Distributions of Crystal Size from DSC Melting Traces for Polyethylenes

Melting curves, obtained by differential scanning calorimetry, are used to estimate crystal size distributions. The proposed theoretical analysis is applied to different types of polyethylene, including high‐density polyethylene (HDPE), metallocene catalyzed linear low‐density polyethylenes (m‐LLDPE), blends of m‐LLDPEs, and Ziegler‐Natta catalyzed LLDPEs (ZN‐LLDPE). Theoretical predictions are in agreement with experimental results. A generalized melting temperature equation successfully predicts the melting temperatures of all the LLDPEs, although it was initially proposed for homogeneous copolymers with excluded comonomers. A new definition of the heat of fusion for pure crystals is proposed. This heat of fusion can be calculated from the average crystal size or the crystal size number distribution.     

Free energy perturbation study on a Trp-binding mutant (Ser88 ->Cys) of the trp-repressor

The Ser⁸⁸Cys mutant of the trp-repressor showed a lower affinityfor the corepressor than the wild-type repressor [G = 1.7 ±0.3 kcal/mol, Chou and Matthews (1989) J. Biol. Chem., 264,18314–18319].A molecular dynamics/free energy cycle perturbation study wasperformed to understand the origin of the decreased affinity.A value (G = 1.58 ± 0.28 kcal/mol) comparable with theexperimental value was obtained by the simulation. Free energycomponent analysis revealed that destabilization of the vander Waals interaction between Ser⁸⁸ and Trp¹⁰⁹ (corepressor)mainly contributed to the decreased affinity of the mutant.The rotational transition of the hydroxyl (sulfhydryl) groupof Ser⁸⁸ (Cys⁸⁸) during the simulations affected the contributionsof Arg⁸⁴ and water to the free energy change in the aporepressorand those of Arg⁸⁴ and Trp ¹⁰⁹ to that in the holorepressor.However, the contributions from different residues compensatedeach other, and the total free energy changes were almost invariablein the various simulations.     

Pervaporation study of water and tert‐butanol mixtures

The permeation behavior of water/tert‐butanol mixture through Sulzer Pervap2510 hydrophilic poly(vinyl alcohol) membranes was investigated and the effects of feed composition and temperature on separation efficiency of the membranes were studied. The pervaporation experiments were carried out with feed water content varying from 0 to 20 wt % according to the existing industrial needs and with the feed temperature from 60 to 100°C. Over this range, both water flux and separation factor increased with increasing water content and feed temperature. These phenomena may be attributed to (1) the strong interaction between water and the membrane, (2) the decoupling effect of the permeants and the membrane at elevated temperatures, and (3) the steric hindrance effect of branch chain alcohol. The permeability ratio (the ideal separation factor) of water to tert‐butanol across the membrane was calculated and found to follow the same relationship with increasing temperature and water content. Both flux and separation factor obtained from the Pervap2510 membrane in this study were much higher than previous reported values, possible causes for which were analyzed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 4082–4090, 2004     

An NMR‐MOUSE® for Analysis of Thin Objects

A special unilateral NMR sensor has been designed for investigations of thin samples with a thickness of less than 1 mm and of surface effects of polymers. For use with the bar‐magnet NMR‐MOUSE®, the so‐called “crazy coil” is introduced with a low penetration depth. It is a flat meander coil etched on a printed circuit board with wiggles in the conductors. The design of the new coil and FEM simulations of the B ₁ field are presented. Different applications are discussed by means of illustrative examples. They are the detection of surface damage in rubber samples, the swelling and drying of a latex membrane exposed to cyclohexane vapor mimicking a chemical sensor, and the drying of a thin sprayed adhesive layer.

Bar‐magnet NMR‐MOUSE® with crazy coil.     

The stability and unfolding of an IgG binding protein based upon the B domain of protein A from Staphylococcus aureus probed by tryptophan substitution and fluorescence spectroscopy

The stability and unfolding of an immunoglobulin (Ig) G bindingprotein based upon the B domain of protein A (SpAB) from Staphylococcusaureus were studied by substituting tryptophan residues at strategiclocations within each of the three a-helical regions (al-a3)of the domain. The role of the C-terminal helix, a3, was investigatedby generating two protein constructs, one corresponding to thecomplete SpAB, the other lacking a part of ct3; the Trp substitutionswere made in both one-and two-domain versions of each of theseconstructs. The fluorescence properties of each of the single-tryptophanmutants were studied in the native state and as a function ofguanidine-HCl-mediated unfolding, and their IgG binding activitieswere determined by a competitive enzyme-linked immunosorbentassay. The free energies of folding and of binding to IgG foreach mutant were compared with those for the native domains.The effect of each substitution upon the overall structure andupon the IgG binding interface was modelled by molecular graphicsand energy minimization. These studies indicate that (i) 3 contributesto the overall stability of the domain and to the formationof the IgG binding site in l and 2, and (ii) al unfolds first,followed by 2 and 3 together.     

Characterization and comparison of diblock and triblock amphiphilic copolymers of poly(δ‐valerolactone)

Three types of pegylated amphiphilic copolymers of poly(δ‐valerolactone) (PVL) were copolymerized with methoxy poly(ethylene glycol) (MePEG) and poly(ethylene glycol) (PEG₄₀₀₀ and PEG_10,000), respectively. Pegylation of PVL allowed copolymers possessing amphiphilic property and efficiently self‐assembled to form micelles with a low critical micelle concentration (CMC) in the range of 10^?7–10^?8M. The average molecular weight of copolymers was in the range of 10,000–20,000 Da, and the polydispersity of copolymers was about 1.7–1.8. Higher mobility of low molecular weight PEG (i.e., MePEG and PEG₄₀₀₀) than high molecular weight PEG_10,000 allowed valerolactone ring opening more efficient in terms of PVL/MePEG and PVL/PEG₄₀₀₀ copolymers possessing longer chain length in hydrophobic domain. Pegylated PVL with low CMC and triblock structure was preferred to encapsulate drug during micelle formation. Although all of these amphiphilic copolymers exhibited controlled release character, the micelles formed by triblock copolymer possessed a more stable core‐shell conformation than that by diblock copolymer, and resulted in the release of drug from triblock micelles slower than that from diblock micelles. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1836–1841, 2006     

Nonionic water‐soluble polymer: Preparation,characterization, and application of poly(1‐vinyl‐2‐pyrrolidone‐co‐hydroxyethylmethacrylate) as a polychelatogen

The free‐radical copolymerization of water‐soluble poly(1‐vinyl‐2‐pyrrolidone‐co‐hydroxyethylmethacrylate) was carried out with a feed monomer ratio of 75:25 mol %, and the total monomer concentration was 2.67M. The synthesis of the copolymer was carried out in dioxane at 70°C with benzoyl peroxide as the initiator. The copolymer composition was obtained with elemental analysis and ¹H‐NMR spectroscopy. The water‐soluble polymer was characterized with elemental analysis, Fourier transform infrared, ¹H‐ and ¹³C‐NMR spectroscopy, and thermal analysis. Additionally, viscosimetric measurements of the copolymer were performed. The thermal behavior of the copolymer and its complexes were investigated with differential scanning calorimetry (DSC) and thermogravimetry techniques under a nitrogen atmosphere. The copolymer showed high thermal stability and a glass transition in the DSC curves. The separation of various metal ions by the water‐soluble poly(1‐vinyl‐2‐pyrrolidone‐co‐hydroxyethylmethacrylate) reagent in the aqueous phase with liquid‐phase polymer‐based retention was investigated. The method was based on the retention of inorganic ions by this polymer in a membrane filtration cell and subsequent separation of low‐molar‐mass species from the polymer/metal‐ion complex formed. Poly(1‐vinyl‐2‐pyrrolidone‐co‐hydroxyethylmethacrylate) could bind metal ions such as Cr(III), Co(II), Zn(II), Ni(II), Cu(II), Cd(II), and Fe(III) in aqueous solutions at pHs 3, 5, and 7. The retention percentage for all the metal ions in the polymer was increased at pH 7, at which the maximum retention capacity could be observed. The interaction of inorganic ions with the hydrophilic polymer was determined as a function of the pH and filtration factor. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 178–185, 2006     

Heat‐resistant hydrophobic–oleophobic coatings

Thermally and chemically durable hydrophobic oleophobic coatings, containing different ceramic particles such as SiO₂, SiC, Al₂O₃, which can be alternative instead of Teflon, have been developed and applied on the aluminum substrates by spin‐coating method. Polyimides, which are high‐thermal resistant heteroaromatic polymers, were synthesized, and fluor oligomers were added to these polymers to obtain hydrophobic–oleophobic properties. After coating, Al surface was subjected to Taber‐abrasion, adhesion, corrosion, and thermal tests. The effects of the particle size of ceramic powders, organic matrix, and heat on the coating material were investigated. Coating material was characterized by FTIR spectrophotometer. Surface properties and thermal resistance of the coating materials were investigated by SEM and TGA analyses. After thermal curing, contact angles of these coatings with H₂O and n‐hexadecane were measured. It was observed that coatings like ceramic particles are more resistant against scratch and abrasion than the other coatings. Also, they are harder than coatings, which do not include ceramic particles. It was seen that coatings, containing Fluorolink D10H, have high‐contact angles with water and n‐hexadecane. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2386–2392, 2006     

Volatile compounds of original African black and white shea butter from Tchad and Cameroon

Shea butter is used as an edible vegetable fat in many African countries. It can be utilized as a substitute or complete replacement for cocoa butter in various applications and plays an important role in traditional African medicinal practice. Although detection of volatile compounds by solid‐phase micro‐extraction gas‐chromatography mass‐spectroscopy (SPME‐GC‐MS) is a very reliable and reproducible technique, which can be used as an important part of authenticity checking, production monitoring and contamination detection, no published data about volatile compounds of shea butter are available so far. In this investigation, the characteristic volatiles in the headspace of original African shea butter samples were identified by using SPME‐capillary‐GC coupled to a mass selective detector. Almost 100 different volatile components were identified, e.g. fatty acids, saturated and unsaturated aldehydes and ketones, terpenes, and typical Maillard reaction products such as methylfuranes and pyrazines. Furthermore, the samples have been olfactorily evaluated by a panel of professional flavorists and trained analytical chemists. It can be stated that variations in processing conditions of shea butter result in considerable differences in the composition of headspace volatiles, detected by SPME‐GC‐MS and human olfaction.     

Synthesis and properties of polystyrene‐b‐poly(ethylene oxide)‐b‐polystyrene triblock copolymers

A series of well‐defined and property‐controlled polystyrene (PS)‐b‐poly(ethylene oxide) (PEO)‐b‐polystyrene (PS) triblock copolymers were synthesized by atom‐transfer radical polymerization, using 2‐bromo‐propionate‐end‐group PEO 2000 as macroinitiatators. The structure of triblock copolymers was confirmed by ¹H‐NMR and GPC. The relationship between some properties and molecular weight of copolymers was studied. It was found that glass‐transition temperature (T_g) of copolymers gradually rose and crystallinity of copolymers regularly dropped when molecular weight of copolymers increased. The copolymers showed to be amphiphilic. Stable emulsions could form in water layer of copolymer–toluene–water system and the emulsifying abilities of copolymers slightly decreased when molecular weight of copolymers increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 727–730, 2006