γ辐照对聚己内酯性能的影响

研究了不同分子量的聚己内酯的辐照特性，聚已内酯(PCL)的分子量越大，辐射交联所需的凝胶化剂量越低。结果表明，溶胶分数s √s与I／D的关系很好地符合Charlesby-Pinner关系式，说明PCL的辐射交联属于无规交联。辐射交联对PCL的力学性能影响显著，辐射剂量越大，拉伸强度和断裂伸长率下降越多，但分子量较高的PCL的抗张强度受辐射剂量的影响较小。动态力学分析(DMA)分析表明，聚己内酯辐照交联后的弹性模量和耐热性能显著提高。     

The effect of ethyl-lactate and ethyl-acetate plasticizers on PCL and PCL–HA composites foamed with supercritical CO2

The present study reports foaming of polycaprolactone (PCL) and PCL nano- and micro-composites with dispersed hydroxyapatite (HA) particles by means of binary mixtures of supercritical CO₂ (scCO₂) and either ethyl lactate (EL) or ethyl acetate (EA) as plasticizer. The effect of the size and concentration of HA particles, as well as the effects of the plasticizer type and the incorporation route were investigated aiming to fabricate porous scaffolds with uniform morphology and controlled pore size distribution. For this purpose, foaming experiments were carried out by selecting two operating temperatures, 40 and 45 °C, and two soaking times, 1 and 17 h. Furthermore, a double step of depressurization was used to promote the development of a double-scale pore size structure in porous scaffolds useful for tissue engineering.The results of this study indicated that supercritical foaming of PCL and PCL–HA composites is enhanced when the selected operating temperature and time are 45 °C and 17 h, respectively. Furthermore, although both EL and EA plasticizers enhanced the low temperature foaming of the materials, we demonstrated that the route of incorporation of the plasticizer is a critical aspect for enhancing composite foaming and scaffold fabrication. From this point of view, the best results were achieved when EA was pre-mixed with the polymeric powder for preparing a dough for the foaming process.     

Preparation and characterization of zinc modified calcium silicate/polycaprolactone with graphene oxide composite coating for bone repair applications

The goal of biomaterial interest is the ease of the bone tissue regeneration process or the replacement of damaged bone and other tissues with recently generated bone tissue. Calcium silicate (CaSi) bioceramic is a vital material for bone tissue engineering, predominantly for bone repair. Though, the low toughness of calcium silicate imitates its load-bearing applications. The electrophoretic deposition technique was used to coat various concentrations of Zn²⁺ substituted CaSi on TNT. In this work, a novel as-obtained an appropriate orthopedic implant hybrid material by charged calcium ions of mineralized calcium silicate united with PCL-negatively charged graphene oxide [Zn-CaSi (S₁-S₃)/PCL (P₁-P₃)/GO]. Hence, the effectively as-obtained [Zn-CaSi (S₁-S₃)/PCL (P₁-P₃)/GO] bone-like apatite on the ternary composite coatings on the surface was proven via XRD, FT-IR, FESEM with EDAX spectra, HR-TEM and BET analyses etc., Moreover, the TNT/S₂/P₂@GO ternary composite coatings exhibit better mechanical properties and antibacterial activity. The metal ions released from the coatings were calculated via ICP-AES studies. Moreover, the cell viability and also the live/dead staining of MG63 human osteoblasts cells on the subsequent composite coating material for better cell growth in orthopedic applications.     

Optimized allylamine deposition for improved pluripotential cell culture

Deposition of allylamine (ALL) by plasma enhanced chemical vapor deposition has been optimized on silicon based models. Simultaneous energy recoil detection analysis and Rutherford backscattering spectra show that 100 W deposition is ideal in terms of polymerized film formation and H content while, lower or higher power induce reduced film retention or excessive cross linking, respectively. Surface composition of the ALL film was further probed by X-ray photoelectron spectroscopy revealing a monocomponent N 1s spectrum compatible with the presence of primary amines. Optimized ALL films were applied to polycaprolactone (PCL) surfaces after Ar plasma activation with implications in the chemistry and wettability of this biocompatible polymer. Human mesenchymal stem cells (hMSCs) were cultured on ALL coated PCL surface and controls. ALL functionalized PCL was found to be especially attractive for the formation of confluent monolayers of hMSCs after 72 h of culture.     

Chemical modification of zein by bifunctional polycaprolactone (PCL)

Prepolymer was synthesized by use of PCL and hexamethylene diisocyanate (HDI), and then used to prepare modified zein-based polymers (ZPs). Solid-state ¹³C NMR results showed that at least four amino acids (Glu, Gln, Tyr and His) reacted with the prepolymer, and urea-urethane links were prominent. Thermal analysis indicated that micro-phase separation formed between zein matrix and PCL-HDI (PCLH) component in ZPs. With the increasing PCLH content, the melting point of PCL in ZP decreased, and the T_g of zein reduced due to plasticizer role of PCLH. The breaking elongation of modified zein containing 10% PCLH content, increased about 15 times while its strength at break only reduced by about 2 times than that of commercial zein. In addition, with the increasing PCLH content, the flexibility of modified zein sheet improved dramatically with negligible reduction in strength. This indicates that PCL was an elastic fraction in ZPs. Therefore, it is an effective way to improve the mechanical properties of zein by modification with PCL, showing a potential in the field of biodegradable polymers.     

Investigation of cancer cell behavior on nanofibrous scaffolds

Tissue engineering and the use of nanofibrous biomaterial scaffolds offer a unique perspective for studying cancer development in vitro. Current in vitro models of tumorigenesis are limited by the use of static, two-dimensional (2D) cell culture monolayers that lack the structural architecture necessary for cell-cell interaction and three-dimensional (3D) scaffolds that are too simplistic for studying basic pathological mechanisms. In this study, two nanofibrous biomaterials that mimic the structure of the extracellular matrix, bacterial cellulose and electrospun polycaprolactone (PCL)/collagen I, were investigated as potential 3D scaffolds for an in vitro cancer model. Multiple cancer cell lines were cultured on each scaffold material and monitored for cell viability, proliferation, adhesion, infiltration, and morphology. Both bacterial cellulose and electrospun PCL/collagen I, which have nano-scale structures on the order of 100-500 nm, have been used in many diverse tissue engineering applications. Cancer cell adhesion and growth were limited on bacterial cellulose, while all cellular processes were enhanced on the electrospun scaffolds. This initial analysis has demonstrated the potential of electrospun PCL/collagen I scaffolds toward the development of an improved 3D in vitro cancer model.     

Characterization of the Plasticized GAP/PEG and GAP/PCL Block Copolyurethane Binder Matrices and its Propellants

Though glycidyl azide polymer (GAP) is a well‐known and promising energetic polymer, propellants based on it suffer from poor mechanical and low‐temperature properties. To overcome these problems, plasticized GAP‐based copolymeric binders were prepared and investigated through the incorporation of flexible‐structural polyethylene glycol (PEG) and polycaprolactone (PCL) into a binder recipe under a Desmodur N‐100 polyisocyanate (N‐100)/isophorone diisocyanate (IPDI) (2 : 1, wt. ratio) mixed curative system. The nitrate esters (NEs) or GAP oligomer were used as energetic plasticizers at various ratios to the polymers. The GAP/PCL binders held the plasticizers much more than the GAP/PEG binders did. The glass transition temperatures (T_g) of segmented copolymeric binders were more dependent on the plasticizer level than the PEG or PCL content. The increase in the plasticizer content decreased the mechanical strength and modulus of binders, while the change of strain was modest. Finally, the NE plasticized GAP‐based solid propellants showed enhanced mechanical and thermal properties by the incorporation of PEG or PCL. The properties of GAP/PCL propellants were superior to those of GAP/PEG propellants.     

Effect of composite coating with poly-dopamine/PCL on the corrosion resistance of magnesium

We report the use of poly(ε-caprolactone) (PCL) and poly-dopamine (PD) as a protective coating that inhibits corrosion of the underlying magnesium metal. The PD coating layer also improved the adhesion of the PCL layer, which has been found to have a significant effect on corrosion behavior. In this study, electrochemical methods were employed to investigate the corrosion behavior of Mg after applying PCL composite coatings. Potentiodynamic polarization measurements determined that the PCL coating pretreated with PD effectively inhibited metal corrosion. In addition, the coating layer with improved adhesion has shown the possibility of inhibiting metal corrosion.     

Synthesis and Characterization of Poly(glycidyl nitrate‐block‐caprolactone‐block‐glycidyl nitrate) (PGN‐PCL‐PGN) Tri‐Block Copolymer as a Novel Energetic Binder

An energetic binder was synthesized through ring opening copolymerization of glycidyl nitrate (GLYN) with polycaprolactone (PCL) as a macroinitiator to form tri‐block copolymer PGN‐PCL‐PGN. Effect of monomer concentration, catalyst, reaction time and solvent was investigated in polymerization. Resulting tri‐block copolymer was characterized by Fourier transform infrared spectroscopy (FT‐IR), nuclear magnetic resonance spectroscopy (NMR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The DSC result shows that glass transition temperature of tri‐block copolymer (T_g=−56.2 °C) is lower than PGN (T_g=−35 °C). In optimal condition, the M_w of this polymer was obtained 2900 g/mol.     

辐射交联聚己内酯的非等温结晶动力学研究

研究γ辐照对聚己内酯(Polycaprolactone,PCL)非等温结晶行为的影响,利用Ozawa方程和莫志深方法对辐射交联PCL的非等温结晶过程进行了分析。结果表明,辐射交联PCL的结晶过程为异相成核的单轴生长模式,结晶速率变快,结晶度也有所增加。辐射对PCL的结晶过程影响较复杂,低剂量时,结晶活化能随剂量的增加而下降,更高剂量时,结晶活化能随剂量反而升高,由Kissinger方程计算出的结晶活化能为54—64kJ/mol。