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GPC
Terms modified by GPC Selected AbstractsOutput power leveling of wind turbine generators using pitch angle control for all operating regions in wind farmELECTRICAL ENGINEERING IN JAPAN, Issue 4 2007Tomonobu Senjyu Abstract Effective utilization of renewable energies such as wind energy instead of fossil fuels is desirable. Wind energy is not constant and windmill output is proportional to the cube of the wind speed, which causes the generated power of wind turbine generators (WTGs) to fluctuate. In order to reduce the output power fluctuation of wind farms, this paper presents an output power leveling control strategy for a wind farm based on both the average wind farm output power and the standard deviation of the wind farm output power, a cooperative control strategy for WTGs, and pitch angle control using a generalized predictive controller (GPC) in all WTG operating regions. Simulation results using an actual detailed model for wind farm systems show the effectiveness of the proposed method. © 2007 Wiley Periodicals, Inc. Electr Eng Jpn, 158(4): 31, 41, 2007; Published online in Wiley InterScience (www.interscience. wiley.com). DOI 10.1002/eej.20448 [source] Synthesis and Optoelectronic Properties of Nonpolar Polyrotaxane Insulated Molecular Wires with High Solubility in Organic Solvents,ADVANCED FUNCTIONAL MATERIALS, Issue 21 2008Michael J. Frampton Abstract Hydrophilic polyanionic conjugated polyrotaxanes are readily synthesized in water by Suzuki coupling, but their high polarity and ionic nature limit the potential applications of these materials. Here, we demonstrate three methods for transforming these polar polyelectrolytes into nonpolar lipophilic insulated molecular wires. A water-soluble polyfluorene- alt -biphenylene ,-cyclodextrin (CD) polyrotaxane was converted into nonpolar derivatives by methylation of the carboxylic acid groups with diazomethane and conversion of the hydroxyl groups of the CDs to benzyl ethers, trihexylsilyl ethers, benzoyl esters, and butanoate esters to yield polyrotaxanes that are soluble in organic solvents such as chloroform and cyclohexane. Elemental analysis, NMR spectroscopy, and gel permeation chromatography (GPC) data support the proposed structures of the organic-soluble polyrotaxanes. The extents of reaction of the polyrotaxane CD hydroxyl groups were 55% for trihexylsilyl chloride/imidazole; 81% for benzyl chloride/sodium hydride; 72% for benzoyl chloride/pyridine/4-dimethylaminopyridine; and 98% butanoic anhydride/pyridine/4-dimethylaminopyridine. Alkylation, silylation, and esterification increase the bulk of the encapsulating sheath, preventing interstrand aggregation, increasing the photoluminescence efficiency in the solid state and simplifying the time-resolved fluorescence decay. The organic-soluble polyrotaxanes were processed into polymer light-emitting diodes (PLEDs) from solution in nonpolar organic solvents, thereby excluding ionic impurities from the active layer. [source] On the Origin of Green Emission in Polyfluorene Polymers: The Roles of Thermal Oxidation Degradation and Crosslinking,ADVANCED FUNCTIONAL MATERIALS, Issue 8 2004W. Zhao Abstract The green emission of poly(9,9,,-dioctylfluorenyl-2,7,,-diyl), end-capped by polyhedral oligomeric silsequioxanes, (PFO-POSS) has been investigated by photoluminescence (PL) and photoexcitation (PE), gel permeation chromatography (GPC), and transmission Fourier transform infrared (FTIR) spectroscopy. The green emission is closely correlated with thermal oxidation degradation and crosslinking of the polymer and is enhanced by annealing at elevated temperatures. The green-to-blue emission intensity ratio, used to assess the emission properties of thin (90,nm) films, was 3.70, 4.35, and 1.54 for an air-annealed film, its insoluble residue (crosslinked), and a film cast from its soluble portion, respectively. For thick (5,6,,m) film, the ratios are 13.33, 13.33, and 0.79, respectively. However, FTIR spectroscopy of thick films leads to the conclusion that the carbonyl-to-aromatic ring concentration ratio are 0.018, 0.015, and 0.032, respectively. Focusing on the recast films, the green emission is relatively low while the carbonyl concentration is relatively high. This suggests that the energy traps at crosslinked chains play an important role in green emission. It is likely that the crosslinking enhances the excitation energy migration and energy transfer to the defects by hindering chain segment twisting. [source] Improvement of tracking performance in designing a GPC-based PID controller using a time-varying proportional gainIEEJ TRANSACTIONS ON ELECTRICAL AND ELECTRONIC ENGINEERING, Issue 4 2006Takao Sato An effective design method of a proportional-integral-derivative (PID) controller is proposed. The PID parameters of the PID controller are designed on the basis of a generalized predictive control (GPC) law. The PID controller has a time-varying proportional gain, and the PID parameters are designed using the future reference trajectory of the GPC. Finally, numerical examples are shown for illustrating the effectiveness of the proposed method. © 2006 Institute of Electrical Engineers of Japan. Published by John Wiley & Sons, Inc. [source] Online trained support vector machines-based generalized predictive control of non-linear systemsINTERNATIONAL JOURNAL OF ADAPTIVE CONTROL AND SIGNAL PROCESSING, Issue 10 2006S. Iplikci Abstract In this work, an online support vector machines (SVM) training method (Neural Comput. 2003; 15: 2683,2703), referred to as the accurate online support vector regression (AOSVR) algorithm, is embedded in the previously proposed support vector machines-based generalized predictive control (SVM-Based GPC) architecture (Support vector machines based generalized predictive control, under review), thereby obtaining a powerful scheme for controlling non-linear systems adaptively. Starting with an initially empty SVM model of the unknown plant, the proposed online SVM-based GPC method performs the modelling and control tasks simultaneously. At each iteration, if the SVM model is not accurate enough to represent the plant dynamics at the current operating point, it is updated with the training data formed by persistently exciting random input signal applied to the plant, otherwise, if the model is accepted as accurate, a generalized predictive control signal based on the obtained SVM model is applied to the plant. After a short transient time, the model can satisfactorily reflect the behaviour of the plant in the whole phase space or operation region. The incremental algorithm of AOSVR enables the SVM model to learn the new training data pair, while the decremental algorithm allows the SVM model to forget the oldest training point. Thus, the SVM model can adapt the changes in the plant and also in the operating conditions. The simulation results on non-linear systems have revealed that the proposed method provides an excellent control quality. Furthermore, it maintains its performance when a measurement noise is added to the output of the underlying system. Copyright © 2006 John Wiley & Sons, Ltd. [source] Constrained closed-loop control of depth of anaesthesia in the operating theatre during surgeryINTERNATIONAL JOURNAL OF ADAPTIVE CONTROL AND SIGNAL PROCESSING, Issue 5 2005M. Mahfouf Abstract The constrained version of generalized predictive control (GPC) which employs the quadratic programming (QP) approach is evaluated for on-line administration of an anaesthetic drug in the operating theatre during surgery. In the first instance, a patient simulator was developed using a physiological model of the patient and the necessary control software was validated via a series of extensive simulation experiments. Such a validated system was then transferred into the operating theatre for a series of clinical evaluation trials. The clinical trials, which were performed with little involvement of the design engineer, led to a good regulation of unconsciousness using fixed-parameters as well the adaptive version of the algorithm. Furthermore, the constrained algorithm displayed good robustness properties against disturbances such as high stimulus levels and allowed for safe and economically effective administration of the anaesthetic agent isoflurane. Copyright © 2005 John Wiley & Sons, Ltd. [source] Support vector machines-based generalized predictive controlINTERNATIONAL JOURNAL OF ROBUST AND NONLINEAR CONTROL, Issue 17 2006S. Iplikci Abstract In this study, we propose a novel control methodology that introduces the use of support vector machines (SVMs) in the generalized predictive control (GPC) scheme. The SVM regression algorithms have extensively been used for modelling nonlinear systems due to their assurance of global solution, which is achieved by transforming the regression problem into a convex optimization problem in dual space, and also their higher generalization potential. These key features of the SVM structures lead us to the idea of employing a SVM model of an unknown plant within the GPC context. In particular, the SVM model can be employed to obtain gradient information and also it can predict future trajectory of the plant output, which are needed in the cost function minimization block. Simulations have confirmed that proposed SVM-based GPC scheme can provide a noticeably high control performance, in other words, an unknown nonlinear plant controlled by SVM-based GPC can accurately track the reference inputs with different shapes. Moreover, the proposed SVM-based GPC scheme maintains its control performance under noisy conditions. Copyright © 2006 John Wiley & Sons, Ltd. [source] Effects of Post-Anthesis Drought and Waterlogging on Accumulation of High-Molecular-Weight Glutenin Subunits and Glutenin Macropolymers Content in Wheat GrainJOURNAL OF AGRONOMY AND CROP SCIENCE, Issue 2 2009D. Jiang Abstract Drought and flooding during grain filling have become major constraints to wheat quality and yield. The impacts of water deficits and waterlogging during the grain filling on contents of high-molecular-weight glutenin subunits (HMW-GS) and of glutenin macropolymers (GMP) in grains of the winter wheat cultivar Yumai 34 with high grain protein content (GPC) and Yangmai 9 with low GPC were studied. At maturity, GPC was higher under drought and lower under waterlogging compared to the control, while contents of GMP and HMW-GS were reduced by the two water-stress treatments. The contents of both HMW-GS and GMP were higher in Yumai 34 than in Yangmai 9. A drought event after anthesis increased the accumulation of HMW-GS during the early grain filling stage. By contrast, waterlogging reduced the accumulation of HMW-GS during the whole grain filling phase. At maturity, the HMW-GS and GMP to protein ratios were also depressed under the two water-stress events, while the HMW-GS to GMP ratio was very close between the three treatments in Yumai 34 and much higher under the control than the drought and waterlogging treaments in Yangmai 9. It is concluded that the variation in GMP content with various water-stress treatments is attributed to the changing in accumulation of HMW-GS in the grain. [source] In-line analysis of the influence of monomeric and oligomeric hindered amine on the hydrolysis of polycarbonate in a PC/ABS blendJOURNAL OF APPLIED POLYMER SCIENCE, Issue 6 2010Vipin V. Rajan Abstract The polycarbonate/polyacrylonitrile butadiene styrene (PC/ABS) blends lose mechanical properties when exposed to outdoor conditions. This is due to the ultraviolet (UV) induced photo-oxidation of the PC phase and the polybutadiene portion of the ABS. It is known that ABS can be stabilised against terrestrial light by the use of hindered amine in combination with a UV absorber. However, such hindered amine cannot be used when PC is present in a multi component polymer blend. The hydrolysis of PC is accelerated when a small amount of hindered amine light stabilisers (HALS) is incorporated in the resin and is exposed to elevated temperature. In this article the effect of monomeric and oligomeric hindered amine on the hydrolysis of PC during the compounding of PC/ABS blend in a twin screw extruder at 240°C is observed by means of in-line UV-vis spectroscopy. Tinuvin 765 was used as monomeric hindered amine and Tinuvin 622 as oligomeric hindered amine. The molecular weight of the compounded sample was determined by gel permeation chromatography (GPC) and the rheological properties were observed using an online viscometer. It was found that the extent of hydrolysis induced by the oligomeric hindered amine is less compared to monomeric amine. It was also observed that polymeric hindered amine imparts better dispersion of the ABS phase into the polymer blend. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 [source] Synthesis and characterization of temperature-sensitive block copolymers from poly(N -isopropylacrylamide) and 4-methyl-,-caprolactone or 4-phenyl-,-caprolactoneJOURNAL OF APPLIED POLYMER SCIENCE, Issue 3 2010Ren-Shen Lee Abstract This study synthesizes thermally sensitive block copolymers poly(N -isopropylacrylamide)- b -poly(4-methyl-,-caprolactone) (PNIPA- b -PMCL) and poly(N -isopropylacrylamide)- b -poly(4-phenyl-,-caprolactone) (PNIPA- b -PBCL) by ring-opening polymerization of 4-methyl-,-caprolactone (MCL) or 4-phenyl-,-caprolactone (BCL) initiated from hydroxy-terminated poly(N -isopropylacrylamide) (PNIPA) as the macroinitiator in the presence of SnOct2 as the catalyst. This research prepares a PNIPA bearing a single terminal hydroxyl group by telomerization using 2-hydroxyethanethiol (ME) as a chain-transfer agent. These copolymers are characterized by differential scanning calorimetry (DSC), 1H-NMR, FTIR, and gel permeation chromatography (GPC). The thermal properties (Tg) of diblock copolymers depend on polymer compositions. Incorporating larger amount of MCL or BCL into the macromolecular backbone decreases Tg. Their solutions show transparent below a lower critical solution temperature (LCST) and opaque above the LCST. LCST values for the PNIPA- b -PMCL aqueous solution were observed to shift to lower temperature than that for PNIPA homopolymers. This work investigates their micellar characteristics in the aqueous phase by fluorescence spectroscopy, transmission electron microscopy (TEM), and dynamic light scattering (DLS). The block copolymers formed micelles in the aqueous phase with critical micelle concentrations (CMCs) in the range of 0.29,2.74 mg L,1, depending on polymer compositions, which dramatically affect micelle shape. Drug entrapment efficiency and drug loading content of micelles depend on block polymer compositions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 [source] Preparation of quaternized carboxymethyl chitosan and its capacity to flocculate COD from printing wastewaterJOURNAL OF APPLIED POLYMER SCIENCE, Issue 1 2010Zhao-Sheng Cai Abstract A bioflocculant, quaternized carboxymethyl chitosan (QCMC), was developed by the quaternization of N,O-carboxymethyl chitosan (N,O-CMC) and characterized by FTIR, 1H-NMR, GPC, and potentiometry. The efficiency of the removal of chemical oxygen demand (COD) in printing wastewater by this flocculant was further reported. Results indicated that the capacity of QCMC to remove the COD from tested wastewater was the best one among the investigated flocculants. The pH had great influence on this capacity and the suitable pH for QCMC to treat the tested wastewater was about 5.0. The utilization of aid-flocculant, especially bentonite, could improve this capacity obviously, and the increase of mass ratio of bentonite to QCMC resulted in the increase of the capacities of complex flocculant to remove the COD from the tested wastewater. When the mass ratio of bentonite to QCMC was 40, pH of wastewater was 5.0 and amount of complex flocculant in the wastewater was from 2500 to 3142 mg L,1, the removal ratio of COD was more than 80%. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 [source] Enhanced photodegradation efficiency of polyethylene-TiO2 nanocomposite film with oxidized polyethylene waxJOURNAL OF APPLIED POLYMER SCIENCE, Issue 1 2010Wenjun Fa Abstract A novel photodegradable polyethylene-oxidized polyethylene wax-TiO2 (PE-OPW-TiO2) nanocomposite film was prepared by embedding the organically modified TiO2 nanoparticles into commercial PE in the presence of OPW. The photocatalytic degradation behavior under ultraviolet light or solar light was investigated by examining the weight loss of the composite films, UV,vis transmittance spectrum, scanning electron microscope (SEM), and gel permeation chromatogram (GPC). The results show that OPW, as a dispersant and a compatibiliser, markedly improves the dispersion and compatibility of TiO2 nanoparticles in PE resins. The PE-OPW-TiO2 composite film demonstrates much higher photodegradation efficiency and much better mechanical property than either the PE-TiO2 composite film or the pure PE film. The weight-average molecular weight (Mw) of the PE-OPW-TiO2 composite film decreased 94.3% and the number-average molecular weight (Mn) decreased 84.5% after 38 days solar light irradiation. The photocatalytic degradation mechanism of the film is briefly discussed. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 [source] Synthesis and characterization of new soluble polyamides from an unsymmetrical diamine bearing a bulky triaryl pyridine pendent groupJOURNAL OF APPLIED POLYMER SCIENCE, Issue 6 2010Mousa Ghaemy Abstract New unsymmetrical diamine monomer containing triaryl pyridine pendent group, 2,4-diaminophenyl [4-(2, 6-diphenyl-4-pyridyl) phenyl]ether, was synthesized via aromatic substitution reaction of 1-chloro-2,4-dinitrobenzene with 4-(2,6-diphenyl-4-pyridyl) phenol, followed by Pd/C-catalyzed hydrazine reduction. Five Polyamides (PA) were prepared by the phosphorylation polycondensation of different dicarboxylic diacids with the diamine. Inherent viscosities of PAs were in the range 0.51,0.59 g/dL indicating formation of medium molecular weight polymers. The weight and number average molecular weights of a PA, (PA-d), determined by GPC were 6944 g/mol and 17,369 g/mol, respectively. PAs exhibited glass-transition temperatures (Tg) in the range 140,235°C. These polymers, essentially amorphous, were soluble in polar aprotic solvents such as DMF, NMP, DMAc, DMSO, pyridine, m -cresol, and THF. The initial decomposition temperatures (Ti) of PAs, determined by TGA in air, were in the range 300,380°C indicating their good thermal stability. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 [source] Synthesis and characterization of a silicone resin with silphenylene units in Si-O-Si backbonesJOURNAL OF APPLIED POLYMER SCIENCE, Issue 2 2009Mengqiu Jia Abstract A silicone resin with silphenylene units in Si-O-Si backbones was synthesized by hydrolysis-polycondensation of 1,4-bis(hydroxydimethylsilyl)benzene (BHB) with chlorosilanes. The structure and property of this novel silicone resin were characterized by gel permeation chromatography (GPC), Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), thermogarvimetric analysis (TG), scanning electron microscope (SEM), and electrochemical impedance spectrum (EIS). This silicone resin could be applied as the film forming material of coating when it is prepared under the condition of R/Si, Ph/R, and the content of silphenylene units being 1.3, 0.5, and 10 mol %, respectively. GPC, IR, and NMR results show that the silphenylene units have been incorporated into the polymer of silicone resin. The TG analysis indicates that this novel silicone resin has good heat resistance with the onset degradation temperature of 500.3°C and residual weight of 85.6% at 900°C. SEM results demonstrate that the silicone resin with silphenylene units can form full and uniform films, and its surface morphology of clear paints were not damaged by heat below 350°C. EIS analysis reveals that clear paints of the silicone resin with silphenylene units have good resistance to corrosion. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 [source] Improvement of the thermal stability of polyhydroxybutyrates by grafting with maleic anhydride by different methods: Differential scanning calorimetry, thermogravimetric analysis, and gel permeation chromatographyJOURNAL OF APPLIED POLYMER SCIENCE, Issue 5 2008Shinn-Gwo Hong Abstract The crystallization and thermal degradation behaviors of polyhydroxybutyrate (PHB) grafted with maleic anhydride (MA) by different techniques were analyzed with differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and gel permeation chromatography (GPC). The results of DSC, TGA, and GPC analyses indicated that the grafting method could affect the crystallization rate, crystallinity, and thermal stability of PHB because of changes in the molecular weight of PHB and the amount of MA grafted during the reaction. The reduction of the molecular weight of PHB that reacted during the processing followed this order of methods: melt grafting > solvent grafting > mechanical grafting. However, the grafting ratio of MA followed this order of methods: melt grafting > mechanical grafting > solvent grafting. All three grafting methods significantly improved the thermal stability, therefore increasing the crystallization rate and melting temperature of the as-received PHB. A grafting ratio of MA as low as 0.07 wt % could result in a significant improvement in the heat resistance of PHB. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source] Study of epoxy toughened by in situ formed rubber nanoparticlesJOURNAL OF APPLIED POLYMER SCIENCE, Issue 1 2008Jun Ma Abstract The effect of rubber nanoparticles on mechanical properties and fracture toughness was investigated. Rubber nanoparticles of 2,3 nm were in situ synthesized in epoxy taking advantage of the reaction of an oligomer diamine with epoxy. The chemical reaction was verified by gel permeation chromatography (GPC) and 1HNMR, and the microstructure was characterized by transmission electron microscope. The rubber nanoparticles caused much less Young's modulus deterioration but toughened epoxy to a similar degree in comparison with their peer liquid rubber that formed microscale particles during curing. Fifteen wt % of rubber nanoparticles increased fracture energy from 140 to 840 J/m2 with Young's modulus loss from 2.85 to 2.49 GPa. The toughening mechanism might be the stress relaxation of the matrix epoxy leading to larger plastic work absorbed at the crack tip; there is no particle cavitation or deformation; neither crack deflection nor particle bridging were observed. The compound containing rubber nanoparticles demonstrates Newtonian liquid behavior with increasing shear rate; it shows lower initial viscosity at low shear rate than neat epoxy; this provides supplementary evidence to NMR and GPC result. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source] Synthesis and characterization of dendronized aromatic polyamides with bromomethyl groups in the peripheryJOURNAL OF APPLIED POLYMER SCIENCE, Issue 1 2008Yanru Miao Abstract This paper focused on the synthesis of novel functionalized dendronized aromatic polyamides, which contained a polyamide backbone and polyamide dendrons decorated with bromomethyl groups, by the macromonomer route. The new activating procedure of the synthesis of dendrons and macromonomers using thionyl chloride as an activating agent eliminated the protection/deprotection procedure and reduced side reactions. The structures of the dendrons, macromonomers, and polyamides were confirmed by FTIR, 1H NMR, 13C NMR, and elemental analysis. The properties of the resulting dendronized polyamides, which were compared with that of the linear polyamide (LP), were studied using GPC, XRD, TGA, DSC, inherent viscosity measurement, and solubility experiment. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source] Synthesis and characterization of amphiphilic biodegradable poly(glutamic acid- co -lactic acid- co -glycolic acid) by direct polycondensationJOURNAL OF APPLIED POLYMER SCIENCE, Issue 6 2008Dedai Lu Abstract Poly(glutamic acid- co -lactic acid- co -glycolic acid) (PGLG), an amphiphilic biodegradable copolymer, was synthesized by simply heating a mixture of L -glutamic acid (Glu), DL -lactic acid, and glycolic acid with the present of stannous chloride. The unique branched architecture comprising of glutarimide unit, polyester unit, and polyamide unit was confirmed by NMR spectrum. The PGLG was soluble in many organic solvents and aqueous solution of sodium hydroxide (pH , 9.0). The thermal properties were evaluated using thermogravimetric analysis and differential scanning calorimetry. Molecular weights were determined by 1H NMR end-group analysis and GPC, respectively, and the results indicated that the higher Glu content resulted in a decrease of the molecular weight. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source] Preparation of ethylene/1-octene copolymers from ethylene stock with tandem catalytic systemJOURNAL OF APPLIED POLYMER SCIENCE, Issue 5 2008Tao Jiang Abstract Tandem catalysis offers a novel synthetic route to the production of linear low-density polyethylene. This article reports the use of homogeneous tandem catalytic systems for the synthesis of ethylene/1-octene copolymers from ethylene stock as the sole monomer. The reported catalytic systems involving a highly selective, bis(diphenylphosphino)cyclohexylamine/Cr(acac)3/methylaluminoxane (MAO) catalytic systems for the synthesis of 1-hexene and 1-octene, and a copolymerization metallocene catalyst, rac -Et(Ind)2ZrCl2/MAO for the synthesis of ethylene/1-octene copolymer. Analysis by means of DSC, GPC, and 13C-NMR suggests that copolymers of 1-hexene and ethylene and copolymers of 1-octene and ethylene are produced with significant selectivity towards 1-hexene and 1-octene as comonomers incorporated into the polymer backbone respectively. We have demonstrated that, by the simple manipulation of the catalyst molar ratio and polymerization conditions, a series of branched polyethylenes with melting temperatures of 101.1,134.1°C and density of 0.922,0.950 g cm,3 can be efficiently produced. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source] Unexpected fluorescence emission of poly(,,,- L -malic acid) in aqueous mediumJOURNAL OF APPLIED POLYMER SCIENCE, Issue 3 2007Yaofeng Fan Abstract Unexpected fluorescence of poly(,,,- L -malic acid) (,,,-PMA) without traditional fluorophore was observed firstly. This fluorescent polymer was synthesized via melt polycondensation of L -malic acid. The polymer was characterized by gel permeation chromatography (GPC), nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), thermogravimetry (TG), Fourier transform infrared spectroscopy (IR), Fourier transform Raman spectroscopy (Raman), and X-ray powder diffractometry (XRD). The high molecular weight ,,,-PMA was synthesized by the optimum polycondensation at 130°C for 15 h, followed by fractional precipitation with diethyl ether and petroleum ether. The degree of branching of ,,,-PMA was from 10% to 20% according to the reaction condition. Terminal group of ,,,-PMA was mainly hydroxycarboxylic group companied with a few CHCHCOOH groups owing to dehydration of a normal terminal during the melt polycondensation. A fluorescence emission maximum of ,,,-PMA in water appeared at 420 nm when it was excited at 340 nm. Further study indicated that the fluorescence intensity was concentration-dependent, pH-dependent, and molecular-weight-dependent. The fluorescence formation may result from multichain aggregations, which was formed readily in aqueous solution due to intermolecular hydrogen bonds between branched ,,,-PMA. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007 [source] Synthesis and characterization of novel poly(arylene ether)s based on 9,10-bis-(4-fluoro-3-trifluoromethylphenyl) anthracene and 2,7-bis-(4-fluoro-3-trifluoromethylphenyl) fluoreneJOURNAL OF APPLIED POLYMER SCIENCE, Issue 1 2007Arun K. Salunke Abstract Two new bisfluoro monomers 9,10-bis-(4-fluoro-3-trifluoromethylphenyl) anthracene and 2,7-bis-(4-fluoro-3-trifluoromethylphenyl) fluorene have been synthesized by the cross-coupling reaction of 2-fluoro-3-trifluoromethyl phenyl boronic acid with 9,10-dibromo anthracene and 2,7-dibromo fluorine, respectively. These two bisfluoro compounds were used to prepare several poly(arylene ether)s by aromatic nucleophilic displacement of fluorine with various bisphenols; such as bisphenol-A, bisphenol-6F, bishydroxy biphenyl, and 9,9-bis-(4-hydroxyphenyl)-fluorene. The products obtained by displacement of the fluorine atoms exhibits weight-average molar masses up to 1.5 ×105 g mol,1 and number average molecular weight up to 6.8 × 104 g mol,1 in GPC. These poly(arylene ether)s show very high thermal stability even up to 490°C for 5% weight loss occurring at this temperature in TGA in synthetic air and showed glass transition temperature observed up to 310°C. All the polymers are soluble in a wide range of organic solvents, e.g., CHCl3, THF, NMP, and DMF. Films cast from DMF solution are brittle in nature. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007 [source] Fabrication, structures, and properties of acrylonitrile/methyl acrylate copolymers and copolymers containing microencapsulated phase change materialsJOURNAL OF APPLIED POLYMER SCIENCE, Issue 5 2007Na Han Abstract The polyacrylonitrile-methyl acrylate (AN/MA mole ratio 100/0,70/30) copolymers and copolymers (AN/MA mole ratio 85/15) containing up to 40 wt % of microencapsulated n -octadecane (MicroPCMs) are synthesized in water. The MicroPCMs were incorporated at the step of polymerization. The effect of the MA mole ratio and MicroPCMs content on structures and properties of the copolymers were studied by using Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (1H NMR), scanning electronic microscope (SEM), differential scanning calorimetry (DSC), thermogravimetry analysis (TG), gel permeation chromatography (GPC), and X-ray diffraction (XRD). The feeding ratio agreed well with the composition of the AN/MA copolymers. The copolymers are synthesized in the presence of MicroPCMs. The melting point moves to lower temperature (206°C), while the decomposition temperature moves to higher temperature (309°C) with increasing of the MA mole ratio and microcapsules content. The number,average molecular weight of the copolymer is ,30,000. The crystallinity of the copolymer decreases with increasing of the MA mole ratio and microcapsules content. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2776,2781, 2007 [source] Enzymatic degradation of poly(L -lactic acid) fibers: Effects of small drawingJOURNAL OF APPLIED POLYMER SCIENCE, Issue 3 2007Hideto Tsuji Abstract The enzymatic degradation of poly(L -lactic acid) (PLLA) fibers with different low draw ratios (1.0, 1.2, and 1.4 times) was investigated in tris-HCl buffer solution (pH = 8.6) with proteinase K by the use of gravimetry, scanning electron microscopy (SEM), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and tensile testing. Surprisingly, even the small drawings (1.2 and 1.4 times) disturbed the proteinase K catalyzed enzymatic degradation of the PLLA fibers. This should have been because the enzyme could not attach to the extended (strained) chains in the amorphous regions of the uniaxially oriented PLLA fibers or could not catalyze the cleavage of the strained chains. The accumulation of crystalline residues formed as a result of selective cleavage, and removal of the amorphous chains was not observed, even for as-spun PLLA fibers. This indicated the facile release of formed crystalline residues from the surface of the as-spun PLLA fibers during enzymatic degradation. Such release may have been because the crystalline regions of the as-spun PLLA fibers were oriented with their c axis parallel to the machine direction, as reported for biaxially oriented PLLA films. Gravimetry, SEM, and tensile testing could trace the enzymatic degradation of the PLLA fibers, although the enzymatic degradation of the PLLA fibers was untraceable by GPC and DSC. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2064,2071, 2007 [source] COMPOSITION OF THE SOLUBLE, NONDIALYZABLE COMPONENTS IN RAW CANE SUGARJOURNAL OF FOOD PROCESSING AND PRESERVATION, Issue 5 2001MARY AN GODSHALL The high molecular weight (HMW) material (> 12,000 Da) of ten raw cane sugars from seven countries and two U.S. states was isolated by dialysis and analyzed by gel permeation chromatography (GPC). Simultaneous detection of colorant polymers and polysaccharides was accomplished by using two detectors in series , UV at 214 nm for colorant polymers and refractive index (RI) for carbohydrate polymers. The monosaccharide composition of the nondialyzable raw sugar fraction (the tenate) was determined by hydrolysis with trifluoroacetic acid and with oxalic acid. Aconitic acid was associated with the tenate. The raw sugars were categorized into two types according to their GPC patterns and aconitic acid content. Hydrolysis of individually collected GPC peaks demonstrated that one particular peak contained most of the aconitic acid. [source] Properties of Arrowroot Starch Treated with Aqueous HCl at Ambient TemperatureJOURNAL OF FOOD SCIENCE, Issue 1 2002J.K. John Arrowroot starch was acid-treated using 2.2 M HCl at 29 to 30° C for durations of 0 to 72 h, and properties of the control and modified samples were compared. Increasing length of acid treatment produced a progressive decline in amylose blue value, intrinsic viscosity, and swelling power, as well as an increase in free sugars and solubility. Differential scanning calorimetry (DSC) studies highlighted changes effected by acid-treatment in the gelatinization behavior of the starch samples. Gel permeation chromatography (GPC) studies on 32- and 72-h acid-treated samples indicated a greater proportion of dextrins with a higher percentage of reducing sugars, compared to the control. While X-ray diffraction data suggested minor changes in the crystal phase impacted by acid-treatment, in vitro digestibility of both control and acid-treated samples did not show any appreciable change in overall patterns. [source] Laser desorption/ionization techniques in the characterization of high molecular weight oil fractions.JOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 9 2006Part 1: asphaltenes Abstract The molecular weight distribution of the asphaltene fractions of two types of crude oils from two different Italian fields (samples 1 and 2) was investigated. The analytical tools used to perform these analyses were matrix assisted laser desorption ionization (MALDI) and laser desorption ionization (LDI) mass spectrometry. After observing that the use of the matrix (as well as the addition of Ag+) did not improve the quality of the data compared to that obtained in LDI conditions, all further measurements were performed with the latter technique. Operating under usual conditions of laser power and delay time, a very low resolution was observed, showing only macroscopic differences between the two samples in the molecular weight distribution of the different components. An accurate study on the possible reasons of this undesirable behavior indicates that it can originate from space charge phenomena occurring either in the ion source region or during the flight. A valid parameterization of the delay time and the laser power allowed higher quality spectra to be obtained. Surface-enhanced laser desorption ionization (SELDI) measurements were also performed using normal phase (silica) as the sample holder surface. Under these conditions, better results are obtained, proving that the sample,surface interaction is important to achieve, by means of laser irradiation, a homogeneous set of product ions. Both asphaltene samples were fractionated in five subfractions by gel-permeation chromatography (GPC) to obtain a better separation of the molecular weight distributions; the related spectra confirmed these findings. By using different approaches, relevant and reproducible differences between the asphaltene fractions of the two oil samples were observed. Copyright © 2006 John Wiley & Sons, Ltd. [source] Antibody response to aggregated human interferon alpha2b in wild-type and transgenic immune tolerant mice depends on type and level of aggregationJOURNAL OF PHARMACEUTICAL SCIENCES, Issue 5 2006Suzanne Hermeling Abstract The aim of this study was to determine the sensitivity of transgenic immune tolerant mice for the type and level of aggregation of recombinant human interferon alpha2b (rhIFN,2b). RhIFN,2b was aggregated by metal-catalyzed oxidation or by incubation at elevated temperature and various pHs. Native rhIFN,2b was mixed with oxidized rhIFN,2b at different ratios to obtain samples with different aggregation levels. The preparations were characterized by UV and fluorescence spectroscopy, gel permeation chromatography (GPC), dynamic light scattering (DLS), sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS,PAGE) and Western blotting, and ELISA. The immunogenicity was evaluated in wild-type mice and transgenic mice immune tolerant for hIFN,2. Sera were analyzed by ELISA for the presence of rhIFN,2b-specific antibodies. The oxidized and aged preparations widely differed regarding the level and nature of aggregates. All preparations containing aggregates increased the immune response in the wild-type mice as compared to native rhIFN,2b and were able to break the tolerance of the transgenic mice. The more native-like the conformation of the aggregated proteins, the more immunogenic the preparations were in the transgenic mice. The native-like aggregates prepared via metal catalysis induced a dose-dependent loss of tolerance in the transgenic mice. In conclusion, the transgenic mouse model can be used to screen rhIFN,2b formulations for low levels of immunogenic aggregates obtained under accelerated storage conditions. © 2006 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 95:1084,1096, 2006 [source] Radical copolymerization of vinylidene fluoride with 1-bromo-2,2-difluoroethyleneJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 18 2010G. K. Kostov Abstract The radical copolymerization of vinylidene fluoride (VDF) and 1-bromo-2,2-difluoroethylene (BDFE) in 1,1,1,3,3-pentafluorobutane solution at different monomer molar ratios (ranging from 96/4 to 25/75 mol %) and initiated by tert -butylperoxypivalate (TBPPI, mainly) is presented. Poly(VDF- co -BDFE) copolymers of various aspects (from white powders to yellow viscous liquids) were produced depending on the copolymer compositions. The microstructures of the obtained copolymers were characterized by 19F and 1H NMR spectroscopy and by elementary analysis and these techniques enabled one to assess the contents of both comonomers in the produced copolymers. VDF was shown to be more incorporated in the copolymer than BDFE. From the extended Kelen and Tudos method, the kinetics of the radical copolymerization led to the determination of the reactivity ratios, ri, of both comonomers (rVDF = 1.20 ± 0.50 and rBDFE = 0.40 ± 0.15 at 75 °C) showing that VDF is more reactive than BDFE. Alfrey-Price's Q and e values of BDFE monomer were calculated to be 0.009 (from QVDF = 0.008) or 0.019 (from QVDF = 0.015) and +1.22 (vs. eVDF = 0.40) or +1.37 (vs. eVDF = 0.50), respectively, indicating that BDFE is an electron-accepting monomer. Statistic cooligomers were produced with molar masses ranging from 1,800 to 5,500 g/mol (assessed by GPC with polystyrene standards). A further evidence of the successful copolymerization was shown by the selective reduction of bromine atoms in poly(VDF- co -BDFE) cooligomers that led to analog PVDF. The thermal properties of the poly(VDF- co -BDFE) cooligomers were also determined and those containing a high VDF amount exhibited a high thermal stability. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3964,3976, 2010. [source] A hyperbranched, rotaxane-type mechanically interlocked polymerJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 18 2010Shijun Li Abstract Based on the dibenzo-24-crown-8/1,2-bis(pyridinium)ethane recognition motif, a hyperbranched mechanically interlocked polymer was prepared by polyesterification of an easily available dynamic trifunctional AB2 pseudorotaxane monomer. It was characterized by various techniques including 1H NMR, COSY, NOESY, GPC, viscosity, TGA, dynamic laser light scattering, AFM, and SEM. Its GPC Mn was determined to be 191 kDa with polydispersity 1.7 and its hydrodynamic diameter in a dilute solution in acetone was about 70 nm. This measured Mn value corresponds to about 93 repeating units. The study reported here presents not only a new polymer topology but also a novel and convenient way to prepare mechanically interlocked polymers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4067,4073, 2010 [source] Cyclic alkoxyamine-initiator tethered by azide/alkyne-"click"-chemistry enabling ring-expansion vinyl polymerization providing macrocyclic polymersJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 15 2010Atsushi Narumi Abstract A cyclic initiator for the nitroxide-mediated controlled radical polymerization (NMP) is a powerful tool for the preparation of macrocyclic polymers via a ring-expansion vinyl polymerization mechanism. For this purpose, we prepared a Hawker-type NMP-initiator that includes an azide and a terminal alkyne as an acyclic precursor, which is subsequently tethered via an intramolecular azide/alkyne-"click"-reaction, producing the final cyclic NMP-initiator. The polymerization reactions of styrene with cyclic initiator were demonstrated and the resultant polymers were characterized by the gel permeation chromatography (GPC) and the matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). These results prove that the ring-expansion polymerization of styrene occurred together with the radical ring-crossover reactions originating from the exchange of the inherent nitroxides generating macrocyclic polystyrenes with higher expanded rings. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3402,3416, 2010 [source] | ||||||||||||||||