聚丁二酸丁二醇酯/聚羟基烷酸酯熔融共混物的结晶及流变力学行为

用熔融共混法制备聚丁二酸丁二醇酯(PBS)/聚(3-羟基丁酸酯-co-4-羟基丁酸酯)[Poly(3HB-co-4HB)]复合降解材料,利用差示扫描量热(DSC)、旋转流变仪及万能拉力机对其结晶、流变行为及力学性能进行研究。结果表明,在PBS中加入Poly(3HB-co-4HB)后,发现结晶起始温度(To,c)、结晶峰温度(Tp,c)以及结晶结束温度(Te,c)有所提高,结晶度随着Poly(3HB-co-4HB)的增加呈先增大后下降的趋势;PBS/Poly(3HB-co-4HB)复合降解材料随着Poly(3HB-co-4HB)添加量的增大,断裂伸长率和拉伸强度却呈下降趋势;同时剪切储能模量(G′)、剪切损耗模量(G″)呈现出单增趋势。因此,在复合降解材料中添加适量的Poly(3HB-co-4HB)能改善PBS的结晶、流变及力学行为。     

聚(3-羟基丁酸酯-co-4-羟基丁酸酯)@海藻酸钠复合纤维膜的制备及其对Pb2+和Cu2+的吸附性

采用三氯甲烷和N,N二甲基甲酰胺（DMF）为溶剂,制备聚（3-羟基丁酸酯-co-4-羟基丁酸酯）（P（3HB-co-4HB））纺丝溶液,并通过静电纺丝技术制备P（3HB-co-4HB）纳米纤维膜,用海藻酸钠（SA）对P（3HB-co-4HB）纳米纤维膜进行包覆,获得P（3HB-co-4HB）@SA复合纤维膜。利用SEM、比表面积仪、原子吸收光谱分别表征了P（3HB-co-4HB）@SA复合纤维膜的纤维形态、比表面积、溶液残留液离子浓度。结果表明:纺丝液浓度在12%时,P（3HB-co-4HB）纤维成纤性好;随着静电压增大,P（3HB-co-4HB）纤维直径先减小后增大。P（3HB-co-4HB）支架材料可以使SA的比表面积提高约3.9倍,P（3HB-co-4HB）@SA复合纤维膜对Cu2+离子、Pb2+离子最大吸附量分别为26.25 mg/g和36.25 mg/g,折算为SA的吸附量分别为364.58 mg/g和503.47 mg/g。      

Comparative study of three types of polymer materials co-cultured with bone marrow mesenchymal stem cells for use as a myocardial patch in cardiomyocyte regeneration

The purpose of this study was to investigate the most suitable polymer material for supporting stem cell growth as a myocardial patch. After cell isolation and expansion of mouse bone marrow mesenchymal stem cells (BMSC), the cells were induced to differentiate into cardiomyocytes with 5-azacytidine to determine their differentiation potential. BMSCs were also seeded onto three types of polymer material film, including polyurethane (PU), 3-hydroxybutyrate-co-4-hydroxybutyrate [P(3HB-co-4HB)], and polypropylene carbonate (PPC). The results revealed that cell numbers were more abundant on both the PU and P(3HB-co-4HB) material surfaces. Conversely, the surface of PPC was smooth with only cell lysate debris observed. The average cell counts were as follows: 143.78 ± 38.38 (PU group), 159.50 ± 33.07 [P(3HB-co-4HB) group], and 1.40 ± 0.70 (PPC group). There was no statistically significant difference in cell numbers between the PU and P(3HB-co-4HB) groups. A statistically significant difference was identified between the PPC group and both the PU (P1) and P(3HB-co-4HB) groups (P2). Polymer biomaterial patches composed of PU and P(3HB-co-4HB) permit good stem cell growth. P(3HB-co-4HB) has the potential for development as a clinical alternative to current treatment methods for the regeneration of cardiomyocytes in patients with myocardial infarction.     

SiO2/聚（3-羟基丁酸酯-co-4-羟基丁酸酯）薄膜研究

目的研究纳米SiO2对可生物降解聚(3-羟基丁酸酯-co-4-羟基丁酸酯)(P34HB)包装膜结晶行为和力学性能的影响。方法采用溶液浇铸法制备SiO_2/P34HB纳米复合薄膜,利用红外光谱仪(FTIR)、扫描电镜(SEM)、正置热台显微镜(POM)、差示扫描量热仪(DSC)和万能力学试验机等研究纳米SiO_2对P34HB结构、结晶性和力学性能等的影响。结果纳米SiO_2在P34HB中起到异相成核的作用,SiO2/P34HB复合膜的结晶速率和结晶度得到明显改善。相比P34HB包装膜,当纳米SiO_2质量分数为2%时,SiO_2/P34HB复合膜的弹性模量和拉伸强度分别提高了72.7%和60.9%。结论获得了纳米SiO2改善可生物降解聚(3-羟基丁酸酯-co-4-羟基丁酸酯)包装膜结晶度和力学性能的最佳掺杂比例参数。     

成核剂对聚(3-羟基丁酸酯-co-4羟基丁酸酯)性能的影响

分别以氮化硼(BN)、BRUGGOLENP250、CaCO3和Tm-3为成核剂,用熔融模压法制备了聚(3-羟基丁酸酯-co-4羟基丁酸酯)[P(3HB-co-4HB)]样品,借用偏光显微镜(POM)、差示扫描量热(DSC)、热重分析(TGA)和扫描电镜(SEM)等考察了成核剂种类及用量对P(3HB-co-4HB)结晶形态、熔点、热分解温度、力学性能及断面形态的影响。结果表明,各种成核剂均能有效细化P(3HB-co-4HB)的球晶尺寸,提高其熔点及热分解温度;当成核剂BN的质量分数为5‰~8‰时,P(3HB-co-4HB)的综合性能最好。     

Density and crystallinity of poly (3-hydroxybutyrate/3-hydroxyvalerate) copolymers

Bacteria can produce a range of optically active copolymers of (R)-3-hydroxybutyrate (HB) and (R)-3-hydroxyvalerate (HV). These copolymers have aroused much scientific interest because of their high crystallinity at all HB ∶ HV compositions which suggests the possibility of inclusion of HB and HV in the same crystal. In this paper we look at the assessment of crystallinity by density measurements taking into account the possible changes in crystal and amorphous densities caused by the rejection or inclusion of HV from the crystallites. The approach developed is applicable to crystallization of copolymers and blends whatever the composition of the crystals and makes a distinction between mass fraction and mole fraction crystallinities for cases where the average molar mass of residues in the crystal and amorphous phases differs. While it is impossible to give values for crystallinity without knowing the degree of inclusion of HV into the crystals it is possible to say that the previous suggestions that the crystallinity remains constant independent of HV content and that there is equal concentration of HV in the crystal and amorphous phases are incompatible with the measured sample densities. We also show that the crystallization temperature is an important factor in the balance between the crystallinity and HV content of crystals.     

4-羟基丁酸含量对聚 3-羟基丁酸 与 4-羟基丁酸共聚物性能和结构的影响

目的对3-羟基丁酸4-羟基丁酸共聚酯P(3HB-co-4HB)进行酶解测试。方法通过力学性能测试、失重率分析、热失重分析、X-射线衍射分析、扫描电镜等测试和表征手段对样品的物理性能及生物降解情况进行评价。结果 P(3HB-co-4HB)分子中4HB单体(文中均用摩尔分数表示)的引入提高了材料的柔韧性,材料的脆性下降;失重率方面,4种材料的降解速率从高到低依次为P(3HB)P(3HB-co-5%4HB)(3HB-co-10%4HB)P(3HB-co-15%4HB);酶解前期,材料的热稳定性增强,而酶解后期材料的热稳定性逐渐下降;XRD结果表明材料降解过程中结晶度的变化不明显;P(3HB-co-4HB)分子中随着4HB单体含量的增加,材料表面粗糙度降低,酶解后材料表面被侵蚀,降解速率与失重率结果一致。结论 P(3HB-co-4HB)分子中4HB单体的引入显著影响了材料的机械性能,随着4HB含量的增加,材料的失重率越来越大,热稳定性呈现先上升后下降的趋势,材料表面粗糙度逐渐降低,由于酶解过程属于从表面侵蚀开始,因此酶解过程中样品的结晶度变化不大。     

A comparative investigation of biodegradable polyhydroxyalkanoate films as matrices for in vitro cell cultures

The paper describes the production and investigation of flexible films made of high-purity polyhydroxyalkanoates (PHAs)--polyhydroxybutyrate [poly-(3HB)] and poly-3-hydroxybutyrate-co-poly-3-hydroxyvalerate [poly(3HB-co-3HV)], containing 4-30 mol % hydroxyvalerate. Poly(3HB-co-3HV) films have a more porous structure than poly-(3HB) films, which are more compact, but their surface properties, such as wettability and surface and interface energies, are the same. Sterilisation of the PHA films by conventional methods (heat treatment and gamma-irradiation) did not impair their strength. Cells cultured on PHA films exhibited high levels of cell adhesion. Cell morphology, protein synthesis and DNA synthesis were estimated by extent of 3H-thymidine incorporation into the animal cell cultures of various origins (fibroblasts, endothelium cells, and isolated hepatocytes) in direct contact with PHAs. The investigation showed that this material can be used to make matrices for in vitro proliferous cells. The investigated properties of poly-(3HB) and poly(3HB-co-3HV) films proved to be fundamentally similar.     

GF/P(3HB-co-4HB)-PLA生物基复合材料的制备与性能

为了提高聚（3-羟基丁酸酯-co-4 羟基丁酸酯）-聚乳酸（P（3HB-co-4HB）-PLA）生物基共混材料的力学性能和尺寸稳定性,扩大应用领域,以P（3HB-co-4HB）和PLA共混物为基体,盐酸或偶联剂表面处理的玻璃纤维（GF）为增强材料,采用熔融共混法制备GF/P（3HB-co-4HB）-PLA复合材料。通过傅里叶变换红外光谱仪（FTIR）、扫描电子显微镜（SEM）、热失重分析仪（TGA）和万能电子拉力机等研究了GF表面处理方法对复合材料力学性能、热性能、尺寸稳定性及断面形态的影响。研究结果表明：表面改性GF的加入可显著提高P（3HB-co-4HB）-PLA共混材料的综合性能。经偶联剂表面接枝的GF可均匀分散在P（3HB-co-4HB）-PLA基体中并形成较强的界面结合。添加质量分数20%的偶联剂改性GF使复合材料的拉伸强度、弯曲强度、缺口冲击强度和硬度分别提高了29.38%、20.32%、41.38%和15.31%;初始热分解温度（IDT）和维卡软化温度（VST）分别提高了6.64 ℃和10.7 ℃;室温和60 ℃放置60 d后复合材料试样长度方向的尺寸稳定性分别提高了32.47%和33.70%。     

聚(3-羟基丁酸酯-co-4-羟基丁酸酯)/POSS共混体系的性能

采用熔融模压法分别制备了聚(3-羟基丁酸酯-co-4-羟基丁酸酯)[P(3HB-co-4HB)]和两种多面体笼型硅氧烷(POSS)[八异丁基倍半硅氧烷(OIBS)和八氨基苯基倍半硅氧烷(OAPS)]的共混物,考察了不同含量的OIBS,OAPS对共混体系性能的影响。结果表明,两种POSS都起到成核剂的作用。OIBS,OAPS的质量分数小于1%时,可以提高体系结晶温度,力学性能;随着OIBS,OAPS质量分数的提高,成核性有所增加,但因分散性变差,体系热稳定性和力学性能变差。由于OAPS的活泼氨基可与P(3HB-co-4HB)发生化学反应,改性效果较OIBS优。     

PHB／PPO共混体系的相容性和结晶

采用溶液共混方法对聚β－羟基丁酸酯／聚氧化丙烯共混体系的相容性和结晶行为进行了研究，ＤＳＣ，ＰＯＭ，ＷＡＸＤ等实验结果表明，该体系不是相容体系。但在特殊的组成比下有相容的第三相存在。ＰＰＯ对ＰＨＢ的结晶结构无影响，但对ＰＨＢ的结晶速率和结晶完整性有很大的作用。     

聚羟基丁酸酯的等温与非等温结晶动力学

用差示扫描量热法(DSC)研究了聚羟基丁酸酯(PHB)的等温与非等温结晶动力学。采用Avrami方程分析了等温结晶动力学,Avrami指数n≈2,表明PHB以异相成核的二维平面晶体方式生长,等温结晶活化能为82.4 kJ/min。采用Jeziorny法和莫志深法分析了PHB的非等温结晶动力学,Avrami指数n≈3,表明PHB非等温结晶过程以异相成核的三维球晶方式生长。     

Crystallization and morphology of a bacterial thermoplastic: poly-3-hydroxybutyrate

This paper presents a number of interesting results on the physical properties of poly-3-hydroxybutyrate (PHB). Data are presented on crystallization kinetics, morphology of melt- and solution-crystallized PHB, the variation of lamellar thickness with crystallization temperature, and the assessment of some thermodynamic quantities. These properties include surface free energies, heat of fusion and melting, and glass transition temperatures. It is shown that the special properties of PHB such as the large spherulite size, which is probably due to its exceptional purity, make it an ideal material for model studies of polymer crystallization and morphology. For example, we show that the variation of growth rate with crystallization temperature is consistent with the very latest theories; and that the single crystal morphology has important implications for the understanding of crystal growth in other polymer systems.     

硅烷偶联剂改性的木粉/P34HB复合包装材料的制备

目的研究硅烷偶联剂KH550含量对木粉/P34HB复合包装材料性能的影响。采用KH550改性木粉,提高与聚(3-羟基丁酸酯-4-羟基丁酸酯)(P34HB)的结合强度,改善复合材料的力学性能和界面相容性。方法以KH550为改性剂,木粉和P34HB为原料,利用共混热压工艺制备改性木粉/P34HB复合材料;通过对复合材料的形貌进行观察,以及傅里叶变换红外光谱(FTIR)、热重分析(TGA)和力学性能分析,研究KH550质量分数不同时对复合材料界面相容性、力学性能和热性能的影响。结果添加KH550后,复合材料的的界面相容性得到改善;FTIR分析表明,KH550已经成功接枝到木粉中;适量的KH550提高了复合材料的热稳定性;复合材料的储能模量增加;复合材料的力学性能也有所提高。此外还得到了最佳的KH550添加量,即质量分数为0.5%。结论 KH550不仅使得木粉与P34HB的相容性得到改善,同时也增强了复合包装材料的力学性能和热性能。     

Nucleation,growth and morphology of poly(hydroxybutyrate) and its copolymers

Measurements of the melting temperatures, growth rates and nucleation rates of meltcrystallized polyhydroxybutyrate (PHB) and two poly(hydroxybutyrate-co-hydroxyvalerate) (PHB/HV) copolymers are reported for crystallization over a wide range of temperature. Examples are shown of the spherulitic morphologies obtained. From the variation in melting point with crystallization temperature values for the equilibrium melting points of PHB and PHB/HV are obtained. Growth and nucleation rate measurements are analysed using secondary nucleation theory to obtain approximations to surface energies within the crystals. PHB and PHB/7% HV are described well by secondary nucleation theory. PHB/23% HV exhibits more complex crystallization and melting behaviour, which suggests temperature-dependent exclusion of HV units from the crystals.     

Medium chain length polyhydroxyalkanoates, promising new biomedical materials for the future

Medium chain length polyhydroxyalkanoates, mcl-PHAs (C₆-C₁₄ carbon atoms), are polyesters of hydroxyalkanoates produced mainly by fluorescent Pseudomonads under unbalanced growth conditions. These mcl-PHAs which can be produced using renewable resources are biocompatible, biodegradable and thermoprocessable. They have low crystallinity, low glass transition temperature, low tensile strength and high elongation to break, making them elastomeric polymers. Mcl-PHAs and their copolymers are suitable for a range of biomedical applications where flexible biomaterials are required, such as heart valves and other cardiovascular applications as well as matrices for controlled drug delivery. Mcl-PHAs are more structurally diverse than short chain length PHAs and hence can be more readily tailored for specific applications. Composites have also been fabricated using mcl-PHAs and their copolymers, such as poly (3-hydroxyoctanoate) [P(3HO)] combined with single walled carbon nanotubes and poly(3-hydroxbutyrate-co-3-hydroxyhexanoate) [P(3HB-co-3HHx)] combined with hydroxyapatite. Because of these attractive properties of biodegradability, biocompatibility and tailorability, Mcl-PHAs and their composites are being increasingly used for biomedical applications. However, studies remain limited mainly to P(3HO) and the copolymer P(3HB-co-3HHx), which are the only mcl-PHAs available in large quantities. In this review we have consolidated current knowledge on the properties and biomedical applications of these elastomeric mcl-PHAs, their copolymers and their composites.     

Thermal degradation of poly(3-hydroxybutyrate) and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) in nitrogen and oxygen studied by thermogravimetric-Fourier transform infrared spectroscopy

The thermal degradation behavior of poly(3-hydroxybutyrate) (PHB) and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (P(HB-co-HHx), HHx=12 mol%) has been studied under different environmental conditions by thermogravimetric analysis (TGA) Fourier transform infrared (FT-IR) spectroscopy. It is reported that at higher temperature (>400 degrees C) carbon dioxide and propene are formed from the decomposition product crotonic acid in a nitrogen atmosphere, whereas in an oxygen atmosphere propene oxidizes in a further step to carbon dioxide, carbon monoxide and hydrogen. It was also found that PHB and P(HB-co-HHx) have a similar thermal degradation mechanism. The analysis of the FT-IR-spectroscopic data was performed with 2D and perturbation-correlation moving-window 2D (PCMW2D) correlation spectroscopy.     

Compositional study and cytotoxicity of biodegradable poly(ester urethane)s consisting of poly[(R)-3-hydroxybutyrate] and poly(ethylene glycol)

Biodegradable PHB–PEG multi-block polyurethane copolymers comprising PHB blocks (M_n: 1100, 1740 and 3240) and PEG blocks (M_n: 1960, 3250, 4150 or 7950) were synthesized followed by characterization by GPC, ¹H NMR, and FT-IR. The PHB contents ranged from 9 to 62% by weight. The copolymers displayed improved thermal stabilities compared with their respective precursors. The morphological structures of the copolymers were studied by FT-IR, DSC and XRD. FT-IR revealed the existence of amorphous and crystalline phases of PHB. Both DSC and XRD analyses showed that separate crystalline phases are formed by PEG and PHB blocks in the copolymers. Upon annealing, the melting transition temperature (T_m), melting enthalpy (ΔH_m) and the fractional crystallinity (X_c) of the PEG block increased when the length of PEG incorporated into the copolymer increased. These values were higher when the PHB block length is shorter as the shorter PHB chain does not disrupt the crystallization of PEG as much as the longer PHB chain. A similar disruptive effect on the crystallization of PHB segments was observed by varying PEG chain lengths but the effect is less pronounced compared with the PEG segments. A comparison of the swelling properties of the poly(ester urethane)s showed that the length and crystalline properties of the PHB block significantly affects the water uptake properties of the copolymers. The crystalline properties and the water uptake capacities of the copolymers could be fine-tuned by consideration of the length of the PHB and PEG block incorporated. The results of the cytotoxicity tests demonstrated that the poly(PHB/PEG) urethanes were non-cytotoxic and could potentially be used for biomedical purposes.     

Optical nanocomposites prepared by incorporating bacterial cellulose nanofibrils into poly(3-hydroxybutyrate)

A biocompatible polymeric nanocomposite was prepared by incorporating bacterial cellulose (BC) into a poly(3-hydroxybutyrate) (PHB) matrix. The transparency of the PHB/BC nanocomposite was high due to the homogeneous nano-sized spherulite and nanofibril of PHB and BC, which are smaller than the wavelength of visible rays. The X-ray diffraction patterns of the PHB in the nanocomposite film showed peaks corresponding to the crystallized PHB. The thermal stability of PHB in the nanocomposite film has been improved. The morphology studies showed that the PHB molecules filled vacancies between BC nanofibrils. An increase in the mechanical properties was observed by incorporating the BC into the PHB matrix. This PHB/BC nanocomposite can be considered for various applications, such as display devices, tissue engineering scaffold, and food packaging, because of its improved mechanical properties along with biodegradability and biocompatibility.     

Electrospun nanofibrous biodegradable polyester coatings on Bioglass-based glass-ceramics for tissue engineering

Biodegradable polymeric nanofibrous coatings were obtained by electrospinning different polymers onto sintered 45S5 Bioglass^®-based glass-ceramic pellets. The investigated polymers were poly(3-hydroxybutyrate) (P3HB), poly(3-hydroxybutyrate-co-hydroxyvalerate) (PHBV) and a composite of poly(caprolactone) (PCL) and poly(ethylene oxide) (PEO) (PCL–PEO). The fibrous coatings morphology was evaluated by optical microscopy and scanning electron microscopy. The electrospinning process parameters were optimised to obtain reproducible coatings formed by a thin web of polymer nanofibres. In-vitro studies in simulated body fluid (SBF) were performed to investigate the bioactivity and mineralisation of the substrates by inducing the formation of hydroxyapatite (HA) on the nanofiber-coated pellets. HA crystals were detected on all samples after 7 days of immersion in SBF, however the morphology of the HA layer depended on the characteristic fibre diameter, which in turn was a function of the specific polymer-solvent system used. The bioactive and resorbable nanofibrous coatings can be used to tailor the surface topography of bioactive glass-ceramics for applications in tissue engineering scaffolds.