Monitoring orientation and dynamics of membrane-bound melittin utilizing dansyl fluorescence

Melittin is a cationic hemolytic peptide isolated from the European honey bee, Apis mellifera. In spite of a number of studies, there is no consensus regarding the orientation of melittin in membranes. In this study, we used a melittin analogue that is covalently labeled at its amino terminal (Gly-1) with the environment-sensitive 1-dimethylamino-5-sulfonylnaphthalene (dansyl) group to obtain information regarding the orientation and dynamics of the amino terminal region of membrane-bound melittin. Our results show that the dansyl group in Dns-melittin exhibits red edge excitation shift in vesicles of 1,2-dioleoyl-sn-glycero-3-phosphocholine, implying its localization in a motionally restricted region of the membrane. This is further supported by wavelength-dependent anisotropy and lifetime changes and time-resolved emission spectra characterized by dynamic Stokes shift, which indicates relatively slow solvent relaxation in the excited state. Membrane penetration depth analysis using the parallax method shows that the dansyl group is localized at a depth of approximately 18 A from the center of the bilayer in membrane-bound Dns-melittin. Further analysis of dansyl and tryptophan depths in Dns-melittin shows that the tilt angle between the helix axis of membrane-bound melittin and the bilayer normal is approximately 70 degrees. Our results therefore suggest that melittin adopts a pseudoparallel orientation in DOPC membranes at low concentration.     

Unusual contributions of molecular architecture to rheology and flow birefringence in hyperbranched polystyrene melts

With the increase in sophisticated synthesis methods, it appears that polymer architecture may be a tunable property. Therefore, the role of architecture in rheological and processing properties has received renewed attention, mainly because of dendrimer synthesis and metallocene‐catalyst technology. Linear polymers and hyperbranched polymers represent two ends of branching complexity. Some previous studies have suggested that hyperbranched polymers may behave like unentangled polymers, whereas others have proposed that they exhibit the properties of soft colloids. In an effort to compare the responses of linear and hyperbranched polymers, we synthesized starlike hyperbranched polystyrenes (HBPSs) of various branch lengths and numbers of branches. The HBPSs used in this study were unentangled or weakly entangled, allowing us to study the effect of branch density more readily. Two linear polystyrene (L‐PS) melts and two HBPSs were studied. Using a custom‐built rheooptical apparatus, we characterized the rheology and flow birefringence of these materials. To our knowledge, these are the first flow birefringence measurements on highly branched polymer melts. Our results suggest that the flow behavior of HBPS is significantly different from that of L‐PS: (1) HBPS shows nonterminal behavior in the low‐frequency rheological response; (2) when the stress‐optical rule (SOR) holds, the stress‐optical coefficient of HBPS is much lower than those of analogous linear polymers; and (3) when the branch density is high and the branch length is sufficiently low, the SOR fails for these homopolymer melts. A significant increase in the birefringence for a given amount of stress in the low‐frequency region suggests that there may be a soft core in these materials due to the strong preferential radial orientation of chain segments near the center of a molecule versus those near the periphery. The predominantly elastic response of the soft structures may be responsible for the enhanced form birefringence. Our preliminary results indicate that these materials may exhibit both polymeric and soft‐colloid natures. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2562–2571, 2001     

Click chemistry‐assisted triazole‐substituted azobenzene and fulgimide units in the pendant‐based copoly(decyloxymethacrylate)s for dual‐mode optical switches

Copolymer containing new thermally reversible click chemistry‐assisted triazole‐substituted azobenzene and fulgimide units in the pendant F‐co‐A was prepared by free‐radical solution addition polymerization technique. The F and A were also prepared for comparison. The DSC analysis of F indicates that the polymer possessing the C‐form of fulgimide unit exhibited higher T_m than that of E‐form of the same polymer and revealed that the C‐form of fulgimide unit in F is highly ordered. The cis‐trans back isomerization behavior of the click chemistry‐assisted triazole‐substituted azobenzene unit in film A has thermal irreversibility, while in F‐co‐A it exhibited thermal reversibility. The UV‐exposed film of F‐co‐A heated around T_g leads to cis‐trans back isomerization of azobenzene unit and thermally stable C‐form of fulgimide which retains its conjugated structure where both the photochromic units are converted into planar conformations and exhibit high fluorescence properties. The fluorescence maxima of C‐form in F‐co‐A red shifted compared with F , because the substituted triazole ring in the azobenzene unit stabilized the C‐form of fulgimide unit. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7843–7860, 2008     

A tandem mass spectrometric approach to the identification of O‐glycosylated glargine glycoforms in active pharmaceutical ingredient expressed in Pichia pastoris

Glycoforms of glargine expressed in Pichia pastoris were isolated by high‐performance liquid chromatography and analyzed by a series of chemical and mass spectrometric methods for the identification of various glycoforms, glycosylation position, nature and structure of glycans. Reduction and alkylation, peptide mapping techniques were used to decipher the amino acid site at which glycosylation had taken place. Chemical methods were coupled with mass spectrometry techniques such as electrospray ionization and matrix‐assisted laser desorption/ionization for identification of the glycosylation site. Copyright © 2009 John Wiley & Sons, Ltd.     

Thermotropic main chain liquid crystalline polyesters containing ferrocene and phosphate units: synthesis and characterization

A new series of liquid crystalline main chain copolyesters were prepared, having ferrocene in the mesogenic segment and a methyl phosphate group along with a methylene spacer. The even numbered methylene groups were varied from two to ten. Liquid crystalline behaviour was investigated on a hot stage optical polarized microscope. Thermal properties of the polymers were analysed by TGA and DSC, revealing that the polymers yield high char products, probably caused by the formation of phosphorus and iron oxides. The glass transition (T_g) temperatures of the polymers were found to be fairly low, the result of the incorporation of bulky phosphorus and ferrocene moieties in the chain. The phase behaviour was analysed and correlated with the structure of the polymers. The liquid crystalline textures of the polymers became more transparent with increasing spacer length. Energy minimized structures for the polymer repeating units reveal that both the ferrocene and phosphorus moieties produce more molecular entanglement, thus reducing the T_g and T_m of the polymers.     

Selecting green suppliers based on GSCM practices: Using fuzzy TOPSIS applied to a Brazilian electronics company

Due to an increased awareness and significant environmental pressures from various stakeholders, companies have begun to realize the significance of incorporating green practices into their daily activities. This paper proposes a framework using Fuzzy TOPSIS to select green suppliers for a Brazilian electronics company; our framework is built on the criteria of green supply chain management (GSCM) practices. An empirical analysis is made, and the data are collected from a set of 12 available suppliers. We use a fuzzy TOPSIS approach to rank the suppliers, and the results of the proposed framework are compared with the ranks obtained by both the geometric mean and the graded mean methods of fuzzy TOPSIS methodology. Then a Spearman rank correlation coefficient is used to find the statistical difference between the ranks obtained by the three methods. Finally, a sensitivity analysis has been performed to examine the influence of the preferences given by the decision makers for the chosen GSCM practices on the selection of green suppliers. Results indicate that the four dominant criteria are Commitment of senior management to GSCM; Product designs that reduce, reuse, recycle, or reclaim materials, components, or energy; Compliance with legal environmental requirements and auditing programs; and Product designs that avoid or reduce toxic or hazardous material use.     

Investigation of clay modifier effects on the structure and rheology of supercritical carbon dioxide‐processed polymer nanocomposites

Superior property enhancements in polymer–clay nanocomposites can be achieved if one can significantly enhance the nanoclay dispersion and polymer–clay interactions. Recent studies have shown that nanoclays can be dispersed in polymers using supercritical carbon dioxide (scCO₂). However, there is need for a better understanding of how changing the clay modifier affects the clay dispersability by scCO₂ and the resultant nanocomposite rheology. To address this, the polystyrene (PS)/clay nanocomposites with “weak” interaction (Cloisite 93A clay) and “strong” interaction (Cloisite 15A clay) have been prepared using the supercritical CO₂ method in the presence of a co‐solvent. Transmission electron microscopy images and small‐angle X‐ray diffraction illustrate that composites using 15A and 93A clays show similar magnitude of reduction in the average tactoid size, and dispersion upon processing with scCO₂. When PS and the clays are coprocessed in scCO₂, the “dispersion” of clays appears to be independent of modifier or polymer–clay interaction. However, the low‐frequency storage modulus in the scCO₂‐processed 15A nanocomposites is two orders of magnitude higher than that of 93A nanocomposites. It is postulated that below percolation (solution blended composites), the strength of polymer–clay interaction is not a significant contributor to rheological enhancement. In the scCO₂‐processed nanocomposites the enhanced dispersion passes the percolation threshold and the interactions dictate the reinforcement potential of the clay–polymer–clay network. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 823–831, 2010     

FTIR spectroscopic investigation of thermal effects in semi‐syndiotactic polypropylene

The temperature‐dependent behavior of individual components within metallocene‐catalyzed semisyndiotactic polypropylenes (semi‐sPP) with a wide range of stereoregular content (26 to 96% rr) is studied using Fourier transform infrared (FTIR) spectroscopy and temperature‐modulated differential scanning calorimetry (DSC). Changes in sensitive, high‐resolution absorbance spectra are observed as melt‐slow‐cooled thin films are subjected to stepwise temperature increases. In general, spectral bands previously identified as being sensitive to ordered structures (e.g., conformed chains, crystal morphs) appear to follow overall trends of shifting to lower wavenumbers (energies), broadening, and decreasing in peak area intensity as temperature increases. Peaks that appear due to “splitting” (observed in more stereoregular materials) show a trend toward coalescence as temperature increases; this corresponds to a gradual loss of chain conformational order. Gauche‐gauche‐trans‐trans (ggtt)_n helical and all‐trans (tttt)_n planar zigzag‐conformed chains that participate in the crystalline‐amorphous interfacial region (“mesophase”) appear to be more stable (i.e., they do not lose their conformational order as easily) with increasing temperature in materials with a greater degree of syndiotacticity. Moreover, IR data correspond well with modulated DSC endotherms located near 50 °C and 70 °C. At each transition temperature—thought to represent, respectively, a thermally driven chain conformation from planar zigzags to helices, and a dynamic disorder of helices marked by rapid gauche ? trans isomerization—the IR absorbance ratio, A₉₇₈/A₉₆₃, which represents the relative population of helical chains, undergoes an accelerated decrease. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 439–461, 2005