Microbial nitrogen dynamics in organic and mineral soil horizons along a latitudinal transect in western Siberia

Soil N availability is constrained by the breakdown of N-containing polymers such as proteins to oligopeptides and amino acids that can be taken up by plants and microorganisms. Excess N is released from microbial cells as ammonium (N mineralization), which in turn can serve as substrate for nitrification. According to stoichiometric theory, N mineralization and nitrification are expected to increase in relation to protein depolymerization with decreasing N limitation, and thus from higher to lower latitudes and from topsoils to subsoils. To test these hypotheses, we compared gross rates of protein depolymerization, N mineralization and nitrification (determined using N-15 pool dilution assays) in organic topsoil, mineral topsoil, and mineral subsoil of seven ecosystems along a latitudinal transect in western Siberia, from tundra (67 degrees N) to steppe (54 degrees N). The investigated ecosystems differed strongly in N transformation rates, with highest protein depolymerization and N mineralization rates in middle and southern taiga. All N transformation rates decreased with soil depth following the decrease in organic matter content. Related to protein depolymerization, N mineralization and nitrification were significantly higher in mineral than in organic horizons, supporting a decrease in microbial N limitation with depth. In contrast, we did not find indications for a decrease in microbial N limitation from arctic to temperate ecosystems along the transect. Our findings thus challenge the perception of ubiquitous N limitation at high latitudes, but suggest a transition from N to C limitation of microorganisms with soil depth, even in high-latitude systems such as tundra and boreal forest.

Improvement of carbon materials performance by nitrogen functional groups in electrochemical capacitors in organic electrolyte at severe conditions

N-doped activated carbon fibers have been synthesized by using chemically polymerized aniline as source of nitrogen. Commercial activated carbon fibers (A20) were chemically modified with a thin film of polyaniline (PANI) inside the microporosity of the carbon fibers. The modified activated carbon fibers were carbonized at 600 and 800 °C, respectively. In this way, activated carbon fibers modified with surface nitrogen species were prepared in order to analyze their influence in the performance of electrochemical capacitors in organic electrolyte. Symmetric capacitors were made of activated carbon fibers and N-doped activated carbon fibers and tested in a two-electrode cell configuration, using triethylmethylammonium tetrafluoroborate/propylene carbonate (TEMA-BF4/PC) as electrolyte. The effect of nitrogen species in the degradation or stabilization of the capacitor has been analyzed through floating durability tests using a high voltage charging (3.2 V). The results show higher stabilizing effect in carbonized samples (N-ACF) than in non-carbonized samples and pristine activated carbon fibers, which is attributed to the presence of aromatic nitrogen group, especially positively charged N-functional groups.

Sensible use of primary energy in organic greenhouse production.

This document addresses the direct and indirect use of energy in European organic greenhouse horticulture (OGH) with the aim of reviewing available means for making it more environmental friendly and identifying knowledge gaps that should be addressed to attain this aim. The first observation is that there is no common regulation for energy use in OGH, which is not unexpected, since the need for climatisation is not uniformly distributed in the EU (and outside). Accordingly, the EU directive on organic agriculture does not set limitations on the use of energy, but rather promotes the responsible use of energy and of natural resources. The restrictions and rules of most private standards are slightly more stringent. Some standards have specific restrictions on the amount and sources of energy and/or on the seasonal use of energy for heating. Some standards also address processes that may affect (in)direct energy use, such as cultivation methods, mulching, lighting and growing media or substrates. However, most private standards have no or little restrictions or regulations on energy use. Accordingly, it should not surprise that very little quantitative information is available about energy use in OGH. In the present document we have filled the gaps with data with estimates drawn on energy use in conventional greenhouses. With respect to ongoing research, whereas many of the present research results about energy use and saving in conventional greenhouses are relevant (and also applied) in OGH, little research is devoted to address the energy use that is peculiar to OGH, particularly energy use for humidity control. In short, there are still a lot of knowledge gaps to improve quality and to lower energy use in organic greenhouses. The purpose of this document is a summary of present relevant knowledge about energy use and energy saving and of the perspective for improvement. In particular, the goal is to make an overview on the methods and technologies which can be used to reduce the energy use in OGH. We start from the assumption that methods and technologies that are used for reducing direct and indirect energy in conventional greenhouses can also be applied in organic greenhouses. Research on reducing energy use in conventional greenhouses is also more widely available because the area of conventional greenhouse horticulture is much larger than the area of OGH. When implementing these methods and techniques we should take into account the specific characteristics of organic agriculture like soil-based cultivation, use of organic fertilizers and the limited use of crop protection products. This document is organised as follows: first we report the results of a survey about energy use and relevant standards in the countries participating to the COST action (chapter 1); then we review the energy use for climatisation: heating (chapter 2) and humidity (chapter 3). In chapter 4 we review the available design and management means that would either reduce energy use and/or increase energy use efficiency by increasing productivity of OGH. In chapter 5 we present a short summary of existing information on indirect energy use, that is the energy required to manufacture production means (greenhouse structure and cover, fertilisers, equipment etc.) and for crop protection, particularly steaming, and briefly discuss possible savings. Finally (chapter 6) we review briefly the potential for application of renewable energy sources in OGH.

Linkage: Basic Requirement in any Product of Research in Education

The scientific production, in the field of education, constantly refers to linkage as a special condition to develop research. However, its meaning and the way to achieve that condition are not always clear, particularly for those who are in a training stage of research in education. Meanwhile, the academic production reviewers consider linkage as a very important aspect and essential characteristic of any research project. This paper suggests that linkage involves an epistemological discussion on the research factors in each one of the research stages, such as the construction of the object of study, the definition of methodology, and the data analysis and interpretation, among the most important stages. Linkage takes shape in a written product showing the results from an orderly construction and communication of thought, according to the rules established in a particular field of knowledge.

Effect of acid alcoholic solution in waxy maize starch treatment.

O amido é o polissacarídeo mais abundante presente em plantas, composto por amilose e amilopectina. O amido de milho ceroso apresenta somente amilopectina. A modificação do amido é recomendada para melhorar suas aplicações. A hidrólise ácida é utilizada para alterar as propriedades físico-químicas sem modificar o grânulo e o meio alcoólico ajuda na recuperação da molécula após o tratamento. O objetivo do trabalho foi o tratamento químico com HCl 0,5 mol L-1 durante 1 hora em 100 ml de água, etanol ou metanol. Os equipamentos SETSYS Evolução TGADTA / DSC e Rápido Visco-Analisador (RVA-4) foram usados para avaliar as alterações dos amidos. As curvas TG mostraram três eventos (desidratação, estabilidade e decomposição), com resultados similares para todas as amostras. Este resultado pode estar relacionado a resistência da amilopectina para a hidrólise ácida. Na análise reológica (RVA) o tratamento das amostras mostrou valores mais baixos de perfis de viscosidade. A solução ácida forneceu mudanças nas propriedades de pasta do amido e a solução etanólica (solvente mais apolar) foi maior que as demais soluções. Conclui-se portanto que o tratamento dos amidos forneceu produtos com características térmicas similares e com diferentes respostas mecânicas

A multi-methodological approach for the study of polymorphism in organic pigments and pharmaceuticals

The study of polymorphism has an important role in several fields of materials science, because structural differences lead to different physico-chemical properties of the system. This PhD work was dedicated to the investigation of polymorphism in Indigo, Thioindigo and Quinacridone, as case studies among the organic pigments employed as semiconductors, and in Paracetamol, Phenytoin and Nabumetone, chosen among some commonly used API. The aim of the research was to improve the understanding on the structures of bulk crystals and thin films, adopting Raman spectroscopy as the method of choice, while resorting to other experimental techniques to complement the gathered information. Different crystalline polymorphs, in fact, may be conveniently distinguished by their Raman spectra in the region of the lattice phonons (10-150 cm-1), the frequencies of which, probing the inter-molecular interactions, are very sensitive to even slight modifications in the molecular packing. In particular, we have used Confocal Raman Microscopy, which is a powerful, yet simple, technique for the investigation of crystal polymorphism in organic and inorganic materials, being capable of monitoring physical modifications, chemical transformations and phase inhomogeneities in crystal domains at the micrometre scale. In this way, we have investigated bulk crystals and thin film samples obtained with a variety of crystal growth and deposition techniques. Pure polymorphs and samples with phase mixing were found and fully characterized. Raman spectroscopy was complemented mainly by XRD measurements for bulk crystals and by AFM, GIXD and TEM for thin films. Structures and phonons of the investigated polymorphs were computed by DFT methods, and the comparison between theoretical and experimental results was used to assess the relative stability of the polymorphs and to assist the spectroscopic investigation. The Raman measurements were thus found to be able to clarify ambiguities in the phase assignments which otherwise the other methods were unable to solve.

Unconventional Catalysis in Organic Chemistry: a Computational Mechanistic Study

Catalysis plays a vital role in modern synthetic chemistry. However, even if conventional catalysis (organo-catalysis, metal-catalysis and enzyme-catalysis) has provided outstanding results, various unconventional ways to make chemical reactions more effective appear now very promising. Computational methods can be of great help to reach a deeper comprehension of these chemical processes. The methodologies employed in this thesis are Quantum-Mechanical (QM), Molecular Mechanics (MM) and hybrid Quantum-Mechanical/Molecular Mechanics (QM/MM) methods. In this abstract the results are briefly summarised. The first unconventional catalysis investigated consists in the application of Oriented External Electric Fields (OEEFs) to SN2 and 4e-electrocyclic reactions. SN2 reactions with back-side mechanism can be catalysed or inhibited by the presence of an OEEF. Moreover, OEEFs can inhibit back-side mechanism (Walden inversion of configuration) and promote the naturally unfavoured front-side mechanism (retention of configuration). Electrocyclic ring opening reaction of 3-substituted cyclobutene molecules can occur with inward or outward mechanisms depending on the nature of substituent groups on the cyclobutene structure (torquoselectivity principle). OEEFs can catalyse the naturally favoured pathway or circumvent the torquoselectivity principle leading to different stereoisomers. The second case study is based on Carbon Nanotubes (CNTs) working as nano-reactors: the reaction of ethyl chloride with chloride anion inside CNTs was investigated. In addition to the SN2 mechanism, syn and anti-E2 reactions are possible. These reactions inside CNTs of different radii were examined with hybrid QM/MM methods, finding that these processes can be both catalysed and inhibited by the CNT diameter. The results suggest that electrostatic effects govern the activation energy variations inside CNTs. Finally, a new biochemical approach, based on the use of DNA catalyst was investigated at QM level. Deoxyribozyme 9DB1 catalyses the RNA ligation allowing the regioselective formation of the 3'-5' bond, following an addition-elimination two-step mechanism.

Computational characterization of carbazole-benzonitrile derivatives for applications in Organic Light Emitting Diodes

The technology of Organic Light-Emitting Diodes has reached such a high level of reliability that it can be used in various applications. The required light emission efficiency can be achieved by transforming the triplet excitons into singlet states through Reverse InterSystem Crossing (RISC), which is the main process of a general mechanism called thermally activated delayed fluorescence (TADF). In this thesis, we theoretically analyzed two carbazole-benzonitrile (donor-acceptor) derivatives, 2,5-di(9H-carbazol-9-yl)benzonitrile (p-2CzBN) and 2,3,4,5,6-penta(9H-carbazol-9-yl)benzonitrile (5CzBN), and addressed the problem of how donor-acceptor (D-A) or donor-acceptor-donor (D-A-D) flexible molecular architectures influence the nature of the excited states and the emission intensity. Furthermore, we analyzed the RISC rates as a function of the conformation of the carbazole lateral groups, considering the first electronic states, S0, S1, T1 and T2, involved in TADF process. The two prototype molecules, p-2CzBN and 5CzBN, have a similar energy gap between the first singlet and triplet states (∆EST, a key parameter in the RISC rate), but different TADF performances. Therefore, other parameters must be considered to explain their different behavior. The oscillator strength of p-2CzBN, never tested as emitter in OLEDs, is similar to that of 5CzBN, which is an active TADF molecule. We also note that the presence of a second T2 triplet state, lower in energy than S1 only in 5CzBN, and the reorganization energies, associated with RISC processes involving T1 and T2, are important factors in differentiating the rates in p-2CzBN and 5CzBN. For p-2CzBN, the RISC rate from T2 to S1 is surprisingly higher than that from T1 to S1, in disagreement with El-Sayed rules, due to a large reorganization energy associated to the T1 to S1, process; while the contrary occurs for 5CzBN. These insights are important for designing new TADF emitters based on the benzo-carbazole architecture.

Agroecological management of insect pests on sugarbeets and lettuce cultivated in organic farming

Two-year field trials were conducted in northern Italy with the aim of developing a trapcrop-based agroecological approach for the control of flea beetles (Chaetocnema tibialis (Illiger), Phyllotreta spp. (Chevrolat) (Coleoptera: Chrysomelidae)) and Lygus rugulipennis Poppius (Hemiptera: Miridae), key pests of sugar beet and lettuce, respectively. Flea beetle damage trials compared a trap cropping treatment, i.e., a sugar beet plot with a border of Sinapis alba (L.) and Brassica juncea (L.) with a control treatment, i.e., a sugar beet plot with bare soil as field border. Sugar beets grown near trap crops showed a significant decrease (≈40%) in flea beetle damage compared to control. Moreover, flea beetle damage varied with distance from the edge of the trap plants, being highest at 2 m from the edge, then decreasing at higher distances. Regarding L. rugulipennis on lettuce two experiments were conducted. A semiochemical-assisted trap cropping trial was supported by another test evaluating the efficacy of pheromones and trap placement. In this trial, it was found that pheromone baited traps caught significantly more specimens of L. rugulipennis than unbaited traps. It was also found that traps placed at ground level produced larger catches than traps placed at the height of 70 cm. In the semiochemical-assisted trap cropping experiment, a treatment where lettuce was grown next to two Alfa-Alfa borders containing pheromone baited traps was compared with a control treatment, where lettuce was grown near bare soil. This experiment showed that the above-mentioned strategy managed to reduce L. rugulipennis damage to lettuce by ≈30%. From these studies, it appears that trap crop-based strategy, alone or with baited traps, made it possible to reduce crop damage to economically acceptable levels and to minimize the need for insecticide treatments, showing that those strategy could be implemented in organic farming as a means of controlling insect pests.

Simulation of photoinduced processes in organic chromophores: mapping photochemically relevant states for accurate dynamics

The simulation of ultrafast photoinduced processes is a fundamental step towards the understanding of the underlying molecular mechanism and interpretation/prediction of experimental data. Performing a computer simulation of a complex photoinduced process is only possible introducing some approximations but, in order to obtain reliable results, the need to reduce the complexity must balance with the accuracy of the model, which should include all the relevant degrees of freedom and a quantitatively correct description of the electronic states involved in the process. This work presents new computational protocols and strategies for the parameterisation of accurate models for photochemical/photophysical processes based on state-of-the-art multiconfigurational wavefunction-based methods. The required ingredients for a dynamics simulation include potential energy surfaces (PESs) as well as electronic state couplings, which must be mapped across the wide range of geometries visited during the wavepacket/trajectory propagation. The developed procedures allow to obtain solid and extended databases reducing as much as possible the computational cost, thanks to, e.g., specific tuning of the level of theory for different PES regions and/or direct calculation of only the needed components of vectorial quantities (like gradients or nonadiabatic couplings). The presented approaches were applied to three case studies (azobenzene, pyrene, visual rhodopsin), all requiring an accurate parameterisation but for different reasons. The resulting models and simulations allowed to elucidate the mechanism and time scale of the internal conversion, reproducing or even predicting new transient experiments. The general applicability of the developed protocols to systems with different peculiarities and the possibility to parameterise different types of dynamics on an equal footing (classical vs purely quantum) prove that the developed procedures are flexible enough to be tailored for each specific system, and pave the way for exact quantum dynamics with multiple degrees of freedom.

Photoredox Catalysis and Nucleophilic Organometallic Reagents – Application in Organic Synthesis

The main purpose of my PhD was the combination of the principles of transition metal catalysis with photoredox catalysis. We focused our attention on the development of novel dual catalytic protocols for the functionalization of carbonyl compounds through the generation of transient nucleophilic organometallic species. Specifically, we focused on the development of new methodologies combining photoredox catalysis with titanium and nickel in low oxidation state. Firstly, a Barbier-type allylation of aromatic and aliphatic aldehydes –catalytic in titanium– in the presence of a blue photon-absorbing dye was developed. Parallelly, we were pleased to observe that the developed methodology could also be extended to the propargylation of aldehydes under analogous conditions. After an extensive re–optimization of all the reaction parameters, we developed an enantioselective and diastereoselective pinacol coupling of aromatic aldehydes promoted by non-toxic, cheap and easy to synthetize titanium complexes. The key feature, that allows the complete (dia)stereocontrol played by titanium, is the employment of a red-absorbing organic dye. The tailored (photo)redox properties of the red-absorbing organic dye [nPr–DMQA+][BF4–] promote the selective reduction of Ti(IV) to Ti(III). Moreover, even if the major contribution in dual photoredox and nickel catalysis is devoted to the realization of cross-coupling-type reactions, we wanted to evaluate different possible scenarios. Our focus was on the possibility of exploiting intermediates arising from the oxidative addition of nickel complexes as transient nucleophilic species. The first topic considered regarded the possibility to perform allylation of aldehydes by dual photoredox and nickel catalysis. In the first instance, a non–stereocontrolled version of the reaction was presented. Finally, after a long series of drastic modification of the reaction conditions, a highly enantioselective variant of the protocol was also reported. All the reported methodologies are supported by careful photophysical analysis and, in some cases, computational modelling.

Chemoenzymatic synthesis: a strategy to obtain xylitol monoesters

BACKGROUND: Fatty acid sugar esters are used as non-ionic surfactants in cosmetics, foodstuffs and pharmaceuticals. In particular, monoesters of xylitol have attracted industrial interest due to their outstanding biological activities. In this work, xylitol monoesters were obtained by chemoenzymatic synthesis, in which, first, xylitol was made soluble in organic solvent by chemo-protecting reaction, followed by enzymatic esterification reaction using different acyl donors. A commercial immobilized Candida antartica lipase was used as catalyst, and reactions with pure xylitol were carried out to generate data for comparison. RESULTS: t-BuOH was found to be the most suitable solvent to carry out esterification reactions with both pure and protected xylitol. The highest yields were obtained for reactions carried out with pure xylitol, but in this case by-products, such as di- and tri-esters isomers were formed, which required a multi-step purification process. For the systems with protected xylitol, conversions of 86%, 58% and 24% were achieved using oleic, lauric and butyric acids, respectively. The structures of the monoesters were confirmed by (13)C- and (1)H-NMR and microanalysis. CONCLUSION: The chemoenzymatic synthesis of xylitol monoesters avoided laborious downstream processing when compared with reactions performed with pure xylitol. Monoesters production from protected xylitol was shown to be a practical, economical, and clean route for this process, allowing a simple separation, because there are no other products formed besides xylitol monoesters and residual xylitol. (C) 2009 Society of Chemical Industry

Energy substrate used by workers of leaf-cutting ants during nest excavation

Energy substrate used by workers of leaf-cutting ants during nest excavation. In this study we aimed to ascertain whether leaf-cutting ant workers lose body reserves (fat or sugars) as a function of nest excavation. For each treatment, we isolated 10 workers of Atta sexdens into two experimental groups, Control (C- without excavation) and Soil (S- with excavation), which were kept for different time intervals (0, 24, 48 or 72 hours), totaling 700 tested workers. We then determined the concentration of soluble carbohydrates and total lipid content in them. The total carbohydrates were determined colorimetrically, based on the reaction between carbohydrates and sulfuric acid-phenol. For determination of lipids, the insects were immersed in organic solvent until they reached a constant weight. Our results showed that carbohydrates are consumed during nest excavation activities. In the experimental groups S24, S48 and S72, there was an average reduction of 5.82 (20.42%), 14.31 (44.96%) and 13.27 (43.96%) µ.mg-1 in soluble sugar when compared with the experimental groups that did not excavate. Furthermore, the lipids were not used during this activity. With respect to dry mass of the workers, their values were C0 = 8%, C24 = 10.4%, C48 = 9.2%, C72 = 10%, S24 = 9.2%, S48 = 8.7% and S72 = 8.5%. Our results show experimentally that the source of energy for nest excavation is carbohydrates, whereas lipids are conserved for other activities.

Efeito do polietilenoglicol e da albumina na imobilização de lipase microbiana e na catálise em meio orgânico

Poly (ethylene) glycol (PEG) and bovine serum albumin (BSA), as additive agents, were used to enhance the activity of immobilized microbial lipase in organic solvent. Controlled pore silica (CPS) was selected as matrix and different immobilization procedures were evaluated: directly lipase binding on CPS and simultaneous addition of lipase and additive agent on the same support. The highest coupling yield (59.6%) was attained when the immobilization procedure was performed at lipase loading of 150 U/g support in the presence of PEG-1.500. This immobilized system was used in esterification reactions under repeated batch cycles and the biocatalyst half-life was found to increase 2.7 times when compared with the control.

COMPARISON OF GINGER (Zingiber officiale Roscoe) OLEORESIN OBTAINED WITH ETHANOL AND ISOPROPANOL WITH THAT OBTAINED WITH PRESSURIZED CO2

Ginger (Zingiber officinale Roscoe) belongs to the Zingiberacea family. It is a spice of great commercial importance. In this work ginger oleoresin was obtained with ethanol, isopropanol and liquid carbon dioxide. The chemical compositions of the extract were compared with each other. All oleoresin samples had monoterpenes and sesquiterpenes. Carboxylic acids were found in organic solvent extracts for an extraction time of 2 hours. The component responsible the for pungent characteristic of the oleoresin, gingerois, were detected in samples obtained with organic solvent for extraction times of 6 hours and in samples obtained with CO2 liquid for extraction times of 2 hours.