Capacitive electrolyte-insulator-semiconductor structures functionalised with a polyelectrolyte/enzyme multilayer: New strategy for enhanced field-effect biosensing

A novel strategy for enhanced field-effect biosensing using capacitive electrolyte-insulator-semiconductor (EIS) structures functionalised with pH-responsive weak polyelectrolyte/enzyme or dendrimer/enzyme multilayers is presented. The feasibility of the proposed approach is exemplarily demonstrated by realising a penicillin biosensor based on a capacitive p-Si-SiO(2) EIS structure functionalised with a poly(allylamine hydrochloride) (PAH)/penicillinase and a poly(amidoamine) dendrimer/penicillinase multilayer. The developed sensors response to changes in both the local pH value near the gate surface and the charge of macromolecules induced via enzymatic reaction, resulting in a higher sensitivity. For comparison, an EIS penicillin biosensor with adsorptively immobilised penicillinase has been also studied. The highest penicillin sensitivity of 100 mV/dec has been observed for the EIS sensor functionalised with the PAH/penicillinase multilayer. The lower and upper detection limit was around 20 mu M and 10 mM, respectively. In addition, an incorporation of enzymes in a multilayer prepared by layer-by-layer technique provides a larger amount of immobilised enzymes per sensor area, reduces enzyme leaching effects and thus, enhances the biosensor lifetime (the loss of penicillin sensitivity after 2 months was 10-12%). (C) 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Two-Photon Polymerization for Fabricating Structures Containing the Biopolymer Chitosan

Two-photon polymerization is a powerful tool for fabricating three-dimensional micro/nano structures for applications ranging from nanophotonics to biology. To tailor such structure for specific purposes it is often important to dope them. In this paper we report on the fabrication of structures, with nanometric surface features (resolution of approximately 700 nm), using two-photon polymerization of an acrylic resin doped with the biocompatible polymer chitosan using a guest-host scheme. The fluorescence background in the Raman spectrum indicates the presence of chitosan throughout the structure. Mechanical characterization reveals that chitosan does not affect the mechanical properties of the host acrylic resin and, consequently, the structures exhibit excellent integrity. The approach presented in this work can be used in the fabrication of micro- and nanostructures containing biopolymers for biomedical applications.

Influence of interlayer tunneling on the quantized Hall phases in intentionally disordered multilayer structures

Stability of the quantized Hall phases is studied in weakly coupled multilayers as a function of the interlayer correlations controlled by the interlayer tunneling and by the random variation of the well thicknesses. A strong enough interlayer disorder destroys the symmetry responsible for the quantization of the Hall conductivity, resulting in the breakdown of the quantum Hall effect. A clear difference between the dimensionalities of the metallic and insulating quantum Hall phases is demonstrated. The sharpness of the quantized Hall steps obtained in the coupled multilayers with different degrees of randomization was found consistent with the calculated interlayer tunneling energies. The observed width of the transition between the quantized Hall states in random multilayers is explained in terms of the local fluctuations of the electron density.

Formation of beta-nickel hydroxide plate-like structures under mild conditions and their optical properties

Nanostructural beta-nickel hydroxide (beta-Ni(OH)(2)) plates were prepared using the microwave hydrothermal (MH) method at a low temperature and short reaction times. An ammonia solution was employed as the coordinating agent, which reacts with [Ni(H(2)O)(6)](2+) to control the growth of beta-Ni(OH)(2) nuclei. A trigonal beta-Ni(OH)(2) single phase was observed by X-ray diffraction (XRD) analyses, and the crystal cell was constructed with structural parameters and atomic coordinates obtained from Rietveld refinement. Field emission scanning electron microscopy (FE-SEM) images revealed that the samples consisted of hexagonal-shaped nanoplates with a different particle size distribution. Broad absorption bands assigned as transitions of Ni(2+) in oxygen octahedral sites were revealed by UV-vis spectra. Photoluminescence (PL) properties observed with a maximum peak centered in the blue-green region were attributed to different defects, which were produced during the nucleation process. We present a growth process scheme of the beta-Ni(OH)(2) nanoplates. (C) 2011 Elsevier Inc. All rights reserved.

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.

Epidemics in networks of spatially correlated three-dimensional root-branching structures

Using digitized images of the three-dimensional, branching structures for root systems of bean seedlings, together with analytical and numerical methods that map a common susceptible-infected- recovered (`SIR`) epidemiological model onto the bond percolation problem, we show how the spatially correlated branching structures of plant roots affect transmission efficiencies, and hence the invasion criterion, for a soil-borne pathogen as it spreads through ensembles of morphologically complex hosts. We conclude that the inherent heterogeneities in transmissibilities arising from correlations in the degrees of overlap between neighbouring plants render a population of root systems less susceptible to epidemic invasion than a corresponding homogeneous system. Several components of morphological complexity are analysed that contribute to disorder and heterogeneities in the transmissibility of infection. Anisotropy in root shape is shown to increase resilience to epidemic invasion, while increasing the degree of branching enhances the spread of epidemics in the population of roots. Some extension of the methods for other epidemiological systems are discussed.

Selective excitation through tapered silica fibers of fluorescent two-photon polymerized structures

Two-photon polymerization has emerged as a powerful tool to design complex three-dimensional microstructures for applications ranging from biology to nanophotonics. To broaden the application spectrum of such microstructures, different materials have been incorporated to the polymers, aiming at specific applications. In this paper we report the fabrication of microstructures containing rhodamine 610, which display strong fluorescence upon one- and two-photon excitation. The latter increases light-penetration depth and spatial selectivity of luminescence. We also demonstrate that by using silica submicrometric wires we were able to select individual microstructures to be excited, which could be explored for designing microstructure-based optical circuits.

From Rational Design of Drug Crystals to Understanding of Nucleic Acid Structures: Lamivudine Duplex

A DNA-like duplex of nucleosides is probable to exist even without the 5`-phosphate groups needed to assemble the chain backbone. However, double-stranded helical structures of nucleosides are unknown. Here, we report a duplex of nucleoside analogs that is spontaneously assembled due to stacking of the neutral and protonated molecules of lamivudine, a nucleoside reverse transcriptase inhibitor (NTRI) widely used in anti-HIV drug combinatory medication. The left-handed lamivudine duplex has features similar to those of i-motif DNA, as the face-to-face base stacking and the helix rise per base pair. Furthermore, the protonation pattern on alternate bases expected for it DNA-like duplex stabilized by pairing of neutral and protonated cytosine fragments was observed for the first time in the lamivudine double-stranded helix. This structure demonstrates that hydrogen bonds can substitute for covalent phosphodiester linkage in the stabilization of the duplex backbone. This interesting example of spontaneous molecular self-organization indicates that the 5`-phosphate group could not be a requirement for duplex assembly.

Collapse of rho (xx) Ringlike Structures in 2DEGs Under Tilted Magnetic Fields

In the quantum Hall regime, the longitudinal resistivity rho (xx) plotted as a density-magnetic-field (n (2D) -B) diagram displays ringlike structures due to the crossings of two sets of spin split Landau levels from different subbands [see, e.g., Zhang et al., in Phys. Rev. Lett. 95:216801, 2005. For tilted magnetic fields, some of these ringlike structures ""shrink"" as the tilt angle is increased and fully collapse at theta (c) a parts per thousand 6A degrees. Here we theoretically investigate the topology of these structures via a non-interacting model for the 2DEG. We account for the inter Landau-level coupling induced by the tilted magnetic field via perturbation theory. This coupling results in anticrossings of Landau levels with parallel spins. With the new energy spectrum, we calculate the corresponding n (2D) -B diagram of the density of states (DOS) near the Fermi level. We argue that the DOS displays the same topology as rho (xx) in the n (2D) -B diagram. For the ring with filling factor nu=4, we find that the anticrossings make it shrink for increasing tilt angles and collapse at a large enough angle. Using effective parameters to fit the theta=0A degrees data, we find a collapsing angle theta (c) a parts per thousand 3.6A degrees. Despite this factor-of-two discrepancy with the experimental data, our model captures the essential mechanism underlying the ring collapse.

Synthesis and Crystal Structures of Octahedral Sn(IV) Complexes Prepared from SnCl(2)center dot 2H(2)O and 2-Hydroxyacetophenone (S-benzydithiocarbazate) Ligand (H(2)L)

Two coordination octahedral Sn(IV) complexes [Sn(L)(2)] and cis-[SnCl(2)(L)(dmso)], where H(2)L is 2-hydroxyacetophenone (S-benzydithiocarbazate), were prepared and characterized by elemental analysis, IR, NMR ((1)H, (13)C), (119)Sn Mossbauer spectroscopies and X-ray diffraction techniques to investigate their structural properties. Both crystallize in the Monoclinic system, with parameters: a = 8.1905(3), b = 30.8811(15), c = 12.8959(7) angstrom, beta = 94.465(3)degrees and Z = 4 for [Sn(L)(2)] and a = 8.5247(2), b = 21.5445(7), c = 12.3706(3) angstrom, beta = 96.932(2)degrees and Z = 4 for cis-[SnCl(2)(L)(dmso)]. In both complexes, the Sn(IV) central atom is coordinated in a distorted octahedral geometry with the thiolate ligand (L(2-)) coordinated via O, N and S atoms. The (119)Sn Mossbauer spectroscopy of the complexes were studied and the results revealed that both complexes posses isomer shift (delta) and quadrupole splitting (Delta), which are almost the same.

Vanadium complexes with thiosemicarbazones: Synthesis, characterization, crystal structures and anti-Mycobacterium tuberculosis activity

The development of more efficient anti-tuberculosis drugs is of interest. Three oxovanadium(IV) and three cis-dioxovanadium(V) complexes with thiosemicarbazone derivatives bearing moieties with different lipophilicity have been prepared and had their inhibitory activity against Mycobacterium tuberculosis H(37)Rv ATCC 27294 evaluated. The analytical methods used by the complexes` characterization included IR, EPR, (1)H, (13)C and (51)V NMR spectroscopies, elemental analysis, cyclic voltammetry, magnetic susceptibility measurement and single crystal X-ray diffractometry. [VO(acac)(aptsc)], [VO(acac)(apmtsc)] and [VO(acac)(apptsc)] (acac = acetylacetonate; Haptsc = 2-acetylpyridinethiosemicarbazone; Hapmtsc = 2-acetylpyridine-N(4)-methyl-thiosemicarbazone and Happtsc = 2-acetylpyridine-N(4)-phenyl-thiosemicarbazone) are paramagnetic and their EPR spectra are consistent with the monoanionic N,N,S-tridentate coordination of the thiosemicarbazone ligands, resulting in octahedral structures of rhombic symmetry and with the oxidation state +IV for the vanadium atom. As result of oxidation of the vanadium(IV) complexes above, the diamagnetic cis-dioxovanadium(V) complexes [VO(2)(aptsc)[, [VO(2)(apmtsc)[ and [VO(2)(apptsc)] are formed. Their (1)H, (13)C and (51)V NMR spectra were acquired and support a distorted square pyramidal geometry for them, in accord with the solid state X-ray structures determined for [VO(2)(aptsc)] and [VO(2)(apmtsc)]. In general, the vanadium compounds show comparable or larger anti-M. tuberculosis activities than the free thiosemicarbazone ligands, with MIC values within 62.5-1.56 (mu g/mL). (C) 2008 Elsevier Ltd. All rights reserved.

Crystal structures and thermal behavior of alkaline earth tricyanomethanides

The alkaline earth tricyanomethanides Mg(tcm)(2) center dot 2H(2)O, Ca(tcm)(2), Sr(tcm)(2) - H2O and Ba(tcm)(2) center dot 2H(2)O were prepared from aqueous solutions of the respective chlorides and silver tricyanomethanide. Their IR spectra and thermal behavior are described. The crystal structures of Ca(tcm)(2) and Ba(tcm)(2) center dot 2H(2)O were determined by single crystal X-ray diffraction. The structure of Ca(tcm)(2) is of the type found for several transition metal tricyanomethanides [1], containing two independent interpenetrating networks. Ba(tcm)(2) center dot 2H(2)O has a unique crystal structure corresponding to a three-dimensional coordination polymer with nine fold coordinated Ba atoms connected by water molecules and tricyanomethanide anions.

NMR study of slow motions of HDA hydrocarbons chains inside lamellar structures

Measurements of H-1 and C-13 Nuclear Magnetic Resonance (NMR) for the nano-composite materials formed by the intercalation of hexadecylamine (HDA) in metal oxides (TiO2, V2O5 and MoO3), are reported. The H-1 NMR spin-lattice relaxation in the rotating frame was described by using the spectral density due to Davidson and Cole, which incorporates a distribution of correlation times characterized by a width parameter epsilon. The fitting of the data was obtained for epsilon = 0.74, indicating that the correlation times are distributed over a narrow range in this system. High-resolution C-13 NMR techniques were used to resolve the NMR lines of middle-chain methylene groups in the spectra and variable contact time cross-polarization {H-1-}C-13 experiments were employed to analyze the reorientation dynamics of the CH3 and CH2 groups in the HDA chains.

On the synthesis and structures of the complexes [RuCl(L)(dppb)(N-N)]PF(6) (L = CO, py or 4-NH(2)py; dppb=1,4-bis(diphenylphosphino)butane; N-N=2,2 `-bipyridine or 1,10-phenanthroline) and [(dppb)(CO)Cl(2)-Ru-pz-RuCl(2)(CO)(dppb)] (pz = pyrazine)

The ""Ru(P-P)"" unit (P-P = diphosphine) is recognized to be an important core in catalytic species for hydrogenation of unsaturated organic substrates. Thus, in this study we synthesized six new complexes containing this core, including the binuclear complex [(dppb)(CO)Cl(2)Ru-pz-RuCl(2)(CO)(dPPb)] (pz = pyrazine) which can be used as a precursor for the synthesis of cationic carbonyl species of general formula [RuCl(CO)(dppb)(N-N)]PF(6) (N-N = diimine). Complexes with the formula (RuCl(py)(dppb)(N-N)]PF(6) were synthesized by exhaustive electrolysis of these carbonyl compounds or from the precursors [RuCl(2)(dppb)(N-N)]. The new complexes were characterized by microanalysis, conductivity measurements, IR and (31)P{(1)H)} NMR spectroscopy, cyclic voltammetry and X-ray crystallography. (C) 2010 Elsevier Ltd. All rights reserved.

Structural requirement for PPAR gamma binding revealed by a meta analysis of holo-crystal structures

PPAR gamma is a ligand regulated transcriptional factor that modulates the transcription of several genes involved in fat and sugar metabolism. Due to its easy bacterial expression and crystallization, several crystal structures of holo-PPAR gamma have been reported and deposited in the Protein Data Bank. Here, we investigated the three-dimensional electrostatic properties of 55 PPAR gamma ligands and used this information for clustering them through principal component analysis. We found out that, according to their electrostatic potential, these ligands can be separated in three groups, with different binding features. We also observed that non-selective and selective ligands show different 3D electrostatic properties and are separated in different clusters. The relevance of this analysis for the development of new binders is discussed. (C) 2010 Elsevier Masson SAS. All rights reserved.