Synthesis and properties of novel sulfonated poly(phenylquinoxaline)s as proton exchange membranes

Two series of sulfonated poly(phenylquinoxaline)s (SPPQ-x and SPPQ(O)-x, x refers to molar percentage of sulfonated tetraamine monomer) were first synthesized from a sulfonated tetraamine (4,4'-bis(3,4-diaminophenoxy)biphenyl-3.3'-disulfonic acid) and two aromatic bisbenzils (4-phenylglyoxalylbenzil and p,p'-oxydibenzil) in a mild condition. The structures of SPPQ-x and SPPQ(0)-x were characterized by IR and H-1 NMR spectra. The properties of these polymer films, such as water uptake, water swelling ratio, proton conductivity, thermal properties, methanol permeability, hydrolytic and oxidative stability were also investigated. The resulting polymers generally showed good solubility in DMAc and DMSO. Flexible and tough membranes with high mechanical strength were prepared. They show very high thermal, thermooxidative, hydrolytic stabilities and low methanol permeability. SPPQ-100 with the IEC value (2.41 mmol/g) displays the conductivity of 0.1 S/cm and a swelling ratio of 7.3% at 100 degrees C.

Synthesis and characterization of rigid-rod sulfonated polyimides bearing sulfobenzoyl side groups as proton exchange membranes

A novel wholly aromatic diamine, 2,2 '-bis(3-sulfobenzoyl)benzidine (2,2 '-BSBB), was successfully prepared by the reaction of 2,2 '-dibenzoylbenzidine (2,2 '-DBB) with fuming sulfuric acid. Copolymerization of 1,4,5,8-naphathlenetetracarboxylic dianhydride with 2,2 '-BSBB and 2,2 '-DBB generated a series of rigid-rod sulfonated polyimides. The synthesized copolymers with the -SO3H group on the side chain of polymers possessed high molecular weights revealed by their high viscosity and the formation of tough and flexible membranes. The copolymer membranes exhibited excellent oxidative stability and mechanical properties due to their fully aromatic structure extending through the backbone and pendent groups. They displayed clear anisotropic membrane swelling in water with negligibly small dimensional changes in the plane direction of the membrane. The proton conductivities of copolymer membranes increased with increasing IEC and temperature, reaching value above 1.25 x 10(-1) S/cm at 20 degrees C, which is higher than that of Nafion (R) 117 at the same measurement condition. They displayed reasonably high proton conductivity due to the higher acidity of benzoyl sulfonic acid group, the larger interchain spacing, which is available for water to occupy, taking their lower water uptake (WU) into account. Consequently, these materials proved to be promising as proton exchange membrane.

Preparation and evaluation of a proton exchange membrane based on oxidation and water stable sulfonated polyimides

A series of novel oxidation and water stable sulfonated polyimides (SPIs) were synthesized from 4,4'-binaphthyl-1,1',8,8'-tetracarboxylic dianhydride (BTDA), and wholly aromatic diamine 2,2'-bis(3-sulfobenzoyl) benzidine (2,2'-BSBB) for proton exchange membrane fuel cells. These polyimides could be cast into flexible and tough membranes from m-cresol solutions. The copolymer membranes exhibited excellent oxidative stability and mechanical properties due to their fully aromatic structure extending through the backbone and pendant groups. Moreover, all BTDA-based SPI membranes exhibited much better water stability than those based on the conventional 1,4,5,8-naphthalenecarboxylic dianhydride. The improved water stability of BTDA-based polyimides was attributed to its unique binaphthalimide structure. The SPI membranes with ion exchange capacity (IEC) of 1.36-1.90 mequiv g(-1) had proton conductivity in the range of 0.41 x 10(-1) to 1. 12 x 10(-1) S cm(-1) at 20 degrees C. The membrane with IEC value of 1.90 mequiv g(-1) displayed reasonably higher proton conductivity than Nafion((R)) 117 (0.9 x 10(-1) S cm(-1)) under the same test condition and the high conductivity of 0.184 S cm(-1) was obtained at 80 degrees C. Microscopic analyses revealed that well-dispersed hydrophilic domains contribute to better proton conducting properties. These results showed that the synthesized materials might have the potential to be applied as the proton exchange membranes for PEMFCs.

Depression of net ecosystem CO2 exchange in semi-arid Leymus chinensis steppe and alpine shrub

Uptake and release of carbon in grassland ecosystems is very critical to the global carbon balance and carbon storage. In this study, the dynamics of net ecosystem CO2 exchange (FNEE) of two grassland ecosystems were observed continuously using the eddy covariance technique during the growing season of 2003. One is the alpine shrub on the Tibet Plateau, and the other is the sem-arid Leymus chinensis steppe in Inner Mongolia of China. It was found that the FNEE of both ecosystems was significantly depressed under high solar radiation. Comprehensive analysis indicates that the depression of FNEE in the L. chinensis steppe was the results of decreased plant photosynthesis and increased ecosystem respiration (R-eco) under high temperature. Soil water stress in addition to the high atmospheric demand under the strong radiation was the primary factor limiting the stomatal conductance. In contrast, the depression of FNEE in the alpine shrub was closely related to the effects of temperature on both photosynthesis and ecosystem respiration, coupled with the reduction of plant photosynthesis due to partial stomatal closure under high temperature at mid-day. The R,c of the alpine shrub was sensitive to soil temperature during high turbulence (u* > 0.2 m s(-1)) but its FNEE decreased markedly when the temperature was higher than the optimal value of about 12 degrees C. Such low optimal temperature contrasted the optimal value (about 20 degrees C) for the steppe, and was likely due to the acclimation of most alpine plants to the long-term low temperature on the Tibet Plateau. We inferred that water stress was the primary factor causing depression of the FNEE in the semi-arid steppe ecosystem, while relative high temperature under strong solar radiation was the main reason for the decrease of FNEE in the alpine shrub. This study implies that different grassland ecosystems may respond differently to climate change in the future. (c) 2006 Elsevier B.V All rights reserved.

Separation of acidic compounds by strong anion-exchange capillary electrochromatography

Separation of the acidic compounds in the ion-exchange capillary electrochromatograph (IE-CEC) with strong anion-exchange packing as the stationary phase was studied. It was observed that the electroosmotic flow (EOF) in strong anion-exchange CEC moderately changed with increase of the eluent ionic strength and decrease of the eluent pH, but the acetonitrile concentration in the eluent had almost no effect on the EOF. The EOF in Strong anion-exchange CEC with eluent of low pH value was much larger than that in RP-CEC with Spherisorb-ODS as the stationary phase. The retention of acidic compounds on the strong anion-exchange packing was relatively weak due to only partial ionization of them, and both chromatographic and electrophoretic processes contributed to separation. It was observed that the retention values of acidic compounds decreased with the increase of phosphate buffer and acetonitrile concentration in the eluent as well as the decrease of the applied voltage, and even the acidic compounds could elute before the void time. These factors also made an important contribution to the separation selectivity for tested acidic compounds, which could be separated rapidly with high column efficiency of more than 220 000 plates/m under the optimized separation conditions. (C) 2000 Elsevier Science BN. All rights reserved.

Separation of peptides by strong cation-exchange capillary electrochromatography

Separation of small peptides on ion-exchange capillary electrochromatography (IE-CEC) with strong cation-exchange packing (SCX) as stationary phase was investigated. It was observed that the number of theoretical plates for small peptides varied from 240 000 to 460 000/m, and the relative standard deviation for t(0) and the migration time of peptides were less than 0.57% and 0.27%, respectively for ten consecutive runs. Unusually high column efficiency has been explained by the capillary electrophoretic stacking and chromatofocusing phenomena during the injection and separation of positively charged peptides. The sample buffer concentration had a marked effect on the column efficiency and peak area of the retained peptides. The influences of the buffer concentration and pH value as well as the applied voltage on the separation were investigated. It has been shown that the electrostatic interaction between the positively charged peptides and the SCX stationary phase played a very important role in IE-CEC, which provided the different separation selectivity from those in the capillary electrophoresis and reversed-phase liquid chromatography. A fast separation of ten peptides in less than 3.5 min on IE-CEC by adoption of the highly applied voltage was demonstrated. (C) 2000 Elsevier Science B.V. All rights reserved.

Capillary electrochromatography using a strong cation-exchange column with a dynamically modified cationic surfactant

A novel mode of capillary electrochromatography (CEC), called dynamically modified strong cation-exchange CEC (DMSCX-CEC), is described in this paper. A column packed with a strong cation-exchange (SCX) packing material was dynamically modified with a long-chain quaternary ammonium salt, cetyltrimethylammonium bromide (CTAB), which was added to the mobile phase. CTAB ions were adsorbed onto the surface of the SCX packing material, and the resulting hydrophobic layer on this packing was used as the stationary phase. Using the dynamically modified SCX column, neutral solutes were separated with the CEC mode. The highest number of theoretical plates obtained was about 190 000/m, and the relative standard deviations (RSD's) for migration times and capacity factors of alkylbenzenes were less than 1.0% and 2.0% for five consecutive runs, respectively. The effects of CTAB and methanol concentrations and the pH value of the mobile phase on the electroosmotic flow and the separation mechanism were investigated. Excellent simultaneous separation of the basic and neutral solutes in DMSCX-CEC with a high-pH mobile phase was obtained, A mixture containing the acidic, basic, and neutral compounds was well separated in this mode with a low-pH mobile phase; however, peak tailing for basic compounds was observed in this mobile phase.

Preparation of monolithic silica column with strong cation-exchange stationary phase for capillary electrochromatography

A monolithic silica based strong cation-exchange stationary phase was successfully prepared for capillary electrochromatography. The monolithic silica matrix from a sol-gel process was chemically modified by treatment with 3-mercaptopropyltrimethoxysilane followed by a chemical oxidation procedure to produce the desired function. The strong cation-exchange stationary phase was characterized by its substantial and stable electroosmotic flow (EOF), and it was observed that the EOF value of the prepared column remained almost unchanged at different buffer pH values and slowly decreased with increasing phosphate concentration in the mobile phase. The monolithic silica column with strong cation-exchange stationary phase has been successfully employed in the electrochromatographic separation of beta-blockers and alkaloids extracted from traditional Chinese medicines (TCMs). The column efficiencies for the tested beta-blockers varied from 210,000 to 340,000 plates/m. A peak compression effect was observed for atenolol with the mobile phase having a low phosphate concentration.

Water exchange rates of water-soluble manganese(III) porphyrins of therapeutical potential.

The activation parameters and the rate constants of the water-exchange reactions of Mn(III)TE-2-PyP(5+) (meso-tetrakis(N-ethylpyridinium-2-yl)porphyrin) as cationic, Mn(III)TnHex-2-PyP(5+) (meso-tetrakis(N-n-hexylpyridinium-2-yl)porphyrin) as sterically shielded cationic, and Mn(III)TSPP(3-) (meso-tetrakis(4-sulfonatophenyl)porphyrin) as anionic manganese(iii) porphyrins were determined from the temperature dependence of (17)O NMR relaxation rates. The rate constants at 298 K were obtained as 4.12 x 10(6) s(-1), 5.73 x 10(6) s(-1), and 2.74 x 10(7) s(-1), respectively. On the basis of the determined entropies of activation, an interchange-dissociative mechanism (I(d)) was proposed for the cationic complexes (DeltaS(double dagger) = approximately 0 J mol(-1) K(-1)) whereas a limiting dissociative mechanism (D) was proposed for Mn(III)TSPP(3-) complex (DeltaS(double dagger) = +79 J mol(-1) K(-1)). The obtained water exchange rate of Mn(III)TSPP(3-) corresponded well to the previously assumed value used by Koenig et al. (S. H. Koenig, R. D. Brown and M. Spiller, Magn. Reson. Med., 1987, 4, 52-260) to simulate the (1)H NMRD curves, therefore the measured value supports the theory developed for explaining the anomalous relaxivity of Mn(III)TSPP(3-) complex. A magnitude of the obtained water-exchange rate constants further confirms the suggested inner sphere electron transfer mechanism for the reactions of the two positively charged Mn(iii) porphyrins with the various biologically important oxygen and nitrogen reactive species. Due to the high biological and clinical relevance of the reactions that occur at the metal site of the studied Mn(iii) porphyrins, the determination of water exchange rates advanced our insight into their efficacy and mechanism of action, and in turn should impact their further development for both diagnostic (imaging) and therapeutic purposes.

Fighting for shells: how private information about resource value changes hermit crab pre-fight displays and escalated fight behaviour

Pre-fight displays typically provide honest, but sometimes dishonest, information about resource holding potential and may be influenced by assessment of resource value and hence motivation to acquire the resource. These assessments of potential costs and benefits are also predicted to influence escalated fight behaviour. This is examined in shell exchange contests of hermit crabs in which we establish an information asymmetry about a particularly poor quality shell. The poor shell was created by gluing sand to the interior whereas control shells lacked sand and the low value of the poor shell could not be accurately assessed by the opponent. Crabs in the poor shell showed changes in the use of pre-fight displays, apparently to increase the chances of swapping shells. When the fights escalated, crabs in poor shells fought harder if they took the role of attacker but gave up quickly if in the defender role. These tactics appear to be adaptive but do not result in a major shift in the roles taken or outcome. We thus link resource assessment with pre-fight displays, the roles taken, tactics used during escalation and the outcome of these contests.

MEASUREMENT AND CALCULATION OF ABSOLUTE SINGLE AND MULTIPLE CHARGE EXCHANGE CROSS SECTIONS FOR Feq+ IONS IMPACTING H2O

Charge exchange (CE) plays a fundamental role in the collisions of solar- and stellar-wind ions with lunar and planetary exospheres, comets, and circumstellar clouds. Reported herein are absolute cross sections for single, double, triple, and quadruple CE of Feq+ (q = 5-13) ions with H2O at a collision energy of 7q keV. One measured value of the pentuple CE is also given for Fe9+ ions. An electron cyclotron resonance ion source is used to provide currents of the highly charged Fe ions. Absolute data are derived from knowledge of the target gas pressure, target path length, and incident and charge-exchanged ion currents. Experimental cross sections are compared with new results of the n-electron classical trajectory Monte Carlo approximation. The radiative and non-radiative cascades following electron transfers are approximated using scaled hydrogenic transition probabilities and scaled Auger rates. Also given are estimates of cross sections for single capture, and multiple capture followed by autoionization, as derived from the extended overbarrier model. These estimates are based on new theoretical calculations of the vertical ionization potentials of H2O up to H2O10+.

Do Low-Priced Stocks Drive Long-Term Contrarian Performance on the London Stock Exchange?

We investigate whether low-priced stocks drive long-term contrarian performance on the U.K. market. We find that contrarian performance at low, middle, and high price levels is positive. On the Fama-French risk adjusted basis, we find both low-priced and middle-priced losers have significantly positive returns. When we adjust returns by market and liquidity risk, only middle-priced losers maintain their positive returns. Our results reveal that low-priced stocks are not fully responsible for contrarian performance. Our empirical evidence is generally consistent with the overreaction hypothesis and behavioral models of value investing.

Outperformance in exchange-traded fund pricing deviations: Generalized control of data snooping bias

An investigation into exchange-traded fund (ETF) outperforrnance during the period 2008-2012 is undertaken utilizing a data set of 288 U.S. traded securities. ETFs are tested for net asset value (NAV) premium, underlying index and market benchmark outperformance, with Sharpe, Treynor, and Sortino ratios employed as risk-adjusted performance measures. A key contribution is the application of an innovative generalized stepdown procedure in controlling for data snooping bias. We find that a large proportion of optimized replication and debt asset class ETFs display risk-adjusted premiums with energy and precious metals focused funds outperforming the S&P 500 market benchmark. 

Is it time for standards and a common data exchange format for digital image analysis?

Digital image analysis is at a crossroads. While the technology has made great strides over the past few decades, there is an urgent need for image analysis to inform the next wave of large scale tissue biomarker discovery studies in cancer. Drawing parallels from the growth of next generation sequencing, this presentation will consider the case for a common language or standard format for storing and communicating digital image analysis data. In this context, image analysis data comprises more than simply an image with markups and attached key-value pair metrics. The desire to objectively benchmark competing platforms or a push for data to be deposited to public repositories much like genomics data may drive the need for a standard that also encompasses granular, cell-by-cell data.

Drivers and Barriers of Collaboration in the Value Chain of Paperboard-Packed Consumer Goods

Value chain collaboration has been a prevailing topic for research, and there is a constantly growing interest in developing collaborative models for improved efficiency in logistics. One area of collaboration is demand information management, which enables improved visibility and decrease of inventories in the value chain. Outsourcing of non-core competencies has changed the nature of collaboration from intra-enterprise to cross-enterprise activity, and this together with increasing competition in the globalizing markets have created a need for methods and tools for collaborative work. The retailer part in the value chain of consumer packaged goods (CPG) has been studied relatively widely, proven models have been defined, and there exist several best practice collaboration cases. The information and communications technology has developed rapidly, offering efficient solutions and applications to exchange information between value chain partners. However, the majority of CPG industry still works with traditional business models and practices. This concerns especially companies operating in the upstream of the CPG value chain. Demand information for consumer packaged goods originates at retailers' counters, based on consumers' buying decisions. As this information does not get transferred along the value chain towards the upstream parties, each player needs to optimize their part, causing safety margins for inventories and speculation in purchasing decisions. The safety margins increase with each player, resulting in a phenomenon known as the bullwhip effect. The further the company is from the original demand information source, the more distorted the information is. This thesis concentrates on the upstream parts of the value chain of consumer packaged goods, and more precisely the packaging value chain. Packaging is becoming a part of the product with informative and interactive features, and therefore is not just a cost item needed to protect the product. The upstream part of the CPG value chain is distinctive, as the product changes after each involved party, and therefore the original demand information from the retailers cannot be utilized as such – even if it were transferred seamlessly. The objective of this thesis is to examine the main drivers for collaboration, and barriers causing the moderate adaptation level of collaborative models. Another objective is to define a collaborative demand information management model and test it in a pilot business situation in order to see if the barriers can be eliminated. The empirical part of this thesis contains three parts, all related to the research objective, but involving different target groups, viewpoints and research approaches. The study shows evidence that the main barriers for collaboration are very similar to the barriers in the lower part of the same value chain; lack of trust, lack of business case and lack of senior management commitment. Eliminating one of them – the lack of business case – is not enough to eliminate the two other barriers, as the operational model in this thesis shows. The uncertainty of the future, fear of losing an independent position in purchasing decision making and lack of commitment remain strong enough barriers to prevent the implementation of the proposed collaborative business model. The study proposes a new way of defining the value chain processes: it divides the contracting and planning process into two processes, one managing the commercial parts and the other managing the quantity and specification related issues. This model can reduce the resistance to collaboration, as the commercial part of the contracting process would remain the same as in the traditional model. The quantity/specification-related issues would be managed by the parties with the best capabilities and resources, as well as access to the original demand information. The parties in between would be involved in the planning process as well, as their impact for the next party upstream is significant. The study also highlights the future challenges for companies operating in the CPG value chain. The markets are becoming global, with toughening competition. Also, the technology development will most likely continue with a speed exceeding the adaptation capabilities of the industry. Value chains are also becoming increasingly dynamic, which means shorter and more agile business relationships, and at the same time the predictability of consumer demand is getting more difficult due to shorter product life cycles and trends. These changes will certainly have an effect on companies' operational models, but it is very difficult to estimate when and how the proven methods will gain wide enough adaptation to become standards.