Layer-by-Layer Assembly of Carbon Nanotubes Incorporated in Light-Addressable Potentiometric Sensors

The integration of carbon nanotubes in conjunction with a chemical or biological recognition element into a semiconductor field-effect device (FED) may lead to new (bio)chemical sensors. In this study, we present a new concept to develop field-effect-based sensors, using a light-addressable potentiometric sensor (LAPS) platform modified with layer-by-layer (LbL) films of single-walled carbon nanotubes (SWNTs) and polyamidoamine (PAMAM) dendrimers. Film growth was monitored for each layer adsorbed on the LAPS chip by Measuring current-voltage (IIV) curves. The morphology of the films was analyzed via atomic force microscopy (AFM) and field-emission scanning electron microscopy (FESEM), revealing the formation of a highly interconnected nanostructure of SWNTs-network into the dendrimer layers. Constant current (CC) Measurements showed that the incorporation of the PAMAM/SWNT LbL film containing LIP to 6 bilayers onto the LAPS Structure has a high pH sensitivity of ca. 58 mV/pH. The biosensing ability of the devices was tested for penicillin G via adsorptive immobilization of the enzyme penicillinase atop the LgL film. LAPS architectures modified with the LbL film exhibited higher sensitivity, ca. 100 mV/decade, in comparison to ca. 79 mV/decade for all unmodified LAPS, which demonstrates the potential application of the CNT-LbL Structure in field-effect-based (bio)chemical sensors.

Directed self-assembly of quantum structures by nanomechanical stamping using probe tips

We demonstrate that nanomechanically stamped substrates can be used as templates to pattern and direct the self-assembly of epitaxial quantum structures such as quantum dots. Diamond probe tips are used to indent or stamp the surface of GaAs( 100) to create nanoscale volumes of dislocation-mediated deformation, which alter the growth surface strain. These strained sites act to bias nucleation, hence allowing for selective growth of InAs quantum dots. Patterns of quantum dots are observed to form above the underlying nanostamped template. The strain state of the patterned structures is characterized by micro-Raman spectroscopy. The potential of using nanoprobe tips as a quantum dot nanofabrication technology are discussed.

Hierarchical Assembly of CaMoO(4) Nano-Octahedrons and Their Photoluminescence Properties

Hierarchical assemblies of CaMoO4 (CM) nano-octahedrons were obtained by microwave-assisted hydrothemial synthesis at 120 degrees C for different times. These structures were structurally, morphologically and optically characterized by X-ray diffraction, micro-Raman spectroscopy, field-emission gun scanning electron microscopy, ultraviolet-visible absorption spectroscopy and photoluminescence measurements. First-principle calculations have been carried out to understand the structural and electronic order-disorder effects as a function of the particle/region size. Supercells of different dimensions were constructed to simulate the geometric distortions along both they and z planes of the scheelite structure. Based on these experimental results and with the help of detailed structural simulations, we were able to model the nature of the order-disorder in this important class of materials and discuss the consequent implications on its physical properties, in particular, the photoluminescence properties of CM nanocrystals.

On the relationships between molecular conformations and intermolecular contacts toward crystal self-assembly of mono-, di-, tri-, and tetra-oxygenated xanthone derivatives

Oxygenated xanthones have been extensively investigated over the years, but there are few reports concerning their crystal structure. Our chemical investigations of Brazilian plants resulted in the isolation of four natural products named 1-hydroxyxanthone (I), 1-hydroxy-7-methoxyxanthone (II), 1,5-dihydroxy-3-methoxyxanthone (III), and 1,7-dihydroxy-3,8-dimethoxyxanthone (IV). The structures of these compounds were established on the basis of single crystal X-ray diffraction. The xanthone nucleus conformation is essentially planar with the substituents adopting the orientations less sterically hindered. In addition, classical intermolecular hydrogen bonds (O-H center dot center dot center dot O) present in III and IV give rise to infinite ribbons. However, the xanthone I does not present any intermolecular hydrogen bonds, meanwhile the xanthone II presents only a non-classical one (C-H center dot center dot center dot O). The crystal packing of all xanthone structures is also stabilized by pi-pi interactions. The fingerprint plots, derived from the Hirshfeld surfaces, exhibited significant features of each crystal structures.

Cambrian mafic to felsic magmatism and its connections with transcurrent shear zones of the Borborema Province (NE Brazil): Implications for the late assembly of the West Gondwana

New U-Pb (SHRIMP) and (40)Ar/(39)Ar isotopic data of igneous rocks and mylonites of the Borborema Province (NE Brazil) show that a wide range of tectonothermal events affected the province during the transition from the Precambrian to the Cambrian. Concordant zircon U-Pb data constrained the crystallization age of mafic stocks, mafic to felsic dikes and granite batholiths between 548 and 533 Ma. These bodies were emplaced in a regional strain field combining extension and dextral shearing. The ductile shear deformation overprinted an older basement fabric to develop a low- to medium metamorphic grade vertical mylonite belt that cut the province in the E-W direction. Magnetic fabrics of the Cambrian batholiths determined by anisotropy of magnetic susceptibility are consistent with syntectonic emplacement. The magmatic pulses and shear deformation would have supplied enough heat to reset the synkinematic micas of mylonites to yield (40)Ar/(39)Ar plateau cooling ages between ca. 550 and 510 Ma. These results provide evidence that emplacement of Early Cambrian mafic and felsic magmas were accompanied by regional-scale shear deformations, probably in the consequence of late collisions along the West Gondwana margin. (C) 2010 Published by Elsevier B.V.

Relics of eclogite facies assemblages in the Ceara Central Domain, NW Borborema Province, NE Brazil: Implications for the assembly of West Gondwana

The Borborema Province, in the NE of Brazil, is a rather complex piece in the Brazil-Africa puzzle as it represents the junction of the Dahomeyide/Pharusian, Central African, Aracuai and Brasilia fold belts located between the West-African/Sao Luis, Congo/Sao Francisco and Amazonas craton. The correlation between the Dahomeyides from W-Africa (Ghana, Benin, Togo, and Mali) and the Borborema Province involves the Medio Coreau and Central Ceara domains. The inferred continuation of the main oceanic suture zone exposed in the Dahomeyides of W Africa is buried beneath the Phanerozoic Parnaiba Basin in Brazil (northwest of the Medio Coreau domain) where some high density gravity anomalies may represent hidden remnants of an oceanic suture. In addition to this major suture a narrow, nearly continuous strip composed of mainly mafic pods containing relics of eclogite-facies assemblages associated with partially migmatized granulite-facies metapelitic gneisses has been found further east in the NW Borborema Province. These high pressure mafic rocks, interpreted as retrograded eclogites, are located between the Transbrasiliano Lineament and the Santa Quiteria continental arc and comprise primitive to evolved arc-related rocks with either arc- or MORB-type imprints that can indicate either deep subduction of oceanic lithosphere or roots of continental and oceanic magmatic arcs. Average peak P-T conditions under eclogite-facies metamorphism (T=770 degrees C and P = 17.3 kbar) were estimated using garnet-clinopyroxene thermometry and Jd content in clinopyroxene. Transition to granulite-facies conditions, as well as later widespread re-equilibration under amphibolite facies, were registered both in the basic and the metapelitic rocks and suggest a clockwise P-T path characterized by an increase in temperature followed by strong decompression. A phenomenon possibly related to the exhumation of a highly thickened crust associated with the suturing of the Medio Coreau and Central Ceara domains, two distinct crustal blocks separated by the Transbrasiliano Lineament. (C) 2009 International Association for Gondwana Research. Published by Elsevier B.V. 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.

A three-dimensional network constructed from the assembly of 1,3-diaminopropane-copper(II) and tetracyanopalladate(II) moieties

The coordination polymer [Cu(Pd(CN)(4))(pn)](n) (pn = 1,3-diaminopropane) has been synthesized and characterized by elemental analysis, infrared spectroscopy and single-crystal X-ray diffraction. The crystal structure showed that three cyano groups of each [Pd(CN)(4)] unit bridge Cu(II) centers leading to the formation of a three-dimensional network. A series of bifurcated hydrogen bonds between the amino groups of the diamine and the nonbridging cyano groups of the cyanometallate result in the organization of suprarnolecular chains and rings along the polymer. (c) 2008 Elsevier B.V. All rights reserved.

A three-dimensional network constructed from the assembly of 1,3-diaminopropane-copper(II) and tetracyanopalladate(II) moieties

The coordination polymer [Cu(Pd(CN)(4))(pn)](n) (pn = 1,3-diaminopropane) has been synthesized and characterized by elemental analysis, infrared spectroscopy and single-crystal X-ray diffraction. The crystal structure showed that three cyano groups of each [Pd(CN)(4)] unit bridge Cu(II) centers leading to the formation of a three-dimensional network. A series of bifurcated hydrogen bonds between the amino groups of the diamine and the nonbridging cyano groups of the cyanometallate result in the organization of suprarnolecular chains and rings along the polymer. (c) 2008 Elsevier B.V. All rights reserved.

Gastrointestinal transit and disintegration of enteric coated magnetic tablets assessed by ac biosusceptometry

The oral administration is a common route in the drug therapy and the solid pharmaceutical forms are widely used. Although much about the performance of these formulations can be learned from in vitro studies using conventional methods, evaluation in vivo is essential in product development. The knowledge of the gastrointestinal transit and how the physiological variables can interfere with the disintegration and drug absorption is a prerequisite for development of dosage forms. The aim of this work was to employing the ac biosusceptometry (ACB) to monitoring magnetic tablets in the human gastrointestinal tract and to obtain the magnetic images of the disintegration process in the colonic region. The ac biosusceptometry showed accuracy in the quantification of the gastric residence time, the intestinal transit time and the disintegration time (DT) of the magnetic formulations in the human gastrointestinal tract. Moreover, ac biosusceptometry is a non-invasive technique, radiation-free and harmless to the volunteers, as well as an important research tool in the pharmaceutical, pharmacological and physiological investigations. (c) 2005 Elsevier B.V. All rights reserved.

Relics of eclogite facies assemblages in the Ceara Central Domain, NW Borborema Province, NE Brazil: Implications for the assembly of West Gondwana

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