Coil to extended coil transition in polygalacturonic acid: Conductometric titration and monte carlo simulations

The conformational transition from coil to extended coil for polygalacturonic acid has been studied by conductometric titrations and Monte Carlo simulations. The results of conductometric titrations at different polymer concentrations have been analyzed using the model proposed by Manning,1 which describes the conductivity of polyelectrolitic solutions. This experimental approach provides the transport factor and the average distance between charged groups at different degrees of ionization (α). The mean distances between charged groups have been compared with the values obtained by Monte Carlo simulations. In these simulations the polymer chain is modeled as a self-avoiding random walk in a cubic lattice. The monomers interact through the unscreened Coulombic potential. The ratio between the end-to-end distance and the number of ionized beads provides the average distance between charged monomers. The experimental and theoretical values are in good agreement for the whole range of ionization degrees accessed by conductometric titrations. These results suggest that the electrostatic interactions seem to be the major contribution for the coil to extended coil conformational change. The small deviations for α ≤ 0.5 suggests that the stiffness of the chain, associated with local interactions, becomes increasingly significant as the fraction of charged groups is decreased. © 2000 American Chemical Society.

Morphological, mechanical and rheological properties of nylon 6/acrylonitrile-butadiene-styrene blends compatibilized with MMA/MA copolymers

The morphological, mechanical and rheological properties of nylon 6/acrylonitrile-butadiene-styrene blends compatibilized with MMA-MA [poly(methyl methacrylate-comaleic anhydride)] copolymers were studied. A twin screw extruder was used for melt-blended the polymers and the injection moulding process was used to mold the samples. The main focus was on nylon 6/ ABS blends compatibilized with one MMA-MA copolymer. This copolymer has PMMA segments that appear to be miscible with the styrene-acrylonitrile (SAN) phase of ABS and the anhydride groups can react with amine end groups of the nylon 6 (Ny6) to form graft copolymers at the interface between Ny6 and ABS rich phases. Tensile and impact and morphological properties were enhanced by the incorporation of this copolymer. Transmission electron microscopy (TEM) observations revealed that the ABS domains are finely dispersed in nylon 6 matrix and led to the lowest ductile-brittle transition temperatures and highest impact properties. It can be concluded that the MMA-MA copolymer is an efficient alternative for the reactive compatibilization and can be used as a compatibilizer for nylon 6/ABS blends.© 2003 Kluwer Academic Publishers.

Morphological, mechanical and thermal properties of nylon 6/ABS blends using glycidyl methacrylate-methyl methacrylate copolymers

Nylon6 is an attractive polymer for engineering applications because it has reactive functionality through amine and carboxyl end groups that are capable of reacting. For this reason, it has been used a lot in polymeric blends. Blends of nylon6/ABS (acrylonitrile-butadiene-styrene) were produced using glycidyl methacrylate-methyl methacrylate (GMA-MMA) copolymers as compatibilizer. The binary blends were immiscible and exhibited poor mechanical properties that stemmed from the unfavorable interactions among their molecular segments. This produced an unstable coarse phase morphology and weak interfaces between the phases in the solid state. The presence of the copolymer in the blends clearly led to a more efficient dispersion of the ABS phase and consequently optimized Izod impact properties. However, the compatibilized blend showed poor toughness at room temperature and failed in a brittle manner at subambient temperatures. © 2005 Springer Science + Business Media, Inc.

Estudo eletroquímico da corrosão em chapas de aço galvanizado e fosfatizado por coil-coating

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Water activity of aqueous solutions of ethylene oxide-propylene oxide block copolymers and maltodextrins

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Self-assembly in aqueous solution of amphiphilic graft copolymers from oxidized carboxymethylcellulose

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Direct determination of chromium in empty medicine capsules by tungsten coil atomic emission spectrometry

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Complementary study on the electrical and structural properties of poly(3-alkylthiophene) and its copolymers synthesized on ITO by electrochemical impedance and Raman spectroscopy

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Role of Branching on the Structure of Polymer Brushes Formed from Comb Copolymers

The distinguishing feature of a polymer brush at equilibrium is the stretched configuration of the chains that results from tethering the polymer chains by one end at the solid-fluid interface. The stretched configuration of the chains and the crowded nature of the interfacial layer is the origin of many of the useful properties of polymer brushes: these layers resist compression and aggregation, effectively dissipate shear stresses, and respond reversibly to changes in their solution environment.

Morphology and Deformation Mechanisms and Tensile Properties of Tetrafunctional Multigraft Copolymers

Morphology and deformation mechanisms and tensile properties of tetrafunctional multigraft (MG) polystrene-g-polyisoprene (PS-g-PI) copolymers were investigated dependent on PS volume fraction and number of branch points. The combination of various methods such as TEM, real time synchrotron SAXS, rheo-optical FTIR, and tensile tests provides comprehensive information at different dimension levels.TEMand SAXS studies revealed that the number of branch points has no obvious influence on the microphase-separated morphology of tetrafunction MG copolymers with 16 wt % PS. But for tetrafunctional MG copolymers with 25 wt % PS, the size and integrity of PS microdomains decrease with increasing number of branch point. The deformation mechanisms ofMGcopolymers are highly related to the morphology. Dependent on the microphase-separated morphology and integrity of the PS phase, the strain-induced orientation of the PS phase is at different size scales. Polarized FT-IR spectra analysis reveals that, for all investigated MG copolymers, the PI phase shows strain-induced orientation along SD at molecular scale. The proportion of the PI block effectively bridging PS domains controls the tensile properties of the MGcopolymers at high strain, while the stress-strain behavior in the low-mediate strain region is controlled by the continuity of PS microdomains. The special molecular architecture, which leads to the higher effective functionality of PS domains and the higher possibility for an individual PI backbone being tethered with a large number of PS domains, is proposed to be the origin of the superelasticity for MG copolymers.

Association and Structure of Thermosensitive Comblike Block Copolymers in Aqueous Solutions

The structures and association properties of thermosensitive block copolymers of poly(methoxyoligo( ethylene glycol) norbornenyl esters) in D2O were investigated by small angle neutron scattering (SANS). Each block is a comblike polymer with a polynorbornene (PNB) backbone and oligo ethylene glycol (OEG) side chains (one side chain per NB repeat unit). The chemical formula of the block copolymer is (OEG3NB) 79- (OEG6.6NB) 67, where subscripts represent the degree of polymerization (DP) of OEG and NB in each block. The polymer concentration was fixed at 2.0 wt % and the structural changes were investigated over a temperature range between 25 and 68°C. It was found that at room temperature polymers associate to form micelles with a spherical core formed by the block (OEG3NB) 79 and corona formed by the block (OEG6.6NB) 67 and that the shape of the polymer in the corona could be described by the form factor of rigid cylinders. At elevated temperatures, the aggregation number increased and the micelles became more compact. At temperatures around the cloud point temperature (CPT) T ) 60 °C a correlation peak started to appear and became pronounced at 68 °C due to the formation of a partially ordered structure with a correlation length ∼349 Å.

Electroluminescence of phenylene-vinylene random copolymers with different conjugation lengths

PPV random derivates were synthesized and characterized. Polymer light emitting diodes (PLEDs) were assembled using the random copolymers as emissive layer and showed EL in the blue-green region in function of the method of preparation. The increase in the average conjugation degree in the polymer chain led to the reduction of the turn-on voltage of the device. The addition of Alq3 as ETL increased tenfold the luminescence efficiency. (C) 2009 Elsevier B.V. All rights reserved.

A novel protein refolding protocol for the solubilization and purification of recombinant peptidoglycan-associated lipoprotein from Xylella fastidiosa overexpressed in Escherichia coil

Xylella fastidiosa is a Gram-negative xylem-limited plant pathogenic bacterium responsible for several economically important crop diseases. Here, we present a novel and efficient protein refolding protocol for the solubilization and purification of recombinant X. fastidiosa peptidoglycan-associated lipoprotein (XfPal). Pal is an outer membrane protein that plays important roles in maintaining the integrity of the cell envelope and in bacterial pathogenicity. Because Pal has a highly hydrophobic N-terminal domain, the heterologous expression studies necessary for structural and functional protein characterization are laborious once the recombinant protein is present in inclusion bodies. Our protocol based on the denaturation of the XfPal-enriched inclusion bodies with 8 M urea followed by buffer-exchange steps via dialysis proved effective for the solubilization and subsequent purification of XfPal, allowing us to obtain a large amount of relatively pure and folded protein. In addition, XfPal was biochemically and functionally characterized. The method for purification reported herein is valuable for further research on the three-dimensional structure and function of Pal and other outer membrane proteins and can contribute to a better understanding of the role of these proteins in bacterial pathogenicity, especially with regard to the plant pathogen X. fastidiosa. (C) 2012 Elsevier Inc. All rights reserved.

Evaluation of the biocide activity of phosphorylated and sulfophosphorylated resins

Phosphorylated poly(styrene-co-divinylbenzene) copolymers prepared by aromatic electrophilic substitution reaction with PCl3/AlCl3 were reacted with carbon dissulfite in order to introduce sulfophosphorylated groups into copolymers. These modifications were characterized by FTIR, elemental analysis, spectrophotometry, optical and scanning electron microscopy. The antibacterial activities of the phosphorylated and sulfophorylated copolymers were assessed against Escherichia coli ATCC25922 suspensions (10(3)-10(7) cells mL(-1)) using a column system. The unmodified copolymers did not have antibacterial activity against the E. coil suspensions but the phosphorylated and sulfophorylated copolymers showed significant bactericidal action for all E. coli concentrations. The sulfophosphorylated copolymers had higher antibacterial activity than the phosphorylated ones, mainly for high concentrations of E. coli cells. Published by Elsevier B.V.

Effect of Solvent-Induced Coil to Helix Conformational Change on the Two-Photon Absorption Spectrum of Poly(3,6-phenanthrene)

This paper investigates the effect of solvent-induced conformational changes of poly(3,6-phenanthrene) on their two-photon absorption (2PA). Such effect was studied employing the wavelength-tunable femtosecond Z-scan technique and modeled using the sum-over-essential states approach. We observed a strong reduction of the 2PA cross-section when the sample was prepared in hexane (poor solvent) in comparison to chloroform (good solvent), which is related to the conformation adopted by the polymer in each case. In chloroform it adopts a random coil conformation, as opposed to the one-handed helix conformation in hexane. Our results pointed out that the coil to helix conformation change decreases the degree of molecular planarity of the polymer pi-conjugated backbone, which is primarily responsible for their optical nonlinearity, contributing to diminishing the effective transition dipole moments and, consequently, the 2PA cross-section. Moreover, by studying the nonlinear response with different light polarization, we showed that, although the solvent-induced conformational change does not alter the molecular symmetry of the polymer, it modifies considerably the direction of the transition dipole moments between the excited states.