Synthesis and biological activity of phthalimide‐based polymers containing 5‐fluorouracil

The attachment of anticancer agents to polymers is a promising approach towards reducing the toxic side‐effects and retaining the potent antitumour activity of these agents. A new tetrahydrophthalimido monomer containing 5‐fluorouracil (ETPFU) and its homopolymer and copolymers with acrylic acid (AA) and with vinyl acetate (VAc) have been synthesized and spectroscopically characterized. The ETPFU contents in poly(ETPFU‐co‐AA) and poly(ETPFU‐co‐VAc) obtained by elemental analysis were 21 mol% and 20 mol%, respectively. The average molecular weights of the polymers determined by gel permeation chromatography were as follows: M_n = 8900 g mol^?1, M_w = 13 300 g mol^?1, M_w/M_n = 1.5 for poly(ETPFU); M_n = 13 500 g mol^?1, M_w = 16 600 g mol^?1, M_w/M_n = 1.2 for poly(ETPFU‐co‐AA); M_n = 8300 g mol^?1, M_w = 11 600 g mol^?1, M_w/M_n = 1.4 poly(ETPFU‐co‐VAc). The in vitro cytotoxicity of the compounds against FM3A and U937 cancer cell lines increased in the following order: ETPFU > 5‐FU > poly(ETPFU) > poly(ETPFU‐co‐AA) > poly(ETPFU‐co‐VAc). The in vivo antitumour activities of all the polymers in Balb/C mice bearing the sarcoma 180 tumour cell line were greater than those of 5‐FU and monomer at the highest dose (800 mg kg^?1). © 2002 Society of Chemical Industry     

Gamma‐ray irradiation effect of polyethylene on dimaleimides as a class of new multifunctional monomers

Multifunctional monomers, m‐xylylenedimaleimide, p‐phenylenedimaleimide, m‐phenylenedimaleimide, and p‐phenylenedinadimide, all of which have maleimide groups, were synthesized to increase thermal and radiation stabilities. The synthesized multifunctional monomers showed good compatibility with low‐density polyethylene (LDPE). Mixtures of LDPE and these multifunctional monomers were irradiated with γ‐rays from a Co‐60 source at room temperature in a nitrogen atmosphere. The absorbed dose ranged from 0 to 160 KGy. Among these multifunctional monomers, m‐xylylenedimaleimide was the best in gel fraction enhancement. Crosslinked LDPE with m‐xylylenedimaleimide displayed a higher modulus than that of crosslinked LDPE with triallyl cyanurate. For the elongation property, LDPE with m‐xylylenedimaleimide as a multifunctional monomer showed better results than that with commercial multifunctional monomers such as triallyl cyanurate (TAC) and trimethylol propane triacrylate (TMPTA). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2339–2345, 2003     

Selective O-Alkylation Reaction of Hydroquinone with Methanol over Cs Ion-Exchanged Zeolites

O-alkylation reaction of hydroquinone with excess methanol was performed by using alkali metal ion-exchanged zeolite catalysts in a slurry type reactor to substitute the solid zeolite catalysts for the homogeneous liquid phase catalysts. This was also done to produce selectively mono-alkylated 4-methoxyphenol, a valuable intermediate for the perfume, flavor, food and photo industries. The effects of the basicity of various zeolites and reaction conditions such as temperature, reaction time and the amount of catalyst on the catalytic activity and selectivity were tested to maximize the yield of 4-methoxyphenol. Thus far, 84% selectivity at 95% conversion of hydroquinone was obtained at the optimum reaction conditions (240 ‡C, reaction with 0.6 g catalyst for 16 h), which was thought to result from the strong basic property and shape selectivity of the Cs ion-exchanged NaX zeolite.     

Interfacial tension measurement between immiscible polymers: improved deformed drop retraction method

This paper describes an improvement of the technique to measure interfacial tension in immiscible polymer blends. Our method is based on the droplet retraction method, in which one relates the kinetics of relaxation of a deformed droplet to the interfacial tension between the matrix and droplet. Previously, the problem with this technique has been the difficulty in preparing axisymmetric ellipsoidal droplets. In our work, we demonstrate that perfect axisymmetric ellipsoidal droplets are produced at a later stage of relaxation of short imbedded fibers. With this technique, we utilize the strengths of both the deformed droplet method and the imbedded fiber retraction method while overcoming their shortcomings. The interfacial tension value thus obtained was compared to that by conventional methods. Additionally, the effect of confinement by external walls on the interfacial tension measurement was studied. Confinement affects interfacial tension measurement when the gap between the walls is less than two times the equilibrium drop size.     

Effects of Y2O3 and ZrO2 on the Densification of Si3N4-Zr(Y)O2 Composites

The effects of ZrO₂ and Y₂O₃ on the densification of hotpressed Si₃N₄-Zr(Y)O₂ composites have been studied. High density could not be obtained by the addition of pure or 3-mol%-Y₂O₃-doped ZrO₂ in this composite; however, nearly full density (>97%) could be obtained in Si₃N₄ using 6- and 8-mol%-Y₂O₃-doped ZrO₂. It is concluded that Y₂O₃ diffusing out from the added Zr(Y)O₂ promoted the densification and that ZrO₂ also had some role in the formation of an oxynitride glass.     

Improved mechanical properties of shape‐memory polyurethane block copolymers through the control of the soft‐segment arrangement

High‐performance shape‐memory polyurethane block copolymers, prepared with two types of poly(tetramethylene glycol) (PTMG) used as soft segments, were investigated for their mechanical properties. Copolymers with a random or block soft‐segment arrangement had higher stresses at break and elongations at break than those with only one kind of PTMG. Random copolymers with fewer interchain interactions showed higher elongation than block copolymers. All the copolymers had shape‐recovery ratios higher than 80%. In dynamic mechanical testing, the glass‐transition behavior clearly depended on the soft‐segment arrangement: random copolymers had only one glass‐transition peak, whereas block copolymers showed two separate glass‐transition peaks. Overall, the control of the soft‐segment arrangement plays a vital role in the development of high‐performance shape‐memory polyurethane. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2410–2415, 2004     

Kinetic parameters estimation for cure reaction of epoxy based vinyl ester resin

A new graphical estimation technique is proposed for the determination of the kinetic parameters describing an autocatalytic reaction. A differential scanning calorimeter was used to monitor the reaction kinetics of an epoxy-based vinyl ester resin. The method utilizes information from a zero initial reaction rate, conversation at vitrification, the ratio of reaction rate constants under different isothermal conditions, and characteristics of the phenomenological kinetic model with assumptions being made about the overall reaction order. By fitting data to the integrated reaction rate equation with adjustments for the isothermal conditions, the kinetic parameters are estimated without using a linear or nonlinear regression method. Different kinetic parameters can be estimated from data before and after the gel point which was obtained from the relationship between the glass transition temperature and the degree of cure.     

Electrochemical properties of boron-carbon-nitride films formed by magnetron sputtering

The electrochemical behavior of B_1.0C_2.4N_1.0 thin film was investigated in acidic, neutral and alkaline solutions. The anodic polarization curve of the film in 1 M NaOH showed the anodic dissolution of the film. The curve of the film in 1 M HCl showed no anodic dissolution. The cathodic polarization curve in 1 M NaCl showed shift to a negative potential side, but the anodic polarization curve was the same as that of Pt. The anodic dissolution in 1 M NaOH depended on potentials, that is, no anodic dissolution was recognized in a potential range of −0.2 to 0.1 V but the dissolution rate increased with increasing potential in a range of 0.1-0.6 V. The anodic current density of the film is directly proportional to the dissolution rate at potentials higher than 0.1 V. The dissolution rate of the film was increased with increasing solution pH.     

Amelioration of mechanical brittleness in hyperbranched polymer. 1. Macroscopic evaluation by dynamic viscoelastic relaxation

Hyperbranched poly(ether ketone)-b-linear poly(ether ketone)-b-hyperbranched poly(ether ketone) (HLHPEK) triblock copolymers with two different block compositions were prepared as an approach to improve the mechanical brittleness of hyperbranched poly(ether ketone) (HPEK). From the time-temperature superposition of dynamic shear moduli, G′(ω) and G″(ω), of HPEK and two HLHPEKs, it was investigated that the junction points between G′(ω) and G″(ω) shifted to the higher frequencies and the rubbery plateau region spread wider over the reduced frequency axis as the linear blocks were introduced and their compositions were increased. Such changes in viscoelastic response were consequences of increase in the amount of chain entanglements additionally formed by the linear blocks. In order to verify the effect of the linear block incorporation on amelioration of the mechanical brittleness, the degree of brittleness and its improvement were evaluated from the temperature dependence of the shift factors, a_Ts, experimentally obtained during the superposition of the dynamic moduli and of the average viscoelastic relaxation times, τ_HNs, determined with empirical Havriliak-Negami distribution function. From the nonlinear curve fittings of the a_Ts and the τ_HNs by the Vogel-Tamman-Fulcher equation, the degree of brittleness for HPEK and HLHPEK triblock copolymers were quantified as values of the material parameter D, an indicative of deviation from the linear Arrhenius behavior and a measure of fragility of the given material. The tendency of increasing D values with the linear block compositions confirmed substantial improvement of the mechanical brittleness in the HLHPEK triblock copolymers compared to HPEK. Therefore, the approach to copolymerize HPEK with its chemically analogous linear counterpart was verified to be an effective strategy to impart molecular entanglements and hence ameliorate the mechanical brittleness on the basis of macroscopic rheological evaluation.     

Microwave Dielectric Properties of (1−x)(Na1/2Nd1/2)TiO3−xLa(Mg1/2Ti1/2)O3 via Ordering and Far IR Reflectivity Spectra

Microwave dielectric properties of (1− x )(Na_1/2Nd_1/2)TiO₃(NNT)− x La(Mg_1/2Ti_1/2)O₃(LMT) system have been investigated with focus on structural ordering and far IR reflectivity spectra. A single perovskite phase was found to exist with various superlattice reflections over the entire compositional range. 1:1 ordering observed in the (111) reflection of X-ray diffraction patterns was found to progress significantly in the specimens above x =0.8. The ordering characteristics that presumably related to B-site Mg/Ti ordering were assumed to affect favorably the quality factor at microwave frequencies. The increase of the quality factor also could be explained in terms of the decrease of lattice anharmonicity with LMT by analysis of far IR reflectivity spectra. As expected from the values of pure NNT and LMT, the dielectric constant and the temperature coefficient of frequency tended to gradually decrease with increasing LMT content.