Synthesis and properties of castor oil-based polyurethane containing short fluorinated segment

This study successfully incorporated a short-segment fluorine-containing chain extender (2,2,3,3-tetrafluoro-1,4-butanediol [TF]) into castor oil-based polyurethane (COPU) to synthesize TF/COPUs. The interactions between TF and COPU components were identified by Fourier transform infrared and X-ray photoelectron spectroscopies, the results revealed that the increase in the TF content increased the van der Waals forces in C F…CO and the hydrogen bonding force in C F…H N. Atomic force microscopy indicated that the addition of more TF contributed to a higher level of microphase separation in the TF/COPUs. Thermogravimetric analysis showed that the TF component can enhance the thermal resistance of TF/COPUs. Differential scanning calorimetry and dynamic mechanical analysis indicated that the glass transition temperature (T_g) of TF/COPUs increased with the TF content. The stress–strain testing showed that the tensile strength and elongation at break values decreased with the TF content. This tensile behavior may be due to the molecular weight of a TF/COPU decreased with the TF content as evidenced by the gel permeation chromatography results. The hydrolytic degradation tests of dipping TF/COPUs in 3 wt% NaOH solution indicated that TF could lower the surface free energy and enhance the degradation stability of TF/COPUs.     

Fabrication and Thermal Dissipation Properties of Carbon Nanofibers Derived from Electrospun Poly(Amic Acid) Carboxylate Salt Nanofibers

Polyimides (PIs) possess excellent mechanical properties, thermal stability, and chemical resistance and can be converted to carbon materials by thermal carbonization. The preparation of carbon nanomaterials by carbonizing PI‐based nanomaterials, however, has been less studied. In this work, the fabrication of PI nanofibers is investigated using electrospinning and their transformation to carbon nanofibers. Poly(amic acid) carboxylate salts (PAASs) solutions are first electrospun to form PAAS nanofibers. After the imidization and carbonization processes, PI and carbon nanofibers can then be obtained, respectively. The Raman spectra reveal that the carbon nanofibers are partially graphitized by the carbonization process. The diameters of the PI nanofibers are observed to be smaller than those of the PAAS nanofibers because of the formation of the more densely packed structures after the imidization processes; the diameters of the carbon nanofibers remain similar to those of the PI nanofibers after the carbonization process. The thermal dissipation behaviors of the PI and carbon nanofibers are also examined. The infrared images indicate that the transfer rates of thermal energy for the carbon nanofibers are higher than those for the PI nanofibers, due to the better thermal conductivity of carbon caused by the covalent sp² bonding between carbon atoms.     

Simultaneous purification and site-specific modification of pyrroline-carboxy-lysine proteins

Sticky residue: Pyrroline-carboxy-lysine (Pcl) can be readily incorporated into proteins expressed in E. coli and mammalian cells by using the pyrrolysyl tRNA/tRNA synthetase pair. Pcl can be used as a single amino acid purification tag and can be site-specifically modified with functional probes during the elution process.     

Protective Effect of Caffeic Acid on Paclitaxel Induced Anti-Proliferation and Apoptosis of Lung Cancer Cells Involves NF-κB Pathway

Caffeic acid (CA), a natural phenolic compound, is abundant in medicinal plants. CA possesses multiple biological effects such as anti-bacterial and anti-cancer growth. CA was also reported to induce fore stomach and kidney tumors in a mouse model. Here we used two human lung cancer cell lines, A549 and H1299, to clarify the role of CA in cancer cell proliferation. The growth assay showed that CA moderately promoted the proliferation of the lung cancer cells. Furthermore, pre-treatment of CA rescues the proliferation inhibition induced by a sub-IC(50) dose of paclitaxel (PTX), an anticancer drug. Western blot showed that CA up-regulated the pro-survival proteins survivin and Bcl-2, the down-stream targets of NF-κB. This is consistent with the observation that CA induced nuclear translocation of NF-κB p65. Our study suggested that the pro-survival effect of CA on PTX-treated lung cancer cells is mediated through a NF-κB signaling pathway. This may provide mechanistic insights into the chemoresistance of cancer calls.     

Dynamics of novel hydrogen-bonded acidic fluorinated poly(amide-imide-silica) hybrids studied by solid-state NMR

Novel hydrogen-bonded acidic fluorinated poly(amide-imide-silica) hybrid materials, FPAI-SiO₂ (6E and 6F) series, were synthesized by a sol-gel process. The structures and spin relaxation of the hybrids were characterized by infrared (IR), and ²⁹Si and ¹³C nuclear magnetic resonance (NMR) spectroscopy. The abundant Q⁴ structures implied that in free catalyst the degree of condensation of tetramethoxysilane was enhanced by hydrogen-bonded acidic fluorinated poly(amide-imide). The dynamics on the local mobility of the hybrids was investigated by the time constant for energy exchange between ¹H and ²⁹Si spin system (T_SiH) and spin-diffusion path length (L) measurements. It was found that the faster T_SiH of 6E and 6F hybrids compared with the previous study of similar 6C and 6D hybrids implied that 6E and 6F hybrids had more aggregated structures even though the organic terminal segment changed from rigid imide to more flexible amide. The interactions of the charge transfer between donor and acceptor molecules or π-π aromatic stacking may be the dominant factors to affect the structures of 6E and 6F hybrids. Moreover, M¹ and D² segments of 6F hybrids had the same level mobility and the mobility of the 6F hybrids was little improved as the soft and flexible 1,3-bis(3-aminopropyl)-tetramethyl-disiloxane segment was incorporated in the dense structures of 6F hybrids. All of the L values of 6E and 6F hybrids were on the scale of 3.5-4.0 nm. The result also suggested that 6E and 6F hybrids had similar denser structures as 6D hybrids.     

The morphology and conductivity of polypyrrole/polyurethane alloy films

Polymeric composites with conductivities ranging from 10^–4 to 1 S cm^–1 were prepared by electrochemically polymerizing pyrrole in a matrix of polyurethane. The polypyrrole/polyurethane alloy films obtained were characterized by element analysis, electron microscopy and electrical conductivity measurements. The morphology of the films depended on the solvent, the electrolyte and the current density. The mechanism of the electrochemical polymerization showed that PPy grew in a treelike structure, with molecular chains extending from the electrode surface into the solution. The transition temperature of the PPy/PU increased with the PPy content.     

Solvents effect on the physical properties of semi-dilute poly(N-isopropyl acryl amide) solutions

The physical properties of 5 wt% poly(NIPAM) (M_v=3.22×10⁵) semi-dilute solutions in H₂O, D₂O, and THF (tetrahydrofuran) solvents were studied using dynamic light scattering (DLS) and dynamic shear viscosity (DSV) measurements. The DLS data showed that there were poly(NIPAM) slow mode inter-polymer chains associations in H₂O and D₂O solvents. However, no DLS slow mode was observed in poly(NIPAM)/THF solutions. The DSV data showed that there are shear thickening behavior in these three poly(NIPAM) solutions, resulting in a maximum shear viscosity η_peak in the viscosity η′(ω) versus shear frequency ω curve. The slow mode hydrodynamic radius 〈R_hs〉 of DLS measurements and the zero shear rate viscosity η₀ and maximum viscosity η_peak data of DSV measurements from poly(NIPAM)/H₂O and poly(NIPAM)/D₂O solutions show two critical transition temperatures with T_cr1=30-32 °C and T_cr2=32-34 °C. Poly(NIPASM)/D₂O has higher T_cr1 and T_cr2 than poly(NIPASM)/H₂O. However, no transition temperatures of poly(NIPAM)/THF solution were observed. The different temperature dependencies of these three solutions were attributed to the ‘solubility’ and ‘hydrogen bonding’ effects between poly(NIPAM) with H₂O, D₂O, and THF solvents. Without considering the polymer-solvent hydrogen bonding, the solubility of poly(NIPAM) in solvents decreases in the following sequence: THF>H₂O>D₂O and the degree of polymer-solvent hydrogen bonding increases in the following sequence: THF<H₂O<D₂O. The effects of the degree of ‘hydrogen bonding’ and the ‘solubility’ of polymer in solvents on the physical properties of poly(NIPAM) solutions are discussed.     

Effects of oxidation and particle shape on critical volume fractions of silver‐coated copper powders in conductive adhesives for microelectronic applications

The effects of oxidation and particle shape on critical volume fractions of silver‐coated copper powders in conductive adhesives are investigated. Silver‐coated copper powders with spherical and flake‐shaped particles were oxidized at temperatures of 30°C, 175°C and 240°C for two hours and dispersed in an epoxy matrix. As silver‐coated copper powders are oxidized at 30°C and 175°C, the critical volume fractions of the conductive adhesives are slightly affected by oxidation and particle shape at these temperatures. As the oxidation temperature approaches 240°C, the critical volume fractions of the conductive adhesives are strongly affected by oxidation temperature and particle shape, owing to the formation of oxides such as Cu₂O on the surface of silver‐coated copper powder—Cu diffuses from the interior to the surface of silver‐coated copper powder and reacts with the oxygen in the air. Silver‐coated copper powder with flake‐shaped particles shows lower critical volume fractions in conductive adhesives than silver‐coated copper powder with spherically shaped particles. Polym. Eng. Sci. 44:2075–2082, 2004. © 2004 Society of Plastics Engineers.     

Preparation and characterization of methoxy‐poly(ethylene glycol) side chain grafted onto chitosan as a wound dressing film

Chitosan has received extensive attention as a biomedical material; however, the poor solubility of chitosan is the major limiting factor in its utilization. In this study, chitosan‐based biomaterials with improved aqueous solubility were synthesized. Two molecular weights (750 Da and 2000 Da) of methoxypoly(ethylene glycol) (mPEG) were grafted onto chitosan (mPEG‐g‐chitosan) to form a ～100‐μm‐thick plastic film as a wound dressing. The chemical structures of the mPEG‐g‐chitosan copolymers were confirmed using Fourier transform infrared spectroscopy (FTIR), and the thermal properties were characterized using thermogravimetry analysis (TGA). Their microstructures were observed using scanning electron microscopy (SEM). The other properties were analyzed via the swelling ratio, tensile strength, elongation, and water vapor transmission rate (WVTR). Biocompatibility evaluations through biodegradability, cytotoxicity, and antimicrobial effect studies were also performed. The obtained mPEG‐g‐chitosan copolymers were soluble in slightly acidic aqueous solutions (pH～6.5) at a concentration of 10 wt %. The optimal mPEG‐g‐chitosan hydrogels had swelling ratios greater than 100% and WVTRs greater than 2000 g/m²/day. Their performance against Staphylococcus aureus will be subjected to further improvements with respect to medical applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42340.     

Curing reaction of unsaturated polyester resin modified by dicyclopentadiene

The objective of this research is to prepare modified unsaturated polyester resin(UPR) with good processibility, dimension stability and mechanical properties. In this study, dicyclopentadiene (DCPD) is selected as a modifier and the effect of DCPD content on the curing behavior of the modified UPR is examined via Differential Scanning Calorimetry (DSC) and Rheometrics Dynamic Analysis (RDA) experiments. The results of ¹H NMR identification for the chemical structure of modified UPR show that the trans-structure of UPR decreases as the DCPD content increases. The curing time necessary to reach peak maximum in DSC during the curing reaction lengthens as the stereo obstacles formed by the binary rings increase.