Temperature-rise fractionation of poly(3-alkyl thiophenes)

In this article, we have investigated a temperature-rise fractionation procedure for poly(3-hexyl thophene) (P3HT) and poly(3-octyl thophene) (P3OT) that provides well-defined molecular weight (MW) fractions with improved molecular weight distributions (MWD) when compared with Soxhlet extraction. This process involves dispersing the material over C18-boned silica stationary phase in a jacketed column and using incremental rises in column temperature (T_col) to gradually improve solvent quality and selectively dissolve higher molecular weight samples with a narrow polydispersity (PDI). Fractionation of P3HT with ΔT_col = 5 °C in methylene chloride (MC) yielded 7 fractions ranging from M_p of 20 to 53 kg/mol with an average PDI of 1.80 compared with a mother sample of 3.10. Predominant recovery of P3HT was acquired for fractions with T_col > 20 °C (30 wt %). Subsequent separation of P3OT in methylene chloride, with a reduced ΔT_col of 3 °C per fraction, due to increased solubility from the longer alkyl chain, generated 8 fractions with a weight range of M_n = 22 to 57 kg/mol with an mean PDI of 1.23 with the mother sample having PDI = 2.34, demonstrating the tunability of this method. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2547–2555, 2009     

Application of a crystallization kinetics model to simulate the effect of operation conditions on Crystaf profiles and calibration curves

Crystallization analysis fractionation (Crystaf) is a polymer characterization technique used to estimate chemical composition distributions (CCDs) of semicrystalline copolymers. The Crystaf profile can be transformed into a CCD using a calibration curve that relates average comonomer content to peak crystallization temperature. The calibration curve depends on copolymer molecular properties and Crystaf operation conditions. In this investigation, we applied a crystallization kinetics model to simulate Crystaf calibration curves and to quantify how Crystaf calibration curves depend on these factors. We applied the model to estimate the CCDs of three ethylene/1‐hexene copolymers from Crystaf profiles measured at different cooling rates and showed that our predictions agree well with the CCDs described by Stockmayer's distribution. We have also used this new methodology to investigate the effects of cooling rate, molecular weight, and comonomer type on Crystaf profiles and calibration curves. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 866–876, 2009     

Using flow field-flow fractionation (Fl-FFF) for observation of salinity effect on the size distribution of humic acid aggregates

Flow field-flow fractionation (Fl-FFF) was used to investigate the effect of salinity on the size distribution of humic acid (HA) aggregates in estuarine water. In water with high salinity as estuarine water, size distributions were slightly broadened with increasing contact time between HA and estuarine water. At the longest contact times (89 days) and highest salinity value (28 psu, g kg^?1), the peak maxima were observed at 1.7 and 8.6 nm when detected at 254 nm, and at 1.9 and 9.1 nm when detected at 400 nm. In addition, Fl-FFF with an inductively coupled plasma mass spectrometry was applied to examine the effect of salinity on the size distribution of Cd, Ce, Cu, Mn and Pb-binding HA aggregates in estuarine water with different salinity values. At 1 day contact time, the peak maxima of Cd, Ce, Cu, Mn and Pb-binding HA aggregates in water with increased salinity values were increased and gave the larger breadth of size distribution. The larger size fraction of HA aggregates showed more affinity for Pb, Cd, Ce and Mn than Cu whereas the smaller size fraction of humic aggregates showed preferential binding towards Cu.     

New separation methodologies for the distinction of the growth phases of Saccharomyces cerevisiae cell cycle

In the present work two separation techniques, namely the gravitational field-flow fractionation (GrFFF) and the reversed-flow gas chromatography (RFGC), are proposed for the distinction of the growth phases of Saccharomyces cerevisiae (AXAZ-1) yeast cycle at different temperatures (30 °C, 25 °C, 20 °C, and 15 °C) and pH (2.0, 3.0, 4.0 and 5.0) values. During the fermentation processes, differences observed in the peak profiles, obtained by GrFFF, can be related with the unlike cell growth. The distinction of the phases of AXAZ-1 cell cycle with the GrFFF, was also confirmed with the RFGC technique, which presented similar fermentation time periods for the alcoholic fermentation phases. Simultaneously, the reaction rate constant for each phase of the fermentation process and the activation energies were determined with the aid of the RFGC technique. Finally, the application of both the GrFFF and the RFGC techniques, in combination with high-performance liquid chromatography, allowed us to find the ideal experimental conditions (temperature and pH) for the alcoholic fermentation by AXAZ-1. The results indicate that S. cerevisiae cells performed better at 30 °C, whereas at lower temperatures decreases in the fermentation rate and in the number of viable cells were observed. Moreover, the pH of the medium (pH 5.0) resulted in higher fermentation rates and ethanol productivities.     

Optimisation of ambient and high temperature asymmetric flow field-flow fractionation with dual/multi-angle light scattering and infrared/refractive index detection

Asymmetric flow field-flow fractionation (AF4) enables to analyse polymers with very high molar masses under mild conditions in comparison to size exclusion chromatography (SEC). Conventionally, membranes for AF4 are made from cellulose. Recently, a novel ceramic membrane has been developed which can withstand high temperatures above 130 °C and chlorinated organic solvents, thus making it possible to characterise semicrystalline polyolefins by HT-AF4. Two ceramic membranes and one cellulose membrane were compared with regard to their quality of molar mass separation and the loss of the polymer material through the pores. Separating polystyrene standards as model compounds at different cross-flow gradients the complex relationship between cross-flow velocity, separation efficiency, the molar mass and peak broadening could be elucidated in detail. Moreover, the dependence of signal quality and reproducibility on sample concentration and mass loading was investigated because the evaluation of the obtained fractograms substantially depends on the signal intensities. Finally, the performance of the whole system was tested at high temperature by separating PE reference materials of high molar mass.     

Natural anti-HIV agents. Part 3: Litseaverticillols A-H, novel sesquiterpenes from Litsea verticillata

Bioassay directed-fractionation led to the identification of litseaverticillols A-H (1-8) from the leaves and twigs of Litsea verticillata Hance. These new sesquiterpenes possess a unique skeleton that was recently designated as ‘litseane’. The structures of these compounds were determined by spectroscopic means including 1D and 2D NMR data. Structural configurations were determined by ROESY experiments. Mosher ester reactions and optical rotation measurements established the sesquiterpenes 1-8 as racemates. Isolates 1-8 inhibited HIV-1 replication in HOG.R5 cells with IC₅₀ values ranging from 2 to 15 μg/ml (8-58 μM) while affecting the growth of HOG.R5 at concentrations 2-3-fold higher. Based on this data, structure-activity relationships can be discerned, suggesting compounds of this class are good candidates for analog production.     

Crystallization and melting of polyethylene copolymers: Differential scanning calorimetry and atomic force microscopy studies

The Hoffman–Lauritzen theory of secondary, surface nucleation and growth was primarily relied upon for about 40 years after its introduction in about 1960 to rationalize the crystallization of flexible chain polymers into lamellar crystals. However, in about 1998, Strobl and coworkers introduced a different model for crystallization, based on the stage‐wise formation of lamellae. Two major components of this model were as follows: (1) the concept of the formation of a mesomorphic melt as a precursor to crystallization and (2) the control of the melting temperature range of lamellar crystals of homogeneous polyolefin copolymers by an inner degree of order or perfection rather than on the crystal thickness. The first concept is in disagreement with the HL theory and the second with the Gibbs‐Thomson theory, which associates melting temperature with lamella thickness. In the present study, differential scanning calorimetry and atomic force microscopy were successfully employed to monitor the in situ quiescent crystallization of polyethylene homopolymer and copolymer. In the present study, evidence was not found to support the concept of lamellae with equal thickness melting over a broad temperature range. Some evidence was found that might be interpreted to support the concept of a mesomorphic melt as a precursor to crystallization. At present, the model promoted by Strobl and coworkers appears to be at an uncertain stage at which strong proof or disproof are not available. However, this alternative model has injected a new vitality into the study of crystallization of flexible chain polymers. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2369–2388, 2006     

Preserving the activity of cellulase in a batch foam fractionation process

Foam fractionation isone of the low operating-cost techniques for removing proteins from a dilute solution. The initial bulk solution pH and air superficial velocity play an importantrole in the foam-fractionation process. Denaturation of proteins (enzymes) can occur, however, during the foamfractionation process from the shear forces resulting from bursting air bubbles. At the extreme bulk solution pHs (lower than 3.0 and higher than 10.0), the en zymatic activity of cellulase in the foamate phase drops significantly. Within these two pH boundsan increase in the air superficial velocity, V_o, and a decrease in the bulk solution pH leads to a decrease in the separation ratio (SR), defined as theratio of the protein concentration in the foamate to the protein concentration in the residue. On the other hand, an increase in V_o provides a higher foamate-protein recovery. The process efficiency is defined as the product of foamate-protein recovery times the SR times the cellulase activity. The optimal operating condition of the cellulase foamfractionation process is taken into account at the maximum value of the processefficiency. In this study, that optimal condition is atan air superficial velocity of 32 cm/min and a bulk-solution pH of 10.0. At this condition, the recovered foamate is about 80% of the original protein mass, the SR is about 12, and the en zymatic activity is about 60% of the original cellulase activity.     

Crystallizability of ethylene homopolymers by crystallization analysis fractionation

The effect of molecular weight and long‐chain branching on the crystallization analysis fractionation (CRYSTAF) of ethylene homopolymers was investigated. Several ethylene homopolymers were prepared with different molecular weights and levels of long‐chain branching to isolate these effects from the dominant effect of comonomer content on crystallizability measured by CRYSTAF. Molecular weight effects might be significant for samples with number‐average molecular weights below 5000, but this effect can be corrected if terminal methyl groups are taken into account. Long‐chain branching has only a very small effect on the CRYSTAF profile of the samples investigated in this study. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1616–1628, 2001