Characterization of 3D Printed Poly(3-Hydroxybutyric-Co-3-Hydroxyvalerate) by Fused Granular Fabrication through Thermal and Mechanical Analyses

Poly[R-3-hydroxybutyrate-co-(R-3-hydroxyvalerate)] (PHBVs) copolymers are promising biopolymers, which could substitute petroleum-based plastics for various applications. PHB and PHBV pellets were processed on a customized 3D printer via Fused Granular Manufacturing (FGM) approach modified with a Mahor screw extruder. To anticipate the behaviour of PHBVs when transformed using conventional thermo-mechanical shaping processes, thermal and mechanical analyses were carried out in order to better understand the effect of annealing temperature on their crystallization behaviour and mechanical properties of PHB polymer and PHBV copolymer. The objectives of the present work were to propose an experimental strategy to study the melting and crystallization events, crystalline structure changes, and mechanical performances of both PHB homopolymer and PHBV copolymer according to identical thermal annealing treatments. A monitoring of 3D printed PHB and PHBV structures was achieved by coupling Differential Scanning Calorimetry (DSC) and tensile tests. .

Poly3D软件及其在地学中的应用

免费的Poly3D边界元软件基于位移不连续性方法,它不仅能够模拟断层或裂缝的静态生长,而且所采用的多边形单元可以很好地表示出复杂多边的不连续界面。该软件在地学中的应用较为广泛,诸如裂缝形成、由断层互相作用造成的应力扰动和滑移量分布、地下断层形态的确定、低于地震识别精度的断层的预测、地震触发等等。

门多萨假单胞菌DS04-T对Poly(3HB-co-4HB)的降解研究

考察了门多萨假单胞菌DS04-T对Poly(3HB-co-4HB)的降解行为。以Poly(3HB-co-4HB)为唯一碳源,分别考察培养时间、培养温度、摇床转速、装液量、培养基起始pH值、接种量等因素对降解行为的影响。结合正交试验优化获得了菌株的最佳产酶条件:培养时间为28h,培养温度为30℃,培养基初始pH值为7.3,摇床转速为150r/min,培养基装液量为120mL(250mL三角瓶),接种量为1.5%(体积分数),此条件下菌株对Poly(3HB-co-4HB)的降解酶活力可达(26.2±0.7)U.mL-1。

Miscibility, Crystallization, and Rheological Behavior of Solution Casting Poly（3-hydroxybutyrate）/poly（ethylene succinate） Blends Probed by Differential Scanning Calorimetry, Rheology, and Optical Microscope Techniques

The miscibility and crystallization of solution casting biodegradable poly（3-hydroxybuty- rate）/poly（ethylene succinate） （PHB/PES） blends was investigated by differential scanning calorimetry, rheology, and optical microscopy. The blends showed two glass transition temperatures and a depression of melting temperature of PHB with compositions in phase diagram, which indicated that the blend was partially miscible. The morphology observation supported this result. It was found that the PHB and PES can crystallize simultaneously or upon stepwise depending on the crystallization temperatures and compositions. The spherulite growth rate of PHB increased with increasing of PES content. The influence of compositions on the spherulitic growth rate for the partially miscible polymer blends was discussed.

Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) supports adhesion and migration of mesenchymal stem cells and tenocytes

AIM: To establish the potential of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx) as a material for tendon repair. METHODS: The biocompatibility of PHBHHx with both rat tenocytes (rT) and human mesenchymal stem cells (hMSC) was explored by monitoring adhesive characteristics on films of varying weight/volume ratios coupled to a culture atmosphere of either 21% O2 (air) or 2% O2 (physiological normoxia). The diameter and stiffness of PHBHHx films was established using optical coherence tomography and mechanical testing, respectively. RESULTS: Film thickness correlated directly with weight/volume PHBHHx (r2 = 0.9473) ranging from 0.1 mm (0.8% weight/volume) to 0.19 mm (2.4% weight/volume). Film stiffness on the other hand displayed a biphasic response which increased rapidly at values > 1.6% weight/volume. Optimal cell attachment of rT required films of ≥ 1.6% and ≥ 2.0% weight/volume PHBHHx in 2% O2 and 21% O2 respectively. A qualitative adhesion increase was noted for hMSC in films ≥ 1.2% weight/volume, becoming significant at 2% weight/volume in 2% O2. An increase in cell adhesion was also noted with ≥ 2% weight/volume PHBHHx in 21% O2. Cell migration into films was not observed. CONCLUSION: This evaluation demonstrates that PHBHHx is a suitable polymer for future cell/polymer replacement strategies in tendon repair.

Photochemical reactions of poly(3-butoxythiophene-2,5-diyl) with chloroform

Photochemical reactions of poly(3-butoxythiophene-2,5-diyl) with chloroform under irradiation with light were studied. The reactions were separately carried out under air, oxygen, and nitrogen. The obtained results showed that this reaction belongs to the pseudo-first-order reaction with a rate constant kobs of 1.4×10?5 s?1 at room temperature. The presence or absence of air, oxygen, and nitrogen did not have obvious effects on the reaction rate under irradiation with light.

Synthesis of Poly (3-acetylpyrrolyl methine) with Azobenzene Side Groups and Study on Its Third-order Nonlinear Optical Property

A novel soluble π-conjugated polymer, poly [（3-acetylpyrrole-2, 5-diyl） p-（N, N-dimethylamino） azobenzylidene] （PAPDMAABE）, was synthesized by condensation of 3-acetylpyrrole with 4-aldehyde-4＇-dimethylaminoazobenzene （ADMAA）. The chemical structure of PAPDMAABE was characterized by Fourier transform infrared spectroscopy （FTIR）, ^1H-NMR, and UV-Vis-NIR spectra. Transmission electron microscope （TEM） analysis for PAPDMAABE indicates that part of PAPDMAABE is in crystal state, due to the short-range order of the polymer. Thermogravimetric analysis （TGA） curve shows that the polymer has good thermal stability and its decomposition temperature is 248℃. The optical band gap of PAPDMAABE obtained from the optical absorption spectrum is about 1.73 eV. The resonant third-order nonlinear optical property of PAPDMAABE at 532 nm was studied using degenerate four-wave mixing （DFWM） technique. The resonant third-order nonlinear optical susceptibility of the polymer is about 7.48×10^-8 esu.

Effect of poly(3-hydroxyalkanoates) as natural polymers on mesenchymal stem cells

Mesenchymal stem cells(MSCs)are stromal multipotent stem cells that can differentiate into multiple cell types,including fibroblasts,osteoblasts,chondrocytes,adipocytes,and myoblasts,thus allowing them to contribute to the regeneration of various tissues,especially bone tissue.MSCs are now considered one of the most promising cell types in the field of tissue engineering.Traditional petri dish-based culture of MSCs generate heterogeneity,which leads to inconsistent efficacy of MSC applications.Biodegradable and biocompatible polymers,poly(3-hydroxyalkanoates)(PHAs),are actively used for the manufacture of scaffolds that serve as carriers for MSC growth.The growth and differentiation of MSCs grown on PHA scaffolds depend on the physicochemical properties of the polymers,the 3D and surface microstructure of the scaffolds,and the biological activity of PHAs,which was discovered in a series of investigations.The mechanisms of the biological activity of PHAs in relation to MSCs remain insufficiently studied.We suggest that this effect on MSCs could be associated with the natural properties of bacteria-derived PHAs,especially the most widespread representative poly(3-hydroxybutyrate)(PHB).This biopolymer is present in the bacteria of mammalian microbiota,whereas endogenous poly(3-hydroxybutyrate)is found in mammalian tissues.The possible association of PHA effects on MSCs with various biological functions of poly(3-hydroxybutyrate)in bacteria and eukaryotes,including in humans,is discussed in this paper.

Synthesis of Poly[(3-octanoylpyrrole-2,5-diyl)-p-(N,N-dimethylamino)benzylidene] and Its Properties by Nitrogen Ion Implantation

A novel soluble π-conjugated polymer, poly[(3-octanoylpyrrole-2,5-diyl)-p-(N,N-dimethylamino)benzylidene](POPDMABE), was synthesized firstly by the condensation of 3-octanoylpyrrole with para-dimethylaminobenzaldehyde. The chemical structure of the polymer was characterized by FTIR and 1H NMR spectrometries. The polymer is a potential nonlinear optical(NLO) material. According to the function of optical forbidden band gap(E_g) and photon energy(hν), the optical forbidden band gaps of the polymer before and after ion implantation were calculated. The resonant third-order nonlinear optical properties of POPDMABE before and after ion implantation were also studied by using the degenerate four-wave mixing(DFWM) technique at 532 nm. When the energy is 25 keV and the dose is 2.2×10 17 ions/cm 2, the {polymer′s} optical forbidden band gap is about 1.63 eV which is smaller than that of the non-implanted sample(1.98 eV) and the resonant third-order NLO susceptibility of POPDMABE is about 4.3×10 -7 esu, 1 order of magnitude higher than that of the non-implanted sample(4.1×10 -8 esu). The results show that nitrogen ion implantation is an effective method to improve the resonant third-order NLO property of the polymer.

A Study on Preparation and Use of Nano Poly Pyrrole and Nano Poly (3,4-Ethylenedioxythiophene) Coated Glassy Carbon Electrode For The Determination of Antihistamine in Pharmaceutical and Urine Sample

Pheniramine maleate (PA), an antihistamine, was determined by Differential Pulse Stripping voltammetry using nano polypyrrole (Ppy) and nano poly(3,4-ethylenedioxythiophene) (PEDOT) modified glassy carbon electrodes. The cyclic voltammetric behavior of pheniramine was studied in aqueous acidic, neutral and alkaline conditions. One well-defined oxidation peak was observed in the cyclic voltammograms at all pHs. The influence of pH, scan rate and concentration revealed irreversible electron transfer and the oxidation was diffusion controlled adsorption. The SEM analysis confirmed good accumulation of PA on the electrode surface. A systematic study of influence of various experimental parameters that affect the stripping voltammetric response was carried out and the maximum peak current conditions were arrived at. Calibration was made under maximum peak current conditions. The range of study was 0.05 to 0.4 μg/mL on Ppy/GCE and 0.025 to 0.4μg/mL on PEDOT/GCE and the lower limit of determination were 0.035μg/mL on Ppy/GCE and 0.016μg/mL on PEDOT/GCE. The suitability of the method for the determination of PA in pharmaceutical preparations and urine samples was also ascertained.

Annealed Treatment Effect in Poly（3-hexylthiophene）：Methanofullerene Solar Cells

Polymer photovoltaic devices based on poly（3-hexylthiophene） （P3HT） ： [6,6]-phenyl-C61-butyricacid methyl ester （PCBM） 1：1 weight-ratio blend are reported. The effects of various annealing treatments on the device performance are investigated. Thermal annealing shows significant improvement of the device performances. For devices at 130℃ annealing, maximum power conversion efficiency （PCE） of 3.3% and All factor up to 60.3% is achieved under air mass 1.5, 100 m W/cm^2 illumination. We discuss the effect of thermal annealing by the results of ultraviolet-visible absorption spectroscopy （UV-vis）, dark current-voltage curve, atomic force microscopy （AFM）.

Production of Poly(3-Hydroxybutyrate)by Fed-Batch Culture of Alcaligenes Eutrophus at Phosphorus Limitation in 50 L fermenter

Poly(3-hydroxybutyrate) (PHB) is an intracellular carbon and energy storage material accumulated by many kinds of microorganism under unfavorable growth conditions. For the production of PHB, Alcaligenes eutrophus has been widely used because it is easy to grow, and its physiological and biochemical changes during the PHB synthesis is understood in details. A very high concentration and productivity of PHB could be obtained by fed-batch culture of Alcaligenes eutrophus with phosphate limitation in 50 L fermenter.

DOPING LEVEL INCREASE OF POLY(3-METHYLTHIOPHENE)FILM DURING ELECTROCHEMICAL POLYMERIZATION PROCESS

The Raman spectra of poly(3-methylthiophene) (PMeT) films with different thicknesses, which have been electrochemically deposited on a flat stainless steel electrode surface by direct oxidation of 3-methylthiophene in boron trifluoride diethyl etherate (BFEE) at a constant applied potential of 1.38 V (versus SCE), have been investigated by excitation with a 633-nm laser beam. The spectroscopic results demonstrated that the doping level of PMeT film was increasing during film growth. This finding was also confirmed by electrochemical examination. Moreover, the Raman bands assigned to radical cations and dications in doped PMeT films were found approximately at 1420 and 1400 cm(-1), respectively. Radical cations and dications coexist on the backbone of PMeT as conductive species and their concentrations increase with the increase of doping level. Successive cyclic voltammetry was proved to be an effective approach to improving the doping level of as-grown thin compact PMeT film.

BIOSYNTHESIS AND THERMAL PROPERTIES OF POLY(3-HYDROXYBUTYRATE-co-3-HYDROXYVALERATE)WITH LARGE VARIETY OF HYDROXYVALERATE CONTENTS BY BACILLUS CEREUS

Biosynthesis and thermal properties of poly（3-hydroxybutyrate-co-3-hydroxyvalerate） （PHBV） with different HV （hydrovalerate） content produced by a Bacillus cereus strain were investigated. A large variety of HV contents （up to about 90 mol%） of PHBV could be produced by this strain. Combined nitrogen sources containing both yeast extract and ammonium sulphate were better for cell growth and polyhydroxyalkanoates （PHA） production than either yeast extract or ammonium sulphate alone. Propionic acid is more favorable for the production of HV content than that of valeric acid. Finally, thermal properties of PHBV produced by this strain are found close to the results of other groups.

The Crystallization of Poly (3-dodecyltbiophene) in an Oriented Solidification Environment

The crystallization behaviors of poly (3-dodecylthiophene) (P3DDT) under two different oriented solidification conditions. i e..' two different relative relations (90° and 180°) between the directions of gravity and solidification. were investigated. X-ray diffraction results reveal that although similar layered structures are formed, under the condition of the relative relation 180°. temperature; gradient has greater effects on the perfect degree of the layered structures of P3DDT. It also can be concluded that after recrystallization. the layered structures of P3DDT can be improved at relative relation 90°, but the orderly degree of the arrangements of alkyl side chains are not improved yet, even is reduced for both of the oriented solidification conditions.

Vacuum relaxation and annealing-induced enhancement of mobility of regioregular poly(3-hexylthiophene) field-effect transistors

In order to enhance the performance of regioregular poly（3-hexylthiophene） （RR-P3HT） field-effect transistors （FETs）, RR-P3HT FETs are prepared by the spin-coating method followed by vacuum placement and annealing. This paper reports that the crystal structure, the molecule interconnection, the surface morphology, and the charge carrier mobility of RR-P3HT films are affected by vacuum relaxation and annealing. The results reveal that the field-effect mobility of RR-P3HT FETs can reach 4.17×10^-2m^2/（V·s） by vacuum relaxation at room temperature due to an enhanced local self-organization. Furthermore, it reports that an appropriate annealing temperature can facilitate the crystal structure, the orientation and the interconnection of polymer molecules. These results show that the field-effect mobility of device annealed at 150 ℃ for 10 minutes in vacuum at atmosphere and followed by placement for 20 hours in vacuum at room temperature is enhanced dramatically to 9.00×10^-2m^2/（V·s）.

FABRICATION OF HIGHLY HYDROPHOBIC FILMS OF POLY(3-HEXADECYL PYRROLE) NANOPARTICLES BY LANGMUIR-BLODGETT TECHNIQUE

Thin films of poly（3-hexadecyl pyrrole） （P3HDP） nanoparticles have been fabricated by using Langmuir-Blodgett film deposition technique. The structures and morphology of the films were studied by using infrared spectroscopy, scanning and transmission microscopes. The experimental results demonstrated that the nanoparticles were formed by self-assembling P3HDP at air-water surface. The water contact angles of these films with different deposition layers were measured to be as high as 110°.

SYNTHESIS OF SOLUBLE POLY(3-HEXYL-2,5-THIENYLENE VINYLENE) FROM THIOPHENE

Soluble poly(3-hexyl-2,5-thienylene vinylene) (PHTV) was readily synthesized from thiophene in a yield better than that of the precursor method to prepare poly(thienylene vinylene) (PTV). The bandgap of the polymer is about 1.8 eV, which is comparable with that of PTV. Owing to the introduction of alkyl side groups onto the backbone of the polymer, it can be dissolved in common organic solvents such as chloroform, THF and toluene. The synthesis of soluble PHTV is a very important approach to preventing oxidation and to improving the properties and the processbility of the PTV. The existence of alkyl side groups in PHTV does not affect its, bandgap and thermal properties as compared with PTV. After doping with FeCl3, the conductivity of PHTV is as high as 1.1 x 10(-2) S/cm. The soluble PHTV can be easily transformed into thin film with much better quality than that of the PTV film prepared by the traditional precursor method, which is very important for fabricating devices with good properties.

Gas Sensitivity of Poly (3, 4-ethylene dioxythiophene) Prepared by a Modified LB Film Method

An arachidic acid/poly （3, 4-ethylene dioxythiophene） （AA/PEDOT） multilayer Langmuir-Blodgett （LB） film was prepared by a modified LB film method. The theories were utilized to explain the effects between HCl molecule and LB film. The gas sensitivity mechanism of poly （3, 4-ethylene dioxythiophene） （PEDOT） multilayer film can be explained by the charge transfer between p system of PEDOT and oxidization HCl system. The gas sensitivity of PEDOT LB film deposited interdigital electrode to HCl was tested. The results showed that film thickness, treating temperature, deposition speed had different influence on film gas sensitivity. The AA/PEDOT film deposited device exhibited nonlinear behavior to HCl gas at lower concentration （20-60 ppm） and linear response behavior at higher gas concentration was observed. The time of the compound LB film of the AA/PEDOT responding to the 30 ppm HCl gas is about 20 seconds, which is far quicker than the time of the film to the PEDOTPRESS film（about 80 seconds）. It is not higher film press to better film. When the film press attains 45 mNs/m, the sensitivity of the AA/PEDOT film on the contrary descends.