix was recovered in liquids traps after the thermal treatment, therefore the contaminant could be recovered for further recycling. The high amount of hexadecane collected without suffering chemical transformations indicated that the main mechanism for the hexadecane removal was evaporation. The analysis of the light gases released from contaminated samples indicated negligible or null hexadecane pyrolysis reaction rates, confirming that the evaporation/desorption of the contaminant are the processes that governed the removal of the contaminant from the soil. For the soil tested, of a relatively low surface area, good removal efficiencies (higher than 99.9%) were detected at about 300 degrees C, being higher temperatures not necessary to significantly improve the contamination removal.     

有机硅烷偶联剂对水性聚氨酯材料性能的影响

以IPDI为硬段,PTMG1000为软段,TMP为交联剂,APTES为封端剂,合成了一系列硅烷偶联剂改性水性聚氨酯乳液,并制备了水性聚氨酯的固化膜.FT-IR分析表明,APTES上的一NH2 与聚铵酯的端--NCO发生反应,成功地将硅烷结构引入聚氨酯分子中.TG分析表明,APTES的改性,提高了聚氨酯热稳定性.随着w(...     

纸浆细纤维化对纤维基聚氨酯合成的影响

利用物理检测、SEM观察、XPS检测等方法探究了打浆前后纤维基聚氨酯复合材料的物理指标、表面形态以及成键情况,分析了纸浆细纤维化对纤维基聚氨酯复合材料性能的影响。通过对纤维基聚氨酯复合材料的物理性能检测分析可知,当咪唑-TDI-PEG400聚氨酯预聚体乳液加入量为10%时,随着浆料打浆度的提升,复合材料的抗张指数、湿抗张指数、耐折度、撕裂指数逐渐升高。当浆料打浆度为55°SR时,复合材料的抗张指数、湿抗张指数、耐折度、撕裂指数分别为空白样品的1.06、9.75、1.12、1.12倍。通过SEM也可以观察到,打浆度越高,纤维间的膜状包裹以及纤维间的桥接也逐渐增加。最后通过XPS表征抄片表面价键结合状态,发现随着打浆度的提升,抄片表面的氨基甲酸酯键含量逐渐提高。在打浆度为75°SR时,氨基甲酸酯的含量为1.63%,为10°SR抄片的6.30倍。     

Effect of polyurethane composition and the fabrication process on scaffold properties

The microdomain structure of polyurethanes (PUR) determines their unique physical properties and makes polyurethanes attractive candidates for various tissue engineering applications. 3D scaffolds based on polyurethanes with different contents of hard segments were fabricated by a salt-leaching/polymer coagulation method. The process parameters were carefully considered, particularly the polymer solution concentration and characteristics of the polyurethane, which are the critical parameters for the control of porosity and pore size distribution. In this study, 3D polyurethane scaffolds were fabricated with interconnected pores and porosity from 64% to 80%. Pore size distribution was evaluated using quantitative image analysis and mercury intrusion porosimetry (MIP). The scaffolds fabricated from polyurethanes with 70 wt.% of hard-domain content were found to have the best compression properties.