Electrocatalysis of CO2/CO interconversion and hydrogen evolution in bicarbonate buffers: from solution to interfacial reactions

Bicarbonate buffer is largely found in nature due to its ability to regulate pH variations around neutral values. As the pH changes, so does the speciation of the buffer. At low pH the main buffer species is carbon dioxide, which for increasing pH transforms into bicarbonate, and then into carbonate. Besides the acid-base reactions in solution, the buffer species may react at the electrified interface to be reduced or oxidized.Given the importance of storing intermittent renewable electricity into chemical bonds using abundant reactants, such as carbon dioxide, it is crucial to understand the interplay of electrochemical and homogeneous reactions. Hence, in this PhD thesis we studied how the presence of a buffer in the electrolytes affects relevant electrocatalytic reactions, i.e. CO2 electrochemical reduction (Chapter 2 and 4), hydrogen evolution reaction (Chapter 4 and 5) and CO electrooxidation (Chapter 3). A special focus is placed on the employment of well-defined mass transport techniques in combination with digital simulations.Catalysis and Surface Chemistr

Timing of desiccant application in soybeans: physiological quality of seeds

O presente trabalho teve como objetivo avaliar o efeito da aplicação de diferentes dessecantes aplicados em diferentes estádios reprodutivos na qualidade fisiológica de sementes de soja. O delineamento experimental utilizado foi em blocos casualizados com quatro repetições. Os tratamentos foram dispostos em um esquema fatorial, sendo que para a cultivar MSOY 6101, de ciclo super precoce, utilizou-se 3x3x5x2, dois dessecantes (glifosato e paraquat) e uma testemunha (sem dessecação), três estádios fenológicos (R6, R7 e R8), cinco épocas de amostragem (2, 4, 6, 8 e 10 dias após aplicação) e duas posições de avaliação na planta (ápice e base). Para a cultivar MG/BR 46 (Conquista) de ciclo precoce, utilizou-se 3x2x5x2, sendo nesse caso somente dois estádios fenológicos (R7 e R8). Diante dos resultados obtidos pode-se concluir que o glifosato influencia negativamente a qualidade fisiológica de sementes, principalmente, quando avaliada por meio do teste de comprimento de raiz. O herbicida paraquat não altera a qualidade fisiológica das sementes. As sementes obtidas com aplicação de dessecantes no estádio R6 são de qualidade fisiológica inferior às obtidas com aplicação nos estádios R7 e R8.The objective of this study was to evaluate the effect of different desiccants on the physiological quality of soybean seeds when applied to different reproductive stages. The experiment was conducted in the 2005/06 crop season using a randomized block design of four repetitions and two varieties. For the very early maturing MSOY 6101 variety, a factorial 3x3x5x2 design was used, with two desiccant treatments (glyphosate and paraquat) and a control (no desiccation), applied at three growth stages (R6, R7 and R8), with five sampling times (2; 4; 6; 8 and 10 days after application) and two evaluation positions on the plant (apex and base). The early maturing MG/BR 46 (Conquista) cultivar was evaluated in a 3x2x5x2 design with treatments applied at only two growth stages (R7 and R8). The results showed that glyphosate adversely affected physiological seed quality, mainly for root length, whereas paraquat caused no apparent effect. The seeds from desiccant applications in the R6 stage showed a lower physiological quality compared to those obtained from applications in the R7 and R8 stages

The Effect of N Fertilization on Wheat under Inoculation with Azospirillum brasilense

The biological nitrogen fixation (BNF) process in wheat (Triticum aestivum L.) occurs by diazotrophic bacteria, particularly Azospirillum brasilense. However, researches are lacking on BNF efficiency to define how much mineral nitrogen (N) can be applied to achieve more sustainable high yields, and if urea with the urease enzyme inhibitor is less harmful, benefiting BNF in grasses (cereals). Therefore, the objective was to evaluate the effect of N sources (urea and Super N, urea with urease enzyme inhibitor N‐(n‐butyl thiophosphoric triamide) (NBPT) and N rates (0, 50, 100, 150, and 200 kg ha−1) applied in topdressing associated with inoculation with A. brasilense, regarding the leaf N concentration, leaf chlorophyll index (LCI), accumulation of N in the straw and grains, the nitrogen utilization efficiency (NUE), recovery of the applied nitrogen (RAN), physiological efficiency (FE), agronomic efficiency (AE), and wheat grain yield in the Brazilian Cerrado (tropical savanna) region. The N sources provide similar N accumulations in straw and grains, and wheat grain yield. Inoculation with A. brasilense afforded higher N grain concentration (increase in protein content more sustainably) by applying less N fertilizer in topdressing. Inoculation with A. brasilense increased the AE, RAN, and NUE

HCMV envelope glycoprotein diversity demystified

Human cytomegalovirus (HCMV) is the leading viral cause of congenital birth defects and is responsible for morbidity and mortality in immunosuppressed individuals. Considerable efforts have been deployed over the last decade to develop a vaccine capable of preventing HCMV infection. However, in recent clinical trials, vaccines showed at best modest efficacy in preventing infection. These findings might be explained by the high level of sequence polymorphism at the genomic level. To investigate if genomic variation also leads to antigenic variation, we performed a bioinformatic sequence analysis and evaluated the percentage of conservation at the amino acid level of all the proteins present in the virion envelope. Using more than two hundred sequences per envelope glycoprotein and analyzing their degree of conservation, we observe that antigenic variation is in large part limited to three proteins. In addition, we demonstrate that the two leading vaccine candidates, the pentamer and gB complexes, are well conserved at the amino acid level. These results suggest that despite genomic polymorphism, antigenic variability is not involved in the modest efficacy observed in the recent clinical trials for a HCMV vaccine. We therefore propose that next-generation vaccines should focus on stabilizing and refining the gB domains needed to induce a protective humoral response

Understanding hydrogen evolution reaction in bicarbonate buffer

Catalysis and Surface Chemistr

Electrolyte buffering species as oxygen donor shuttles in CO electrooxidation

Electrolyte buffering species have been shown to act as proton donors in the hydrogen evolution reaction (HER). Analogously, we study here whether these electrolyte species may participate in other reactions by investigating CO electrooxidation (COOR) on a gold rotating disk electrode. This model system, characterized by fast kinetics, exhibits a dffusion-limited regime, which helps in the identification of the species dictating the diffusion-limited current. Through a systematic concentration dependence study in a variety of buffers, we show that electrolyte buffering species act as oxygen donor shuttles in COOR, lowering the reaction overpotential. A similar correlation between electrolyte and electrocatalytic activity was observed for COOR on a different electrode material (Pt). Probing the electrode-electrolyte interface by attenuated total reflection infrared spectroscopy (ATR-FTIR) and modelling the surface speciation to include the effect of the solution reactions, we propose that the buffer conjugated base generates the oxygen donor (i.e. OH-) through its acid-base reaction with water.Horizon 2020(H2020)722614-ELCORELCatalysis and Surface Chemistr

HCMV Envelope Glycoprotein Diversity Demystified

Human cytomegalovirus (HCMV) is the leading viral cause of congenital birth defects and is responsible for morbidity and mortality in immunosuppressed individuals. Considerable efforts have been deployed over the last decade to develop a vaccine capable of preventing HCMV infection. However, in recent clinical trials, vaccines showed at best modest efficacy in preventing infection. These findings might be explained by the high level of sequence polymorphism at the genomic level. To investigate if genomic variation also leads to antigenic variation, we performed a bioinformatic sequence analysis and evaluated the percentage of conservation at the amino acid level of all the proteins present in the virion envelope. Using more than two hundred sequences per envelope glycoprotein and analyzing their degree of conservation, we observe that antigenic variation is in large part limited to three proteins. In addition, we demonstrate that the two leading vaccine candidates, the pentamer and gB complexes, are well conserved at the amino acid level. These results suggest that despite genomic polymorphism, antigenic variability is not involved in the modest efficacy observed in the recent clinical trials for a HCMV vaccine. We therefore propose that next-generation vaccines should focus on stabilizing and refining the gB domains needed to induce a protective humoral response

Electrolyte effects on CO2 electrochemical reduction to CO

The electrochemical reduction of CO2 (CO2RR) constitutes an alternative to fossil fuel-based technologies for the production of fuels and commodity chemicals. Yet the application of CO2RR electrolyzers is hampered by low energy and Faradaic efficiencies. Concomitant electrochemical reactions, like hydrogen evolution (HER), lower the selectivity, while the conversion of CO2 into (bi)carbonate through solution acid−base reactions induces an additional concentration overpotential. During CO2RR in aqueous media, the local pH becomes more alkaline than the bulk causing an additional consumption of CO2 by the homogeneous reactions. The latter effect, in combination with the low solubility of CO2 in aqueous electrolytes (33 mM), leads to a significant depletion in CO2 concentration at the electrode surface. The nature of the electrolyte, in terms of pH and cation identity, has recently emerged as an important factor to tune both the energy and Faradaic efficiency. In this Account, we summarize the recent advances in understanding electrolyte effects on CO2RR to CO in aqueous solutions, which is the first, and crucial, step to further reduced products. To compare literature findings in a meaningful way, we focus on results reported under well-defined mass transport conditions and using online analytical techniques. The discussion covers the molecular-level understanding of the effects of the proton donor, in terms of the suppression of the CO2 gradient vs enhancement of HER at a given mass transport rate and of the cation, which is crucial in enabling both CO2RR and HER. These mechanistic insights are then translated into possible implications for industrially relevant cell geometries and current densities.Catalysis and Surface Chemistr

Antibody-driven design of a human cytomegalovirus gHgLpUL128L subunit vaccine that selectively elicits potent neutralizing antibodies

The use of neutralizing antibodies to identify the most effective antigen has been proposed as a strategy to design vaccines capable of eliciting protective B-cell immunity. In this study, we analyzed the human antibody response to cytomegalovirus (human cytomegalovirus, HCMV) infection and found that antibodies to glycoprotein (g)B, a surface glycoprotein that has been developed as a HCMV vaccine, were primarily nonneutralizing. In contrast, most of the antibodies to the complex formed by gH, gL, protein (p)UL128, pUL130, and pUL131 (the gHgLpUL128L pentamer) neutralized HCMV infection with high potency. Based on this analysis, we developed a single polycistronic vector encoding the five pentamer genes separated by “self-cleaving” 2A peptides to generate a stably transfected CHO cell line constitutively secreting high levels of recombinant pentamer that displayed the functional antigenic sites targeted by human neutralizing antibodies. Immunization of mice with the pentamer formulated with different adjuvants elicited HCMV neutralizing antibody titers that persisted to high levels over time and that were a hundred- to thousand-fold higher than those found in individuals that recovered from primary HCMV infection. Sera from mice immunized with the pentamer vaccine neutralized infection of both epithelial cells and fibroblasts and prevented cell-to-cell spread and viral dissemination from endothelial cells to leukocytes. Neutralizing monoclonal antibodies from immunized mice showed the same potency as human antibodies and targeted the same as well as additional sites on the pentamer. These results illustrate with a relevant example a general and practical approach of analytic vaccinology for the development of subunit vaccines against complex pathogens