Chain extension in electrospun polystyrene fibres: a SANS study

Small angle neutron scattering techniques were used to quantify the size and shape of the chain conformation in electrospun fibres of atactic polystyrene prepared from solutions in methyl ethyl ketone. Aligned arrays of fibres were collected onto a rotating collector with tangential velocity varying between 0 ms-1 and approximately 15 ms-1. The measured radii of gyration of the polystyrene chains were found to be slightly higher than that expected for samples prepared from solutions in the concentrated regime. The ratio of the radius of gyration parallel and perpendicular to the chain axis was found to be approximately 1.05 in contrast to the substantial macroscopic shape transformation intrinsic to electrospinning. When the tangential velocity of the rotating collector was greater than the flight velocity of the fibres (ca. 4 ms-1), a further extension of the polymer chains was observed with a ratio of the radii of gyration increasing to 1.20 at the highest collector speeds. It is proposed that the heterogeneous processes involved, particularly solvent evaporation and the formation of a polymer skin during electrospinning play a significant role in determining the level of molecular anisotropy in the fibres.

Structure and spectra of dichloro(hydroxy-methoxy-di(2-pyridyl)methane)copper(II)

The non-electrolyte dichloro(hydroxy-methoxy-di(2-pyridylmethane)copper(II), resulting from the reaction of di(2-pyridyl)ketone and copper(II) chloride in methanol solution, was isolated and characterized and its structure was determined by X-ray diffraction. The pyridyl nitrogens and the chloride anions virtually from a basal plane in which lies the copper atom, while the oxygen of the methoxy group is in an apical position at a distance of 2.497 (3)Å. The nitrogenous base adopts the boat conformation with the pyridyl rings forming a dihedral angle of 108.72 (14)°. The nearest interatomic copper distance of 3.940(3)Å precludes copper-copper interactions, while the proximity of copper to the out-of-plane chlorine atoms [3.109(3)Å] suggests weakly bound chloro-bridged dimers. Spectral changes indicate that protic molecules displace the methoxy group and water affords the corresponding 1,1-diol.

Direct iminization of PEEK

Semi-crystalline poly(ether ketone)s are important high-temperature engineering thermoplastics, but are difficult to characterize at the molecular level because of their insolubility in conventional organic solvents. Here we report that polymers of this type, including PEEK, react cleanly at high temperatures with low-volatility aralkyl amines to afford stable, noncrystalline poly(ether-imine)s, which are readily soluble in solvents such as chloroform, THF and DMF and so characterizable by conventional size-exclusion chromatography.

Analysis of time-related metabolic fluctuations induced by ethionine in the rat

The time-course of metabolic events following response to a model hepatotoxin ethionine (800 mg/kg) was investigated over a 7 day period in rats using high-resolution (1)H NMR spectroscopic analysis of urine and multivariate statistics. Complementary information was obtained by multivariate analysis of (1)H MAS NMR spectra of intact liver and by conventional histopathology and clinical chemistry of blood plasma. (1)H MAS NMR spectra of liver showed toxin-induced lipidosis 24 h postdose consistent with the steatosis observed by histopathology, while hypertaurinuria was suggestive of liver injury. Early biochemical changes in urine included elevation of guanidinoacetate, suggesting impaired methylation reactions. Urinary increases in 5-oxoproline and glycine suggested disruption of the gamma-glutamyl cycle. Signs of ATP depletion together with impairment of the energy metabolism were given from the decreased levels in tricarboxylic acid cycle intermediates, the appearance of ketone bodies in urine, the depletion of hepatic glucose and glycogen, and also hypoglycemia. The observed increase in nicotinuric acid in urine could be an indication of an increase in NAD catabolism, a possible consequence of ATP depletion. Effects on the gut microbiota were suggested by the observed urinary reductions in the microbial metabolites 3-/4-hydroxyphenyl propionic acid, dimethylamine, and tryptamine. At later stages of toxicity, there was evidence of kidney damage, as indicated by the tubular damage observed by histopathology, supported by increased urinary excretion of lactic acid, amino acids, and glucose. These studies have given new insights into mechanisms of ethionine-induced toxicity and show the value of multisystem level data integration in the understanding of experimental models of toxicity or disease.

Conformational modulation of sequence recognition in synthetic macromolecules

The different triplet sequences in high molecular weight aromatic copolyimides comprising pyromellitimide units ("I") flanked by either ether-ketone ("K") or ether-sulfone residues ("S") show different binding strengths for pyrene-based tweezer-molecules. Such molecules bind primarily to the diimide unit through complementary π-π-stacking and hydrogen bonding. However, as shown by the magnitudes of 1H NMR complexation shifts and tweezer-polymer binding constants, the triplet "SIS" binds tweezer-molecules more strongly than "KIS" which in turn bind such molecules more strongly than "KIK". Computational models for tweezer-polymer binding, together with single-crystal X-ray analyses of tweezer-complexes with macrocyclic ether-imides, reveal that the variations in binding strength between the different triplet sequences arise from the different conformational preferences of aromatic rings at diarylketone and diarylsulfone linkages. These preferences determine whether or not chain-folding and secondary π−π-stacking occurs between the arms of the tweezermolecule and the 4,4'-biphenylene units which flank the central diimide residue.

Investigating flavonoids as molecular templates for the design of small-molecule inhibitors of cell signaling

Epidemiological and clinical trials reveal compelling evidence for the ability of dietary flavonoids to lower cardiovascular disease risk. The mechanisms of action of these polyphenolic compounds are diverse, and of particular interest is their ability to function as protein and lipid kinase inhibitors. We have previously described structure-activity studies that reinforce the possibility for using flavonoid structures as templates for drug design. In the present study, we aim to begin constructing rational screening strategies for exploiting these compounds as templates for the design of clinically relevant, antiplatelet agents. We used the platelet as a model system to dissect the structural influence of flavonoids, stilbenes, anthocyanidins, and phenolic acids on inhibition of cell signaling and function. Functional groups identified as relevant for potent inhibition of platelet function included at least 2 benzene rings, a hydroxylated B ring, a planar C ring, a C ring ketone group, and a C-2 positioned B ring. Hydroxylation of the B ring with either a catechol group or a single C-4' hydroxyl may be required for efficient inhibition of collagen-stimulated tyrosine phosphorylated proteins of 125 to 130 kDa, but may not be necessary for that of phosphotyrosine proteins at approximately 29 kDa. The removal of the C ring C-3 hydroxyl together with a hydroxylated B ring (apigenin) may confer selectivity for 37 to 38 kDa phosphotyrosine proteins. We conclude that this study may form the basis for construction of maps of flavonoid inhibitory activity on kinase targets that may allow a multitargeted therapeutic approach with analogue counterparts and parent compounds.

A Ring Contraction Strategy toward a Diastereoselective Total Synthesis of (+)-Bakkenolide A

A diastereoselective route to (+)-bakkenolide A is presented from the readily available optically active Wieland-Miescher ketone. This novel synthesis of this sesquiterpene lactone features the following as key stereoselective transformations: (i) the ring contraction reaction of a octalone mediated by thallium(III) nitrate (TTN); (ii) a hydrogenation to create the cis-fused junction; and (iii) the formation of the C7 quaternary center through an enolate intermediate. Furthermore, during this work, the absolute configuration of a trinorsesquiterpene isolated from Senecio Humillimus was assigned.

Chemoselective screening for the reduction of a chiral functionalised (+/-)-2-(phenylthio)cyclohexanone by whole cells of Brazilian micro-organisms

The use of whole cells of micro-organisms to bring about the biotransformation of an organic compound offers a number of advantages, but problems caused by enzymatic Promiscuity may be encountered upon With Substrates hearing more than one functional group. A one-pot screening method, in which whole fungal cells were incubated with a Mixture of 4-rnethylcyclohexanone I and phenyl methyl Sulfide 2, has been employed to determine the chemoselectivity of various biocatalysts. The hyphomycetes, Aspergillus terreus CCT 3320 and A. terreus URM 3571, catalysed the oxidation of 2 accompanied by the reduction of I to 4-methylcyclohexanol 1a and, for strain A. terreus CCT 3320, the Baeyer-Villiger oxidation of 1. The Basidomycetes, Trametes versicolor CCB 202, Pycnoporus sanguineus CCB 501 and Trichaptum byssogenum CCB 203, catalysed the oxidation of 2 and the reduction 1, but no Baeyer-Villiger reaction products were detected. In contrast. Trametes rigida CCB 285 catalysed the biotransformation of 1 to 1a, exclusively, in the absence of any detectable Sulfide oxidation reactions. The chemoselective reduction Of (+/-)-2-(phenylthio)cyclohexanone 3 by T. rigida CCB 285 afforded exclusively the (+)-cis-(1R,2S) and (+)-trans-(1S,2S) diastereoisomers of 2-(phenylthio)cyclohexan-1-ol 3a in moderate yields (13% and 27%, respectively) and high enantiomeric excesses (>98%). Chemoselective screening for the reduction of a ketone and/or the oxidation Of a Sulfide group in one pot by whole cells of micro-organisms represents an attractive technique with applications in the development of synthesis of complex molecule hearing different functional groups. (C) 2008 Published by Elsevier Ltd.

Kinetic resolution of iodophenylethanols by Candida antarctica lipase and their application for the synthesis of chiral biphenyl compounds

The kinetic resolution of (+/-)-iodophenylethanols was carried out using lipase from Candida antarctica and in some cases the enantiomeric excesses were high (up to >98%). Enantiomerically enriched (S)-iodophenylethanols produced by the enzymatic resolution process were used in the synthesis of chiral biphenyl compounds by the Suzuki reaction with good yields (63-65%). (C) 2010 Elsevier Ltd. All rights reserved.

Photochemical Production of MicromolarSuperoxideStandards in Aqueous SolutionT

Superoxide(O2-) is a reactive free radical that rapidly undergoes disproportionation to hydrogen peroxide and oxygen. This property makes preparation of superoxide standard for instrument calibration difficult. McDowell et al. (1983) showed photolysis of ketone and alcohol as a convenient method to generate superoxide through triplet and radical intermediates reacting with molecular oxygen. This study expands on this past work and investigates detailed mechanism of the reaction.

Effectiveness of different solid-phase microextraction fibres for differentiation of selected Madeira island fruits based on their volatile metabolite profile: identification of novel compounds

A headspace solid-phase microextraction (HS-SPME) procedure based on five commercialised fibres (85 μm polyacrylate – PA, 100 μm polydimethylsiloxane – PDMS, 65 μm polydimethylsiloxane/divinylbenzene – PDMS/DVB, 70 μm carbowax/divinylbenzene – CW/DVB and 85 μm carboxen/polydimethylsiloxane – CAR/PDMS) is presented for the characterization of the volatile metabolite profile of four selected Madeira island fruit species, lemon (Citrus limon), kiwi (Actinidia deliciosa), papaya (Carica papaya L.) and Chickasaw plum (Prunus angustifolia). The isolation of metabolites was followed by thermal desorption gas chromatography–quadrupole mass spectrometry (GC–qMS) methodology. The performance of the target fibres was evaluated and compared. The SPME fibre coated with CW/DVB afforded the highest extraction efficiency in kiwi and papaya pulps, while in lemon and plum the same was achieved with PMDS/DVB fibre. This procedure allowed for the identification of 80 compounds, 41 in kiwi, 24 in plums, 23 in papaya and 20 in lemon. Considering the best extraction conditions, the most abundant volatiles identified in kiwi were the intense aldehydes and ethyl esters such as (E)-2-hexenal and ethyl butyrate, while in Chicasaw plum predominate 2-hexenal, 2-methyl-4-pentenal, hexanal, (Z)-3-hexenol and cyclohexylene oxide. The major compounds identified in the papaya pulp were benzyl isothiocyanate, linalool oxide, furfural, hydroxypropanone, linalool and acetic acid. Finally, lemon was shown to be the most divergent of the four fruits, being its aroma profile composed almost exclusively by terpens, namely limonene, γ-terpinene, o-cymene and α-terpinolene. Thirty two volatiles were identified for the first time in the fruit or close related species analysed and 14 volatiles are reported as novel volatile metabolites in fruits. This includes 5 new compounds in kiwi (2-cyclohexene-1,4-dione, furyl hydroxymethyl ketone, 4-hydroxydihydro-2(3H)-furanone, 5-acetoxymethyl-2-furaldehyde and ethanedioic acid), 4 in plum (4-hydroxydihydro-2(3H)-furanone, 5-methyl-2-pyrazinylmethanol, cyclohexylene oxide and 1-methylcyclohexene), 4 in papaya (octaethyleneglycol, 1,2-cyclopentanedione, 3-methyl-1,2-cyclopentanedione and 2-furyl methyl ketone) and 2 in lemon (geranyl farnesate and safranal). It is noteworthy that among the 15 volatile metabolites identified in papaya, 3-methyl-1,2-cyclopentanedione was previously described as a novel PPARγ (peroxisome proliferator-activated receptor γ) agonist, having a potential to minimize inflammation.

Tricomas foliares em tomateiro com teores contrastantes do aleloquímico 2-tridecanona

Duas espécies de tomateiro, Lycopersicon esculentum Mill. (Linhagem TOM 556- padrão com baixo teor da metil cetona 2-tridecanona (2-TD) e Lycopersicon hirsutum Dunal var. glabratum Mill. (Linhagem PI 134417- padrão com elevado teor de 2-TD), foram analisadas em conjunto para identificação e quantificação de tricomas foliares. A parte experimental constou da identificação dos tricomas, baseado na presença ou ausência da cabeça secretora na extremidade apical dos tricomas, arranjo e número de células da cabeça, comprimento dos tricomas, e da quantificação do número de tricomas glandulares e não glandulares nos folíolos. O delineamento utilizado para o número de tricomas foi inteiramente casualizado e as médias comparadas pelo teste de Tukey, a 5%. A identificação e quantificação para as espécies foram: a) TOM 556: Tricomas não glandulares do tipo II + III + V (2590 cm-2 de área foliolar); glandular do tipo VI (16 cm-2); glandular do tipo VII (138 cm-2); b) PI 134417: não glandulares do tipo II + III + V (140 cm-2 de área foliolar); glandular do tipo I + IV (843 cm-2); glandular do tipo VI (83 cm-2); glandular do tipo VII (11 cm-2). As maiores concentrações da 2-TD nos folíolos, estão associadas às maiores densidades de tricomas glandulares presentes em ambas espécies.

Desgaste de polímeros estruturais de engenharia em contato de deslizamento com cilindro metálico

Present work proposed to map and features the wear mechanisms of structural polymers of engineering derived of the sliding contact with a metallic cylindrical spindle submitted to eccentricity due to fluctuations in it is mass and geometric centers. For this it was projected and makes an experimental apparatus from balancing machine where the cylindrical counterbody was supported in two bearings and the polymeric coupon was situated in a holder with freedom of displacement along counterbody. Thus, the experimental tests were standardized using two position of the two bearings (Fixed or Free) and seven different positions along the counterbody, that permit print different conditions to the stiffness from system. Others parameters as applied normal load, sliding velocity and distance were fixed. In this investigation it was used as coupon two structural polymers of wide quotidian use, PTFE (polytetrafluroethylene) and PEEK (poly-ether-ether-ketone) and the AISI 4140 alloy steel as counterbody. Polymeric materials were characterized by thermal analysis (thermogravimetric, differential scanning calorimetry and dynamic-mechanical), hardness and rays-X diffractometry. While the metallic material was submitted at hardness, mechanical resistance tests and metallographic analysis. During the tribological tests were recorded the heating response with thermometers, yonder overall velocity vibration (VGV) and the acceleration using accelerometers. After tests the wear surface of the coupons were analyzed using a Scanning Electronic Microscopy (SEM) to morphological analysis and spectroscopy EDS to microanalysis. Moreover the roughness of the counterbody was characterized before and after the tribological tests. It was observed that the tribological response of the polymers were different in function of their distinct molecular structure. It were identified the predominant wear mechanisms in each polymer. The VGV of the PTFE was smaller than PEEK, in the condition of minimum stiffness, in function of the higher loss coefficient of that polymer. Wear rate of the PTFE was more of a magnitude order higher than PEEK. With the results was possible developed a correlation between the wear rate and parameter (E/ρ)1/2 (Young modulus, E, density, ρ), proportional at longitudinal elastic wave velocity in the material.

Estudo comparativo das propriedades mecânicas em compósitos da fibra modal e poliester

In the present work, three composites with distinct reinforcements (polyester, modal e polyester + modal), all if a unsaturated orthophthalic polyester resin as matrix were used, in order to conduct a comparative study by mechanical tests and water absorption. The fibre mats were prepared in a mat preparatory by immersion developed in the Textile Engineering Laboratory. The composites were manufactured using a closed mould process by compression using an unsaturated orthophthalic polyester resin as matrix and 1% MEK (methyl ethyl ketone peroxide) as an initiator. In each composite twelve samples with the dimensions of 150x25x3 mm were cut randomly for the mechanical analysis (tension x extension, three points bending and water absorption and Scanning Electron Micsroscopy). The mechanical tests were carried out in the Laboratório de Metais e Ensaios Mecânicos UFRN . All the analyses were carried out according to the ASTM norms. The resultant samples from the mechanical analysis were subjected for the Scanning Electron Microscopy analysis. Based on the results obtained, it was observed that the reinforced composite with two fibres (modal + polyester) presented better results in comparison to the other two composites both in the tension/extension as well on the three point bending tests. In the water absorption test, it was possible to observe an equilibrium in the water absorption by the modal and polyester composite, due to the union of the two fibres. In the SEM images, the regions of rupture in the composites as well as the adsorption between the fiber and the matrix could be observed

Fabricação de eco-composito com a fibra de lã canina

The Sustainability has been evidence in the world today; organizations have sought to be more and more into this philosophy in their processes, whether products or attendance. In the present work were manufactured eco-composites with animal fiber (dog wool) that is currently discarded into the environment without any use. The fibers were characterized and made matting (non-woven). The phases of the project were consisted to develop methods and to convert these fibers (booster) blended with polyester resin (matrix) in different proportions (10%, 20% and 30%) at the composite. Were studied fiber characteristics, mechanical properties of the composites, water absorption and scanning electron microscopy. Initially, the fibers were treated with solution of sodium hydroxide of 0.05 mols, and then taken to matting preparing at the textile engineering laboratory - UFRN. The composites were made by compression molding, using an orthophthalic polyester resin as matrix and 1% MEK (methyl ethyl ketone peroxide) as initiator (catalyst). To evaluate the mechanical tests (tensile and flexural) and water absorption were made twelve specimens with dimensions 150x25x3 mm were cut randomly. According to the standard method, tensile tests (ASTM 3039) bending tests (ASTM D790) were performed at the mechanical testing of metals at laboratory UFRN. The results of these tests showed that the composite reinforced with 30% had a better behavior when exposed to tension charge; while on the three points bending test showed that the composite reinforced with 10% had a better behavior. In the water absorption test it was possible to see that the highest absorption happened on the composite reinforced with 30%. In the micrographs, it was possible to see the regions of rupture and behavior of the composite (booster / matrix)