Chemoenzymatic approaches to obtain chiral-centered selenium compounds

The synthesis of chiral-centered selenium compounds is presented. Enantioselective oxidations of these organoselenium compounds were performed using a wide range of biocatalysts, including Baeyer-Villiger monooxygenases, oxidoreductases-containing Aspergillus terreus and lipase (Cal-B) in the presence of oxidants. Finally, efficient synthesis of enantiopure organoselenium compounds using a kinetic resolution approach mediated by Cal-B was achieved. (C) 2012 Elsevier Ltd. All rights reserved.

A comparative study of the electrochemical oxidation of the herbicide tebuthiuron using boron-doped diamond electrode

The thiadiazolylurea derivative tebuthiuron (TBH) is commonly used as an herbicide even though it is highly toxic to humans. While various processes have been proposed for the removal of organic contaminants of this type from wastewater, electrochemical degradation has shown particular promise. The aim of the present study was to investigate the electrochemical degradation of TBH using anodes comprising boron-doped (5000 and 30000 ppm) diamond (BDD) films deposited onto Ti substrates operated at current densities in the range 10-200 mA cm(-2). Both anodes removed TBH following a similar pseudo first-order reaction kinetics with k(ap)p close to 3.2 x 10(-2) min(-1). The maximum mineralization efficiency obtained was 80%. High-pressure liquid chromatography with UV-VIS detection established that both anodes degraded TBH via similar intermediates. Ion chromatography revealed that increasing concentrations of nitrate ions (up to 0.9 ppm) were formed with increasing current density, while the formation of nitrite ions was observed with both anodes at current densities >= 150 mA cm(-2). The BDD film prepared at the lower doping level (5000 ppm) was more efficient in degrading TBH than its more highly doped counterpart. This unexpected finding may be explained in terms of the quantity of impurities incorporated into the diamond lattice during chemical vapor deposition. (C) 2012 Elsevier Ltd. All rights reserved.

Magnetic Tuning of All-Organic Binary Alloys between Two Stable Radicals

Mixtures of 2-(4,5,6,7-tetrafluorobenzimidazol-2-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (F4BImNN) and 2-(benzi-midazol-2-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (BImNN.) crystallize as solid solutions (alloys) across a wide range of binary compositions. (F4BImNN)(x)(BImNN)((1-x)) with x < 0.8 gives orthorhombic unit cells, while x >= 0.9 gives monoclinic unit cells. In all crystalline samples, the dominant intermolecular packing is controlled by one-dimensional (1D) hydrogen-bonded chains that lead to quasi-1D ferromagnetic behavior. Magnetic analysis over 0.4-300 K indicates ordering with strong 1D ferromagnetic exchange along the chains (J/k = 12-22 K). Interchain exchange is estimated to be 33- to 150-fold weaker, based on antiferromagnetic ordered phase formation below Neel temperatures in the 0.4-1.2 K range for the various compositions. The ordering temperatures of the orthorhombic samples increase linearly as (1 - x) increases from 0.25 to 1.00. The variation is attributed to increased interchain distance corresponding to decreased interchain exchange, when more F4BImNN is added into the orthorhombic lattice. The monoclinic samples are not part of the same trend, due to the different interchain arrangement associated with the phase change.

Boron uptake in normal melanocytes and melanoma cells and boron biodistribution study in mice bearing B16F10 melanoma for boron neutron capture therapy

Information on B-10 distribution in normal tissues is crucial to any further development of boron neutron capture therapy (BNCT). The goal of this study was to investigate the in vitro and in vivo boron biodistribution in B16F10 murine melanoma and normal tissues as a model for human melanoma treatment by a simple and rapid colorimetric method, which was validated by HR-ICP-MS. The B16F10 melanoma cell line showed higher melanin content than human melanocytes, demonstrating a greater potential for boronophenylalanine uptake. The melanocytes showed a moderate viability decrease in the first few minutes after BNCT application, stabilizing after 75 min, whereas the B16F10 melanoma showed the greatest intracellular boron concentration at 150 min after application, indicating a different boron uptake of melanoma cells compared to normal melanocytes. Moreover, at this time, the increase in boron uptake in melanoma cells was approximately 1.6 times higher than that in normal melanocytes. The B-10 concentration in the blood of mice bearing B16F10 melanoma increased until 90 min after BNCT application and then decreased after 120 min, and remained low until the 240th minute. On the other hand, the B-10 concentration in tumors was increased from 90 min and maximal at 150 min after application, thus confirming the in vitro results. Therefore, the present in vitro and in vivo study of B-10 uptake in normal and tumor cells revealed important data that could enable BNCT to be possibly used as a treatment for melanoma, a chemoresistant cancer associated with high mortality.

OPTIMUM RATIO OF CALCIUM AND BORON IN THE NUTRIENT SOLUTION OR IN CASTOR BEAN SHOOT FOR FRUIT YIELD AND SEED OIL CONTENT

Calcium (Ca) and boron (B) have been reported as the major macro-and micronutrient required for castor bean plant yield. The objective of this study was to determine the Ca: B ratios (in the growth media and plant tissue) for fruit yield and shoot dry weight of the castor bean (Ricinus communis L.), grown in a nutrient solution, and to evaluate Ca and B supply on concentration and total uptake of Ca, potassium (K), magnesium (Mg), and B, as well on the seed oil content. The treatments were arranged in a 3 x 3 factorial fashion, consisting of three rates of Ca (40, 80, and 160 mg L-1) and three of B (0.32, 0.96, and 1.60 mg L-1). Calcium and B rates increased the shoot and root dry weight and fruit yield at a Ca: B ratio in the nutrient solution of 166 and 100, respectively. Symptoms of B deficiency were observed in plants supplied with 0.32 mg B L-1, regardless of the Ca concentration in the nutrient solution. Plants which showed visual symptoms of Ca deficiency cultivated with 40 mg Ca L-1 presented concentration of Ca in plant tissue up to 10 g kg(-1). The concentration and total Ca and B uptake increased with the rates of them. Notwithstanding, the shoot Ca accumulation was improved by B rates. In addition, there were no decreases in K and Mg uptake due to Ca rates. Furthermore, addition of 80 mg L-1 of Ca and 1.60 mg L-1 of B in the growth media increased the seed oil content. The Ca: B ratio in the diagnostic leaf associated with the highest plant dry weight (shoot and root) and fruit yield, was 500 (16 to 20 g kg(-1) of Ca, and for 30 to 40 mg kg(-1) of B).

Exploiting the enantioselectivity of Baeyer-Villiger monooxygenases via boron oxidation

The enantioselective carbon-boron bond oxidation of several chiral boron-containing compounds by Baeyer-Villiger monooxygenases was evaluated. PAMO and M446G PAMO conveniently oxidized 1-phenylethyl boronate into the corresponding 1-(phenyl)ethanol (ee = 82-91%). Cyclopropyl boronic esters were also oxidized but with no enantioselectivity. beta-Boryl carboxylic esters were not oxidized by any BVMOs. (C) 2012 Elsevier Ltd. All rights reserved.

Sulfur Radicals as Tethers for the Adsorption of Aromatic Molecules on Silicon Surface

In this work we employ the state of the art pseudopotential method, within a generalized gradient approximation to the density functional theory, to investigate the adsorption process of benzenethiol and diphenyl disulfide with the silicon (001) surface. A direct comparison of different adsorption structures with Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) allow us to identify that benzenethiol and diphenyl disulfide dissociatively adsorb on the silicon surface. In addition, theoretically obtained data suggests that the C6H5SH:Si(001) presents a higher Schottky barrier height contact when compared to other similar aromatic molecules.

Boron site preference in ternary Ta and Nb boron suicides

X-ray single crystal (XSC) and neutron powder diffraction data (NPD) were used to elucidate boron site preference for five ternary phases. Ta3Si1-xBx (x=0.112(4)) crystallizes with the Ti3P-type (space group P4(2)/n) with B-atoms sharing the 8g site with Si atoms. Ta5Si3-x (x=0.03(1); Cr5B3- type) crystallizes with space group 14/mcm, exhibiting a small amount of vacancies on the 4 alpha site. Both, Ta-5(Si1-xBx)(3), X=0.568(3), and Nb-5(Si1-xBx)(3), x=0.59(2), are part of solid solutions of M5Si3 with Cr5B3-type into the ternary M-Si-B systems (M=Nb or Ta) with B replacing Si on the 8h site. The D8(8)-phase in the Nb-Si-B system crystallizes with the Ti5Ga4-type revealing the formula Nb5Si3B1-x (x=0.292(3)) with B partially filling the voids in the 2b site of the Mn5Si3 parent type. (C) 2012 Elsevier Inc. All rights reserved.

In vitro organogenesis of Eucalyptus grandis: effects of boron and calcium

The in vitro organogenesis of woody species plays an essential role in the improvement of forest products by providing saplings with high commercial value. Furthermore, mineral nutrition plays an important role in the induction of organogenic responses. The objective of this study was to evaluate the effects of boron and calcium in the organogenesis of nodal segments from seedlings of Eucalyptus grandis growing under in vitro conditions. The concentration of boron and calcium in MS medium was modified to induce organogenic responses in 45-day-old nodal segments used as explants. After 60 days, the fresh weight, dry weight, ratio of fresh and dry weight, relative water content and relative matter content accumulated by the explants were evaluated. The concentrations of boron and calcium in the culture medium influenced the in vitro organogenic control of Eucalyptus grandis. Reduced combinations of boron and calcium induced callus formation and dry matter accumulation in the explants. A boron concentration of 100% (1.10 mg L-1) combined with 100% (119.950 mg L-1) and 200% (239.900 mg L-1) of calcium, and 200% (2.20 mg L-1) of boron combined with 100% (119.950 mg L-1) of calcium allowed the induction of well-developed buds, which can be used for the regeneration of micro-plants.

Mountain centered icefields in northern Scandinavia

Mountain centered glaciers have played a major role throughout the last three million years in the Scandinavian mountains. The climatic extremes, like the present warm interglacial or cold glacial maxima, are very short-lived compared to the periods of intermediate climate conditions, characterized by the persistence of mountain based glaciers and ice fields of regional size. These have persisted in the Scandinavian mountains for about 65% of the Quaternary. Mountain based glaciers thus had a profound impact on large-scale geomorphology, which is manifested in large-scale glacial landforms such as fjords, glacial lakes and U-shaped valleys in and close to the mountain range. Through a mapping of glacial landforms in the northern Scandinavian mountain range, in particular a striking set of lateral moraines, this thesis offers new insights into Weichselian stages predating the last glacial maximum. The aerial photograph mapping and field evidence yield evidence that these lateral moraines were overridden by glacier ice subsequent to their formation. The lateral moraines were dated using terrestrial cosmogenic nuclide techniques. Although the terrestrial cosmogenic nuclide signature of the moraines is inconclusive, an early Weichselian age is tentatively suggested through correlations with other landforms and stratigraphical archives in the region. The abundance and coherent spatial pattern of the lateral moraines also allow a spatial reconstruction of this ice field. The ice field was controlled by topography and had nunataks protruding also where it was thickest close to the elevation axis of the Scandinavian mountain range. Outlet glaciers discharged into the Norwegian fjords and major valleys in Sweden. The process by which mountain based glaciers grow into an ice sheet is a matter of debate. In this thesis, a feedback mechanism between debris on the ice surface and ice sheet growth is presented. In essence, the growth of glaciers and ice sheets may be accelerated by an abundance of debris in their ablation areas. This may occur when the debris cover on the glacier surface inhibits ablation, effectively increasing the glaciers mass balance. It is thus possible that a dirty ablation area may cause the glacier to advance further than a clean glacier under similar conditions. An ice free period of significant length allows soil production through weathering, frost shattering, and slope processes. As glaciers advance through this assemblage of sediments, significant amounts of debris end up on the surface due to both mass wastage and subglacial entrainment. Evidence that this chain of events may occur, is given by large expanses of hummocky moraine (local name Veiki moraine) in the northern Swedish lowlands. Because the Veiki moraine has been correlated with the first Weichselian advance following the Eemian, it implies a heavily debris charged ice sheet emanating from the mountain range and terminating in a stagnant fashion in the lowlands.

5-substituted triazolinyls as novel counter radicals in controlled radical polymerization

The work is devoted to synthesis of new triazolinyl stable radical derivatives with different substituents at the 5-position of the triazolinyl ring. Obtained results showed great influence of these substituents on the stability of the radical. Electron-rich aromatic substituents at this position stabilize the radical while electron-poor aromatics decrease the stability of the triazolinyl. The triazolinyl radicals synthesized were used as additives for kinetic investigations of controlled radical polymerization of styrene and methylmethacrylate (MMA). The studies performed showed that the more stable radicals provide better control for the polymerization of styrene. In the same time certain instability of the radical is required for realization of controlled polymerization of methylmethacrylate. Based on the kinetic investigations controlled radical polymerization of a variety of monomers including 4-vinylpyridine (4-VP), ethylmethacrylate (EMA), 2,2,2-trifluoroethylmethacrylate (FEMA) and n-butylmethacrylate (BMA)was successfully carried out. Polystyrene and polymethylmethacrylate macroinitiators prepared by triazolinyl mediated controlled radical polymerization were efficiently reinitiated in the presence of a variety of monomers leading to the formation of block copolymers. Using this method PS-b-P-4-VP, PMMA-b-PS, PMMA-b-PBMA, PMMA-b-PFEMA, and PMMA-b-Poly-tert-butylacrylate were successfully synthesized. The results obtained during this work showed the efficiency and flexibility of the method allowing preparation of a range of advanced macromolecular structures.

A study of nitronyl and imino nitroxide radicals attached to heterocyclic cores

Stabile organische Radikale mit zusätzlichen Funktionalitäten wie Donor/Akzepotor Eigenschaften und Ligandeneignung für Übergangsmetallkomplexierung repräsentieren eine synthetische Herausforderung beim Streben nach der Konstruktion hochdimensionaler heterospin Strukturen. In diesem Hinblick wurden acht neue Hochspinbiradikal-Moleküle zusammen mit ihren Monoradikal- Pendants in dieser Arbeit hergestellt. Die Wahl der Liganden als organische Distanzhalter der Radikaleinheiten wurde auf stickstoffhaltige Heterozyklen (Pyridin und Pyrazol) gelenkt. Diese wurden weiterhin mit den stabilen Spinträgern Nitronylnitroxid- (NN) und Iminonitroxidfragmenten (IN) dekoriert. Ihre Synthese beinhaltete mehrstufige Umsetzungen (Brominierung, Iodierung, N- und Carbaldehyd Schutzgruppen, Stille-Kupplung, Grignard Reaktion, etc.) um die Mono- und Dicarbaldehyd-heterocyclenderivate als Schlüsselvorläufer der Radikaleinheiten zu gewinnen. Die Carbaldehyd-Zwischenstufen wurden Kondensationsreaktionen mit 2,3-Dimethyl-2,3-bis(hydroxylamino)-butan unterworfen (üblicherweise in Dioxan unter Argon für ~ 7 Tage), gefolgt von der Oxidation der Bis-hydroxylimidazolidin-Vorläufer unter Phasentransferkatalyse (NaIO4/H2O). Die Radikalmoleküle wurden mit verschiedenen spektroskopischen Methoden untersucht (FT/IR, UV/Vis/ EPR etc.) und ihre Einkristalle mit Röntgenstrahlbeugung gemessen. Die UV/VIS- Lösungsspektren zeigten in einem breiten Bereich verschiedener Lösungsmittelpolaritäten keine spezifische Wechselwirkung zwischen Lösungsmittel und Radikaleinheit, während ihre Stabilitäten in protischen Lösunsgmitteln wie MeOH stark abnahmen. Als Pulver konnten sie jedoch im Kühlschrank an der Luft für eine Jahr gelagert werden, ohne sich zu zersetzen. Die spektroskopischen Fingerabdrücke der Radikale wurden eindeutig identifiziert and erschienen stark abhängig vom Typ des pi-Ringsystems an das die Spinträger gekoppelt wurden. Basierend auf diesen Informationen wurde ein schnelles Protokoll etabliert, das eine direkte Zuordnung der Art der Radikale und ihrer Anzahl ermöglicht, sowie ihre Reinheit und Verunreinigungen zu definieren. In Lösung bestätigte die Analyse der EPR Spektren der Biradikale die starke Austauschwechselwirkung J zwischen den Radikalfragmenten über die Kopplungseinheiten (J >> an, an ist die Stickstoffhyperfeinkopplungskonstante). Dies wurde weiter unterstützt durch die Beobachtungen in gefrorener Lösung über die Nullfeldaufspaltungen und verbotenen Halbfeldübergänge (Δms = 2). Die Temperaturabhängigkeiten der Δms = 2 - EPR Signale wurden bis herunter auf 4 K gemessen und das exakte Vorzeichen und die Größe von J ermittelt. Diese Arbeit unterstreicht die Möglichkeit über synthetische Chemie eine Feineinstellung der „through bond“ Austauschwechselwirkung zwischen verwandten pi- und sigma- konjugierten Heterozyklen zu erreichen, in denen der S = 1 Grundzustand angenommen wird. Zusätzlich zeigten diese Resultate, dass die Übertragung der Spinpolarisation durch verschiedene Koppler sehr effektiv war.