Interaction of oligonucleotide-based amphiphilic block copolymers with cell membrane models

Oligonucleotides have unique molecular recognition properties, being involved in biological mechanisms such as cell-surface receptor recognition or gene silencing. For their use in human therapy for drug or gene delivery, the cell membrane remains a barrier, but this can be obviated by grafting a hydrophobic tail to the oligonucleotide. Here we demonstrate that two oligonucleotides, one consisting of 12 guanosine units (G(12)), and the other one consisting of five adenosine and seven guanosine (A(5)G(7)) units, when functionalized with poly(butadiene), namely PB-G(12) and PB-A(5)G(7), can be inserted into Langmuir monolayers of dipalmitoyl phosphatidyl choline (DPPC), which served as a cell membrane model. PB-G(12) and PB-A(5)G(7) were found to affect the DPPC monolayer even at high surface pressures. The effects from PB-G(12) were consistently stronger, particularly in reducing the elasticity of the DPPC monolayers, which may have important biological implications. Multilayers of DPPC and nucleotide-based copolymers could be adsorbed onto solid supports, in the form of Y-type LB films, in which the molecular-level interaction led to lower energies in the vibrational spectra of the nucleotide-based copolymers. This successful deposition of solid films opens the way for devices to be produced which exploit the molecular recognition properties of the nucleotides. (C) 2010 Elsevier Inc. All rights reserved.

Silsesquioxane as a New Building Block Material for Modified Electrodes Fabrication and Application as Neurotransmitters Sensors

Nanostructured films comprising a 3-n-propylpyridiniunn silsesquioxane polymer (designated as SiPy(+)Cl(-)) and copper (II) tetrasulfophthalocyanine (CuTsPc) were produced using the Layer-by-Layer technique (LbL). To our knowledge this is the first report on the use of silsesquioxane derivative polymers as building blocks for nanostructured thin films fabrication. Deposition of the multilayers were monitored by UV-Vis spectroscopy revealing the linear increment in the absorbance of the Q-band from CuTsPc at 617 nm with the number of SiPy(+)Cl(-)/CuTsPc or CuTsPc/SiPy(+)Cl(-) bilayers. FTIR analyses showed that specific interactions between SiPy+Cl- and CuTsPc occurred between SO(3)(-) groups of tetrasulfophthalocyanine and the pyridinium groups of the polycation. Morphological studies were carried out using the AFM technique, which showed that the roughness and thickness of the films increase with the number of bilayers. The films displayed electroactivity and were employed to detection of dopamine (DA) and ascorbic acid (AA) using cyclic voltammetry, at concentrations ranging from 1.96 x 10(-4) to 1.31 x 10(-3) molL(-1). The number and the sequence of bilayers deposition influenced the electrochemical response in presence of DA and AA. Using differential pulse technique, films comprising SiPy(+)/CuTsPc were able to distinguish between DA and ascorbic acid (AA), with a potential difference of approximately with 500 mV, in the concentration range of 9.0 x 10(-5) to 2.0 x 10(-4) molL(-1), in pH 3.0.

Paleomagnetic data and K-Ar ages from Mesozoic units of the Santa Marta massif: A preliminary interpretation for block rotation and translations

We report 6 K-Ar ages and paleomagnetic data from 28 sites collected in Jurassic, Lower Cretaceous and Paleocene rocks of the Santa Marta massif, to test previous hypothesis of rotations and translations of this massif, whose rock assemblage differs from other basement-cored ranges adjacent to the Guyana margin. Three magnetic components were identified in this study. A first component has a direction parallel to the present magnetic field and was uncovered in all units (D 352, I = 25.6, k = 57.35, a95 = 5.3, N = 12). A second component was isolated in Cretaceous limestone and Jurassic volcaniclastic rocks (D = 8.8, I = 8.3, k = 24.71, a95 = 13.7, N = 6), and it was interpreted as of Early Cretaceous age. In Jurassic sites with this component, Early Cretaceous K-Ar ages obtained from this and previous studies are interpreted as reset ages. The third component was uncovered in eight sites of Jurassic volcaniclastic rocks, and its direction indicates negative shallow to moderate inclinations and northeastward declinations. K-Ar ages in these sites are of Early (196.5 +/- 4.9 Ma) to early Late Jurassic age (156.6 +/- 8.9 Ma). Due to local structural complexity and too few Cretaceous outcrops to perform a reliable unconformity test, we only used two sites with (1) K-Ar ages, (2) less structural complexity, and (3) reliable structural data for Jurassic and Cretaceous rocks. The mean direction of the Jurassic component is (D = 20.4, I = -18.2, k = 46.9, a95 = 5.1, n = 18 specimens from two sites). These paleomagnetic data support previous models of northward along-margin translations of Grenvillian-cored massifs. Additionally, clockwise vertical-axis rotation of this massif, with respect to the stable craton, is also documented; the sense of rotation is similar to that proposed for the Perija Range and other ranges of the southern Caribbean margin. More data is needed to confirm the magnitudes of rotations and translations. (C) 2009 Elsevier Ltd. All rights reserved.

Dinuclear Azide-Bridged Copper(II) Complex as Building Block for the Assembly of a 2D-Supramolecular Array

A novel Schiff base-copper(II) complex [Cu(2)L(2)(N(3))(2)](ClO(4))(2) 1, where L = (4-imidazolyl)ethylene-2-amino-1-ethylpyridine (apyhist), containing azide-bridges between adjacent copper ions in a dinuclear arrangement was isolated and characterized both in the solid state and in solution by X-ray crystallography and different spectroscopic techniques. Azide binding constants were estimated from titrations of the precursor [CuL(H(2)O)(2)](2+) solutions with sodium azide, giving rise to the azido-bridged species, [Cu(2)L(2)(N(3))(2)](2+). Raman spectra showed asymmetric stretching band at 2060 cm(-1), indicating the presence of azido ligands with a symmetric mu(1,) (1) binding geometry. EPA spectra, in frozen methanol/water solutions at 77 K, exhibited characteristic features of copper centers in tetragonal pyramidal coordination geometry, exhibiting magnetic interactions between them. Further, in solid state, two different values for magnetic coupling in this species were obtained, J/k = -(5.14 +/- 0.02) cm(-1) attributed to the mu(1, 1) azide-bridge mode, and J`z`/k = -(2.94 +/- 0.11) cm(-1) for the interaction between dinuclear moieties via water/perchorate bridges. Finally, an attempt was made to correlate structure and magnetic data for this dinuclear asymmetric end-on azido bridged-copper(II) 1 complex with those of another correlated dinuclear system, complex [Cu(2)L(2)Cl(2)](ClO(4))(2) 2, containing the same tridentate diimine ligand, but with chloro-bridged groups between the copper centres.

Block Copolymers Containing (R)-3-Hydroxybutyrate and Isosorbide Succinate or (S)-Lactic Acid Mers

A new aliphatic block copolyester was synthesized in bulk from transesterification techniques between poly((R)-3-hydroxybutyrate) (PHB) and poly(isosorbide succinate) (PIS). Additionally, other two block copolyesters were synthesized in bulk either from transesterification reactions involving PHB and poly(l-lactide) (PLLA) or from ring-opening copolymerization of l-lactide and hydroxyl-terminated PHB, as result of a previous transesterification reactions with isosorbide. Two-component blends of PHB and PIS or PLLA were also prepared as comparative systems. SEC, MALDI-TOF mass spectrometry (MALDI-TOFMS), (1)H and (13)C NMR spectroscopy, WAXD, solubility tests, and TG thermal analysis were used for characterization. The block copolymer structures of the products were evidenced by MALDI-TOFMS, (13)C NMR, and WAXD data. The block copolymers and the corresponding binary blends presented different solubility properties, as revealed by solubility tests. Although the incorporation of PIS sequences into PHB main backbone did not enhance the thermal stability of the product, it reduced its crystallinity, which could be advantageous for faster biodegradation rate. These products, composed of PHB and PIS or PLLA sequences, are an interesting alternative in biomedical applications.

Deposição da calda de pulverização em cultivares de soja no estádio R1

Com o objetivo de quantificar a quantidade e a uniformidade dos depósitos da calda de pulverização em duas cultivares de soja ('CD 208' e 'CD 216'), no estádio R1, por meio de diferentes pontas e volumes de pulverização, foram conduzidos dois experimentos na área, na Faculdade de Ciências Agronômicas UNESP- Botucatu, São Paulo (SP). Os tratamentos avaliados foram: pontas de jato plano (AI 110015 a 150L ha-1, AI 11002 a 200 e 250L ha-1); pontas de jato plano duplo (TJ 60 11002 a 150, 200 e 250L ha-1); pontas de jato cônico (TX-6 a 150, TX-8 a 200 e TX-10 a 250L ha-1) e pontas de jato plano duplo e baixa deriva (DGTJ 11002 a 200L ha-1). O delineamento utilizado foi de blocos ao acaso com quatro repetições. Para a avaliação da deposição, foi utilizado na pulverização o corante Azul Brilhante FDC- 1 (500mg L-1). Foram coletadas 25 plantas em cada repetição, divididas em região basal e apical. A determinação do conteúdo depositado foi realizada com a leitura de absorbância no comprimento de onda de 630nm, e os dados transformados em depósitos por grama de matéria seca foram ajustados às curvas de regressão, por meio do modelo de Gompertz. Os maiores depósitos avaliados nas cultivares 'CD 208' e 'CD 216' corresponderam aos tratamentos AI 11002 250L ha-1 e TJ 60 11002 250L ha-1, respectivamente. Os resultados da uniformidade da distribuição da calda de pulverização foram contraditórios aos da quantidade de depósitos. em todas as avaliações, o tratamento de maiores depósitos apresentou menor uniformidade na distribuição.

Spray deposition on weeds of common bean crops

A.C.P. Rodrigues-Costa, D. Martins, N.V. Costa, and M.R.R. Pereira. 2011. Spray deposition on weeds of common bean crops. Cien. Inv. Agr. 38(3): 357-365. Weed control failure in common bean (Phaseolus vulgaris L.) production may be related to inappropriate herbicide application techniques. The purpose of this study, therefore, was to evaluate the amount of spray solution deposition that occurred on the weeds, Bidens pilosa L. and Brachiaria plantaginea (Link) Hitch., both within and between rows of common beans. The research was arranged in a randomized block design with four replications. The following 6 spray nozzles were used: flat fan nozzles XR 110015 VS (150 L ha(-1)) and XR 11002 VS (200 L ha(-1)); cone nozzles TX VK 6 (150 L ha(-1)) and TX VK 8 (200 L ha(-1)); and twin flat fan nozzles TJ60 11002 VS (150 L ha(-1)) and TJ60 11002 VS (200 L ha-1). The results showed that the loss of the spray solution on the soil occurred mainly within the bean rows and with a high intensity when using a nozzle spraying 200 L ha(-1). At 30 days after sowing, the TX (150 L ha(-1)) nozzle was the only nozzle that promoted deposits of less than 210.0 mu L g(-1) of dry mass. The spray nozzles showed a good performance in the deposition of the spray solution on the weeds that occurred both within and between the rows. However, for both species there was great variation in individual deposits depending on their location in relationship to the plants.

Bundle Block Adjustment of CBERS-2B HRC Imagery Combining Control Points and Lines

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