Correlation Between Molecular Conformation, Packing, and Dynamics in Oligofluorenes: A Theoretical/Experimental Study

Fluorene-based systems have shown great potential as components in organic electronics and optoelectronics (organic photovoltaics, OPVs, organic light emitting diodes, OLEDs, and organic transistors, OTFTs). These systems have drawn attention primarily because they exhibit strong blue emission associated with relatively good thermal stability. It is well-known that the electronic properties of polymers are directly related to the molecular conformations and chain packing of polymers. Here, we used three oligofluorenes (trimer, pentamer, and heptamer) as model systems to theoretically investigate the conformational properties of fluorene molecules, starting with the identification of preferred conformations. The hybrid exchange correlation functional, OPBE, and ZINDO/S-CI showed that each oligomer exhibits a tendency to adopt a specific chain arrangement, which could be distinguished by comparing their UV/vis electronic absorption and C-13 NMR spectra. This feature was used to identify the preferred conformation of the oligomer chains in chloroform-cast films by comparing experimental and theoretical UV/vis and C-13 NMR spectra. Moreover, the oligomer chain packing and dynamics in the films were studied by DSC and several solid state NMR techniques, which indicated that the phase behavior of the films may be influenced by the tendency that each oligomeric chain has to adopt a given conformation.

Biological invasions and the acoustic niche: the effect of bullfrog calls on the acoustic signals of white-banded tree frogs

Invasive species are known to affect native species in a variety of ways, but the effect of acoustic invaders has not been examined previously. We simulated an invasion of the acoustic niche by exposing calling native male white-banded tree frogs (Hypsiboas albomarginatus) to recorded invasive American bullfrog (Lithobates catesbeianus) calls. In response, tree frogs immediately shifted calls to significantly higher frequencies. In the post-stimulus period, they continued to use higher frequencies while also decreasing signal duration. Acoustic signals are the primary basis of mate selection in many anurans, suggesting that such changes could negatively affect the reproductive success of native species. The effects of bullfrog vocalizations on acoustic communities are expected to be especially severe due to their broad frequency band, which masks the calls of multiple species simultaneously.

Root niche separation can explain avoidance of seasonal drought stress and vulnerability of overstory trees to extended drought in a mature Amazonian forest

Large areas of Amazonian evergreen forest experience seasonal droughts extending for three or more months, yet show maximum rates of photosynthesis and evapotranspiration during dry intervals. This apparent resilience is belied by disproportionate mortality of the large trees in manipulations that reduce wet season rainfall, occurring after 2-3 years of treatment. The goal of this study is to characterize the mechanisms that produce these contrasting ecosystem responses. A mechanistic model is developed based on the ecohydrological framework of TIN (Triangulated Irregular Network)-based Real Time Integrated Basin Simulator + Vegetation Generator for Interactive Evolution (tRIBS+VEGGIE). The model is used to test the roles of deep roots and soil capillary flux to provide water to the forest during the dry season. Also examined is the importance of "root niche separation," in which roots of overstory trees extend to depth, where during the dry season they use water stored from wet season precipitation, while roots of understory trees are concentrated in shallow layers that access dry season precipitation directly. Observational data from the Tapajo's National Forest, Brazil, were used as meteorological forcing and provided comprehensive observational constraints on the model. Results strongly suggest that deep roots with root niche separation adaptations explain both the observed resilience during seasonal drought and the vulnerability of canopy-dominant trees to extended deficits of wet season rainfall. These mechanisms appear to provide an adaptive strategy that enhances productivity of the largest trees in the face of their disproportionate heat loads and water demand in the dry season. A sensitivity analysis exploring how wet season rainfall affects the stability of the rainforest system is presented. Citation: Ivanov, V. Y., L. R. Hutyra, S. C. Wofsy, J. W. Munger, S. R. Saleska, R. C. de Oliveira Jr., and P. B. de Camargo (2012), Root niche separation can explain avoidance of seasonal drought stress and vulnerability of overstory trees to extended drought in a mature Amazonian forest, Water Resour. Res., 48, W12507, doi:10.1029/2012WR011972.

Analysis of 16S rRNA and mxaF genes revealing insights into Methylobacterium niche-specific plant association

The genus Methylobacterium comprises pink-pigmented facultative methylotrophic (PPFM) bacteria, known to be an important plant-associated bacterial group. Species of this group, described as plant-nodulating, have the dual capacity of producing cytokinin and enzymes, such as pectinase and cellulase, involved in systemic resistance induction and nitrogen fixation under specific plant environmental conditions. The aim hereby was to evaluate the phylogenetic distribution of Methylobacterium spp. isolates from different host plants. Thus, a comparative analysis between sequences from structural (16S rRNA) and functional mxaF (which codifies for a subunit of the enzyme methanol dehydrogenase) ubiquitous genes, was undertaken. Notably, some Methylobacterium spp. isolates are generalists through colonizing more than one host plant, whereas others are exclusively found in certain specific plant-species. Congruency between phylogeny and specific host inhabitance was higher in the mxaF gene than in the 16S rRNA, a possible indication of function-based selection in this niche. Therefore, in a first stage, plant colonization by Methylobacterium spp. could represent generalist behavior, possibly related to microbial competition and adaptation to a plant environment. Otherwise, niche-specific colonization is apparently impelled by the host plant.

Form III-like conformation and Form I-like packing in a chloroform channel solvate of the diuretic drug chlortalidone

Chlortalidone (CTD) is an antihypertensive drug for which only two solid state phases have been structurally elucidated thus far. Here, we have prepared a chloroform solvate thereof, namely, CTD Form IV, and its structure was compared to those of Form I and Form III. Its two conformers exhibit a dual structural feature in relation to the antecedent polymorphs. Both CTD molecules of Form IV adopt a Form III-like conformation, which is featured, if the conformation of CTD Form I is used as a reference, by a rotation of about 90 degrees on the axis of the C-C bond bridging the substituted benzene and isoindolinyl rings. However, CTD Form IV assembles as in the Form I crystal packing despite the different stacking fashion of their centrosymmetric dimers. In contrast to Form I, there is no offset stacking in Form IV, which forces a bend of ca. 24 degrees between the planes passing through the isoindolinyl moieties of two [100]-stacked dimers. Chloroform molecules at a maximum stoichiometry of 0.25 mol per mol of the drug play a stabilizing role in the assembly of Form IV by filling the channels formed on the crystals.

Molecular mapping of the regenerative niche in a murine model of myocardial infarction

Adult stem cells are distributed through the whole organism, and present a great potential for the therapy of different types of disease. For the design of efficient therapeutic strategies, it is important to have a more detailed understanding of their basic biological characteristics, as well as of the signals produced by damaged tissues and to which they respond. Myocardial infarction (MI), a disease caused by a lack of blood flow supply in the heart, represents the most common cause of morbidity and mortality in the Western world. Stem cell therapy arises as a promising alternative to conventional treatments, which are often ineffective in preventing loss of cardiomyocytes and fibrosis. Cell therapy protocols must take into account the molecular events that occur in the regenerative niche of MI. In the present study, we investigated the expression profile of ten genes coding for chemokines or cytokines in a murine model of MI, aiming at the characterization of the regenerative niche. MI was induced in adult C57BL/6 mice and heart samples were collected after 24 h and 30 days, as well as from control animals, for quantitative RT-PCR. Expression of the chemokine genes CCL2, CCL3, CCL4, CCL7, CXCL2 and CXCL10 was significantly increased 24 h after infarction, returning to baseline levels on day 30. Expression of the CCL8 gene significantly increased only on day 30, whereas gene expression of CXCL12 and CX3CL1 were not significantly increased in either ischemic period. Finally, expression of the IL-6 gene increased 24 h after infarction and was maintained at a significantly higher level than control samples 30 days later. These results contribute to the better knowledge of the regenerative niche in MI, allowing a more efficient selection or genetic manipulation of cells in therapeutic protocols.

Body packing by rectal insertion of cocaine packets: a case report

Background: Body packing is used for international drug transport, immediate drug concealment during a police searching or introducing drugs inside prisons. Despite the high level of specialization of dealers who have started to manufacture more complex packs, up to 5% of patients could develop intoxication due to pack rupture. Bowel obstruction is another acute complication. Case presentation: A 27-year-old black male patient was sent to the hospital by court order for clinical evaluation and toxicological examination. The patient was conscious, oriented, had good color, normal arterial pressure and heart rate, and no signs of acute intoxication. Abdominal examination revealed discrete pain upon deep palpation and a small mass in the left iliac fossa. A plain abdominal radiograph revealed several oval structures located in the rectum and sigmoid. Fasting and a 50 g dose of activated charcoal every six hours were prescribed. After three days, the patient spontaneously evacuated 28 cocaine packs. Conclusion: Adequate clinical management and prompt identification of potential complications are of fundamental importance in dealing with body packing.

Analysis of 16S rRNA and mxaF genes reveling insights into Methylobacterium niche-specific plant association

The genus Methylobacterium comprises pink-pigmented facultative methylotrophic (PPFM) bacteria, known to be an important plant-associated bacterial group. Species of this group, described as plant-nodulating, have the dual capacity of producing cytokinin and enzymes, such as pectinase and cellulase, involved in systemic resistance induction and nitrogen fixation under specific plant environmental conditions. The aim hereby was to evaluate the phylogenetic distribution of Methylobacterium spp. isolates from different host plants. Thus, a comparative analysis between sequences from structural (16S rRNA) and functional mxaF (which codifies for a subunit of the enzyme methanol dehydrogenase) ubiquitous genes, was undertaken. Notably, some Methylobacterium spp. isolates are generalists through colonizing more than one host plant, whereas others are exclusively found in certain specific plant-species. Congruency between phylogeny and specific host inhabitance was higher in the mxaF gene than in the 16S rRNA, a possible indication of function-based selection in this niche. Therefore, in a first stage, plant colonization by Methylobacterium spp. could represent generalist behavior, possibly related to microbial competition and adaptation to a plant environment. Otherwise, niche-specific colonization is apparently impelled by the host plant.

Parallel Layout Construction Algorithm for Irregular Shape Packing Problems

Cutting and packing problems arise in a variety of industries, including garment, wood and shipbuilding. Irregular shape packing is a special case which admits irregular items and is much more complex due to the geometry of items. In order to ensure that items do not overlap and no item from the layout protrudes from the container, the collision free region concept was adopted. It represents all possible translations for a new item to be inserted into a container with already placed items. To construct a feasible layout, collision free region for each item is determined through a sequence of Boolean operations over polygons. In order to improve the speed of the algorithm, a parallel version of the layout construction was proposed and it was applied to a simulated annealing algorithm used to solve bin packing problems. Tests were performed in order to determine the speed improvement of the parallel version over the serial algorithm

Two-Dimensional Bin Packing Problem with Guillotine Restrictions

This thesis, after presenting recent advances obtained for the two-dimensional bin packing problem, focuses on the case where guillotine restrictions are imposed. A mathematical characterization of non-guillotine patterns is provided and the relation between the solution value of the two-dimensional problem with guillotine restrictions and the two-dimensional problem unrestricted is being studied from a worst-case perspective. Finally it presents a new heuristic algorithm, for the two-dimensional problem with guillotine restrictions, based on partial enumeration, and computationally evaluates its performance on a large set of instances from the literature. Computational experiments show that the algorithm is able to produce proven optimal solutions for a large number of problems, and gives a tight approximation of the optimum in the remaining cases.

Packing a trunk : a physically based approach with full motional freedom

Geometric packing problems may be formulated mathematically as constrained optimization problems. But finding a good solution is a challenging task. The more complicated the geometry of the container or the objects to be packed, the more complex the non-penetration constraints become. In this work we propose the use of a physics engine that simulates a system of colliding rigid bodies. It is a tool to resolve interpenetration conflicts and to optimize configurations locally. We develop an efficient and easy-to-implement physics engine that is specialized for collision detection and contact handling. In succession of the development of this engine a number of novel algorithms for distance calculation and intersection volume were designed and imple- mented, which are presented in this work. They are highly specialized to pro- vide fast responses for cuboids and triangles as input geometry whereas the concepts they are based on can easily be extended to other convex shapes. Especially noteworthy in this context is our ε-distance algorithm - a novel application that is not only very robust and fast but also compact in its im- plementation. Several state-of-the-art third party implementations are being presented and we show that our implementations beat them in runtime and robustness. The packing algorithm that lies on top of the physics engine is a Monte Carlo based approach implemented for packing cuboids into a container described by a triangle soup. We give an implementation for the SAE J1100 variant of the trunk packing problem. We compare this implementation to several established approaches and we show that it gives better results in faster time than these existing implementations.

Il modello green office come nicchia strategica per la transizione sostenibile del sistema universita the green office model as strategic niche for sustainability transition of hei systems

Nella prima parte di questo progetto di tesi, ho analizzato tutte le nozioni teoriche rilevanti in merito alla teoria della transizione. Il primo concetto condiviso in questa trattazione è quello di transizione. Nella parte finale del capitolo, il focus si sposta sul ruolo, in una generica transizione, delle nicchie. Lo strumento centrale in questa struttura sono gli esperimenti di transizione, i quali forniscono un approccio alternativo ai progetti di innovazione classica che sono incentrati nell'ottenimento di soluzioni a breve termine. Vi è dunque una forte relazione tra nicchia e sperimentazione. Infine la trattazione si concentra sul tema dello Strategic Niche Management. Nel secondo capitolo, analizzo il tema della sostenibilità inserita in un contesto universitario. Questa sezione si focalizza sulle strategie di alto livello richieste per dare avvio alla transizione universitaria verso la sostenibilità, identificando gli ostacoli e gli elementi portanti, e definendo una vision al fine di concretizzarla. Il capitolo guida, passo per passo, le università che tentano di mettere in pratica il proprio obiettivo e la vision di sviluppo sostenibile. Una delle problematiche principali per stimare gli sforzi verso la sostenibilità nelle università è costituita in modo particolare dagli strumenti di valutazione. Per questo motivo, è stata sviluppata la valutazione grafica della sostenibilità nell'università (GASU). Al fine di riassumere quanto detto fin qui ed avere un quadro generale più chiaro dell'organizzazione di un campus universitario che mira a diventare sostenibile, ho utilizzato lo strumento gestionale della SWOT Analysis. Negli ultimi due capitoli, infine, analizzo nel dettaglio il modello Green Office. La teorizzazione di questo modello e l'elaborazione dei 6 principi del Green Office sono state effettuate da rootAbility. Le seguenti pagine presentano 3 casi studio di come i 6 principi dei Green Office sono stati adattati alle 3 unità di sostenibilità guidate da studenti e supportate da staff qualificato. L'oggetto della trattazione sono i principali GO affermatisi nei Paesi Bassi. A seguito dell'introduzione del modello relativo al Green Office e dell'illustrazione degli esempi presi in esame, è stato sfruttato lo strumento della feasibility analysis al fine di giudicare se l'idea di business sia praticabile. Il mezzo con cui ho condotto l'analisi sotto riportata è un questionario relativo al modello di Green Office implementato, nel quale viene chiesto di valutare gli aspetti relativi alla organizational feasibility e alla financial feasibility. Infine nella sezione finale ho considerato i Green Office come fossero un unico movimento. L'analisi mira a considerare l'impatto globale del Green Office Movement nei sistemi universitari e come, a seguito del loro consolidarsi nella struttura accademica, possano divenire prassi comune. La struttura proposta contiene elementi sia da il SNM (Strategic Niche Management) che dal TE (Transition Experiment).

C-clamp and pelvic packing for control of hemorrhage in patients with pelvic ring disruption

Exsanguinating hemorrhage is the major cause of death in patients with pelvic ring disruption.