A novel enzymatic biodegradable route for PLA/EVA blends under agricultural soil of Vietnam

Poly lactic acid (PLA) has attracted a lot of attention in recent years because of its good properties such as high transparency, high tensile strength and excellent biodegradability. However, high modulus and low strain are its shortage, making it unfeasible to be applied as packaging materials. To overcome this limitation, in this study, PLA is mixed with ethylene vinyl acetate (EVA). The morphological, thermal and mechanical properties of the enzymatically degraded PLA/EVA blends were fully investigated under agricultural soil of Red River Delta, Vietnam. It was demonstrated that some new strains were responsible for the biodegradation of PLA/EVA. To best of our knowledge, these strains were not reported in the literature up to now.     

Synthesis and evaluation of rosin-based polymers as film coating materials

Rosin-based polymers (R-1 and R-2) were synthesized and characterized for physicochemical properties, molecular weight (Mw), polydispersity (Mw/Mn), glass transition temperature (Tg), and thermogravimetry (TGA). Films of the polymers were cast on a mercury substrate by solvent evaporation technique. Free films were characterized for surface topography by scanning electron microscopy (SEM), water vapor transmission rate (WVTR), tensile strength, percentage elongation, and modulus of elasticity. The polymers were further evaluated as film coating materials by evaluating drug release from coated pellets with diclofenac sodium as a model drug. Drug was loaded on non-pareil seeds by a solution-layering technique and coated with varying concentrations of polymer solutions. Sustained release of the drug was observed from coated pellets. The newly synthesized rosin-based polymers promise considerable utility for pharmaceutical coating.     

Processing and characterization of solid and microcellular poly(lactic acid)/polyhydroxybutyrate-valerate (PLA/PHBV) blends and PLA/PHBV/Clay nanocomposites

The morphology, microstructure, tensile properties, and dynamic mechanical properties of solid and microcellular poly(lactic acid) (PLA)/polyhydroxybutyrate-valerate (PHBV) blends, as well as PLA/PHBV/clay nanocomposites, together with the thermal and rheological properties of solid PLA/PHBV blends and PLA/PHBV/clay nanocomposites, were investigated. Conventional and microcellular injection-molding processes were used to produce solid and microcellular specimens in the form of ASTM tensile test bars. Nitrogen in the supercritical state was used as the physical blowing agent in the microcellular injection molding experiments. In terms of rheology, the PLA/PHBV blends exhibited a Newtonian fluid behavior, and their nanocomposite counterparts showed a strong shear-thinning behavior, over the full frequency range. An obvious pseudo-solid-like behavior over a wide range of frequencies in the PLA/PHBV/clay nanocomposites suggested a strong interaction between the PLA/PHBV blend and the nanoclay that restricted the relaxation of the polymer chains. PLA/PHBV/clay nanocomposites possess a higher modulus and greater melt strength than PLA/PHBV blends. The addition of nanoclay also decreased the average cell size and increased the cell density of microcellular PLA/PHBV specimens. As a crystalline nucleating agent, nanoclay significantly improved the crystallinity of PHBV in the blend, thus leading to a relatively high modulus for both solid and microcellular specimens. However, the addition of nanoclay had less of an effect on the tensile strength and strain-at-break.     

聚乙二醇增容纳米纤维素/聚乳酸共混体系的研究

采用溶液浇铸法制备纳米纤维素/聚乳酸/聚乙二醇三元复合材料,与纯聚乳酸相比,该复合材料的抗张强度和断裂伸长率分别提高了41.2%和38.4%.傅立叶红外(FT-IR)表明聚乙二醇的存在使纳米纤维素和聚乳酸之间形成了强烈的氢键作用,明显改善了纳米纤维素和聚乳酸之间的相容性,提高了界面黏结力.扫描电子显微镜(SEM)观察了...     

接枝共聚法制备PEG/CDA高分子固-固相变材料及其表征

通过接枝共聚法制备了PEG/CDA复合高分子固一固相变材料,用DSC差示扫描量热法及FTIR对其进行了表征,用正交试验法L9(34)研究了PEG分子量、PEG/CDA的质量比对相变材料储热性能,相变温度等的影响,以及反应时间对接枝反应的影响.结果表明,当PEG相对分子量为6000,PEG/CDA质量比为9:1,接枝反应时间为150 min时,材料的储热性最好.     

Evaluation of blends of high and low calcium fly ashes for use as supplementary cementing materials

The present paper outlines the results of a research attempt aimed at developing and evaluating the performance of ternary blended cements, incorporating mixtures of two different types of fly ash (of high and low calcium content). The main target of this study was to investigate whether and by what means, the introduction of a certain type of fly ash into a fly ash–cement (FC) matrix containing a different type of ash, can improve the performance of the initial binary system. For achieving this, new pozzolans were prepared by mixing, in selected proportions, a high lime fly ash with an ash of lower calcium content. The efficiency of the new materials was examined in terms of active silica content, pozzolanic activity potential, strength development, k-values and progress of the pozzolanic action by means of fixed lime capabilities. The results obtained demonstrated that the mixtures containing equal amounts of each fly ash were the most effective for moderate cement substitution, whilst for higher replacements the intermixture possessing the highest active silica content shows supremacy at almost all hydration ages. The superior performance of the ternary fly ash blends was mainly attributed to synergistic effects detected for all the ashes utilized. These were quantified in each case and almost linear correlations were obtained with the k-values of the most efficient ternary mixes.     

Evaluation of PHBHHx and PHBV/PLA fibers used as medical sutures

Two types of fibers were prepared by using bio-based materials: a mono-filament made from poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx) and a multi-filament made from poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and polylactic acid (PLA) blend. The two fibers were evaluated for mechanical properties, biocompatibility and degradability for the potential application as medical sutures. The PHBHHx fiber showed remarkable biocompatibility by H.E. Stainning, with very little impact to the surrounding tissues. The degradation of the fiber was observed by SEM after implantation for 36 weeks, and the major degradation product was detected after 96 weeks. Consistently, the PHBHHx fiber maintained more than half of the mechanical properties after 96 weeks. The other fiber was prepared by twisting PHBV/PLA blend strands to a bunch, and showed high biocompatibility and relatively high degradability. The bunched structure loosed after 36 weeks of implantation. These low-cost and easily prepared fibers have great potential in medical applications, since they could avoid the formation of fibrous capsule, reduce the size of scar, and degrade into non-toxic and even beneficial products.     

Co-electrospun blends of PU and PEG as potential biocompatible scaffolds for small-diameter vascular tissue engineering

A small-diameter vascular graft (inner diameter 4 mm) was fabricated from polyurethane (PU) and poly(ethylene glycol) (PEG) solutions by blend electrospinning technology. The fiber diameter decreased from 1023 ± 185 nm to 394 ± 106 nm with the increasing content of PEG in electrospinning solutions. The hybrid PU/PEG scaffolds showed randomly nanofibrous morphology, high porosity and well-interconnected porous structure. The hydrophilicity of these scaffolds had been improved significantly with the increasing contents of PEG. The mechanical properties of electrospun hybrid PU/PEG scaffolds were obviously different from that of PU scaffold, which was caused by plasticizing or hardening effect imparted by PEG composition. Under hydrated state, the hybrid PU/PEG scaffolds demonstrated low mechanical performance due to the hydrophilic property of materials. Compared with dry PU/PEG scaffolds with the same content of PEG, the tensile strength and elastic modulus of hydrated PU/PEG scaffolds decreased significantly, while the elongation at break increased. The hybrid PU/PEG scaffolds demonstrated a lower possibility of thrombi formation than blank PU scaffold in platelet adhesion test. The hemolysis assay illustrated that all scaffolds could act as blood contacting materials. To investigate further in vitro cytocompatibility, HUVECs were seeded on the scaffolds and cultured over 14 days. The cells could attach and proliferate well on the hybrid scaffolds than blank PU scaffold, and form a cell monolayer fully covering on the PU/PEG (80/20) hybrid scaffold surface. The results demonstrated that the electrospun hybrid PU/PEG tubular scaffolds possessed the special capacity with excellent hemocompatibility while simultaneously supporting extensive endothelialization with the 20 and 30% content of PEG in hybrid scaffolds.     

Dynamic wettability study on the functionalized PEGylated layer on a polylactide surface constructed by the coating of aldehyde-ended poly(ethylene glycol) (PEG)/polylactide (PLA) block copolymer

A block copolymer of α-acetal-poly(ethylene glycol) and polylactide(PEG/PLA) was prepared and utilized as a surface modifier to construct a functionalized PEG layer on a PLA substrate by simple coating. An active functional group, aldehyde, was readily prepared by the derivatization of an α-acetal group at the tethered PEG-chain end and can be further utilized to link bioactive functionality molecules such as sugars and proteins. The PEGylated surface thus prepared was characterized by the method of dynamic wetting using the Wilhelmy plate technique and by the surface/interfacial free energy calculation. The results of the dynamic wetting study suggested that the interactions of PEG on the surface with water induce the reorientation of the hydrophilic PEG component to accommodate itself optimally with the water phase, resulting in a significant reduction in the interfacial free energy. By employing the extended Fowkes’ equation, the polar interactions are accurately estimated in the free energy calculation of PEGylated surface; the polar components in surface free energy may be divided into two contributions with distinctive characteristics; one is the γ_s^h component reflecting water-interactive Lewis sites and the other is the γ_s^p component reflecting the dipole moment on the surface. The γ_s^p component, related to the PEG conformation via the dipole moment on the substrate, was suggested to be a determinant factor in the protein adsorption. Because these surfaces have both non-fouling and ligand-binding properties, they might support the selective binding and the growth of particular cell populations, and eventually, they are expected to have a high utility in biomedical fields including the field of tissue engineering.     

复合电沉积制备（Ni-Mo）-TiO2电极及其电催化析氢性能

为开发新型廉价高效的析氢材料,用恒电流复合电沉积方法制备了(Ni-Mo)-TiO2复合电极,讨论了TiO2悬浮量和电沉积时间对电极催化析氢性能的影响.用XRD和SEM对电极的晶体结构和表面形貌进行了表征,以稳态极化曲线对电极的催化析氢特性进行了评价.结果表明,(Ni-Mo)-TiO2电极是纳米TiO2粒子相和纳米晶Ni-Mo固溶体相构成的复合电极.电极具有较高的催化析氢活性.在25℃、0.5mol.dm-3H2SO4溶液中其表观交换电流密度是Ni-Mo合金电极的2.6倍,是Ni电极的60倍.在电流密度为100mA·cm-2时,电极电势相对于Ni-Mo电极正移了120mV,相对于Ni电极正移了542mV.催化活性的提高源于反应机理的改变,表观活化吉布斯自由能相对于Ni-Mo合金电极降低了24.48kJ·mol-1.     

冠脉支架表面PLGA涂层制备及其血液相容性研究

采用静电喷涂沉积(electrospray deposition ESD)法在冠脉支架表面制备了PLGA涂层.采用OLYMPUS体式显微镜、原子力显微镜(AFM)观察了涂层宏观表面形貌及三维形貌;通过对涂层支架进行球囊扩张考察了PLGA涂层与支架的结合力;通过血小板粘附实验和动态凝血时间测定研究PLGA涂层的血液相容性.结果表明:ESD法在冠脉支架表面制备PLGA涂层,支架筋拐角处无明显的聚合物胶体缠绕、粘连且涂层表面光滑;PLGA涂层将316L不锈钢基体的微坑覆盖,基体Ra=16.174nm,PLGA涂层Ra=0.149nm,涂层表面粗糙度小;涂层支架撑开后在最大塑性变形位置无涂层撕裂、翘起等缺陷,涂层与支架有良好结合力;PLGA涂层血小板粘附量少,变形小,未引起血小板激活,动态凝血时间长,直到50min未产生凝血,PLGA涂层具有较好的血液相容性.     

Synthesis of polypyrrole film by pulse galvanostatic method and its application as supercapacitor electrode materials

Polypyrrole (PPy) film-coated stainless steel electrodes were prepared from aqueous solution containing 0.5 M p-toluene sulphonic acid and 0.1 M pyrrole using pulse galvanostatic method (PGM) and galvanostatic method (GM). The morphology was characterized by scanning electron microscopy. The electrochemical properties of PPy films were investigated with cyclic voltammetry, charge–discharge tests, and ac impedance spectroscopy. The results showed that the PGM-PPy films exhibited higher specific capacitance, better high-rate discharge ability and lower resistance, and were more promising for applications in supercapacitor than GM-PPy films. The specific capacitance (SC) of PGM-PPy films was 403 F g⁻¹ in 1 M H₂SO₄ electrolyte and 281 F g⁻¹ in 1 M NaNO₃ electrolyte.     

Fluoride-selective optical sensor based on aluminum(III)-octaethylporphyrin in thin polymeric film: further characterization and practical application

More detailed analytical studies of a new fluoride-selective optical sensor based on the use of aluminum(III)-octaethylporphyrin and a lipophilic pH indicator (4',5'-dibromofluorescein octadecyl ester; ETH-7075) within a thin plasticized poly(vinyl chloride) film are reported. The sensor exhibits extraordinary optical selectivity for fluoride over a wide range of other anions, including anions with far more positive free energies of hydration (e.g., perchlorate, thiocyanate, nitrate, etc.). UV-visible spectrophotometric studies of the sensing films indicate that fluoride interacts with the Al(III) center of the porphyrin structure, yielding both a change in the Soret band lambda(max) of the porphyrin and a change in the protonation state of the pH indicator within the film. The same change in spectral properties of the metalloporphyrin occurs in the absence of added pH indicator or with added tetraphenylborate derivative anionic sites, but optical responses to fluoride in these cases are shown to be irreversible. The presence of the pH indicator and the simultaneous fluoride/proton coextraction equilibrium chemistry is shown to greatly enhance the reversibility of fluoride binding to the Al(III) porphyrin. Optical response toward fluoride can be observed in the range of 0.1 microM-1.6 mM. Optical selectivity coefficients of <10(-6) for common anions (e.g., sulfate, chloride, nitrate, etc.) and <10(-4) for perchlorate and thiocyanate are obtained. Measurements of fluoride in drinking water via the new optical sensor are shown to correlate well with values obtained for the same samples using a classical LaF3-based fluoride ion-selective electrode method.     

Suitability of various excipients as carrier and coating materials for liquisolid compacts

Context: The liquisolid technology is a promising technique for the release enhancement of poorly soluble drugs. With this approach, liquids such as solutions or suspensions of poorly soluble drugs in a non-volatile liquid vehicle are transformed into acceptably flowing and compressible powders. As fast-release liquisolid compacts require a high amount of liquid vehicle, more effective tableting excipients for liquid adsorption are needed to reduce tablet weight.

Objective: The aim of this study was to investigate the suitability of various novel tableting excipients as carrier and coating materials for liquisolid compacts.

Materials and methods: Liquisolid compacts containing the liquid drug tocopherol acetate (TA) as model drug and various excipients were prepared. The effect of liquid drug content on the flowability and tabletability of the liquisolid powder blends as well as the disintegration of the liquisolid compacts was studied. From this data, the maximum liquid adsorption capacity of the respective mixtures of carrier and coating materials could be determined.

Results and discussion: The liquid adsorption capacity depends on the specific surface area of the investigated excipients. Fujicalin^® and especially Neusilin^® are more effective carrier materials for liquid adsorption than Avicel^®, which is often used for liquisolid systems. Moreover, Florite^® and Neusilin^® turned out to be more suitable as coating materials than the commonly used Aerosil^® due to their better tableting properties.

Conclusion: If Neusilin^® is used as carrier and coating material instead of Avicel^® (carrier material) and Aerosil^® (coating material), the TA adsorption capacity is increased by a factor of 7.     

SC-CO2纤维粘接法制备PLA/TCP/Collagen组织工程支架材料

在超临界CO2(SC-CO2)循环萃取条件下制备PLA/TCP/Collagen(PTC)多孔组织工程支架材料,研究了胶原含量对支架材料的总孔隙率、开孔率、孔洞形态和力学性能的影响,以及胶原纤维在支架材料中的分布.结果表明:用SC-CO2反复循环萃取法制备的PTC支架材料开孔率可达到82.81%,比不加胶原的PLA/TCP支架高约25%;孔径为200-500 μm,孔洞之间出现重要的"隧道"结构;胶原纤维在SC-CO2反复循环萃取法处理后保持着网络形态,在支架中分布均匀;胶原纤维加入使支架材料的压缩模量和压缩强度明显下降.     

Use of polymeric materials as a solid phase for radioimmunoassay and immunoradiometric assay techniques

Poly(acrylamide-acrylic acid-acrylonitrile)-ferrous sulfate, p(AM-AA-AN)-FeSO₄·7H₂O, resin was used as a solid phase for estimation of thyroid stimulating hormone (TSH) by radioimmunoassay (RIA) and immunoradiometric assay (IRMA) techniques. Comparison with cellulose particles as a known polymer solid phase was made. The tracers for RIA and IRMA were prepared by radioiodination of TSH antigen and TSH monoclonal antibody, respectively, using Iodogen as oxidizing agent. The tracers were purified by gel chromatography on Sephadex G-25 column. The polyclonal anti-TSH antibody was prepared via immunization of three white New Zealand rabbits with highly purified TSH antigen. The polymer was prepared by addition of aqueous solution of comonomer (AA-AN) and FeSO₄ as cross-linker to polyacrylamide p(AM) and irradiation of the mixture at ambient temperature in a ⁶⁰Co γ-cell. The polymer prepared and cellulose particles were activated using 1,1-carbonyldiimidazole, and these activated particles were coupled with the polyclonal TSH antibody. Optimization and validation of the RIA and IRMA techniques were made.     

Effect of diisocyanates as compatibilizer on the properties of ramie/poly(lactic acid) (PLA) composites

Ramie/PLA composites with the diisocyanates as compatibilizer were fabricated by extrusion and injection molding. The influence of different diisocyanates and various diisocyanate content on the mechanical properties and thermal properties of the composites was investigated. The presence of the diisocyanates in the composites lead to the improvements in mechanical properties and thermal properties of the composites. The morphologies of fracture surface using scanning electron microscopy (SEM) provided evidence of improved interfacial adhesion between ramie and PLA from the addition of the diisocyanates. The composites containing isophorone diisocyanate (IPDI) showed the best mechanical properties. The comparison of various IPDI content showed that the composites with 1.5% IPDI could get the optimum mechanical properties, and the excess diisocyanate content resulted in the decrease in the mechanical properties of the composites. However, IPDI content had almost no effect on the crystallization and melting behavior of the ramie/PLA composites.     

Additive manufacturing of mechanical testing samples based on virgin poly (lactic acid) (PLA) and PLA/wood fibre composites

3D printing in additive manufacturing is considered as one of key technologies to the future high-precision manufacturing in order to benefit diverse industries in building construction, product development, biomedical innovation, etc. The increasing applications of 3D printed components depend primarily on their significant merits of reduced weight, minimum used materials, high precision and shorter production time. Furthermore, it is very crucial that such 3D printed components can maintain the same or even better material performance and product quality as those achieved by conventional manufacturing methods. This study successfully fabricated 3D printed mechanical testing samples of PLA and PLA/wood fibre composites. 3D printing parameters including infill density, layer height and the number of shells were investigated via design of experiments (DoE), among which the number of shells was determined as the most significant factor for maximising tensile strengths of PLA samples. Further, DoE work evaluated the effect of material type (i.e., neat PLA and PLA/wood fibres) and the number of shells on tensile, flexural and impact strengths of material samples. It is suggested that material type is the only predominant factor for maximising all mechanical strengths, which however are consistently lower for PLA/wood fibre composites when compared with those of neat PLA. Increasing the number of shells, on the other hand, has been found to improve almost all strength levels and decrease infill cavities. The full text can be downloaded at https://link.springer.com/article/10.1007/s40436-018-0211-3