Between photocatalysis and photosynthesis: Synchrotron spectroscopy methods on molecules and materials for solar hydrogen generation

Energy research is to a large extent materials research, encompassing the physics and chemistry of materials, including their synthesis, processing toward components and design toward architectures, allowing for their functionality as energy devices, extending toward their operation parameters and environment, including also their degradation, limited life, ultimate failure and potential recycling. In all these stages, X-ray and electron spectroscopy are helpful methods for analysis, characterization and diagnostics for the engineer and for the researcher working in basic science.This paper gives a short overview of experiments with X-ray and electron spectroscopy for solar energy and water splitting materials and addresses also the issue of solar fuel, a relatively new topic in energy research. The featured systems are iron oxide and tungsten oxide as photoanodes, and hydrogenases as molecular systems. We present surface and subsurface studies with ambient pressure XPS and hard X-ray XPS, resonant photoemission, light induced effects in resonant photoemission experiments and a photo-electrochemical in situ/operando NEXAFS experiment in a liquid cell, and nuclear resonant vibrational spectroscopy (NRVS). (C) 2012 Elsevier B.V. All rights reserved.

Sequestration of the abrin A chain to the nucleus by BASP1 increases the resistance of cells to abrin toxicity

Abrin, a type II ribosome-inactivating protein, comprises A and B subunits wherein the A subunit harbours toxin activity and the B subunit has a galactose-specific lectin activity. The entry of the protein inside the cell is through the binding of the B chain to cell surface glycoproteins followed by receptor-mediated endocytosis and retrograde transport. A previous study from our laboratory showed that different cell lines exhibited differences of as great as similar to 200-fold in abrin toxicity, prompting the present study to compare the trafficking of the toxin within cells. Observations made in this regard revealed that the abrin A chain, after being released into the cytosol, is sequestered into the nucleus through interaction with a cellular protein of similar to 25 kDa, BASP1 (brain acid-soluble protein 1). The nuclear localization of the A chain is seen predominantly in cells that are less sensitive to abrin toxicity and dependent on the levels of BASP1 in cells. The sequestration by BASP1 renders cells increasingly resistant to the inhibition of protein synthesis by abrin and the nucleus act as a sink to overcome cellular stress induced

Enhancing hydrogen storage capacity of pyridine-based metal organic framework

Using first principles calculations, we show that the storage capacity as well as desorption temperature of MOFs can be significantly enhanced by decorating pyridine (a common linker in MOFs) by metal atoms. The storage capacity of metal-pyridine complexes are found to be dependent on the type of decorating metal atom. Among the 3d transition metal atoms, Sc turns out to be the most efficient storing unto four H-2 molecules. Most importantly, Sc does not suffer dimerisation on the surface of pyridine, keeping the storage capacity of every metal atom intact. Based on these findings, we propose a metal-decorated pyridine-based MOFs, which has potential to meet the required H-2 storage capacity for vehicular usage. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Anti-inflammatory activity of the ethanol extract of Dictamnus dasycarpus leaf in lipopolysaccharide-activated macrophages

Background: Dictamnus dasycarpus is widely used as a traditional remedy for the treatment of eczema, rheumatism, and other inflammatory diseases in Asia. The current study investigates the molecular mechanism of anti-inflammatory action of the ethanol extract of Dictamnus dasycarpus leaf (DE) in lipopolysaccharide (LPS)-stimulated RAW 264.7 cells. Methods: Nitric oxide (NO) production was assessed by Griess reaction and the mRNA and protein expressions of pro inflammatory cytokines, transcription factor, and enzymes were determined by real-time RT-PCR and immunoblotting analysis. Results: DE (0.5 and 1 mg/mL) suppressed the NO production by 10 and 33%, respectively, compared to the untreated group in LPS-stimulated RAW 264.7 cells. DE (0.5 and 1 mg/mL) reduced the mRNA expression of key transcription factor nuclear factor-kappa B by 7 and 24%, respectively compared to the untreated group in LPS activated macrophage. The pro inflammatory cytokines such as tumor necrosis factor a and interleukin 1 beta were also decreased by DE treatment. Moreover, the protein expression of pro inflammatory enzymes, inducible nitric oxide synthase and cyclooxygenase 2 were also dramatically attenuated by DE in a dose dependent manner. Conclusions: These results suggest that Dictamnus dasycarpus leaf has a potent anti-inflammatory activity and can be used for the development of new anti-inflammatory agents.

Solution processable diketopyrrolopyrrole (DPP) cored small molecules with BODIPY end groups as novel donors for organic solar cells

Two novel triads based on a diketopyrrolopyrrole (DPP) central core and two 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) units attached by thiophene rings have been synthesised having high molar extinction coefficients. These triads were characterised and used as donor materials in small molecule, solution processable organic solar cells. Both triads were blended with PC71BM as an acceptor in different ratios by wt% and their photovoltaic properties were studied. For both the triads a modest photovoltaic performance was observed, having an efficiency of 0.65%. Moreover, in order to understand the ground and excited state properties and vertical absorption profile of DPP and BODIPY units within the triads, theoretical DFT and TDDFT calculations were performed.

Remarkable enhancement in hydrogen storage on free-standing Ti3B and BC3 supported Ti-3 clusters

Hydrogen storage capacity of Tin-1B (n = 3-7) clusters is studied and compared with that of the pristine Ti-n (n = 3-7), using density functional theory (DFT) based calculations. Among these clusters, Ti3B shows the most significant enhancement in the storage capacity by adsorbing 12 H-2, out of which three are dissociated and the other nine are stored as dihydrogen via Kubas-interaction. The best storage in Ti3B is owed to a large charge transfer from Ti to B along with the largest distance of Ti empty d-states above the Fermi level, which is a distinct feature of this particular cluster. Furthermore, the effect of substrates on the storage capacity of Ti3B was assessed by calculating the number of adsorbed H-2 on Ti-3 cluster anchored onto B atoms in the B-doped graphene, BC3, and BN substrates. Similar to free-standing Ti3B, Ti-3 anchored onto boron atom in BC3, stores nine di-hydrogen via Kubas interaction, at the same time eliminating the total number of non-useful dissociated hydrogen. Gibbs energy of adsorption as a function of H-2 partial pressure, indicated that at 250 K and 300 K the di-hydrogens on Ti-3@BC3 adsorb and desorb at ambient pressures. Importantly, Ti-3@BC3 avoids the clustering, hence meeting the criteria for efficient and reversible hydrogen storage media. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

The electronic, chemical and electrocatalytic processes and intermediates on iron oxide surfaces during photoelectrochemical water splitting

We re-assess experimental soft X-ray absorption spectra of the oxygen K-shell which we recorded operando from iron oxide during photoelectrochemical water splitting in KOH electrolyte. In particular, we refer to recently reported transitional electron hole states which originate within the charge carrier depletion layer of the iron oxide and on the iron oxide surface. For the latter we find that an intermediate oxy-peroxo species is formed on the iron oxide with increasing bias potential, which disappears upon further polarization of the electrode, concomitantly with the evolution and disappearance of the aforementioned surface state. The oxygen spectra contain also the spectroscopic signatures of the electrolyte water, the position of which changes with increasing bias potential towards lower X-ray energies, revealing the breaking and formation of hydrogen bonds in the water during the experiment. Combined with potential dependent impedance spectroscopy data we are able to sketch the molecular structure of chemical intermediates and their charge carrier dynamics. (C) 2015 Elsevier B.V. All rights reserved.

Field application of anabolic steroids in carp seed production. II. Rearing of spawn to fry stage.

Two synthetic androgenic steroids, Ethylestrenol (17 β - Hydroxy - 17 α ethyl - estr - 4 - en - 3 - one) and Stanozolal (17 β - Hydroxy- 17 α - methyl - 5 a - androstano - 3, 2 - C - pyrazole) were fed via diet at 3 ppm to the spawn of Rohu and Mrigal which were reared up to fry stage over a period of 15 days in earthen carp nurseries. Both hormones enhanced growth of spawn. A maximum of 25.78% increase in length and 25.69% increase in weight as compared to the controls has been recorded. Growth rate was recorded to be 0.8 mm & 2.48 mg/day (control), and 1.13 mm & 2.67 mg/day (Stanozolol treated) in case of Mrigal spawn; and 0.91 mm & 2.39 mg/day (control), 1.12 mm & 2.90 mg/day (Ethylestrenol treated), and 1.10 mm & 2.57 mg/day (Stanozolol treated) in case of Rohu spawn. A decrease in the values of Relative Condition Factor upon hormone administration was also noticed.

A ferrugem do eucalipto na região Sul do Brasil.

2010

Konspiracja i podziemie zbrojne w Wielkopolsce 1945-1949. Powstanie, rozwój i rozbicie przez aparat bezpieczeństwa

Wydział Historyczny

Los primeros pasos en el escorzo de la figura humana. "Un análisis desde la geometría"

A través de un recorrido histórico centrado en el Renacimiento, se exponen las aportaciones más significativas de teóricos y artistas en la evolución del escorzo de la figura humana desde un punto de vista geométrico. Los artistas que con sus dibujos y escritos ayudaban a otros en el aprendizaje de la representación, se apresuraron a incluir el estudio del escorzo en sus tratados, buscando métodos que facilitaran su dibujo sobre cualquier soporte y en cualquier posición en el espacio. En este artículo se analizan y enlazan los trazados propuestos por los estudiosos de la geometría, con las obras de arte que reflejan importantes avances en este sentido. Soportes como el lienzo, el muro o la bóveda, presentan al pintor superficies diferentes de trabajo y en distintas posiciones en el espacio. La figura humana, protagonista en la escena, tendrá que adaptarse a ellos para ser contemplada desde unos espacios arquitectónicos cada vez más amplios y con más posibilidades. Fue necesario dominar la perspectiva en la pintura, y muy particularmente en la mural, para ofrecer composiciones cada día más ambiciosas y sorprendentes.

Boronic acids as partners in multicomponent reactions

Tese de doutoramento, Farmácia (Química Farmacêutica e Terapêutica), Universidade de Lisboa, Faculdade de Farmácia, 2014

Negritude e literatura de cordel: uma épica da interculturalidade ante o supranacional

Escrever é um dos mais poderosos instrumentos usados pela mídia para levar informações vitais. Nesse sentido, o efeito das “novas ideologias”, para valorização da identidade afro-brasileira, incidem diretamente sobre a produção literária como uma mensagem rigorosamente direcionada a um público menos especializado como receptor. O presente artigo discute a relação entre o gênero cordel e algumas das políticas culturais aplicadas no nordeste do Brasil. Tal estratégia vem comprovar não apenas o processo ativo de negociação entre os grupos subalternizados e os discursos dos poderes hegemônicos, mas também a reatualização do gênero literário do cordel, com o aparecimento de novos narradores e temáticas. Como se observa estes narradores estão plenamente conscientes dos seus papéis políticos ante a comunidade de que, fazem parte. Circulando em um espaço geográfico urbano, a produção não depende da condição econômica de seus leitores para sua aquisição, uma vez que sua distribuição centraliza-se na informação gratuita. Ao contrário da literatura “tradicional”, o real e o verossímil possuem objetivos definidos como informar e ensinar o destinatário sobre a nova lei em vigor. Nesse caso, a literatura cumpre de imediato um de seus papéis clássicos, o de ser útil, revestindo-se de funções igualmente nobres, provocando a “catarse social” de indivíduos pela aquisição de um saber inerente `a sua condição de cidadão.

The determinants of net interest margins & net interest spreads in the Russian & Japanese Commercial Banking sectors

This study presents an empirical investigation of the determinants of net interest margins and spreads in the Russian and Japanese banking sectors with a particular focus on commercial banks. Net interest mar-gins and spreads serve as indicators of financial intermediation efficiency. This paper employed a bank-level unbalanced panel dataset prolonging from 2005 to 2014. My main empirical results show that bank characteristics explain the most of the variation in not only net interest margins but also in spreads. Capi-talization, liquidity risk, inflation, economic growth, private and government debt are important determi-nants of margin in Russia. In Japan to the contrary loan and deposit market concentration along with bank size do predominate. Common significant variables in both countries are the substitution effect, cost effi-ciency and profitability. Turning to net interest spreads, micro- and macro-specific variables are the main significant drivers in Russia. I reach the conclusion that there are no significant determinants of net interest spreads in Japan within the original selection of variables, but operating efficiency and deposits to total funding seem to prevail. In both countries, there are solid differences in the net interest margins as well as spreads once the pre- and the post-crisis periods are considered.

(A) BODIPY as a versatile fluorophore (B) Synthesis of PNAs via Staudinger reaction

(A) In recent years, 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) fluorophores have attracted considerable interest due to their unique photochemical properties. However detailed studies on the stability of BODIPY and analogues under acidic and basic conditions have been lacking. Thus the stability of a series of BODIPY analogues in acidic (di- and trichloroacetic acid) and basic (aqueous ammonium hydroxide) conditions was investigated using 11B NMR spectroscopy. Among the analogues tested, 4,4-diphenyl BODIPY was the most stable under the conditions used in the experiments. It was found that reaction of 4,4-dimethoxy BODIPY with dichloroacetic acid gave mixed anhydride 4,4-bis(dichloroacetoxy) BODIPY in good yields. Treatment of the latter mixed anhydride with alcohols such as methanol and ethanol in the presence of a base afforded corresponding borate esters, whereas treatment with 1,2-diols such as ethylene glycol and catechol in the presence of a base gave corresponding cyclic borate esters. Furthermore treatment of 4,4-difluoro-8-methyl-BODIPY with secondary amines in dihalomethane resulted in carbon–carbon bond formation at the meso-methyl position of BODIPY via Mannich-type reactions. The resulting modified BODIPY fluorophores possess high fluorescent quantum yields. Five BODIPY analogues bearing potential ion-binding moieties were synthesized via this Mannich-type reaction. Among these, the BODIPY bearing an aza-18-crown-5 tether was found to be selective towards copper (II) ion, resulting in a large blue shift in absorption and sharp fluorescent quenching, whereas aza-15-crown-4 analogue was selected towards fluoride ion, leading to effective florescent quenching and blue shift. (B) Peptide nucleic acids (PNA), as mimics of natural nucleic acids, have been widely applied in molecular biology and biotechnology. Currently, the preparation of PNA oligomers is commonly achieved by a coupling reaction between carboxyl and amino groups in the presence of an activator. In this thesis attempts were made towards the synthesis of PNA through the Staudinger ligation reactions between C-terminal diphenylphosphinomethanethiol thioesters and N-terminal α-azido PNA building blocks.