Thermal stability of porous it‐PMMA thin film obtained by the extraction of st‐PMAA from it‐PMMA/st‐PMAA stereocomplex with layer‐by‐layer assembly on a substrate

The functionality of porous isotactic (it) poly(methyl methacrylate) (PMMA) thin films, which were previously developed by the selective extraction of syndiotactic (st) poly(methacrylic acid) (PMAA) from the it‐PMMA/st‐PMAA stereocomplex thin film on a substrate using the layer‐by‐layer assembly method was investigated after thermal treatment (70, 80, and 90 °C) in water for 4 h. Quartz crystal microbalance analysis and infrared spectra measurements revealed that the st‐PMAA incorporation ability of the porous it‐PMMA thin film decreased in order at 80 and 90 °C, while there was no decrease observed at 70 °C. X‐ray diffraction analysis also supported the thermal stability of the porosity at 70 °C, whereas two it‐PMMA crystalline peaks (2θ = 9° and 14°) were generated during heating at 90 °C. The loss of the functionality of the it‐PMMA thin film was thus shown to be due to crystallization, which was caused by the increase in polymer‐chain mobility during the heating process. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3265–3270, 2010     

Evaluation of CP Sil 8 CB film thickness for the capillary GC determination of methyl mercury

Different commercially available CP-Sil 8 CB capillary columns have been tested with a mixed standard containing methyl mercury chloride, ethyl mercury chloride and a stable nonpolar chlorinated hydrocarbon. The aim of the study was to see whether the columns tested could be used without special pretreatments and precautions for the determination of organo-mercury compounds. The GC conditions in these determinations where similar to those conditions used for the determination of chlorinated pesticides. The best peak shapes where found using a normal packed column injector, modified with a commercially available insert for on-column injections on wide bore columns, and a 5.35 m thick stationary phase. It was concluded that this CP Sil 8 CB column gave good results although minor interactions between the organomercury compounds and the column could be seen.     

Optimisation of mould surface temperature and bottle residence time in mould for the carbonated soft drink PET containers

Polyethylene terephthalate (PET) bottles, which are usually produced by injection stretch blow moulding (ISBM) are widely used for carbonated soft drinks (CSD) storage and transportation. Stretch rod movement, blow pressure, preform temperature profile, mould surface temperature and material properties are among the most important factors affecting the final product's quality in terms of the thickness distribution, burst pressure and top-load resistance of the bottles. However, the residence time of the blown bottle inside the mould is also an important factor affecting its final properties. Especially in PET bottle production for hot fillings, the residence time is a very important factor because the longer the residence time the better the crystalline structure of the PET. In this production, the lid section is desired to have a fully crystalline form so that it can withstand hot fluids. In this study, the aim was to optimise the mould surface temperature and the blown bottle's residence time inside the mould for 1 L soft drink PET bottle production based on the final properties using the ECHIP 7 design of experiment (DOE) program. The method employed through this program was a quadratic one. Optimum process parameters were determined by the response surface method (RSM) and the process settings ensuring maximum top-load, burst pressure, Tg and degree of crystallinity were regarded to be optimum. It was found that the optimum mould surface temperature and blown bottle residence time inside the mould were 10 °C and 20 s, respectively.     

Effect of inorganic phase on polymeric relaxation dynamics in PMMA/silica hybrids studied by dielectric analysis

Dielectric relaxation spectroscopy was used to investigate the effect of the inorganic phase on the polymeric relaxation dynamics in PMMA/silica hybrids synthesized in situ via sol-gel processes. It was found that the large-scale molecular motions of PMMA were influenced by the addition of silica, inducing longer mean relaxation times, more heterogeneous relaxing environments and the higher activation energy. Explanations based on hydrogen-bond interactions between two phases and a fraction of entrapped chain segments in silica networks were proposed to understand the influence of the silica.     

Terpolymerization of methyl methacrylate, poly(ethylene glycol) methyl ether methacrylate or poly(ethylene glycol) ethyl ether methacrylate with methacrylic acid and sodium styrene sulfonate: determination of the reactivity ratios

Materials bearing ionic monomers were obtained through free radical terpolymerization of methyl methacrylate (MMA), poly(ethylene glycol) methyl ether methacrylate (PMEM) or poly(ethylene glycol) ethyl ether methacrylate (PEEM) with methacrylic acid (MA) and sodium styrene sulfonate (NaSS). The reactions were carried out in dimethyl sulfoxide using azobis(isobutyronitrile) as initiator. The reactivity ratios of the different couple of monomers were calculated according to the general copolymerization equation using the Finnemann-Ross, Kelen-Tüdos and Tidwell-Mortimer methods. The values of the reactivity ratios indicate that the different monomer units can be considered as randomly distributed along the chains for terpolymerizations of MMA, PMEM or PEEM with MA and NaSS. The average composition of the comonomers in the different terpolymers were calculated, showing a good agreement between the experimental and theoretical compositions. The instantaneous compositions are constant until about 70% of conversion. For higher conversions, the insertion of ionic monomers increases or decreases according to the system studied.     

The role of crystalline, mobile amorphous and rigid amorphous fractions in the performance of recycled poly (ethylene terephthalate) (PET)

The action of thermo-mechanical degradation induced by mechanical recycling of poly(ethylene terephthalate) was simulated by successive injection moulding cycles. Degradation reactions provoked chain scissions and a reduction in molar mass mainly driven by the reduction of diethyleneglycol to ethylene glycol units in the flexible domain of the PET backbone, and the formation of -OH terminated species with shorter chain length. The consequent microstructural changes were quantified taking into account a three-fraction model involving crystalline, mobile amorphous (MAF) and rigid amorphous fractions (RAF). A remarkable increase of RAF, to a detriment of MAF was observed, while the percentage of crystalline fraction remained nearly constant. A deeper analysis of the melting behaviour, the segmental dynamics around the glass-rubber relaxation, and the macroscopic mechanical performance, showed the role of each fraction leading to a loss of thermal, viscoelastic and mechanical features, particularly remarkable after the first processing cycle.     

Development of a solid‐phase microextraction fiber coated with poly(methacrylic acid‐ethylene glycol dimethacrylate) and its application for the determination of chlorophenols in water coupled with GC

A solid‐phase microextraction (SPME) fiber coated with poly(methacrylic acid‐ethylene glycol dimethacrylate) coupled to GC with a micro electron‐capture detector was developed for the determination of four chlorphenols in water samples for the first time. A novel and simple method for the preparation of this novel SPME fiber was proposed by copolymerization of methacrylic acid and ethylene glycol dimethacrylate in an appropriate solvent using a glass capillary as a “mold”. The factors affecting the polymerization were optimized in detail. Furthermore, the extraction performance of the poly(methacrylic acid‐ethylene glycol dimethacrylate) fiber was evaluated. Moreover, experimental headspace‐SPME parameters, such as extraction temperature, extraction time, salt concentration, stirring speed, and pH, were optimized by orthogonal array experimental designs. Under the optimized conditions, the target analytes were linear in the range of 0.2–50 ng/mL, and the correlation coefficients were all greater than 0.99. RSD was less than 8.9%, and the detection limits were in the range of 0.1–10 ng/L. Four cholorphenols were detected from tap and lake water samples using the proposed method, with the recoveries of spiked natural water samples were ranged from 91.8 to 110.8, and 90.6 to 111.4% for tap and lake water samples, respectively.     

碳氟等离子体改性PET表面的反应机制的研究

利用CF₄与cH₄/CF₄等离子体来处理涤沦膜(PET),讨论了不同摩尔比的碳氟等离子体改性PET表面的作用机制.利用变角x光电子能谱(XPS)和接触角测试技术研究了改性后PET表面的结构和性质.结果表明,碳氟等离子体的处理可以显著地改善PET表面的憎水性.不同摩尔比的碳氟混合气体的作用机制不同,其中碳氟混合气体等离子体以聚合为主,在PET表面形成均匀的改性层;而纯CF₄气体则以刻蚀为主,含氟基团主要分布在PET表面.     

Chemical assays of end-groups displayed on the surface of poly(ethylene terephthalate) (PET) films and membranes by radiolabeling

Poly(ethylene terephthalate) (PET) films and track-etched microporous membranes naturally display, on their surfaces, reactive chain-ends, i.e. carboxyl and hydroxyl functions. These were assayed by suitable activation (reaction with carbodiimide and tosyl chloride, respectively), followed by coupling with ³H-lysine and liquid scintillation counting of the sample-associated radioactivity. Values ranging between 5 and 30 pmol/cm² (open surface) of labeled end-groups were obtained, depending on the physico-chemical nature of the samples. Basic hydrolysis enriched the PET films with both types of endings (15–25 pmol/cm²). Reduction of films with the NaBH₄-catechol complex in tetrahydrofuran enriched their surfaces with hydroxyl groups. However, this procedure was not readily applicable to the surface modification of membranes; we observed an erosion effect that was confirmed by scanning electron microscope analyses. In contrast with the reduction process, the oxidation with KMnO₄ in 1.2N H₂SO₄ could be easily applied to the modification of either films or membranes; their surfaces were significantly enriched with carboxyl groups (15–50 pmol/cm²). This surface modification strategy has been used for the covalent coupling of adhesive proteins on PET membranes developed as supports for cell cultivation.     

Determination of parabens in cosmetic products by solid-phase microextraction of poly(ethylene glycol) diacrylate thin film on fibers and ultra high-speed liquid chromatography with diode array detector

The fabrication of a solid-phase microextraction (SPME) fiber through UV-induced polymerization of poly(ethylene glycol) diacrylate (PEG-DA) for determination of parabens in cosmetic products is presented in this work. The PEG-DA polymer coating was covalently attached to the fiber by introducing a surface modification with 3-(trichlorosilyl)propyl methacrylate (TPM). The PEG-DA polymer thin film coated on the fiber was homogeneous and wrinkled, which led to an increase of the surface area and high extraction efficiency. The extraction performances of the prepared SPME fibers were assessed by preconcentration of parabens including methylparaben, ethylparaben, propylparaben and benzylparaben from cosmetic products. The analysis was performed on an ultra high-speed liquid chromatography with diode array detector. The prepared SPME fibers exhibited good repeatability (for one fiber) and reproducibility (fiber-to-fiber) with RSDs of 5.4 and 6.9%, respectively. The optimized SPME method supported a wide linear range of 0.50-160 μg/mL and the detection limits for parabens were in the range of 0.12-0.15 μg/mL (S/N=3). The developed method was successfully applied for determination of parabens in cosmetic products with different natures.     

Homo‐ and copolymerization of methyl methacrylate with ethylene by novel Ziegler‐Natta‐Type nickel catalysts based on N,O‐nitro‐substituted chelate ligands

New Nickel (II) catalytic systems based on N,O chelate ligands, activated by methylaluminoxane, have been checked in the homopolymerization of methyl methacrylate (MMA) and its copolymerization with ethylene. In particular, the bis(8‐hydroxy‐5‐nitro‐quinolate)nickel(II)/methylaluminoxane system as well as the catalysts obtained by oxidative addition of either 8‐hydroxy‐5‐nitro‐quinoline or 8‐hydroxy‐5,7‐dinitro‐quinoline or 4‐nitro‐2‐(p‐nitrobenzylideneamino)‐phenol to Ni(cod)₂, subsequently activated by methylaluminoxane, have been employed. The influence of the reaction parameters on the catalytic activity and the characteristics of the resulting polymers has been investigated. All the obtained poly(methyl methacrylate) samples display a largely prevailing syndiotacticity degree, high molecular weights and a rather large polydispersity. The catalytic systems obtained through the oxidative procedure are able also to give copolymers of MMA with ethylene producing highly linear polyethylenes containing a low amount (1.5–2 mol %) of MMA counits, thus affording materials with improved surface properties. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 620–633, 2006     

Preparation of W1/O/W2 emulsion to limit the diffusion of Fe3+ in the Fricke gel 3D dosimeter

The irradiation of tumors in radiotherapy requires accurate 3D dosimetry. The Fricke 3D dosimeters, which were considered to be high potential of application in 3D dosimetry, suffer from a reduced temporal integrity of dose distribution caused by Fe³⁺ ions diffusion. To overcome the drawback, we firstly synthesized a kind of amphiphilic molecules with critical micelle concentration of 0.45 g/L and hydrophile‐lipophile balance value of 10, then prepared multiple emulsions by self‐assembling those molecules in Fricke solution under liquid paraffin, and finally obtained Fricke hydrogel embedded with the multiple emulsions. The diffusion coefficient of Fe³⁺ ions in the embedded Fricke hydrogel was measured to be 0.17 mm²/h. The hydrogel dosimeter exhibits considerable potential for use in dose verification applications.     

Polyethylene terephthalate–multiwall nanotubes nanocomposites: Effect of nanotubes on the conformations,crystallinity and crystallization behavior of PET

PET‐nanotube composite samples were manufactured by mixing neat PET with a PET‐multiwall carbon nanotube masterbatch. Fourier transform infrared (FTIR) spectroscopy was utilized to monitor the gauche and trans conformations of the polymeric chains with respect to the nanotube content. The crystallinity as well as the crystallization behavior of the polymer were studied via differential scanning calorimetry (DSC). An increase of the trans conformations and crystallinity was recorded at low NT contents followed by a sharp decrease at 1 wt % of nanotubes, further addition of nanotubes led once again to increase of the trans conformations and crystallinity. This behavior was attributed to the aggregations formation which as shown via transmission electron microscopy (TEM) was initiated at concentrations above 0.5 wt %. Discordance between the FTIR and DSC results in the case of the PET sample showed that the later bears relatively more trans non‐crystalline conformers than the nanocomposite samples. Thus it appears that the nanotubes incorporate the trans non‐crystalline segments into the crystalline phase. This work has shown that even a minor addition of carbon nanotubes (even 0.1 wt %) alters the crystallization behavior of the polymer dramatically, yielding a novel nanocomposite material rather than a simple mixture of two ingredients. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 668–676, 2008     

Temperature program optimization by computer simulation for the capillary GC analysis of fatty acid methyl esters on biscyanopropyl siloxane phases

The selectivity of capillary columns coated with biscyanopropyl siloxane stationary phases for the separation of fatty acid methyl esters has been optimized by means of computer-assisted column temperature optimization software. Temperature programming rates yielding the highest resolution in the shortest analysis time were selected for split, splitless, and on-column injection operated in the constant pressure and pressure programmed modes.     

Reference standards for quantitative trace analysis of PCB's by GC. Technical PCB formulations for the calibration of ECD and MSD responses

Summary The composition of any technical PCB formulation can be determined directly by analyzing the PCB sample by gas chromatography with a flame ionization detector (GC-FID), provided the relative molecular masses of the components are known. The responses of electron capture and selected-ion monitoring, mass-spectra detectors can then be calibrated for individual PCB congeners by correlation of the chromatographic patterns with those of concentrated PCB samples obtained by GC-FID. This procedure, which uses a given technical PCB formulation as a secondary reference standard mixture, is to be preferred over existing calibration methods, when results with ±10% errors are acceptable because commercial PCB formulations cover the whole range of chlorination products.     

A simple and rapid method for the determination of taxol produced by fungal endophytes from medicinal plants using high performance thin layer chromatography

 Taxol is an important anticancer drug used widely in the clinical field. In this study, some endophytic fungi were isolated from selected medicinal plants, and were screened for their potential in the production of taxol, using a rapid separation technique of high performance thin layer chromatography (HPTLC). Of the 20 screened fungi, only 13 fungal species produced taxol in the artificial culture medium. The results of HPTLC showed that the 13 fungal species had identical ultraviolet (UV) characteristics, positive reactivity with a spray reagent, yielding a blue spot, which turned to dark gray after 24 hours, and had Rf values identical to that of the authentic taxol. The amount of taxol was also quantified by comparing the peak area and the peak height of the fungal samples with those of authentic taxol.     

Quadruple click reactions for the synthesis of cysteine‐terminated linear multiblock copolymers

Synthesis of cysteine‐terminated linear polystyrene (PS)‐b‐poly(ε‐caprolactone) (PCL)‐b‐poly(methyl methacrylate) (PMMA)/or poly(tert‐butyl acrylate)(PtBA)‐b‐poly(ethylene glycol) (PEG) copolymers was carried out using sequential quadruple click reactions including thiol‐ene, copper‐catalyzed azide–alkyne cycloaddition (CuAAC), Diels–Alder, and nitroxide radical coupling (NRC) reactions. N‐acetyl‐L ‐cysteine methyl ester was first clicked with α‐allyl‐ω‐azide‐terminated PS via thiol‐ene reaction to create α‐cysteine‐ω‐azide‐terminated PS. Subsequent CuAAC reaction with PCL, followed by the introduction of the PMMA/or PtBA and PEG blocks via Diels–Alder and NRC, respectively, yielded final cysteine‐terminated multiblock copolymers. By ¹H NMR spectroscopy, the DP_ns of the blocks in the final multiblock copolymers were found to be close to those of the related polymer precursors, indicating that highly efficient click reactions occurred for polymer–polymer coupling. Successful quadruple click reactions were also confirmed by gel permeation chromatography. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Diels‐alder click reaction for the preparation of polycarbonate block copolymers

The Diels‐Alder reaction as a click reaction strategy is applied to the preparation of well‐defined polycarbonate (PC)‐block copolymers. A well‐defined α‐anthracene‐terminated polycarbonate (PC‐anthracene) is prepared using 9‐anthracene methanol as an initiator in the ring opening polymerization of benzyl 5‐methyl‐2‐oxo‐1,3‐dioxane‐5‐carboxylate in CH₂Cl₂ at room temperature for 5 h. Next, a well‐defined α‐furan protected maleimide‐terminated‐poly(ethylene glycol) (PEG₁₁‐MI or PEG₃₇‐MI), ‐poly(methyl methacrylate) (PMMA₂₆‐MI), and ‐poly(ε‐caprolactone) (PCL₂₇‐MI) were clicked with the PC‐anthracene at reflux temperature of toluene to yield their corresponding PC‐based block copolymers (PC‐b‐PEG, PC‐b‐PMMA, and PC‐b‐PCL). The homopolymer precursors and their block copolymers were characterized by using the GPC, NMR and UV analysis. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Mixed polyelectrolyte coatings on glassy carbon electrodes: Ion-exchange, permselectivity properties and analytical application of poly-l-lysine-poly(sodium 4-styrenesulfonate)-coated mercury film electrodes for the detection of trace metals

The present work describes the preparation, optimization and characterization of mixed polyelectrolyte coatings of poly-l-lysine (PLL) and poly(sodium 4-styrenesulfonate) (PSS) for the modification of thin mercury film electrodes (MFEs). The novel-modified electrodes were applied in the direct analysis of trace metals in estuarine waters by square-wave anodic stripping voltammetry (SWASV). The effects of the coating morphology and thickness and also of the monomeric molar ratio PLL/PSS on the cation-exchange ability of the PLL–PSS polyelectrolyte coatings onto glassy carbon (GC) were evaluated using target cationic species such as dopamine (DA) or lead cation. Further, the semi-permeability of the PLL–PSS-coated electrodes based both on electrostatic interactions and on molecular size leads to an improved anti-fouling ability against several tensioactive species. The analytical usefulness of the PLL–PSS-mixed polyelectrolyte coatings on thin mercury film electrodes is demonstrated via SWASV measurements of trace metals (lead, copper and cadmium at the low nanomolar level; accumulation time of 180 s) in estuarine waters containing moderate levels of dissolved organic matter, resulting in a fast and direct methodology requiring no sample pretreatment.