Gamma transition intensity determination using multidetector coincidence data

This work describes two similar methods for calculating gamma transition intensities from multidetector coincidence measurements. In the first one, applicable to experiments where the angular correlation function is explicitly fitted, the normalization parameter from this fit is used to determine the gamma transition intensities. In the second, that can be used both in angular correlation or DCO measurements, the spectra obtained for all the detector pairs are summed up, in order to get the best detection statistics possible, and the analysis of the resulting bidimensional spectrum is used to calculate the transition intensities; in this method, the summation of data corresponding to different angles minimizes the influence of the angular correlation coefficient. Both methods are then tested in the calculation of intensities for well-known transitions from a (152)Eu standard source, as well as in the calculation of intensities obtained in beta-decay experiments with (193)Os and (155)Sm sources, yielding excellent results in all these cases. (C) 2009 Elsevier B.V. All rights reserved.

Interaction of polysaccharide-protein complex from Agaricus blazei with Langmuir and Langmuir-Blodgett films of phospholipids

The use of natural substances in health applications may be hampered by the difficulties in establishing the mechanisms of action, especially at molecular-level. The protein-polysaccharide complex extracted from the mushroom Agaricus blazei Murill, referred to as CAb, has been considered for treating various diseases with probable interaction with cell membranes. In this study, we investigate the interaction between CAb and a cell membrane model represented by a Langmuir monolayer of dimyristoyl phosphatidic acid (DMPA). CAb affects the structural properties of DMPA monolayers causing expansion and increasing compressibility. In addition, interaction with DMPA polar heads led to neutralization of the electrical double layer, yielding a zero surface potential at large areas per molecule. CAb remained at the interface even at high surface pressures, which allowed transfer of Langmuir-Blodgett (LB) films onto solid supports with the CAb-DMPA mixture. The mass transferred, according to quartz crystal microbalance (QCM) measurements, increased linearly with the number of deposited layers. With UV-vis absorption, fluorescence and FTIR spectroscopies, we confirmed that the LB films contain polysaccharides, proteins and DMPA. Therefore, the CAb biological action must be attributed not only to polysaccharides but also to proteins in the complex. (C) 2008 Elsevier Inc. All rights reserved.

Synthesis of azopolymers with controlled structure and photoinduced birefringence in their LB films

The molecular architecture of azopolymers may be controlled via chemical synthesis and with selection of a suitable film-forming method, which is important for improving their properties for practical uses. Here we address the main challenge of combining the photoinduced birefringence features of azopolymers with the higher thermal and mechanical stabilities of poly(methyl methacrylate) (PMMA) using Atom Transfer Radical Polymerization (ATRP) to synthesize diblock- and triblock-copolymers of an azomonomer and the monomer methyl methacrylate. Langmuir-Blodgett (LB) films made with the copolymers mixed with cadmium stearate displayed essentially the same optically induced birefringence characteristics, in terms of maximum and residual birefringence and time for writing, as the mixed LB films with the homopolymer poly[4-(N-ethyl-N-(2-methacryloxyethyl))amino-2`-chloro-4`-nitroazobenzene] (HPDR13), also synthesized via ATRP. In fact, the controlled architecture of HPDR13 chains led to Langmuir films that could be more closely packed and reach higher collapse pressures than the corresponding films obtained with HPDR13-conv synthesized via conventional radicalar polymerization. This allowed LB films to be fabricated from neat HPDR13, which was not possible with HPDR13-conv. The enhanced organization in the LB films produced with controlled azopolymer chains, however, led to a smaller free volume available for isomerization of the azochromophores, thus yielding a lower photoinduced birefringence than in the HPDR13-conv films. The combination of ATRP synthesis and LB technology is then promising to obtain optical storage in films with improved thermal and mechanical processabilities, though a further degree of control must be sought to exploit film organization while maintaining the necessary free volume in the films. (C) 2008 Elsevier Ltd. All rights reserved.

Detection of microwaves using the organic semiconductor poly(p-phenylenevinylene)

We report a new procedure to convert the polymer precursor poly(xylylidene tetrahydrothiophenium chloride) (PTHT) into poly(p-phenylenevinylene) (PPV) using microwave irradiation. Spin-coated PTHT films were irradiated at room temperature under ambient conditions in a commercial microwave oven, with varying power from 20W to 100W. Complete conversion was reached within only 5 min of irradiation for powers above 50W, yielding PPV films with absorption and photoluminescence spectra that are practically indistinguishable from the spectra of thermally converted PPV films, which require ca. 2 h of a high temperature (similar to 200 degrees C) thermal treatment. In addition to a much faster conversion procedure, the irradiation with microwaves led to a red shift in the absorption spectrum of a PTHT film, which varied linearly with the time of irradiation. These films can then be used as low-cost, easy-to-use detectors of microwaves. (C) 2010 Elsevier B.V. All rights reserved.

Classical and fragment-based hologram structure-activity relationships for a series of analgesic cyclic imides

Cyclic imides have been widely employed in drug design research due to their multiple pharmacological and biological properties. In the present study, two-dimensional quantitative structure-activity relationship (2D QSAR) studies were conducted on a series of potent analgesic cyclic imides using both classical and hologram QSAR (HQSAR) methods, yielding significant statistical models (classical QSAR, q(2) = 0.80; HQSAR, q(2) = 0.84). The models were then used to evaluate an external data test, and the predicted values were in good agreement with the experimental results, indicating their consistency for untested compounds.

Precambrian history of the Zona Transversal of the Borborema Province, NE Brazil: Insights from Sm-Nd and U-Pb geochronology

The Borborema Province has three major subprovinces. The northern subprovince lies north of the Patos shear zone and is comprised of Paleoproterozoic cratonic basement with Archean nuclei, plus overlying Neoproterozoic supracrustal rocks and Brasiliano plutonic rocks. The central subprovince occurs between the Patos and Pernambuco shear zones and is mainly comprised of the Zona Transversal. The southern subprovince occurs between the Pernamabuco shear zone and the Sao Francisco craton and is comprised of a tectonic collage of various blocks, terranes, or domains ranging in age from Archean to Neoproterozoic. This report focuses on the Zona Transversal, especially on Brasiliano rocks for which we have the most new information. Paleoproterozoic gneisses with ages of 2.0-2.2 Ga occur discontinuously throughout the Zona Transversal. The Cariris Velhos suite consists of metavolcanic, metasedimentary, and metaplutonic rocks yielding U-Pb zircon ages of 995-960 Ma. This suite is mainly confined to a 100 km wide belt that extends for more than 700 km within the Alto Pajeu terrane. Sm-Nd model ages in metaigneous rocks cluster about 1.3-1.6 Ga, indicating that older crust was involved in genesis of their magmas. Brasiliano supracrustal rocks dominate the Pianco-Alto Brigida terrane, and they probably also constitute significant parts of the Alto Pajeu and Rio Capibaribe terranes. They are only slightly older than early stages of Brasiliano plutonism, with detrital zircon ages at least as young as 620 Ma; most T(DM) ages range from 1.2 to 1.6 Ga. Brasiliano plutons range from ca. 640 to 540 Ma, and their T(DM) ages range from 1.2 to 2.5 Ga. Previous workers have shown significant correlations among U-Pb ages, Sm-Nd model ages, petrology, and geochemistry, and we are able to reinforce and extend these correlations. Stage I plutons formed 640 -610 Ma and have T(DM) ages less than 1.5 Ga. Stage 11 (610-590 Ma) contains few plutons, but coincides with the peak of compressional deformation, metamorphism, and formation of migmatites. Stage III plutons (590 to ca. 575 Ma) have older T(DM) ages (ca. 1.8-2.0 Ga), as do Stage IV plutons (575 to ca. 550 Ma; T(DM) from 1.9 to 2.4 Ga). Stage III plutons formed during the transition from compressional to transcurrent deformation, while Stage IV plutons are mainly post-tectonic. Stage V plutons (550-530 Ma) are commonly undeformed (except along younger shear zones) and have A-type geochemistry. The five stages have distinct geochemical properties, which suggest that the tectonic settings evolved from early, arc-related magma-genesis (Stage I) to within-plate magma-genesis (Stage V), with perhaps some intermediate phases of extensional environments. (C) 2011 Elsevier Ltd. All rights reserved.

THE RIO APA CRATON IN MATO GROSSO DO SUL (BRAZIL) AND NORTHERN PARAGUAY: GEOCHRONOLOGICAL EVOLUTION, CORRELATIONS AND TECTONIC IMPLICATIONS FOR RODINIA AND GONDWANA

The Rio Apa cratonic fragment crops out in Mato Grosso do Sul State of Brazil and in northeastern Paraguay. It comprises Paleo-Mesoproterozoic medium grade metamorphic rocks, intruded by granitic rocks, and is covered by the Neoproterozoic deposits of the Corumbi and Itapocurni Groups. Eastward it is bound by the southern portion of the Paraguay belt. In this work, more than 100 isotopic determinations, including U-Pb SHRIMP zircon ages, Rb-Sr and Sm-Nd whole-rock determinations, as well as K-Ar and Ar-Ar mineral ages, were reassessed in order to obtain a complete picture of its regional geological history. The tectonic evolution of the Rio Apa Craton starts with the formation of a series of magmatic arc complexes. The oldest U-Pb SHRIMP zircon age comes from a banded gneiss collected in the northern part of the region, with an age of 1950 +/- 23 Ma. The large granitic intrusion of the Alumiador Batholith yielded a U-Pb zircon age of 1839 +/- 33 Ma, and from the southeastern part of the area two orthogneisses gave zircon U-Pb ages of 1774 +/- 26 Ma and 1721 +/- 25 Ma. These may be coeval with the Alto Terere metamorphic rocks of the northeastern corner, intruded in their turn by the Baia das Garcas granitic rocks, one of them yielding a zircon U-Pb age of 1754 +/- 49 Ma. The original magmatic protoliths of these rocks involved some crustal component, as indicated by the Sm-Nd TDm model ages, between 1.9 and 2.5 Ga. Regional Sr isotopic homogenization, associated with tectonic deformation and medium-grade metamorphism occurred at approximately 1670 Ma, as suggested by Rb-Sr whole rock reference isochrons. Finally, at 1300 Ma ago, the Ar work indicates that the Rio Apa Craton was affected by widespread regional heating, when the temperature probably exceeded 350 degrees C. Geographic distribution, age and isotopic signature of the fithotectonic units suggest the existence of a major suture separating two different tectonic domains, juxtaposed at about 1670 Ma. From that time on, the unified Rio Apa continental block behaved as one coherent and stable tectonic unit. It correlates well with the SW corner of the Amazonian Craton, where the medium-grade rocks of the Juruena-Rio Negro tectonic province, with ages between 1600 and 1780 Ma, were reworked at about 1300 Ma. Looking at the largest scale, the Rio Apa Craton is probably attached to the larger Amazonian Craton, and the actual configuration of southwestern South America is possibly due to a complex arrangement of allochthonous blocks such as the Arequipa, Antofalla and Pampia, with different sizes, that may have originated as disrupted parts of either Laurentia or Amazonia, and were trapped during later collisions of these continental masses.

Measurement error models with a general class of error distribution

In general, the normal distribution is assumed for the surrogate of the true covariates in the classical error model. This paper considers a class of distributions, which includes the normal one, for the variables subject to error. An estimation approach yielding consistent estimators is developed and simulation studies reported.

Protein Assembly onto Cationic Supported Bilayers

Cationic supported bilayers on latex are useful to isolate and immobilize oppositely charged proteins as a monomolecular layer over a range of low protein concentrations and particle number densities. Cholera toxin (CT) from Vibrio cholerae, an 87 kDa AB(5) hexameric protein and bovine serum albumin (BSA) self-assembled on dioctadecyldimethylammonium bromide (DODAB) supported bilayers with high affinity yielding highly organized and monodisperse particulates at 5 x 10(9) particles/mL, over a range of low protein concentrations (0-0.025 mg/mL BSA or CT). Protein association onto the bilayer-covered polystyrene sulfate (PSS) was determined from adsorption isotherms, dynamic light scattering for size distributions and zeta-potential analysis revealing a monomolecular, thin and highly organized protein layer surrounding each particle with potential for biospecific recognition such as antigen-antibody, receptor-ligand, hybridization of oligonucleotide sequences, all of them important in immunodiagnosis, selective biomolecular chromatographic separations, microarrays design and others.

1,4-Diamino-2-butanone, a wide-spectrum microbicide, yields reactive species by metal-catalyzed oxidation

The alpha-aminoketone 1,4-diamino-2-butanone (DAB), a putrescine analogue, is highly toxic to various microorganisms, including Trypanosoma cruzi. However, little is known about the molecular mechanisms underlying DAB`s cytotoxic properties. We report here that DAB (pK(a) 7.5 and 9.5) undergoes aerobic oxidation in phosphate buffer, pH 7.4, at 37 degrees C, catalyzed by Fe(II) and Cu(II) ions yielding NH(4)(+) ion, H(2)O(2), and 4-amino-2-oxobutanal (oxoDAB). OxoDAB, like methylglyoxal and other alpha-oxoaldehydes, is expected to cause protein aggregation and nucleobase lesions. Propagation of DAB oxidation by superoxide radical was confirmed by the inhibitory effect of added SOD (50 U ml(-1)) and stimulatory effect of xanthine/xanthine oxidase, a source of superoxide radical. EPR spin trapping studies with 5,5-dimethyl-1-pyrroline-1-oxide (DMPO) revealed an adduct attributable to DMPO-HO(center dot), and those with alpha-(4-pyridyl-1-oxide)-N-tert-butylnitrone or 3,5-dibromo-4-nitrosobenzenesulfonic acid, a six-line adduct assignable to a DAB(center dot) resonant enoyl radical adduct. Added horse spleen ferritin (HoSF) and bovine apo-transferrin underwent oxidative changes in tryptophan residues in the presence of 1.0-10 mM DAB. Iron release from HoSF was observed as well. Assays performed with fluorescein-encapsulated liposomes of cardiolipin and phosphatidylcholine (20:80) incubated with DAB resulted in extensive lipid peroxidation and consequent vesicle permeabilization. DAB (0-10 mM) administration to cultured LLC-MK2 epithelial cells caused a decline in cell viability, which was inhibited by preaddition of either catalase (4.5 mu M) or aminoguanidine (25 mM). Our findings support the hypothesis that DAB toxicity to several pathogenic microorganisms previously described may involve not only reported inhibition of polyamine metabolism but also DAB pro-oxidant activity. (C) 2011 Elsevier Inc. All rights reserved.

Interactions between Bacteriophage DNA and Cationic Biomimetic Particles

The interaction between giant bacteriophage DNA and cationic biomimetic particles was characterized from sizing by dynamic light-scattering, zeta-potential analysis, turbidimetry, determination of colloid stability, visualization from atomic force microscopy (AFM), and determination of cytotoxicity against E. coli from colony forming unities counting. First, polystyrene sulfate (PSS) particles with different sizes were covered by a dioctadecyldimethylammonium bromide (DODAB) bilayer yielding the so-called cationic biomimetic particles (PSS/DODAB). These cationic particles are highly organized, present a narrow size distribution and were obtained over a range of particle sizes. Thereafter, upon adding lambda, T5 or T2-DNA to PSS/DODAB particles, supramolecular assemblies PSS/DODAB/DNA were obtained and characterized over a range of DNA concentrations and particle sizes (80-700 nm). Over the low DNA concentration range, PSS/DODAB/DNA assemblies were cationic, colloidally stable with moderate polydispersity and highly cytotoxic against E. coli. From DNA concentration corresponding to charge neutralization, neutral or anionic supramolecular assemblies PSS/DODAB/DNA exhibited low colloid stability, high polydispersity and moderate cytotoxicity. Some nucleosome mimetic assemblies were observed by AFM at charge neutralization (zeta-potential equal to zero).

Acetyl Radical Production by the Methylglyoxal-Peroxynitrite System: A Possible Route for L-Lysine Acetylation

Methylglyoxal is an a-oxoaldehyde putatively produced in excess from triose phosphates, aminoacetone, and acetone in some disorders, particularly in diabetes. Here, we investigate the nucleophilic addition of ONOO(-), known as a potent oxidant and nucleophile, to methylglyoxal, yielding an acetyl radical intermediate and ultimately formate and acetate ions. The rate of ONOO(-) decay in the presence of methylglyoxal [k(2,app) = (1.0 +/- 0.1) x 10(3) M(-1) s(-1); k(2) approximate to 1.0 x 10(5) M(-1) s(-1)] at pH 7.2 and 25 degrees C was found to be faster than that reported with monocarbonyl substrates (k(2) < 10(3) M(-1) diacetyl (k(2) = 1.0 x 10(4) M(-1) s(-1)), or CO(2) (k(2) = 3-6 x 10(4) M(-1) s(-1)). The pH profile of the methylglyoxal peroxynitrite reaction describes an ascendant curve with an inflection around pH 7.2, which roughly coincides with the pK(a) values of both ONOOH and H(2)PO(4)(-) ion. Electron paramagnetic resonance spin trapping experiments with 2-methyl-2-nitrosopropane revealed concentration-dependent formation of an adduct that can be attributed to 2-methyl-2-nitrosopropane-CH(3)CO(center dot) (a(N) = 0.83 mT). Spin trapping with 3,5-dibromo-4-nitrosobenzene sulfonate gave a signal that could be assigned to a methyl radical adduct [a(N) = 1.41 mT; a(H) = 1.35 mT; a(H(m)) = 0.08 mT]. The 2-methyl-2-nitrosopropane-CH(3)CO(center dot) adduct could also be observed by replacement of ONOO(-) with H(2)O(2), although at much lower yields. Acetyl radicals could be also trapped by added L-lysine as indicated by the presence of W-acetyl-L-lysine in the spent reaction mixture. This raises the hypothesis that ONOO(-)/H(2)O(2) in the presence of methylglyoxal is endowed with the potential to acetylate proteins in post-translational processes.

Detection and Characterization of Cholesterol-Oxidized Products Using HPLC Coupled to Dopant Assisted Atmospheric Pressure Photoionization Tandem Mass Spectrometry

Oxidation of cholesterol (Ch) by a variety of reactive oxygen species gives rise mainly to hydroperoxides and aldehydes. Despite the growing interest in Ch-oxidized products, the detection and characterization of these products is still a matter of concern. In this work, the main Ch-oxidized products, namely, 3 beta-hydroxycholest-5-ene-7 alpha-hydroperoxide (7 alpha-OOH), 3 beta-5 alpha-cholest-6-ene-5-hydroperoxide (5 alpha-OOH), 3 beta-hydroxycholest-4-ene-6 alpha-hydroperoxide (6 alpha-OOH), 3 beta-hydroxycholest-4-ene-6 beta-hydroperoxide (6 beta-OOH), and 3 beta-hydroxy-5 beta-hydroxy-B-norcholestane-6 beta-carboxaldehyde (ChAld), were detected in the same analysis using high-performance liquid chromatography (HPLC) coupled to dopant assisted atmospheric pressure photoionization tandem mass spectrometry. The use of selected reaction monitoring mode (SRM) allowed a sensitive detection of each oxidized product, while the enhanced product ion mode (EPI) helped to improve the confidence of the analyses. Isotopic labeling experiments enabled one to elucidate mechanistic features during fragmentation processes. The characteristic fragmentation pattern of Ch-oxidized products is the consecutive loss of 1120 molecules, yielding cationic fragments at m/z 401, 383, and 365. Homolytic scissions of the peroxide bond are also seen. With (18)O-labeling approach, it was possible to establish a fragmentation order for each isomer. The SRM transitions ratio along with EPI and (18)O-labeled experiments give detailed information about differences for water elimination, allowing a proper discrimination between the isomers:Phis is of special interest considering the emerging role of Ch-oxidized products in the development of diseases.

Facile Synthesis of Koser`s Reagent and Derivatives from Iodine or Aryl Iodides

The first one-pot synthesis of neutral and electron-rich [hydroxy(tosyloxy)iodo]arenes (HTIBs) from iodine and arenes is presented, thereby avoiding the need for expensive iodine(III) precursors. A large set of including a polyfluorinated analogue, can be obtained from the corresponding aryl iodide under the same conditions. The reaction proceeds under mild conditions, without excess reagents, and is fast and high-yielding. Together, the two presented routes give access to a wide range of HTIBs, which are useful reagents in a variety of synthetic transformations.

Kinetic resolution of a drug precursor by Burkholderia cepacia lipase immobilized by different methodologies on superparamagnetic nanoparticles

Burkholderia cepacia lipase was immobilized on superparamagnetic nanoparticles using three different methodologies (adsorption, chemisorption with carboxibenzaldehyde and chemisorption with glutaraldehyde) and employed in the kinetic resolution of a chiral drug precursor, (RS)-2-bromo-1-(phenyl)ethanol, via enantioselective acetylation reaction. An excellent improvement of lipase catalytical performance was observed. Free B. cepacia lipase gave the ester (S)-2 with poor E-value <30, and after its immobilization to magnetic nanoparticles the E-value was up to >200. The effect of several reaction parameters in the kinetic resolution was studied. The best results for kinetic resolution were obtained using vinyl acetate as acetyl donor and toluene as solvent, typically yielding the ester in high enantiomeric excess (>99%) and E-value (E > 200). Of the three tested immobilization methods, chemisorption with glutaraldehyde was the best one in terms of temperature stability and yield product. (C) 2010 Elsevier B.V. All rights reserved.