Software Security Design and Testing

Elektroninen kaupankäynti ja pankkipalvelut ovat herättäneet toiminnan jatkuvuuden kannalta erittäin kriittisen kysymyksen siitä, kuinka näitä palveluja pystytään suojaamaan järjestäytynyttä rikollisuutta ja erilaisia hyväksikäyttöjä vastaan.

Thromboxane prostaglandin receptor antagonist and carotid atherosclerosis progression in patients with cerebrovascular disease of ischemic origin: a randomized controlled trial.

BACKGROUND AND PURPOSE: Thromboxane prostaglandin receptors have been implicated to be involved in the atherosclerotic process. We assessed whether Terutroban, a thromboxane prostaglandin receptor antagonist, affects the progression of atherosclerosis, as measured by common carotid intima-media thickness and carotid plaques. METHODS: A substudy was performed among 1141 participants of the aspirin-controlled Prevention of Cerebrovascular and Cardiovascular Events of Ischemic Origin with Terutroban in Patients with a History of Ischemic Stroke or Transient Ischemic Attack (PERFORM) trial. Common carotid intima-media thickness and carotid plaque occurrence was measured during a 3-year period. RESULTS: Baseline characteristics did not differ between Terutroban (n=592) and aspirin (n=549) treated patients and were similar as in the main study. Mean study and treatment duration were similar (28 and 25 months, respectively). In the Terutroban group, the annualized rate of change in common carotid intima-media thickness was 0.006 mm per year (95% confidence interval, -0.004 to 0.016) and -0.005 mm per year (95% confidence interval, -0.015 to 0.005) in the aspirin group. There was no statistically significant difference between the groups in the annualized rate of change of common carotid intima-media thickness (0.011 mm per year; 95% confidence interval, -0.003 to 0.025). At 12 months of follow-up, 66% of Terutroban patients had no emergent plaques, 31% had 1 to 2 emergent plaques, and 3% had ≥3 emergent plaques. In the aspirin group, the corresponding percentages were 64%, 32%, and 4%. Over time, there was no statistically significant difference in the number of emergent carotid plaques between treatment modalities (rate ratio, 0.91; 95% confidence interval, 0.77-1.07). CONCLUSIONS: Compared with aspirin, Terutroban did not beneficially affect progression of carotid atherosclerosis among well-treated patients with a history of ischemic stroke or transient ischemic attacks with an internal carotid stenosis <70%. CLINICAL TRIAL REGISTRATION URL: http://www.controlled-trials.com. Unique identifier: ISRCTN66157730.

Predation on common tern eggs by the yellow-legged gull at the Ebro Delta

The Ebro Delta holds a large seabird community, including a common tern (Sterna hirundo) local population of 3,085 pairs in 2000 which breeds scattered in several colonies. At El Canalot colony, 1,178 (1999) and 1,156 pairs (2000) of this species bred distributed in 32 and 38 sub-colonies respectively. These sub-colonies varied in size from 1 to 223 pairs and were placed near the main breeding colonies of yellow-legged gulls (Larus cachinnans) and Audouin´s gulls (L. audouinii), which are potential egg-predators of terns. We studied egg predation during 1999 (6 sub-colonies) and 2000 (27 sub-colonies). Overall, we found that 10.6% of the nests in 1999 and 16.7% in 2000 suffered partial or total egg predation, being total in 81.1% of the predatory events. Predation was significantly higher in small sub-colonies (< 11 pairs): 49.4% in 1999 and 75.5% in 2000. Only attacks from yellow-legged gulls were observed, and defence behaviour of terns was significantly more frequent against this gull species (40.5 hours of observation), suggesting that in most cases the egg predation recorded was due to this species. Probability of egg predation was significantly and negatively correlated with distance to the nearest yellow-legged gull sub-colony, although this relationship was no more significant after adjustment for sub-colony size. On the other hand, distance to the nearest Audouin´s gull sub-colony did not show any effect. Our results suggest that the impact of large gulls (at least yellow-legged gulls) upon smaller seabirds breeding in the area might be important, especially when they are breeding in small sub-colonies. Further studies are needed to analyse the general impact of large gulls upon the breeding populations of other colonial bird species in the area.

Emotions in International Politics. Beyond Mainstream International Relations

In recent years, social scientists have increasingly recognized the interconnectedness of thought on emotions. Nowhere is the role of passions more evident than international politics, where pride, anger, guilt, fear, empathy, and other feelings are routinely on display. But in the absence of an overarching theory of emotions, how can we understand their role at the international level? Emotions in International Politics fills the need for theoretical tools in the new and rapidly growing subfield of international relations. Eminent scholars from a range of disciplines consider how emotions can be investigated from an international perspective involving collective players, drawing evidence from such emotionally fraught events as the Rwandan genocide, World War II, the 9/11 attacks, and the Iranian nuclear standoff. The path-breaking research collected in Emotions in International Politics will be a valuable theoretical guide to understanding conflict and cooperation in international relations.

Pre-dispersal predation effect on seed packaging strategies and seed viability.

An increased understanding of intraspecific seed packaging (i.e. seed size/number strategy) variation across different environments may improve current knowledge of the ecological forces that drive seed evolution in plants. In particular, pre-dispersal seed predation may influence seed packaging strategies, triggering a reduction of the resources allocated to undamaged seeds within the preyed fruits. Assessing plant reactions to pre-dispersal seed predation is crucial to a better understanding of predation effects, but the response of plants to arthropod attacks remains unexplored. We have assessed the effect of cone predation on the size and viability of undamaged seeds in populations of Juniperus thurifera with contrasting seed packaging strategies, namely, North African populations with single-large-seeded cones and South European populations with multi-small-seeded cones. Our results show that the incidence of predation was lower on the single-large-seeded African cones than on the multi-small-seeded European ones. Seeds from non-preyed cones were also larger and had a higher germination success than uneaten seeds from preyed cones, but only in populations with multi-seeded cones and in cones attacked by Trisetacus sp., suggesting a differential plastic response to predation. It is possible that pre-dispersal seed predation has been a strong selective pressure in European populations with high cone predation rates, being a process which maintains multi-small-seeded cones and empty seeds as a strategy to save some seeds from predation. Conversely, pre-dispersal predation might not have a strong effect in the African populations with single-large-seeded cones characterized by seed germination and filling rates higher than those in the European populations. Our results indicate that differences in pre-dispersal seed predators and predation levels may affect both selection on and intraspecific variation in seed packaging.

Neurologie [Neurology].

In 2015, cerebral stimulation becomes increasingly established in the treatment of pharmacoresistant epilepsy. Efficacy of endovascular treatment has been demonstrated for acute ischemic stroke. Deep brain stimulation at low frequency improves dysphagia and freezing of gait in Parkinson patients. Bimagrumab seems to increase muscular volume and force in patients with inclusion body myositis. In cluster-type headache, a transcutaneous vagal nerve stimulator is efficient in stopping acute attacks and also reducing their frequency. Initial steps have been undertaken towards modulating memory by stimulation of the proximal fornix. Teriflunomide is the first oral immunomodulatory drug for which efficacy has been shown in preventing conversion from clinical isolated syndrome to multiple sclerosis.

PEC1/AtABCG32 transport function in cuticle biosynthesis

Most aerial parts of the plants are covered by a hydrophobic coating called cuticle. The cuticle is formed of cutin, a complex mixture of esterified fatty acids that are embedded and associated with waxes. The cuticle often appears as a superposition of layers of different composition: The cuticle proper formed of cutin and a mixture of waxes and underneath, the cuticle layer containing cutin, intracuticular waxes and polysaccharides of the cell wall. In addition to its involvement in plant development by preventing organ fusions, the cuticle acts as a barrier to prevent water loss and protect plants against environmental aggressions such as excessive radiation or pathogens attacks. PEC1/AtABCG32 is an ABC transporter from the PDR family involved in cutin biosynthesis. Characterization of the peci mutant in Arabidopsis thaliana showed that PEC1 plays a significant role in the diffusion barrier formation in leaves and petals. The cuticles of leaves and flowers of peci are permeable and the cuticular layer rather than the cuticular proper was altered in the petals, underlining the importance of this particular layer in the maintenance of the diffusion barrier. Chemical analysis on the flower cutin monomer composition of ped mutant revealed a decrease in hydroxylated cutin monomers, suggesting a function of PEC1 in the incorporation of these monomers in the polymer cutin. However, the exact nature of the substrates of PEC1 remained elusive. PEC1 homologues in barley and rice, respectively HvABCG31/EIBI1 and OsABCG31, are also implicated in cuticle biosynthesis. Interestingly, the rice mutant displays more severe phenotypes such as dwarfism and spreading necrosis conducting to the seedling death. In this work, we further characterized osabcg31 mutant and hairpin-RNAi downregulated OsABCG31 plant lines showing reduced growth and cuticle permeability. Our analysis showed a decrease in hydroxylated cutin monomers and severe disruptions in the cuticle, which explain the permeability. Further insights into the function of the cuticle in rice resistance/susceptibility to Pathogens were obtained after inoculation with Magnaporthe oryzae, the fungus responsible for the rice blast disease. Osabcg31 as well as the transgenic lines downregulating OsABCG31 showed increased resistance to the fungus. However, only later steps of infection are reduced . and no impact is obseived on the germination or penetration stages, suggesting that the cuticle disruption per se is not responsible for the resistance. We further investigated the cause of the resistance by analyzing the expression of defense related gene in osabcg31 prior to infection. We found that osabcg31 constitutively express defense related genes, which may explain the resistance, the dwarfism and the cell death. osabcg31 is thus a tool to study the connection between cuticle, plant development and defense signaling networks in rice. The transport function of PEC1 family members is still unknown. In order to link cutin biosynthesis and transport activity, we combined ped mutation with mutations in cutin synthesis related genes. Here, we show that PEC1 acts independently from GPAT4 and GPAT8 pathway and partially overlaps with GPAT6 biosynthesis pathway that leads to the production of hydroxylated C16 cutin precursor 2-Mono(10,16-dihydroxyhexadecanoylJglycerol (2-MHG). In addition, we noticed that despite a comparable cutin monomer composition, ped mutant leaves cuticle are permeable while that of gpat6 mutant are not. This finding raises the possibility of PEC1 being required for the incorporation of C16 hydroxylated monomers and their structural arrangement rather than their direct transport towards the cuticle. A careful investigation of the cuticle permeability, cutin composition and ultrastructure during leave development in Wt plants and ped mutants revealed a possible different regulation of several pathways of cutin biosynthesis and showed the importance of PEC1 function early during leave cuticle maturation. In order to elucidate the transport activity of PEC1, we successfully expressed PEC1 in Nicotiana benthamiana plant system for direct transport experiments. This system will be used to test the PEC 1-dependent transport of potential substrates such as sn-2-monoacylglycerol loaded with a hydroxylated C16 fatty acid. -- Toutes les parties aériennes des plantes sont recouvertes d'une couche hydrophobe appelée «cuticule». Cette cuticule est composée de cutine, un polymère d'acides gras estérifiés, et de cires. La cuticule apparaît souvent sous forme de couches superposées: une première couche extérieure appelée «cuticle proper» formée de cutine et d'un mélange de cires, et une deuxième couche, la «cuticle layer», formée de cutine associée à des cires intracuticulaires et des polysaccharides pariétaux. La cuticule joue le rôle de barrière prévenant contre la perte d'eau et les agressions environnementales. AtABCG32/PEC1 est un transporteur ABC de la famille des PDR impliqué dans la synthèse de la cutine. L'étude du mutant peci d'Arabidopsis thaliana a révélé une fonction de PEC1 dans la formation de la barrière de diffusion. La cuticule des feuilles et fleurs de peci est perméable. Des altérations de la «cuticle layer» ont été démontrées, soulignant son importance dans le maintien de la barrière. L'analyse de la composition de la cutine de peci a montré une réduction spécifique en monomères hydroxylés, suggérant un rôle de PEC1 dans leur incorporation dans la cuticule. Cependant, la nature exacte des substrats de PEC1 n'a pas été identifiée. PEC1 possède deux homologues chez l'orge et le riz, respectivement HvABCG31 et OsABCG31, et qui sont impliqués dans la biosynthèse de la cuticule. Chez le riz, des phénotypes plus sévères ont été observés tels que nanisme et nécroses conduisant à la mort des jeunes plants. Dans cette étude, nous avons continué la caractérisation de osabcg31 ainsi que des lignées de riz sous exprimant le gène OsABCG31 et présentant une cuticule perméable tout en ayant une meilleure croissance. Notre étude a démontré une réduction des monomères hydroxylés de cutine et une désorganisation de la structure de la cuticule, aggravée dans le mutant osabcg31. Ce résultat explique la perméabilité observée. Des mformations P|us approfondies sur l'implication de la cuticule dans la résistance aux pathogènes ont été obtenues après inoculation du mutant osabcg31 et les lignées sous- exprimant OsABCG31 avec une souche virulente de Magnaporthe Oryzae, le champignon responsable de la pyriculariose du riz. Les différentes lignées testées ont démontré une résistance au pathogène. Cependant, seules les étapes tardives de l'infection sont réduites et aucun impact n'est observé sur la germination des spores ou la pénétration du champignon, suggérant que les modifications de la cuticule ne sont pas directement à l'origine de la résistance. L'analyse de l'expression de gènes impliqués dans la résistance à Magnaporthe.oryzae a mis en évidence l'expression constitutive de ces gènes en l'absence de tout contact avec le pathogène. Ceci explique la résistance, le nanisme et la mort cellulaire observés. Ainsi, osabcg31 représente un outil efficace pour l'étude intégrée des systèmes de régulation de la défense, de développement des plantes et la cuticule. La nature des substrats transportés par PEC1/AtABCG32 reste inconnue. Dans le but d'établir une liaison entre biosynthèse de cutine et transport des précurseurs par PEC1, la mutation peci a été combinée avec des mutants impliqués dans différentes voies de biosynthèse. Cette étude a démontré une fonction indépendante de PEC1 de la voie de biosynthèse impliquant les enzymes GPAT4 et GPAT8, et une fonction partiellement indépendante de la voie impliquant GPAT6 qui mène à la production de précurseurs sn-2- monoacylglycerol chargés en acides gras en C16 (2-MHG). De plus, malgré un profil similaire en monomères de cutine, gpat6 conserve une cuticule imperméable alors que celle de PEC1 est perméable. Ceci suggère que PEC1 est nécessaire à l'incorporation des monomères en C16 et leur arrangement structurel plutôt que simplement à leur transport direct. L'étude approfondie de la perméabilité cuticulaire, de la structure ainsi que de la composition en cutine pendant le développement des feuilles de peci et la plante sauvage a révélé l'existence de différentes régulations des voies de biosynthèses des monomères et a démontré l'importance de PEC1 dans les premières étapes de la mise en place de la cuticule. Pour identifier les substrats transportés, l'expression de PEC1 chez le système hétérologue Nicotiana benthamiana a été conduite avec succès. Ce système sera utilisé pour tester le transport de substrats potentiels tels que le sn-2-monoacylglycerol chargé en acide gras en C16.

Review of Rewriting Terror: The 9/11 Terrorists in American Fiction (Juanjo Bermúdez de Castro, 2012)

In the wake of the terrorist attacks of September 11, 2001, many authors of fiction, filmmakers, journalists, public figures and scholars have attempted to narrate, recreate, explain, reflect on, and theorize about the event and its aftermath.

”Kyllähän nyt pitäs olla jo semmonen aika, että pääsis niin kö keskustelemhan näistä asioista.” Tutkimus lappilaisten sotavankien, partisaanien uhrien ja huutolaisten elämänkulusta, voimavaroista, terveydestä ja sairauksista

Research into the course of life, mental stamina and health status of wartime prisoners, victims of Soviet partisan attacks, and paupers in Finnish Lapland The basis of this research comprised the issues raised during the interviews conducted in my work as a general practitioner in Lapland, regarding factors that have possibly affected the life stories and health conditions of Lappish people who had lived through the war as war prisoners, victims of partisan attacks, or paupers. The purpose of the study was to describe how the different life phases and experiences emerged from the interviewees’ stories and to identify their mental stamina. Another goal was to make observations on their health status, in which the main emphasis became to address mental symptoms. The cohort consisted of elderly Finns who lived in Lapland during the war and experienced war imprisonment, pauperism, or became victims of partisan attacks. All three groups consisted of 12 interviewees. The interview transcripts were read several times and then investigated using the content analysis methods applicable to the material. The research methodology was based on building awareness and understanding. Thematic tagging and data coding were used as structured analysis tools. In all three groups most of the interviewees clearly identified their mental stamina, the most fundamental of which were home, family and work. The war prisoners’ injuries and nervous sensibility symptoms had been shown in earlier studies on war prisoners, and on this basis they had been granted disability pensions. However, many of them had suppressed their traumatic experiences and mental difficulties, and they could not talk about these issues until at the time of these interviews held at old age. Four of them still suffered from a post-traumatic stress disorder. The victims of Soviet partisans had had to carry their mental load alone for decades before the cruel ravages on civilians in remote areas of Lapland became publicly known. Most of them still had disturbing nervous sensibility symptoms. Four interviewees had a post-traumatic stress disorder, and in addition to these, the mental symptoms of one had developed into a post-traumatic stress disorder during old age. Many of the interviewees who had been left paupers remembered their childhood as filled with grief and feelings of inferiority, and had nightmares relating to their wartime experiences. Yet none of them suffered from post-traumatic stress disorder. The results showed that the exceptional suffering caused by the war, the wartime imprisonment and the devastating attacks by Soviet partisans had led especially to mental difficulties. These were left almost completely unnoticed in the post-war conditions, and the war victims were unable to seek help on their own. Based on the results, our health care for the elderly should focus on familiarization with the individual experiences and life stories of each elderly person. This can facilitate geriatric diagnostics and individual therapy planning. Empathic familiarization with the life experiences of the elderly may strengthen their mental stamina and improve the quality of successful aging.

Knapsack sets for cryptography

The basic goal of this study is to extend old and propose new ways to generate knapsack sets suitable for use in public key cryptography. The knapsack problem and its cryptographic use are reviewed in the introductory chapter. Terminology is based on common cryptographic vocabulary. For example, solving the knapsack problem (which is here a subset sum problem) is termed decipherment. Chapter 1 also reviews the most famous knapsack cryptosystem, the Merkle Hellman system. It is based on a superincreasing knapsack and uses modular multiplication as a trapdoor transformation. The insecurity caused by these two properties exemplifies the two general categories of attacks against knapsack systems. These categories provide the motivation for Chapters 2 and 4. Chapter 2 discusses the density of a knapsack and the dangers of having a low density. Chapter 3 interrupts for a while the more abstract treatment by showing examples of small injective knapsacks and extrapolating conjectures on some characteristics of knapsacks of larger size, especially their density and number. The most common trapdoor technique, modular multiplication, is likely to cause insecurity, but as argued in Chapter 4, it is difficult to find any other simple trapdoor techniques. This discussion also provides a basis for the introduction of various categories of non injectivity in Chapter 5. Besides general ideas of non injectivity of knapsack systems, Chapter 5 introduces and evaluates several ways to construct such systems, most notably the "exceptional blocks" in superincreasing knapsacks and the usage of "too small" a modulus in the modular multiplication as a trapdoor technique. The author believes that non injectivity is the most promising direction for development of knapsack cryptosystema. Chapter 6 modifies two well known knapsack schemes, the Merkle Hellman multiplicative trapdoor knapsack and the Graham Shamir knapsack. The main interest is in aspects other than non injectivity, although that is also exploited. In the end of the chapter, constructions proposed by Desmedt et. al. are presented to serve as a comparison for the developments of the subsequent three chapters. Chapter 7 provides a general framework for the iterative construction of injective knapsacks from smaller knapsacks, together with a simple example, the "three elements" system. In Chapters 8 and 9 the general framework is put into practice in two different ways. Modularly injective small knapsacks are used in Chapter 9 to construct a large knapsack, which is called the congruential knapsack. The addends of a subset sum can be found by decrementing the sum iteratively by using each of the small knapsacks and their moduli in turn. The construction is also generalized to the non injective case, which can lead to especially good results in the density, without complicating the deciphering process too much. Chapter 9 presents three related ways to realize the general framework of Chapter 7. The main idea is to join iteratively small knapsacks, each element of which would satisfy the superincreasing condition. As a whole, none of these systems need become superincreasing, though the development of density is not better than that. The new knapsack systems are injective but they can be deciphered with the same searching method as the non injective knapsacks with the "exceptional blocks" in Chapter 5. The final Chapter 10 first reviews the Chor Rivest knapsack system, which has withstood all cryptanalytic attacks. A couple of modifications to the use of this system are presented in order to further increase the security or make the construction easier. The latter goal is attempted by reducing the size of the Chor Rivest knapsack embedded in the modified system. '

A Fair and Secure Cluster Formation Process for Ad Hoc Networks

An efficient approach for organizing large ad hoc networks is to divide the nodesinto multiple clusters and designate, for each cluster, a clusterhead which is responsible forholding intercluster control information. The role of a clusterhead entails rights and duties.On the one hand, it has a dominant position in front of the others because it manages theconnectivity and has access to other node¿s sensitive information. But on the other hand, theclusterhead role also has some associated costs. Hence, in order to prevent malicious nodesfrom taking control of the group in a fraudulent way and avoid selfish attacks from suitablenodes, the clusterhead needs to be elected in a secure way. In this paper we present a novelsolution that guarantees the clusterhead is elected in a cheat-proof manner.

Metabólitos secundários de origem vegetal: uma fonte potencial de fármacos antitrombóticos

Cardiovascular diseases are responsible for the largest number of deaths among humans worldwide, including heart attacks, strokes, and thrombosis. The treatment of thrombosis is generally through the administration of anticoagulant and/or antiplatelet drugs, which have some clinical limitations. Plants synthesize a wide variety of bioactive metabolites in response to different stimuli. This review focuses on a number of molecules of vegetal origin belonging to different chemical classes, with significant anticoagulant and antiplatelet effects. Their promising antithrombotic profile confirms the potential of natural products as a source of lead molecules for drug development in the prevention and treatment of thrombosis.

Purificação e caracterização da quitinase de uva (Vitis vinífera L. cv Red Globe) para a produção de quitosana a partir de quitina de camarão

Chitinase is produced by a wide variety of plants as a defense against peste attacks. In this study, grape chitinases were purified 16 times by fractionation in 80% ammonium sulfate followed by dialysis and filtration. Purified chitinases exhibited enzymatic activity toward chitin azure. The yield of purified chitinase was 229 mg/L with chitinase activity of 563 U/g. Chitinases had molecular masses of 24 and 30 kDa, as evaluated by SDS-PAGE 12.5%. Two pH optima were determined 3.0 and 6.0. The optimal temperature was 42 °C. Pre hydrolysis of crystalline shrimp chitin by chitinases caused in an increase in the deacetylation ratio triggered by chitin deacetylase producing chitooligosaccharides with DA (degree acetylation) of 58.8%.

Química Sem Fronteiras: o desafio da energia

Coal, natural gas and petroleum-based liquid fuels are still the most widely used energy sources in modern society. The current scenario contrasts with the foreseen shortage of petroleum that was spread out in the beginning of the XXI century, when the concept of "energy security" emerged as an urgent agenda to ensure a good balance between energy supply and demand. Much beyond protecting refineries and oil ducts from terrorist attacks, these issues soon developed to a portfolio of measures related to process sustainability, involving at least three fundamental dimensions: (a) the need for technological breakthroughs to improve energy production worldwide; (b) the improvement of energy efficiency in all sectors of modern society; and (c) the increase of the social perception that education is a key-word towards a better use of our energy resources. Together with these technological, economic or social issues, "energy security" is also strongly influenced by environmental issues involving greenhouse gas emissions, loss of biodiversity in environmentally sensitive areas, pollution and poor solid waste management. For these and other reasons, the implementation of more sustainable practices in our currently available industrial facilities and the search for alternative energy sources that could partly replace the fossil fuels became a major priority throughout the world. Regarding fossil fuels, the main technological bottlenecks are related to the exploitation of less accessible petroleum resources such as those in the pre-salt layer, ranging from the proper characterization of these deep-water oil reservoirs, the development of lighter and more efficient equipment for both exploration and exploitation, the optimization of the drilling techniques, the achievement of further improvements in production yields and the establishment of specialized training programs for the technical staff. The production of natural gas from shale is also emerging in several countries but its production in large scale has several problems ranging from the unavoidable environmental impact of shale mining as well as to the bad consequences of its large scale exploitation in the past. The large scale use of coal has similar environmental problems, which are aggravated by difficulties in its proper characterization. Also, the mitigation of harmful gases and particulate matter that are released as a result of combustion is still depending on the development of new gas cleaning technologies including more efficient catalysts to improve its emission profile. On the other hand, biofuels are still struggling to fulfill their role in reducing our high dependence on fossil fuels. Fatty acid alkyl esters (biodiesel) from vegetable oils and ethanol from cane sucrose and corn starch are mature technologies whose market share is partially limited by the availability of their raw materials. For this reason, there has been a great effort to develop "second-generation" technologies to produce methanol, ethanol, butanol, biodiesel, biogas (methane), bio-oils, syngas and synthetic fuels from lower grade renewable feedstocks such as lignocellulosic materials whose consumption would not interfere with the rather sensitive issues of food security. Advanced fermentation processes are envisaged as "third generation" technologies and these are primarily linked to the use of algae feedstocks as well as other organisms that could produce biofuels or simply provide microbial biomass for the processes listed above. Due to the complexity and cost of their production chain, "third generation" technologies usually aim at high value added biofuels such as biojet fuel, biohydrogen and hydrocarbons with a fuel performance similar to diesel or gasoline, situations in which the use of genetically modified organisms is usually required. In general, the main challenges in this field could be summarized as follows: (a) the need for prospecting alternative sources of biomass that are not linked to the food chain; (b) the intensive use of green chemistry principles in our current industrial activities; (c) the development of mature technologies for the production of second and third generation biofuels; (d) the development of safe bioprocesses that are based on environmentally benign microorganisms; (e) the scale-up of potential technologies to a suitable demonstration scale; and (f) the full understanding of the technological and environmental implications of the food vs. fuel debate. On the basis of these, the main objective of this article is to stimulate the discussion and help the decision making regarding "energy security" issues and their challenges for modern society, in such a way to encourage the participation of the Brazilian Chemistry community in the design of a road map for a safer, sustainable and prosper future for our nation.

GLOBAL AND LOCAL REACTIVITY DESCRIPTORS FOR PICLORAM HERBICIDE: A THEORETICAL QUANTUM STUDY

In this work, we studied the reactivity of picloram in the aqueous phase at the B3LYP/6-311++G(2d,2p) and MP2/6-311++G(2d,2p) levels of theory through global and local reactivity descriptors. The results obtained at the MP2 level indicate that the cationic form of picloram exhibits the highest hardness while the anionic form is the most nucleophilic. From the Fukui function values, the most reactive site for electrophilic and free radical attacks are on the nitrogen in the pyridine ring. The more reactive sites for nucleophilic attacks are located on the nitrogen atom of the amide group and on the carbon atoms located at positions 2 and 3 in the pyridine ring.