Theoretical studies of the exohedral reactivity of fullerene compounds

Des del descobriment del buckminster ful.lerè el 1985, s'ha despertat un interés enorme per entendre la reactivitat química així com les propietats d'aquests compostos. La funcionalització exoèdrica del ful.lerè més abundant, el C60, està força ben establerta. Tanmateix, la investigació en aquest camp encara continua oberta ja que s'han sintetitzat una gran varietat de derivats molt prometedors donades les seves futures aplicacions. La tesi comprèn quinze capítols que contenen set publicacions relacionades. Els primers dos estudis es basen en la reacció Diels-Alder sobre els anomenats metal.loful.lerens endoèdrics TNT X3N@C78, X= Sc, Y. Aquest projecte de investigació està motivat pel desconeixament existent sobre les possibles conseqüències de l'encapsulació del grup X3N. El tercer estudi descriu minuciosament els canvis detectats en la funcionalització exoèdrica un cop s'ha produït l'encapsulació dels diferents gasos nobles. En aquesta tesi s'estudia en detall l'ús de l'aproximació ONIOM per a estudiar reaccions de cicloaddició en compostos ful.lerènics. Els resultats d'aquest projecte són d'alt interès per a la realització dels estudis posteriors sobre la reacció de Diels-Alder i la 1,3-dipolar en ful.lerens i derivats. Finalment, l'última part d'aquesta tesi es basa en les propietats antioxidants de determinats ful.lerens. A l'últim treball inclòs en aquesta tesi s'estudia en detall el mecanismo de reacció per a la eliminació del ió superòxid en presència de ful.lerens.

Plasmodiophora brassicae in its Environment

Plasmodiophora brassicae Wor. is viewed in this article from the standpoint of a highly evolved and successful organism, well fitted for the ecological niche that it occupies. Physical, chemical, and biological components of the soil environment are discussed in relation to their effects on the survival, growth, and reproduction of this microbe. It is evident that P. brassicae is well equipped by virtue of its robust resting spores for survival through many seasonal cycles. Germination is probably triggered as a result of signals initiated by root exudates. The resultant motile zoospore moves rapidly to the root hair surface and penetration and colonization follow. The short period between germination and penetration is one of greatest vulnerability for P. brassicae. In this phase survival is affected at the very least by soil texture and structure; its moisture; pH; calcium, boron, and nitrogen content; and the presence of active microbial antagonists. These factors influence the inoculum potential (sensu Garrett, 1956) and its viability and invasive capacity. There is evidence that these effects may also influence differentially the survival of some physiologic races of P. brassicae. Considering the interaction of P. brassicae with the soil environment from the perspective of its biological fitness is an unusual approach; most authors consider only the opportunities to destroy this organism. The approach adopted here is borne of several decades spent studying P. brassicae and the respect that has been engendered for it as a biological entity. This review stops at the point of penetration, although some of the implications of the environment for successful colonization are included because they form a continuum. Interactions with the molecular and biochemical cellular environment are considered in other sections in this special edition.

Extended-chain, multinuclear transition metal complexes bridged by cyanodiazenido(1-), [N=N-C=N](-), ligands

Extended-chain complexes containing multiple transition metal centres linked by conjugated mu-cyanodiazenido(1-) ligands [N= N-C N]-have been obtained by reaction of trans-[BrW(dppe)(2)(N2CN)], 1, [dppe = 1,2-bis(diphenylphosphino) ethane] with dirhodium(II) tetra-acetate, bis(benzonitrile) palladium(II) dichloride, and bis(aqua) M(II) bis(hexa. uoroacetylacetonate) (M = Mn, Ni, Cu, Zn): stronger Lewis acids such as tetrakis(acetonitrile) palladium(II) tetra. uoroborate and boron trifl. uoride promote hydrolysis of complex 1, leading to the isolation of a novel carbamoylhydrazido(2-) complex, trans-[BrW(dppe) 2(N2HC=ONH2)](+)[BF4](-).

Seal Formation in Silicon Planar Patch-Clamp Microstructures

This paper presents a microfabricated planar patch-clamp electrode design and looks at the impact of several physical characteristics on seal formation. The device consists of a patch aperture, 1.5-2.5 mum in diameter and 7-12 mum in depth, with a reverse-side deep-etched 80-mum well. The patch aperture was coated with either thermal oxide or plasma-enhanced chemical vapor deposited (PECVD) SiO2. Some of the thermal oxide devices were converted into protruding nozzle structures, and some were boron-doped. Seal formation was tested with cultured N2a neuroblastoma cells. The PECVD oxide devices produced an average seal resistance of 34 MOmega(n = 24), and the thermal oxide devices produced an average seal resistance of 96 MOmega(n = 59). Seal resistance was found to positively correlate with patch aperture depth. Whole-cell recordings were obtained from 14% of cells tested with the thermal oxide devices, including a single recording where a gigaohm seal was obtained.

Tuning chelation by the surfactant-like peptide A6H using predetermined pH values

We examine the self-assembly of a peptide A6H comprising a hexa-alanine sequence A6 with a histidine (H) “head group”, which chelates Zn2+ cations. We study the self assembly of A6H and binding of Zn2+ ions in ZnCl2 solutions, under acidic and neutral conditions. A6H self-assembles into nanotapes held together by a β-sheet structure in acidic aqueous solutions. By dissolving A6H in acidic ZnCl2 solutions, the carbonyl oxygen atoms in A6H chelate the Zn2+ ions and allow for β-sheet formation at lower concentrations, consequently reducing the onset concentration for nanotape formation. A6H mixed with water or ZnCl2 solutions under neutral conditions produces short sheets or pseudocrystalline tapes, respectively. The imidazole ring of A6H chelates Zn2+ ions in neutral solutions. The internal structure of nanosheets and pseudocrystalline sheets in neutral solutions is similar to the internal structure of A6H nanotapes in acidic solutions. Our results show that it is possible to induce dramatic changes in the self-assembly and chelation sites of A6H by changing the pH of the solution. However, it is likely that the amphiphilic nature of A6H determines the internal structure of the self-assembled aggregates independent from changes in chelation.

Shape-controlled continuous synthesis of metal nanostructures

A segmented flow-based microreactor is used for the continuous production of faceted nanocrystals. Flow segmentation is proposed as a versatile tool to manipulate the reduction kinetics and control the growth of faceted nanostructures; tuning the size and shape. Switching the gas from oxygen to carbon monoxide permits the adjustment in nanostructure growth from 1D (nanorods) to 2D (nanosheets). CO is a key factor in the formation of Pd nanosheets and Pt nanocubes; operating as a second phase, a reductant, and a capping agent. This combination confines the growth to specific structures. In addition, the segmented flow microfluidic reactor inherently has the ability to operate in a reproducible manner at elevated temperatures and pressures whilst confining potentially toxic reactants, such as CO, in nanoliter slugs. This continuous system successfully synthesised Pd nanorods with an aspect ratio of 6; thin palladium nanosheets with a thickness of 1.5 nm; and Pt nanocubes with a 5.6 nm edge length, all in a synthesis time as low as 150 s.

A carbon isotope challenge to the snowball Earth

The snowball Earth hypothesis postulates that the planet was entirely covered by ice for millions of years in the Neoproterozoic era, in a self-enhanced glaciation caused by the high albedo of the ice-covered planet. In a hard-snowball picture, the subsequent rapid unfreezing resulted from an ultra-greenhouse event attributed to the buildup of volcanic carbon dioxide (CO(2)) during glaciation(1). High partial pressures of atmospheric CO(2) (p(CO2); from 20,000 to 90,000 p. p. m. v.) in the aftermath of the Marinoan glaciation (similar to 635 Myr ago) have been inferred from both boron and triple oxygen isotopes(2,3). These p(CO2) values are 50 to 225 times higher than present-day levels. Here, we re-evaluate these estimates using paired carbon isotopic data for carbonate layers that cap Neoproterozoic glacial deposits and are considered to record post-glacial sea level rise(1). The new data reported here for Brazilian cap carbonates, together with previous ones for time-equivalent units(4-8), provide p(CO2) estimates lower than 3,200 p. p. m. v.-and possibly as low as the current value of similar to 400 p. p. m. v. Our new constraint, and our reinterpretation of the boron and triple oxygen isotope data, provide a completely different picture of the late Neoproterozoic environment, with low atmospheric concentrations of carbon dioxide and oxygen that are inconsistent with a hard-snowball Earth.

Cloning and characterization of a zebrafish homologue of human AQP1: a bifunctional water and gas channel

Chen LM, Zhao J, Musa-Aziz R, Pelletier MF, Drummond IA, Boron WF. Cloning and characterization of a zebrafish homologue of human AQP1: a bifunctional water and gas channel. Am J Physiol Regul Integr Comp Physiol 299: R1163-R1174, 2010. First published August 25, 2010; doi:10.1152/ajpregu.00319.2010.-The mammalian aquaporins AQP1, AQP4, and AQP5 have been shown to function not only as water channels but also as gas channels. Zebrafish have two genes encoding an AQP1 homologue, aqp1a and aqp1b. In the present study, we cloned the cDNA that encodes the zebrafish protein Aqp1a from the 72-h postfertilization (hpf) embryo of Danio rerio, as well as from the swim bladder of the adult. The deduced amino-acid sequence of aqp1a consists of 260 amino acids and is 59% identical to human AQP1. By analyzing the genomic DNA sequence, we identified four exons in the aqp1a gene. By in situ hybridization, aqp1a is expressed transiently in the developing vasculature and in erythrocytes from 16 to 48 h of development. Later, at 72 hpf, aqp1a is expressed in dermal ionocytes and in the swim bladder. Western blot analysis of adult tissues reveals that Aqp1a is most highly expressed in the eye and swim bladder. Xenopus oocytes expressing aqp1a have a channel-dependent (*) osmotic water permeability (P(f)*) that is indistinguishable from that of human AQP1. On the basis of the magnitude of the transient change in surface pH (Delta pHS) that were recorded as the oocytes were exposed to either CO(2) or NH(3), we conclude that zebrafish Aqp1a is permeable to both CO(2) and NH(3). The ratio (Delta pHS*)CO2/P(f)* is about half that of human AQP1, and the ratio (Delta pHS*)NH3/P(f)* is about one-quarter that of human AQP1. Thus, compared with human AQP1, zebrafish Aqp1a has about twice the selectivity for CO(2) over NH(3).

Influence of macro- and micronutrient fertilization on fungal contamination and fumonisin production in corn grains

The aim of this study was to investigate the effects of nutrients (nitrogen, zinc and boron) on fungal growth and fumonisins production in corn samples obtained at the beginning of grain formation and at harvest. Three nitrogen doses were applied to the corn plants through soil in combination with three zinc doses and two boron doses during sowing. Mycological analysis of grains, using Dichloran Rose-Bengal Chloramphenicol Agar, collected at the beginning of formation demonstrated a fungal population predominantly of yeasts. Analysis of freshly harvested corn revealed a higher frequency of Penicillium spp. (72%) and F verticillioides (27%). High Performance Liquid Chromatography analysis revealed that 100% of grains were contaminated with fumonisins B, at levels ranging from 0.3 to 24.3 mg/kg and 93% contaminated with fumonisin B(2) at levels ranging from 0.05 to 5.42 mg/kg. Nitrogen (50 kg/ha) in combination with boron (0.5 kg/ha) resulted in an increased fumonisin B2 production. (c) 2007 Elsevier Ltd. All rights reserved.

Realistic calculations of carbon-based disordered systems

Carbon nanotubes rank amongst potential candidates for a new family of nanoscopic devices, in particular for sensing applications. At the same time that defects in carbon nanotubes act as binding sites for foreign species, our current level of control over the fabrication process does not allow one to specifically choose where these binding sites will actually be positioned. In this work we present a theoretical framework for accurately calculating the electronic and transport properties of long disordered carbon nanotubes containing a large number of binding sites randomly distributed along a sample. This method combines the accuracy and functionality of ab initio density functional theory to determine the electronic structure with a recursive Green`s functions method. We apply this methodology on the problem of nitrogen-rich carbon nanotubes, first considering different types of defects and then demonstrating how our simulations can help in the field of sensor design by allowing one to compute the transport properties of realistic nanotube devices containing a large number of randomly distributed binding sites.

Disorder-based graphene spintronics

The use of the spin of the electron as the ultimate logic bit-in what has been dubbed spintronics-can lead to a novel way of thinking about information flow. At the same time single-layer graphene has been the subject of intense research due to its potential application in nanoscale electronics. While defects can significantly alter the electronic properties of nanoscopic systems, the lack of control can lead to seemingly deleterious effects arising from the random arrangement of such impurities. Here we demonstrate, using ab initio density functional theory and non-equilibrium Green`s functions calculations, that it is possible to obtain perfect spin selectivity in doped graphene nanoribbons to produce a perfect spin filter. We show that initially unpolarized electrons entering the system give rise to 100% polarization of the current due to random disorder. This effect is explained in terms of different localization lengths for each spin channel which leads to a new mechanism for the spin filtering effect that is disorder-driven.

Crystal engineering using functionalized adamantane

We performed a first-principles investigation on the structural, electronic and optical properties of crystals made of chemically functionalized adamantane molecules. Several molecular building blocks, formed by boron and nitrogen substitutional functionalizations, were considered to build zinc blende and wurtzite crystals, and the resulting structures presented large bulk moduli and cohesive energies, wide and direct bandgaps, and low dielectric constants (low-kappa materials). Those properties provide stability for such structures up to room temperature, superior to those of typical molecular crystals. This indicates a possible road map for crystal engineering using functionalized diamondoids, with potential applications ranging from space filling between conducting wires in nanodevices to nano-electromechanical systems.

Synthesis, Characterization, Luminescence and Defect Centres in CaYAl(3)O(7):Eu(3+) Red Phosphor

CaYAl(3)O(7):Eu(3+) phosphor was prepared at furnace temperatures as low as 550A degrees C by a solution combustion method. The formation of crystalline CaYAl(3)O(7):Eu(3+) was confirmed by powder X-Ray diffraction pattern. The prepared phosphor was characterized by SEM, FT-IR and photoluminescence techniques. Photoluminescence measurements indicated that emission spectrum is dominated by the red peak located at 618 nm due to the (5)D(0)-(7)F(2) electric dipole transition of Eu(3+) ions. Electron Spin Resonance (ESR) studies were carried out to identify the centres responsible for the thermoluminescence (TL) peaks. Room temperature ESR spectrum of irradiated phosphor appears to be a superposition of two distinct centres. One of the centres (centre I) with principal g-value 2.0126 is identified as an O(-) ion while centre II with an isotropic g-factor 2.0060 is assigned to an F(+) centre (singly ionized oxygen vacancy). An additional defect centre is observed during thermal annealing experiments and this centre (assigned to F(+) centre) seems to originate from an F centre (oxygen vacancy with two electrons). The F(+) centre appears to correlate with the observed high temperature TL peak in CaYAl(3)O(7):Eu(3+) phosphor.

Indirect study of (11)B(p,alpha(0))(8)Be and (10)B(p,alpha)(7)Be reactions at astrophysical energies by means of the Trojan Horse Method: recent results

Nuclear (p,alpha) reactions destroying the so-called ""light-elements"" lithium, beryllium and boron have been largely studied in the past mainly because their role in understanding some astrophysical phenomena, i.e. mixing-phenomena occurring in young F-G stars [1]. Such mechanisms transport the surface material down to the region close to the nuclear destruction zone, where typical temperatures of the order of similar to 10(6) K are reached. The corresponding Gamow energy E(0)=1.22 (Z(x)(2)Z(X)(2)T(6)(2))(1/3) [2] is about similar to 10 keV if one considers the ""boron-case"" and replaces in the previous formula Z(x) = 1, Z(X) = 5 and T(6) = 5. Direct measurements of the two (11)B(p,alpha(0))(8)Be and (10)B(p,alpha)(7)Be reactions in correspondence of this energy region are difficult to perform mainly because the combined effects of Coulomb barrier penetrability and electron screening [3]. The indirect method of the Trojan Horse (THM) [4-6] allows one to extract the two-body reaction cross section of interest for astrophysics without the extrapolation-procedures. Due to the THM formalism, the extracted indirect data have to be normalized to the available direct ones at higher energies thus implying that the method is a complementary tool in solving some still open questions for both nuclear and astrophysical issues [7-12].

On the Nucleophilicity of Boryllithium Compounds. A Theoretical Study

Boron compounds are widely used in synthetic chemistry. The synthesis of the compounds is relatively easy, presenting thermodynamic stability and synthetic versatility. Almost all of them show electrophilic reactivity. Recently, some boryllithium species have been reported as a base or a nucleophile in reaction with organic electrophiles in S(N)2 reactions. In the present work, the proton affinity (PA) of boryllithium compounds was calculated. These values can be useful as theoretical reference values and to provide valuable complementary information for the interpretation and discussion of the basicity of these compounds. The proton affinity was calculated using a theoretical method based on density functional theory and high-level theoretical methods through MP2 and G2MP2 levels of theory. In addition, some global and local reactivity indexes based on density functional theory (DFT) on boryllithium compounds were studied. In order to compare and discuss the chemical reactivity of these compounds, some analogues and electrophilic boron compounds were also studied. Our results showed a local and global nucleophilic reactivity of the boryllithium molecules in agreement with the experimental. reactivity. The boryllithium compounds revealed to be strong bases in comparison to other analogue compounds studied in this work.