Pyrene-containing polystyrene segmented copolymer from nitroxide mediated polymerization and its application for the noncovalent functionalization of as-prepared multiwalled carbon nanotubes

This study reports simple and convenient procedures for the preparation of a novel surface modifier for multiwalled carbon nanotubes (CNTs) having uniform and controlled structure through controlled “living” free-radical polymerization technique. The technique afforded pyrene functionalized polystyrene block copolymers (PMAS) having controlled molecular weight, molecular weight distribution and length of each block for effective surface modification of CNTs. The modified CNTs exhibited much improved and stable dispersion in toluene. PMAS-CNT/polystyrene composites afforded clearer and more homogeneous films compared to those containing non-modified CNTs. The polystyrene films containing 2 wt% and 5 wt% of PMAS-CNTs showed improved AC conductivities of approximately 10⁻³ and 10⁻² S/cm, respectively, which were 10 ∼ 10⁶ times higher than those of films containing non-modified CNTs. These results demonstrated that PMAS effectively modified the surface of CNTs, which resulted in improved dispersion of CNTs in polystyrene matrices.     

Synthesis and physico-chemical characterization of Au/TiO2 nanostructures formed by novel “cold” and “hot” nanosoldering of Au and TiO2 nanoparticles dispersed in water

A novel approach to synthesize Au/TiO₂ nanostructures with interesting optical properties is presented and discussed. It is based on the nanoparticle “cold” or “hot” nanosoldering occurring when two water suspensions of Au and TiO₂ nanoparticles are merely mixed at room temperature or laser irradiated after mixing.Thanks to the high fraction and mutual reactivity of surface species, immediately after the mixing process, the encounters between Au and TiO₂ nanoparticles in liquid phase are enough for “cold” nanosoldering of gold nanoparticles onto TiO₂ nanoparticles to occur. The optical characterizations show that this fast process (timescale less than 1 min) is followed by a slower process, attributable to some change of the Au nanoparticles. This latter process is significantly accelerated by the 532 nm laser light illumination. The structural and optical properties of “cold” and “hot” nanosoldered Au-TiO₂ nanoparticles were investigated by TEM, UV-vis and fluorescence spectroscopies.Interesting optical limiting response was detected at laser fluences above 0.8 J/cm². The nature of the nonlinear effect was investigated by the Z-scan technique, determining both the nonlinear absorption coefficient and the refraction index. Such interesting non-linear optical properties are worth to be tailored for specific applications.     

Molecular weight effect on the complexation of poly(methacrylic acid) and poly(ethylene oxide) as studied by high-resolution solid-state C NMR spectroscopy

Complexes of poly(methacrylic acid) (PMAA) and poly(ethylene oxide) (PEO) with different PEO molecular weight were studied by solid-state high-resolution ¹³C NMR spectroscopy, with the emphasis on the PEO molecular weight effect on inter-polymer interaction, morphology and molecular motion. It is found that the crystalline phase of PEO is completely destroyed in the complex. The results of ¹H transverse relaxation times and ¹³C spin-lattice relaxation times indicate that the chain mobility of both PEO and PMAA are greatly restricted by inter-molecular hydrogen-bonding interactions, especially when the molecular weight of PEO is 1500. The bulk structures of the complexes are found to be closely dependent on the molecular weight of PEO. The fraction of “free” PEO segments without forming hydrogen-bonds with PMAA increases with increasing PEO molecular weight.     

A novel approach to graft acrylates onto commercial silicones for release film fabrications by two-step emulsion synthesis

In this study, a two-step emulsion polymerization method was specially designed so as to effectively graft acrylate monomers onto commercial silicones and improve the properties of release films. FT-IR, DSC and grafting ratio tests showed that the grafting reaction happened and a high grafting ratio can be achieved when the silicone content was more than 20%. According to SEM-EDX result, the “sea-island” structure on the surface of release films made by acrylate-modified silicone latexes was proven. The silicones formed the continuous “sea” structure and the grafted acrylate polymers formed the segregated “island” structure. The carbon and silicon distributions were not uniform through the cross-section of release films made by acrylate-modified silicone latexes. After acrylate modification, the surface tension of silicone release films increased from 19-21 mN/m (before acrylate modification) to 30 mN/m and the release force increased from 8.1 g/in. to 47 g/in. As a result, the properties of release films have been effectively improved by our novel method for advanced applications.     

Fabrication of starch blend films with different matrices and their mechanical properties

The objective of the study was to determine the effects of molecular sizes of amylose (AM) and starch granules on the mechanical properties of thermoplastic starch (TPS) blend films. Leached amylose solution from cassava (CS_ AM) and mung bean (MB_AM), and two forms of amylopectin (AP) (granular; g and non-granular; ng) of waxy cassava (WxCS) starch were used. Four types of film matrices were fabricated and all TPS blend films contained same amount of AM and glycerol. Results displayed that molecular weight profiles of starch films and presence of granule remnants significantly controlled the film matrix formation, types of crystal formation, and percent of relative crystallinity (%RC) (p < 0.05). Tensile property of TPS films was controlled by %RC and presence of granule remnants. Percent elongation at break (%E_b) of TPS films increased when the films had a large range of molecular weight distribution (from 5.5 × 10⁷ g/mol to 0.4 × 10⁵ g/mol) and contained a high weight fraction (~58%) of starch molecules with M_w~0.4 × 10⁵ g/mol.     

Fluorinated compounds for advanced IC interconnect applications: a survey of chemistries and processes

The semiconductor industry is now in the early stages of an unprecedented change in materials set for the integrated circuit (IC) interconnect structure. The traditional layers of aluminum conductors and silicon dioxide dielectrics are being replaced by copper thin films and a variety of low k candidates, respectively. In many cases, fluorine confers desirable properties on either the precursors or the final films. At the same time, fluorine presents some potentially adverse effects, which have led to a so-called “fear-of-fluorine” in interconnect applications. This paper will review the proposed uses of fluorinated compounds in the interconnect structures, covering both precursors and the resulting thin films. Both the status of technical studies, and the prospects for commercial implementation, will be addressed.     

Orientation control of ferroelectric polymer molecules using contact-mode AFM

We have developed an orientation control technique for polymer molecules utilizing contact-mode atomic force microscopy (AFM). In this technique, the molecular chains were directly modified by scanning an AFM cantilever tip in contact with the film surface at the temperature just below its melting point. We call this process “modification scan”. Here, we applied this technique to poly(vinylidenefluoride-trifluoroethylene) (P(VDF-TrFE)) thin films on graphite and glass. We prepared a 75-nm thick copolymer crystalline film on graphite whose lamellar plane was perpendicular to the substrate (edge-on), and also prepared a film of the same thickness on glass whose lamellar plane was parallel to the substrate (flat-on). After applying this technique on both films, molecular chains were stretched and aligned to the modification scan direction, and new edge-on crystals were obtained, whose lamellar planes were well-aligned perpendicular to the modification scan direction.     

Static ultrasonic oscillations induced degradation and its effect on the linear rheological behavior of novel propylene based plastomer melts

The ultrasonic degradation of novel propylene based plastomer (DP) melts with different melt viscosities was conducted in a “static” ultrasonic device where the samples were taken from various distances from the tip of an ultrasonic probe. The effects of ultrasonic time, oscillation temperature, ultrasonic intensity and the distance from the ultrasonic probe tip on the degradation behavior of DP melts as well as the ultrasonic degradation effect on the linear rheological behavior of DP melts were studied. The results show that the increase of initial melt viscosity of DP (higher molecular weight) has greater impact on the ultrasonic degradation of DP melt. The molecular weight and intrinsic viscosity of DP decrease with the increase of ultrasonic oscillation time and they approach to a limiting value. The molecular weight distribution of DP increases after ultrasonic degradation. Decreasing oscillation temperature and distance from probe tip and increasing ultrasonic intensity lead to an increase in the degradation of DP melt. The linear rheological behavior measurements of the samples obtained near the ultrasonic probe tip show that ultrasonic oscillations decrease the complex viscosity, zero shear viscosity, viscoelastic moduli, cross modulus, relaxation time and the slope of log G′ − log G″ for DP melts.     

An aptameric molecular beacon-based “Signal-on” approach for rapid determination of rHuEPO-α

The aim of this work is to describe the first example of aptameric molecular beacon (MB)-based probe for the detection of recombinant human erythropoietin (rHuEPO-α) in physiological buffer, using a novel 35 nt ssDNA aptamer (807-35 nt) originally isolated by Systematic Evolution of Ligands by Exponential enrichment (SELEX) technique in our laboratory. Both “Signal-on” and “Signal-off” MB modes were developed, respectively, in which the conformational alteration of aptamer before and after binding to rHuEPO-α can be demonstrated in terms of the correspondingly fluorescent changes. Comparing with “Signal-off” mode, “Signal-on” mode provided higher sensitivity, while with the addition of target rHuEPO-α, quenching between fluorescent 807-35 nt aptamer (F-Apt) and a short quencher-labeled complementary sequence (QDNA) was disturbed by the specific binding between rHuEPO-α and F-Apt. QDNA was thus loosened and released from F-Apt, leading to a consequently full fluorescent restoration. Systematic optimization of parameters in “Signal-on” mode were carried out, the choice of QDNA length, the hybridization site of a small supplementary DNA (SDNA) stabilizer, and the existence of Mg²⁺ cation played essential roles for the performance characterization. A convenient and sensitive determination of rHuEPO-α with a LOD of 0.4 nM was achieved.     

Inkjet-printed gold nanoparticle chemiresistors: Influence of film morphology and ionic strength on the detection of organics dissolved in aqueous solution

The influence of film morphology on the performance of inkjet-printed gold nanoparticle chemiresistors has been investigated. Nanoparticles deposited from a single-solvent system resulted in a “coffee ring”-like structure with most of the materials deposited at the edge. It was shown that the uniformity of the film could be improved if the nanoparticles were deposited from a mixture of solvents comprising N-methyl-2-pyrrolidone and water. Electrical conductivity measurements showed that both “coffee ring” and “flat” films were qualitatively similar suggesting that the films have similar nanoscale structures. To form the functional chemiresistor device, the 4-(dimethylamino)pyridine coating on the nanoparticle was exchanged with 1-hexanethiol to provide a hydrophobic sensing layer. The performance of 1-hexanethiol coated gold nanoparticle chemiresistors to small organic molecules, toluene, dichloromethane and ethanol dissolved in 1 M KCl in regard to changes in impedance and response times was unaffected by the film morphology. For larger hydrocarbons such as octane, the rate of uptake of the analyte into the film was significantly faster when the flatter nanoparticle film was used as opposed to the “coffee ring” film which has a thicker edge. Furthermore, the presence of potassium and chloride ions in the solution media does not significantly affect the impedance of the nanoparticle film at 1 Hz (<2% variation in film impedance over more than four orders of magnitude change in ionic strength). However, the ionic strength of the media affected the partitioning of the analyte into the hydrophobic nanoparticle film. The response of the sensor was found to increase with an increased salt concentration due to a salting-out of the analyte from the solution.     

Quantification of immunoglobulin G and characterization of process related impurities using coupled Protein A and size exclusion high performance liquid chromatography

The present work describes two HPLC-UV methods for multi-protein quantification using (i) only a Protein A sensor cartridge (Protein A HPLC) and (ii) the same Protein A cartridge in combination with a size exclusion HPLC column (PSEC-HPLC). The possibility to simultaneously quantify immunoglobulin G (IgG) besides a non-binding protein such as bovine serum albumin (BSA) increases the applicability of Protein A HPLC. Its most pronounced feature is its independence of the buffer system, pH-value and salt content of the investigated sample solvent, which includes cell media. A comparison with the state-of-the-art, the photometrical Bradford method, shows that Protein A HPLC is as sensitive as Bradford, but that it comes with an extended linear range of 4 orders of magnitude, ranging from 0.15 [μg abs] to 1 [mg abs] absolute injected protein amount. The applicability of the PSEC-HPLC method is demonstrated for the analysis of real cell culture feed samples. While Protein A binds IgG, the SEC-column distributes the feed impurities by their molecular weight. The peak area ratios of IgG and the feed impurities of interest are then plotted against the collected sample fraction. These Protein A-Size-Exclusion-Chromatographic diagrams (PSEC-plot) combine the performance information of feed impurities and IgG in a single plot. Further it is shown that both methods are suitable for the performance evaluation of antibody purification media using static as well as dynamic binding experiments performed on DEAE-Fractogel and Capto Adhere. The investigated test samples were “mock” protein solutions with increasing complexity ranging from simple PBS buffer to serum free cell media and “real” cell culture feed solutions.     

The preparation and characterization of some cellulose graft copolymers. V. ESR study of preirradiation grafting of styrene to cellulose acetate

Previous studies have shown a two-peak molecular weight distribution of the grafted polystyrene side chains from preirradiation-grafted cellulose acetate. ESR has been used to investigate this grafting system in further detail. It was found that the rate of decay of the trapped radicals on adding the monomer solution was quite slow and a substantial proportion remained after 3 days at 25°C. The G value for radicals lost was, however, in good agreement with the G (grafted side chains) produced during the same period. The ESR spectrum does not change on addition of the monomer solution. The explanation offered is that the side chains grow and terminate rapidly compared with the slow overall rate of decay. The grafting yield and the molecular weight of the grafted side chains continue to grow until the reaction is terminated, leading perhaps to the high molecular weight narrow distribution fraction.     

The organo-metal initiated polymerization of vinyl ketones—II : The triethylaluminium initiated polymerization of methyl isopropenyl ketone

A study has been made of the kinetics and mechanism of the triethylaluminium initiated polymerization at 0° of methyl isopropenyl ketone (3-methyl-but-3-ene-2-one) in toluene and tetrahydrofuran. The reaction between triethylaluminium and methyl isopropenyl ketone gives rise to a yellow “ate”-complex which rearranges to the initiating species. A rapid production of linear trimer is followed by a slow polymerization giving rise to a bimodal molecular weight distribution. A coordinate mechanism for the polymerization is proposed.     

Synthesis,doping, and processing of high molecular weight poly(o-methoxyaniline)

High molecular weight poly(o-methoxyaniline) was synthesized using a novel method in which the polymerization occurs in the presence of a neutral salt. The molecular weight of the polymer was greatly affected by the quenching procedure employed to conclude the polymerization. Conventional doping of the base form of poly(o-methoxyaniline) produced a yellow coloration of the doping solution and polymer degradation. It was found that the molecular weight of the polymer decreased significantly after washing or doping with certain aqueous acid media. The gelation conditions of N-methyl pyrrolidinone (NMP) solutions and film preparation were also investigated for polymers of various molecular weights. The gelation time in NMP decreased drastically with the increase in the polymer molecular weight (the same for solution concentration and temperature), until a critical point was reached after which its decrease was very slow. Flexible, free-standing, and stretchable films were readily obtained from the higher molecular weight polymers. Good quality doped gel films with conductivity of up to 1 S/cm were obtained under optimized doping conditions. © 1994 John Wiley & Sons, Inc.     

Modification of morphology of polycarbonate/thermoplastic elastomer blends by supercritical CO2

The effect of supercritical CO₂ on the morphological features of blends of polycarbonate and a commercial thermoplastic elastomer was investigated. The as-prepared films of the blend showed phase separated domains of the elastomer. With the combination of pressure and temperature, the large domains were “burst” into smaller domains. Temperatures higher than the critical temperature are required to cause any change in the morphology. The size distribution of the elastomer domains is effectively narrowed by the supercritical CO₂ treatment. The time of exposure also plays a role. It was also seen that above 60 °C, crystallization of polycarbonate begins. Based on the previous work on this system, it is proposed that enhancement of elongation, Young’s modulus and abrasion resistance would occur due to the reduction in the domain size and distribution.     

端羟基化聚苯乙烯的表面性质

利用Wilhelmy片技术和躺滴法研究了端羟基化聚苯乙烯的表面性质.结果表明,端羟基化对聚苯乙烯在空气面的接触角基本没有影响(89°),而在玻璃面的接触角则大大降低(66°),其降低幅度与分子量及分子量分布有关.这与动态接触角的测定结果基本一致,而且宽分子量分布的端羟基化聚苯乙烯的前进接触角(θa)随着温度的升高而降低,于40℃时达到最低值.而窄分子量分布样品的动态接触角基本不变.样品与不同温度水接触后表面接触角的变化也基本相似.DMA研究结果表明,样品损耗模量、储能模量和tanδ从40℃开始发生突变,刚好与接触角最低值的温度相对应.这是由于宽分子量分布样品中的较低分子量组分在表面聚集,导致表面分子具有较高的活动能力.接触角随温度的变化趋势可能是聚合物表面分子运动能力增加和结晶程度变化等因素综合作用的结果.     

Inclusion of the effects of polydispersity and volatility on the random chain scission statistical analysis for polymer degradation

The statistical product distribution for a linear polydisperse polymer of finite molecular weight was included into the statistical analysis for a system undergoing random chain scission showing the effect of volatilization of species other than monomer. Two sets of equations were derived. One set is for the nonvolatile fraction; the other is for the volatile fraction. Within each set there are three equations, one for the number of polymer molecules, the second for the molar (or number) fraction, and the third for the weight fraction of polymer molecules containing a specific number of repeat units. As degradation proceeds the polydispersity index should converge to a value of 1 rather than 2, which has been reported previously. The expected effects of polydispersity, number‐average degree of polymerization, and volatility were treated individually, and we determined that the molecular weight of a polymer has no theoretical influence on the product distribution. As for the effect of volatility, we determined that only the volatile product distribution would change. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3690–3696, 2000     

Synthesis of PCL–graft–PS by combination of ROP, ATRP, and click chemistry

Poly(ε-caprolactone)–graft–polystyrenes were successfully synthesized by grafting an azide end-functionalized polystyrene onto a PCL backbone with multiple pendant alkyne moieties using a “click” chemistry reaction. Both precursors, the PCL backbone and the PS side chains, were prepared separately by two different living/controlled mechanisms, ring-opening polymerisation and ATRP, respectively. Molecular weights, polydispersity indexes, and chemical compositions of the backbone and branches were controlled. The subsequent copper-catalysed Huisgen 1,3-dipolar cycloaddition of PS onto PCL was achieved at room temperature with high conversion. However, a bimodal molecular weight distribution was observed in size exclusion chromatography due to the presence of unreacted PS. Nevertheless, crude product was purified by selective fractionation in cyclohexane to achieve pure graft copolymers.     

Characterization of an electrochemical mercury sensor using alternating current,cyclic, square wave and differential pulse voltammetry

Here we report the characterization of an electrochemical mercury (Hg²⁺) sensor constructed with a methylene blue (MB)-modified and thymine-containing linear DNA probe. Similar to the linear probe electrochemical DNA sensor, the resultant sensor behaved as a “signal-off” sensor in alternating current voltammetry and cyclic voltammetry. However, depending on the applied frequency or pulse width, the sensor can behave as either a “signal-off” or “signal-on” sensor in square wave voltammetry (SWV) and differential pulse voltammetry (DPV). In SWV, the sensor showed “signal-on” behavior at low frequencies and “signal-off” behavior at high frequencies. In DPV, the sensor showed “signal-off” behavior at short pulse widths and “signal-on” behavior at long pulse widths. Independent of the sensor interrogation technique, the limit of detection was found to be 10 nM, with a linear dynamic range between 10 nM and 500 nM. In addition, the sensor responded to Hg²⁺ rather rapidly; majority of the signal change occurred in <20 min. Overall, the sensor retains all the characteristics of this class of sensors; it is reagentless, reusable, sensitive, specific and selective. This study also highlights the feasibility of using a MB-modified probe for real-time sensing of Hg²⁺, which has not been previously reported. More importantly, the observed “switching” behavior in SWV and DPV is potentially generalizable and should be applicable to most sensors in this class of dynamics-based electrochemical biosensors.     

Carbonaceous species of TSP in urban and rural sites around coal-fired power stations in northwestern Greece

Total suspended particles from urban and rural locations around an industrial complex with four coal-fired power stations were collected for a period of 6 months (January-June 2001). Mass concentrations of TSP and carbonaceous species (TC, EC, OC and BC) were determined for seven sampling sites of the studied area. The contribution of TC mass to the total particle mass was similar for all sites with an average value of 12.36±1.27%. The fraction of elemental carbon (EC) was estimated between 32 and 46% of the total carbon (TC). The relationship between organic and elemental carbon showed the primary origin of organic carbon (direct emissions). The OC/BC ratio values were also considered in order to get information about the enrichment of aerosols in organic carbon. Four conditional categories out of the sampling site ‘collection were additionally extracted (“urban”, “rural”, “far” and “close” location to the power stations) and considered with respect to the values of the ratios OC/BC and OC/EC and the multiple correlation coefficients R² for the concentrations of OC, BC and EC. It has been found that in some cases the correlation coefficients rather than the ratios could inform on the type of site.