Mg(2+) Ions Bind at the C-Terminal Region of Skeletal Muscle alpha-Tropomyosin

Tropomyosin (Tm) is a dimeric coiled-coil protein that polymerizes through head-to-tail interactions. These polymers bind along actin filaments and play an important role in the regulation of muscle contraction. Analysis of its primary structure shows that Tm is rich in acidic residues, which are clustered along the molecule and may from sites for divalent cation binding. In a previous study, we showed that the Mg(2+)-induced increase in stability of the C-terminal half of Tin is sensitive to imitations near the C-terminus. In the present report, we study the interaction between Mg(2+) and full-length Tin and smaller fragments corresponding to the last 65 and 26 Tin residues. Although the smaller Tin peptide (Tm(259-284(W269))) is flexible and to large extent unstructured, the larger Tm(220-284(W269)) fragments forms a coiled coil in solution whose stability increases significantly in the presence of Mg(2+). NMR analysis shows thin Mg(2+) induces chemical shift perturbations in both Tm(220-284(W269)) and Tm(259-284(W269)) in the vicinity of His276, in which are located several negatively charged residues. (C) 2009 Wiley Periodicals, Inc. Biopolymers 91: 583-590, 2009.

Deciphering the role of the electrostatic interactions in the alpha-tropomyosin head-to-tail complex

Skeletal alpha-tropomyosin (Tm) is a dimeric coiled-coil protein that forms linear assemblies under low ionic strength conditions in vitro through head-to-tail interactions. A previously published NMR structure of the Tin head-to-tail complex revealed that it is formed by the insertion of the N-terminal coiled-coil of one molecule into a cleft formed by the separation of the helices at the C-terminus of a second molecule. To evaluate the contribution of charged residues to complex stability, we employed single and double-mutant Tm fragments in which specific charged residues were changed to alanine in head-to-tail binding assays, and the effects of the mutations were analyzed by thermodynamic double-mutant cycles and protein-protein docking. The results show that residues K5, K7, and D280 are essential to the stability of the complex. Though D2, K6, D275, and H276 are exposed to the solvent and do not participate in intermolecular contacts in the NMR structure, they may contribute to head-to-tail complex stability by modulating the stability of the helices at the Tm termini.

Adsorption of anionic amphiphilic polyelectrolytes onto amino-terminated solid surfaces

The adsorption behavior of several amphiphilic polyelectrolytes of poly(maleic anhydride-alt-styrene) functionalized with naphthyl and phenyl groups, onto amino-terminated silicon wafer has been studied by means of null- ellipsometry, atomic force microscopy (AFM) and contact angle measurements. The maximum of adsorption, Gamma(plateau), varies with the ionic strength, the polyelectrolyte structure and the chain length. Values of Gamma(plateau) obtained at low and high ionic strengths indicate that the adsorption follows the ""screening-reduced adsorption"" regime. Large aggregates were detected in solution by means of dynamic light scattering and fluorescence measurements. However. AFM indicated the formation of smooth layers and the absence of aggregates. A model based on a two-step adsorption behavior was proposed. In the first one, isolated chains in equilibrium with the aggregates in solution adsorbed onto amino-terminated surface. The adsorption is driven by electrostatic interaction between protonated surface and carboxylate groups. This first layer exposes naphtyl or phenyl groups to the solution. The second layer adsorption is now driven by hydrophobic interaction between surface and chains and exposes carboxylate groups to the medium, which repel the forthcoming chain by electrostatic repulsion. Upon drying some hydrophobic naphtyl or phenyl groups might be oriented to the air, as revealed by contact angle measurements. Such amphiphilic polyelectrolyte layers worked well for the building-up of multilayers with chitosan. (C) 2010 Elsevier Ltd. All rights reserved.

Resolution and Absolute Configuration Assignment of a Natural Racemic Chromane from Peperomia obtusifolia (Piperaceae)

The resolution of the natural racemic chromane 3,4-dihydro-5-hydroxy-2,7-dimethyl-8-(3 ``-methyl-2 ``-butenyl)-2-(4`-methyl-1`,3`-pentadienyl)-2H-1-benzopyran-6-carboxylic acid (1) isolated from the leaves of Peperomia obtusifolia has been accomplished using stereoselective HPLC. The absolute coil figuration of the resolved enantiomers was determined by the analysis of optical rotations and CD spectra. The finding of a racemic mixture instead of an enantiomerically pure metabolite raises questions about the final steps in the biosynthesis of this class of natural products, suggesting that the intramolecular chromane ring formation step may not be enzymatically controlled at all in P. obtusifolia. Chirality 21:799-801, 2009. (C) 2008 Wiley-Liss, Inc.

Low cost selective sensor for carbonyl compounds in air based on a novel conductive poly(p-xylylene) derivative

A novel poly(p-xylylene), PPX, derivative bearing phenyl side groups was electrochemically synthesized in 85% yield. The polymer, poly(2-phenyl-p-xylylene) (PPPX), presented a major fraction (88%) soluble in common organic solvents. It showed to be thermally resistant up to 140 degrees C. UV-VIS analysis revealed an Egap of similar to 3.0 eV. Gas sensors made from thin films of CSA doped PPPX deposited on interdigitated electrodes exhibited significant changes in electrical conductance upon exposure to five carbonyl compounds: acetaldehyde, propionaldehyde. benzaldehyde, acetone and butanone. Three-dimensional plots of relative response vs. time of half-response vs. time of half-recovery showed good discrimination between the five carbonyl Compounds tested. (C) 2008 Elsevier B.V. All rights reserved.

Lysozyme binding to poly(4-vinyl-N-alkylpyridinium bromide)

The adsorption behavior of polycations at ionic strengths (1) ranging from 0.001 to 0.1 onto silicon wafers was studied by means of ellipsometry, contact angle measurements and atomic force microscopy (AFM). Polycations chosen were bromide salts of poly(4-vinylpyridine) N-alkyl quaternized with linear aliphatic chains of 2 and 5 carbon atoms, QPVP-C2 and QPVP-C5, respectively. Under 1 0.001 the reduction of screening effects led to low adsorbed amounts of QPVP-C2 or QPVP-C5 (1.0 +/- 0.1 mg/m(2)), arising from the adsorption of extended chains. Upon increasing l to 0.1, screening effects led to conformational changes of polyelectrolyte chains ill Solution and to higher adsorbed amount values (1.9 +/- 0.2 mg/m(2)). Advancing contact angle theta(a) measurements performed with water drops onto QPVP-C2 and QPVP-C5 adsorbed layers varied from (45 +/- 2)degrees to (50 +/- 5)degrees, evidencing the exposure of both hydrophobic alkyl groups and charged moieties. The adsorption of lysozyme (LYZ) molecules to QPVP-C5 layers was more pronounced than to QPVP-C2 films. Antimicrobial effect of LYZ bound to QPVP-C2 or QPVP-C5 layers or to Si wafers was evaluated with enzymatic assays using Micrococcus luteus as Substrates. The adsorption behavior of QPVP-C2 and QPVP-C5 at the water-air interface was studied by means Of surface tension measurements. Only QPVP-C5 was able to reduce water Surface tension. Mixtures of LYZ and QPVP-C5 were more efficient in reducing Surface tension than pure LYZ solution, evidencing co-adsorption at liquid-air interface. Moreover, antimicrobial action observed for mixtures of LYZ and QPVP-C5 was more pronounced than that measured for pure LYZ. Hydrophobic interaction between LYZ and QPVP-C5 ill Solution seems to drive the binding and to preserve LYZ secondary structure. (c) 2008 Elsevier Inc. All rights reserved.

Polymeric electronic gas sensor for determining alcohol content in automotive fuels

In this paper we describe the electrosynthesis of poly[(2-bromo-5-hexyloxy- 1,4-phenylenevinylene)-co-(1,4-phenylenevinylene)] (BHPPV-co-PPV), a novel conducting copolymer, and its application as active layer of a chemiresistive gas sensor suitable for quantification of ethanol present in ethanol-gasoline mixtures normally present in the fuel tanks of flex-fuel vehicles. This information is crucial for the smooth operation of the engine since it permits optimal air:fuel ratio regulation. The sensor consists of an interdigitated electrode coated with a thin polymer film doped with dodecylbenzenesulfonic acid. On exposure to fuel vapours at room temperature, the device presents a linear correlation between its electrical conductance and the ethanol concentration in the fuel. (C) 2008 Elsevier B.V. All rights reserved.

A selective conductive polymer-based sensor for volatile halogenated organic compounds (VHOC)

A novel poly(p-xylylene), PPX, derivative bearing alkoxyphenyl side groups was electrochemically synthesized in 87% yield. The polymer, poly(4`-hexyloxy-2,5-biphenyleneethylene) (PHBPE), presented a fraction (92%) soluble in common organic solvents. It showed to be thermally resistant up to 185 degrees C. UV-vis analysis revealed an E-gap of 3.5 eV Gas sensors made from thin films of 10-camphorsulfonic acid-doped PHBPE deposited on interdigitated electrodes exhibited significant changes in electrical conductance upon exposure to five VHOCs: 1,2-dichloroethane, bromochloromethane, trichloromethane, dichloromethane and tetrachloromethane. The conductance decreased after exposure to tetrachloromethane and increased after exposure to all the other VHOCs. Three-dimensional plots of relative response versus time of half response versus time of half recovery showed good discrimination between the five VHOCs tested. (c) 2008 Elsevier B.V. All rights reserved.

Development of a spectrophotometric Sequential Injection Analysis (SIA) procedure for determination of ammonium: A Response Surface Methodology (RSM) approach

This paper describes the optimization and use of a Sequential Injection Analysis (SIA) procedure for ammonium determination in waters. Response Surface Methodology (RSM) was used as a tool for optimization of a procedure based on the modified Berthelot reaction. The SIA system was designed to (i) prepare the reaction media by injecting an air-segmented zone containing the reagents in a mixing chamber, (ii) to aspirate the mixture back to the holding coil after homogenization, (iii) drive it to a thermostated reaction coil, where the flow is stopped for a previously established time, and (iv) to pump the mixture toward the detector flow cell for the spectrophotometric measurements. Using a 100 mu mol L(-1) ammonium solution, the following factors were considered for optimization: reaction temperature (25 - 45 degrees C), reaction time (30 - 90 s), hypochlorite concentration (20 - 40 mmol L(-1)) nitroprusside concentration (10 - 40 mmol L(-1)) and salicylate concentration (0.1 - 0.3 mol L(-1)). The proposed system fed the statistical program with absorbance data for fast construction of response surface plots. After optimization of the method, figures of merit were evaluated, as well as the ammonium concentration in some water samples. No evidence of statistical difference was observed in the results obtained by the proposed method in comparison to those obtained by a reference method based on the phenol reaction. (C) 2010 Elsevier B.V. All rights reserved.

The role of cross-linking structures to the formation of one-dimensional nano-organized polyaniline and their Raman fingerprint

In the present work. the resonance Raman. UV-vis-NIR and scanning electron microscopic (SEM) data of nanorods (about similar to 300 rim in diameter) and nanofibers (about similar to 93 nm in diameter) of PANI are presented and compared. The PANI samples were synthesized in aqueous media with dodecybenzenesulfonic acid (DBSA) and beta-naphtalenesulfonic acid (beta-NSA) as dopants, respectively. The presence of hands at 578, 1400 and 1632cm(-1) in the Raman spectra of PANI-NSA and PANI-DBSA shows that the formation of cross-linking structures is a general feature of the PANI chains prepared in micellar media. It is proposed that these structures are responsible for the one-dimensional PANI morphology formation. In addition, the Raman band at 609cm(-1) of PANI fibers is correlated with the extended PANI chain coil formation. (C) 2008 Elsevier B.V. All rights reserved.

Excited-state dynamics of polyfluorene derivatives in solution

The excited-state dynamics of two polyfluorene copolymers, one fully conjugated containing phenylene vinylene units alternated with 9,9`-dihexylfluorenyl groups and the other segmented by -(CH2)(8)- spacer, were studied in dilute solution of different solvents using a picosecond single-photon timing technique. The excited-state dynamics of the segmented copolymer follows the Forster resonant energy-transfer model which describes intrachain energy-transfer kinetics among random oriented chromophores. Energy transfer is confirmed by analysis of fluorescence anisotropy relaxation with the measurement of a short decay component of about 60 ps. The fluorescence decay surface of the fully conjugated copolymer is biexponential with decay times of about 470 and 900 ps, ascribed to deactivation of chain moieties containing trans and cis isomers already in a photostationary condition. Thus, energy transfer is very fast due to the conjugated nature and rigid-rod-like structure of this copolymer chain.

Intrachain Energy Migration to Weak Charge-Transfer State in Polyfluorene End-Capped with Naphthalimide Derivative

Polyfluorene end-capped with N-(2-benzothiazole)-1 8-naphthalimide (PF-BNI) is a highly fluorescent material with fluorescence emission modulated by solvent polarity Its low energy excited state is assigned as a mixed configuration state between the singlet S(1) of the fluorene backbone (F) with the charge transfer (CI) of the end group BNI The triexponential fluorescence decays of PF-BNI were associated with fast energy migration to form an intrachain charge-transfer (ICCT) state polyfluorene backbone decay and ICCT deactivation Time-resolved fluorescence anisotropy exhibited biexponential relaxation with a fast component of 12-16 ps in addition to a slow one in the range 0 8-1 4 ns depending on the solvent showing that depolarization occurs from two different processes energy migration to form the ICCT state and slow rotational diffusion motion of end segments at a longer time Results from femtosecond transient absorption measurements agreed with anisotropy decay and showed a decay component of about 16 ps at 605 nm in PF BNI ascribed to the conversion of S(1) to the ICCT excited state From the ratio of asymptotic and initial amplitudes of the transient absorption measurement the efficiency of intrachain ICCT formation is estimated in 0 5 which means that on average, half of the excited state formed in a BNI-(F)(n)-BNI chain with n = 32 is converted to its low energy intrachain charge-transfer (ICCT) state

Calucaltion of waste heat from hot rolled steel coils at SSAB and its recovery

Hot rolling process is heat input process. The heat energy in hot rolled steel coils can be utilized. At SSAB Strip Product Borlänge when the hot rolled steel coils came out of the hot rolling mill they are at the temperature range of 500°C to 800°C. Heat energy contained by the one hot rolled steel coil is about 1981Kwh whereas the total heat energy for the year 2008 is 230 GWh/year.The potential of heat is too much but the heat dissipation rate is too slow. Different factors on which heat dissipation rate depends are discussed.Three suggestions are proposed to collect the waste heat from hot rolled steel coils.The 2nd proposal in which water basin is suggested would help not only to collect the waste heat but to decrease in the cooling time.

Replacing Finned Copper withCorrugated Stainless Steel, forthe Heat Exchangers of a SolarCombisystem Store : Performance and EconomicEvaluation

The importance of investigating cost reduction in materials and components for solar thermal systems is crucial at the present time. This work focuses on the influence of two different heat exchangers on the performance of a solar thermal system. Both heat exchangers studied are immersed helically coiled, one made with corrugated stainless steel tube, and the other made with finned copper tube with smooth inner surface.A test apparatus has been designed and a simple test procedure applied in order to study heat transfer characteristics and pressure drop of both coils. Thereafter, the resulting experimental data was used to perform a parameter identification of the heat exchangers, in order to obtain a TRNSYS model with its corresponding numerical expression. Also a representative small-scale combisystem model was designed in TRNSYS, in order to study the influence of both heat exchangers on the solar fraction of the system, when working at different flow rates.It has been found that the highest solar fraction is given by the corrugated stainless steel coil, when it works at the lowest flow rate (100 l/hr). For any higher flow rate, the studied copper coil presents a higher solar fraction. The advantageous low flow performance of stainless steel heat exchanger turns out to be beneficial for the particular case of solar thermal systems, where it is well known that low flow collector loops lead to enhanced store stratification, and consequently higher solar fractions.Finally, an optimization of the stainless steel heat exchanger length is carried out, according to economic figures. For the given combisystem model and boundary conditions, the optimum length value is found between 10 and 12 m.

Copolimeros de propileno-etileno com baixos teores de etileno : estrutura, morfologia e propriedades

A estrutura básica predomínante encontrada em todos os copolímeros foi a de longos blocos de polipropileno cristalizáveis, separados por unidades isoladas de etileno, que atuaram como defeitos cristalínos, reduzindo o grau de cristalínidade, além da perfeição e da espessura dos cristais. O gradual aumento do teor de etileno nas amostras origínais, até aproximadamente5 moI % provocou redução progressiva no comprimento dos blocos de propileno em ambas as frações cristalizável e elastomérica. Acima daquela concentração, o etileno mostrou por principal efeito a elevação do teor de borracha de etileno-propileno(EPR), refletíndo-seem pronunciado aumento da resistência ao impacto dos copolímeros, com pouca alteração do comprimento das seqüências propiJênicas nas frações cristaJizáveJe elastomérica. A estrutura e a morfologia da borracha EPR gerada foram analisadas, observando-se sua excepcional dispersão na fase contínua cristalína. Análise das curvas de fusão por DSC, utilizando-se conceitos cínéticos, demonstrou a existência de uma energia de ativação aparente de fusão, associada à introdução de unidades etilênicas nas cadeias, e relacionada ao processo de fusão dos cristais poliméricos. A redução de cristalínidade das amostras e o aumento de mobilidade de cadeia da fase amorfa para teores crescentes de etileno resultaram em redução da rigidez dos copolímeros. Propriedades ópticas, como "haze" e brilho mostraram-se dependentesdo balanço entre o teor de cristais e o teor de borracha. Um balanço global das propriedades analisadas sugere uma composição ótima para aplicações típicas de copolímeros de propileno-etileno aquela com teores de etileno entre 4 e 6 moI % (aproximadamente 3 -4 % em massa).