MORPHOLOGY AND DYNAMIC-MECHANICAL PROPERTIES OF NYLON 66/POLY(ETHER IMIDE) BLENDS

The morphology and dynamic mechanical properties of blends of poly(ether imide) (PEI) and nylon 66 over the full composition range have been investigated. Torque changes during mixing were also measured. Lower torque values than those calculated by the log-additivity rule were obtained, resulting from the slip at the interface due to low interaction between the components. The particle size of the dispersed phase and morphology of the blends were examined by scanning electron microscopy. The composition of each phase was calculated. The blends of PEI and nylon 66 showed phase-separated structures with small spherical domains of 0.3 similar to 0.7 mu m. The glass transition temperatures (T(g)s) of the blends were shifted inward, compared with those of the homopolymers, which implied that the blends were partially miscible over a range of compositions. T-g1, corresponding to PEI-rich phase, was less affected by composition than T-g2, corresponding to nylon 66-rich phase. This indicated that the fraction of PEI mixed into nylon 66-rich phase increased with decreasing PEI content and that nylon 66 was rarely mixed into the PEI-rich phase. The effect of composition on the secondary relaxations was examined. Both T-beta, corresponding to the motion of amide groups in nylon 66, and T-gamma, corresponding to that of ether groups in PEI, were shifted to higher temperature, probably because of the formation of intermolecular interactions between the components.

INFLUENCE OF ESTER GROUP-SIZE IN PMAS ON BETA-PHASE CRYSTALLIZATION OF PVF2 IN HIGHLY ORIENTED FILMS OF PVF2/PMAS BLENDS

Influence of ester group size in polymethacrylates (PMAs) , including PMMA, PEMA and PBMA, on beta phase crystallization of poly(vinylidene fluoride) (PVF2) in highly oriented films of PVF2/PMAs=80/20 blends has been investigated by FTIR and TEM. The melt-drawn films of pure PVF2 consist of highly oriented lamellae, in which the alpha phase is predominant. Adding a given amount of PMAs (20 wt%) into PVF2 results in formation of fibrillar crystals and increase of relative amount of the beta phase. The influence extent is in order of PMMA > PEMA > PBMA, regarding the ester group size in the PMAs.

BLENDS OF POLY[3,3-BIS(CHLOROMETHYL)OXETANE] WITH POLY(VINYL ACETATE) .1. THERMAL AND MECHANICAL-PROPERTIES

Blends of poly[3,3-bis(chloromethyl)oxetane] (Penton) with poly(vinyl acetate) were prepared. Compatibility, morphology, thermal behavior, and mechanical properties of blends with various compositions were studied using differential scanning calorimetry (DSC), dynamic mechanical measurements (DMA), tensile tests, and scanning electron microscopy (SEM). DMA study showed that the blends have two glass transition temperatures (T(g)). The T(g) of the PVAc rich phase shifts significantly to lower temperatures with increasing Penton content, suggesting that a considerable amount of Penton dissolves in the PVAc rich phase, but that the Penton rich phase contains little PVAc. The Penton/PVAc blends are partially compatible. DSC results suggest that PVAc can act as a beta-nucleator for Penton in the blend. Marked negative deviations from simple additivity were observed for the tensile strength at break over the entire composition range. The Young's modulus curve appeared to be S-shaped, implying that the blends are heterogeneous and have a two-phase structure. This was confirmed by SEM observations.

CDNA cloning and mRNA expression of the lipopolysaccharide- and beta-1,3-glucan-binding protein gene from scallop Chlamys farreri

Lipopolysaccharide and beta-1,3-glucan-binding protein (LGBP) play a crucial role in the innate immune response of invertebrates as a pattern recognition protein (PRP). The scallop LGBP gene was obtained from Chlamys farreri challenged by Vibrio anguillarum by randomly sequencing cDNA clones from a whole body cDNA library, and by fully sequencing a clone with homology to known LGBP genes. The scallop LGBP consisted of 1876 nucleotides with a canonical polyadenylation signal sequence AATAAA and a poly(A) tail, encoding a polypeptide of 440 amino acids with the estimated molecular mass of 47.16 kDa and a predicted isoelectric point of 5.095. The deduced amino acid sequence showed a high similarity to that of invertebrate recognition proteins from blue shrimp, black tiger shrimp, mosquito, freshwater crayfish, earthworms, and sea urchins, with conserved features including a potential polysaccharide-binding motif, a glucanase motif, and N-glycosylation sites. The temporal expression of LGBP genes in healthy and V. anguillarum-challenged C farreri scallop, measured by real-time semiquantitative reverse transcription polymerase chain reaction (PCR), showed that expression was up-regulated initially, followed by recovery as the stimulation cleared. Results indicated that scallop LGBP was a constitutive and inducible acute-phase protein that could play a critical role in scallop-pathogen interaction. (C) 2004 Elsevier B.V. All rights reserved.

Ionic liquid as plasticizer for europium(III)-doped luminescent poly(methyl methacrylate) films

Flexible luminescent polymer films were obtained by doping europium(III) complexes in blends of poly(methyl methacrylate) (PMMA) and the ionic liquid 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C(6)mim][Tf2N]. Different europium(III) complexes have been incorporated in the polymer/ionic liquid matrix: [C(6)mim][Eu(nta)(4)], [C(6)mim][Eu(tta)(4)], [Eu(tta)(3)(phen)] and [choline](3)[Eu(dpa)(3)], where nta is 2-naphthoyltrifluoroacetonate, tta is 2-thenoyltrifluoroacetonate, phen is 1,10-phenanthroline, dpa is 2,6-pyridinedicarboxylate ( dipicolinate) and choline is the 2-hydroxyethyltrimethyl ammonium cation. Bright red photoluminescence was observed for all the films upon irradiation with ultraviolet radiation. The luminescent films have been investigated by high-resolution steady-state luminescence spectroscopy and by time-resolved measurements. The polymer films doped with beta-diketonate complexes are characterized by a very intense D-5(0) -> F-7(2) transition ( up to 15 times more intense than the D-5(0) -> F-7(1)) transition, whereas a marked feature of the PMMA films doped with [choline](3)[Eu(dpa)(3)] is the long lifetime of the D-5(0) excited state (1.8 ms).

The vascular targeting agent combretastatin-A4 and a novel cis-Restricted {beta}-Lactam Analogue, CA-432, induce apoptosis in human chronic myeloid leukemia cells and ex vivo patient samples including those displaying multidrug resistance

Combretastatin-A4 (CA-4) is a natural derivative of the African willow tree Combretum caffrum. CA-4 is one of the most potent antimitotic components of natural origin, but it is, however, intrinsically unstable. A novel series of CA-4 analogs incorporating a 3,4-diaryl-2-azetidinone (β-lactam) ring were designed and synthesized with the objective to prevent cis -trans isomerization and improve the intrinsic stability without altering the biological activity of CA-4. Evaluation of selected β-lactam CA-4 analogs demonstrated potent antitubulin, antiproliferative, and antimitotic effects in human leukemia cells. A lead β-lactam analog, CA-432, displayed comparable antiproliferative activities with CA-4. CA-432 induced rapid apoptosis in HL-60 acute myeloid leukemia cells, which was accompanied by depolymerization of the microtubular network, poly(ADP-ribose) polymerase cleavage, caspase-3 activation, and Bcl-2 cleavage. A prolonged G(2)M cell cycle arrest accompanied by a sustained phosphorylation of mitotic spindle checkpoint protein, BubR1, and the antiapoptotic proteins Bcl-2 and Bcl-x(L) preceded apoptotic events in K562 chronic myeloid leukemia (CML) cells. Molecular docking studies in conjunction with comprehensive cell line data rule out CA-4 and β-lactam derivatives as P-glycoprotein substrates. Furthermore, both CA-4 and CA-432 induced significantly more apoptosis compared with imatinib mesylate in ex vivo samples from patients with CML, including those positive for the T315I mutation displaying resistance to imatinib mesylate and dasatinib. In summary, synthetic intrinsically stable analogs of CA-4 that display significant clinical potential as antileukemic agents have been designed and synthesized.

beta-ADRENERGIC ACTIVITY PRESERVES GLUT4 PROTEIN IN GLYCOLYTIC FIBERS IN FASTING

Glucose transporter 4 (GLUT4) expression in adipose tissue decreases during fasting. In skeletal muscle, we hypothesized that GLUT4 expression might be maintained in a beta-adrenergic-dependent way to ensure energy disposal for contractile function. Herein we investigate beta-blockade or beta-stimulation effects on GLUT4 expression in oxidative (soleus) and glycolytic [extensor digitorum longus (EDL)] muscles of fasted rats. Fasting increased GLUT4 mRNA in soleus (24%) and EDL (40%) but the protein content increased only in soleus (30%). beta 1-beta 2-, and beta 1-beta 2-beta 3-blockade decreased (20-30%) GLUT4 mRNA content in both muscles, although GLUT4 protein decreased only in EDL. When mRNA and GLUT4 protein regulations were discrepant, changes in the mRNA poly(A) tail length were detected, indicating a posttranscriptional modulation of gene expression. These results show that beta-adrenergic activity regulates GLUT4 gene expression in skeletal muscle during fasting, highlighting its participation in preservation of GLUT4 protein in glycolytic muscle. Muscle Nerve 40: 847-854, 2009

T3 rapidly modulates TSH beta mRNA stability and translational rate in the pituitary of hypothyroid rats

Whereas it is well known that T3 inhibits TSH beta gene transcription, its effects on TSH beta mRNA stability and translation have been poorly investigated. This study examined these possibilities, by evaluating the TSH beta transcripts poly(A) tail length, translational rate and binding to cytoskeleton, in pituitaries of thyroidectomized and sham-operated rats treated with T3 or saline, and killed 30 min thereafter. The hypothyroidism induced an increase of TSH beta transcript poly(A) tail, as well as of its content in ribosomes and attachment to cytoskeleton. The hypothyroid rats acutely treated with T3 exhibited a reduction of TSH beta mRNA poly(A) tail length and recruitment to ribosomes, indicating that this treatment decreased the stability and translation rate of TSH beta mRNA. Nevertheless, acute T3 administration to sham-operated rats provoked an increase of TSH beta transcripts binding to ribosomes. These data add new insight to an important role of T3 in rapidly regulating TSH gene expression at posttranscriptional level. (C) 2010 Elsevier Ireland Ltd. All rights reserved.

Effects of 15d-PGJ(2)-loaded poly(D,L-lactide-co-glycolide) nanocapsules on inflammation

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

Cathodic stripping voltammetric determination of ceftazidime with reactive accumulation at a poly-L-lysine modified hanging mercury drop electrode

Ceftazidime is hydrolysed only slowly at pH 10 at room temperature. This is indicated by a small cathodic stripping voltammetric peak obtained at pH 10 at a hanging mercury drop electrode at about -0.6 V which corresponds to the reduction of the hydrolysis product. This peak is enhanced more than tenfold by the addition of poly-L-lysine (PLL) to the electrolyte solution. The optimum accumulation potential is between 0 and -0.1 V: the size of the peak decreases steadily, however, as the accumulation potential is moved to more negative potentials and is about one-sixth the size for accumulation at -0.4 V. Existing knowledge of the organic chemistry of cephalosporins indicates that the accumulation must involve an aminolysis reaction of the unprotonated PLL with the beta-lactam ring of the ceftazidime. The limit of detection (3 sigma) in standard solutions was calculated to be 1 x 10(-10) mol l(-1). The detection limit in buffer solution containing 1% of urine was calculated to be 5 x 10(-9) mol l(-1), i.e. 5 x 10(-6) mol l(-1) in the urine. (C) 1999 Elsevier B.V. B.V. AU rights reserved.

Poole-Frenkel effect in amorphous poly(p-phenylene sulfide)

The conductivity of poly(p-phenylene sulfide) (PPS) amorphous samples sandwiched between metallic electrodes has been studied as a function of applied voltage, temperature, and electrode material. The voltage (U) dependence of the currents for electric fields within the range 10(3)-10(6) V/cm exhibits exp beta U-1/2 behavior with beta = beta(Schottky) below the glass transition temperature (T-g congruent to 90 degrees C), and beta = beta(Poole-Frenkel) above T-g. Coordinated temperature measurements of de currents with different metallic contacts and thermally stimulated currents (TSC) indicate, however, that the conductivity at T < T-g is consistent with the so-called ''anomalous'' Poole-Frenkel effect rather than the Schottky effect. Consequently, the p-type conductivity in amorphous PPS is proposed to be a bulk-limited process due to ionization of two different types of acceptor centers in the presence of neutral hole traps. (C) 1996 John Wiley & Sons, Inc.

Phase transition in poly(vinylidene fluoride) investigated with micro-Raman spectroscopy

The phase transition from the non-polar a-phase to the polar beta-phase of poly(vinylidene fluoride) (PVDF) has been investigated using micro-Raman spectroscopy, which is advantageous because it is a nondestructive technique. Films of alpha-PVDF were subjected to stretching under controlled rates at 80 degrees C, while the transition to P-PVDF was monitored by the decrease in the Raman band at 794 cm(-1) characteristic of the a-phase, along with the concomitant increase in the 839 cm-1 band characteristic of the P-phase. The alpha ->beta transition in our PVDF samples could be achieved even for the sample stretched to twice (2 X -stretched) the initial length and it did not depend on the stretching rate in the range between 2.0 and 7.0 mm/min. These conclusions were corroborated by differential scanning calorimetry (DSC) and X-ray diffraction experiments for PVDF samples processed under the same conditions as in the Raman scattering measurements. Poling with negative corona discharge was found to affect the a-PVDF morphology, improving the Raman bands related to this crystalline phase. This effect is minimized for films stretched to higher ratios. Significantly, corona-induced effects could not be observed with the other experimental techniques, i.e., X-ray diffraction and infrared spectroscopy.

STUDY OF POLING BEHAVIOR OF BIAXIALLY STRETCHED POLY(VINYLIDENE FLUORIDE) FILMS USING THE CONSTANT-CURRENT CORONA TRIODE

This article reports systematic results of corona poling measurements obtained on biaxially stretched polyvinylidene fluoride films charged in dry air. Charging was performed using the constant current corona triode. The dependence of the poling process on the sample thickness, charging current, and successive charging processes was investigated. Phase transitions from alpha to delta and to beta phases were observed when virgin samples were corona charged. The thermal pulse technique showed that the polarization profiles during charging can be made consistently almost uniform and that the ferroelectric reorientation can be associated with the rising plateau region displayed on potential buildup curves. (C) 1995 American Institute of Physics.

Electrical transport properties of doped poly (p-phenylene)

An experimental study of the temperature dependent dc electrical conductivity of doped poly (p-phenylene) in the range of 50-300 K has been presented. The results have been analyzed in the framework of some hopping models. We have observed that hopping models are not consistent with the temperature dependence of the conductivity data over the entire temperature range of measurement. We find that the logarithmic conductivity is proportional to T-beta, wherethe exponent beta is independent of temperature. It is shown that the most probable transport process in this material for the entire range of temperature is due to multiphonon-assisted hopping of the charge carriers that interact weakly with phonons. The parameters obtained from the fits of the experimental data to this model appear reasonable.

Morphology of poly(vinylidene fluoride) and poly(o-metoxyaniline) blends

Blends of poly(o-methoxyaniline) - POMA - and poly(vinylidene fluoride) - PVDF - of various compositions were prepared from organic solvent solutions. Flexible, free-standing and stretchable films were obtained by casting, which were characterized by conductivity measurements, electron microscopy and differential scanning calorimetry. As expected, the blends conductivity increases with increasing contents of the conducting polymer. The onset of the conductivity at low contents of conducting polymer indicates a low percolation threshold for the blends. Despite the presence of the conductive host, the blends displayed the crystalline spherulitic morphology and the beta-phase characteristic of pure PVDF. This morphology appears to be destroyed, however, if the film is stretched by zone-drawing.