Modeling the Effect of Vapor Wall Deposition on the Formation of Secondary Organic Aerosol in Chamber Studies

Laboratory chamber experiments are used to investigate formation of secondary organic aerosol (SOA) from biogenic and anthropogenic precursors under a variety of environmental conditions. Simulations of these experiments test our understanding of the prevailing chemistry of SOA formation as well as the dynamic processes occurring in the chamber itself. One dynamic process occurring in the chamber that was only recently recognized is the deposition of vapor species to the Teflon walls of the chamber. Low-volatility products formed from the oxidation of volatile organic compounds (VOCs) deposit on the walls rather than forming SOA, decreasing the amount of SOA formed (quantified as the SOA yield: mass of SOA formed per mass of VOC reacted). In this work, several modeling studies are presented that address the effect of vapor wall deposition on SOA formation in chambers.

A coupled vapor-particle dynamics model is used to examine the competition among the rates of gas-phase oxidation to low volatility products, wall deposition of these products, and mass transfer to the particle phase. The relative time scales of these rates control the amount of SOA formed by affecting the influence of vapor wall deposition. Simulations show that an effect on SOA yield of changing the vapor-particle mass transfer rate is only observed when SOA formation is kinetically limited. For systems with kinetically limited SOA formation, increasing the rate of vapor-particle mass transfer by increasing the concentration of seed particles is an effective way to minimize the effect of vapor wall deposition.

This coupled vapor-particle dynamics model is then applied to α-pinene ozonolysis SOA experiments. Experiments show that the SOA yield is affected when changing the oxidation rate but not when changing the rate of gas-particle mass transfer by changing the concentration of seed particles. Model simulations show that the absence of an effect of changing the seed particle concentration is consistent with SOA formation being governed by quasi-equilibrium growth, in which gas-particle equilibrium is established much faster than the rate of change of the gas-phase concentration. The observed effect of oxidation rate on SOA yield arises due to the presence of vapor wall deposition: gas-phase oxidation products are produced more quickly and condense preferentially onto seed particles before being lost to the walls. Therefore, for α-pinene ozonolysis, increasing the oxidation rate is the most effective way to mitigate the influence of vapor wall deposition.

Finally, the detailed model GECKO-A (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere) is used to simulate α-pinene photooxidation SOA experiments. Unexpectedly, α-pinene OH oxidation experiments show no effect when changing either the oxidation rate or the vapor-particle mass transfer rate, whereas GECKO-A predicts that changing the oxidation rate should drastically affect the SOA yield. Sensitivity studies show that the assumed magnitude of the vapor wall deposition rate can greatly affect conclusions drawn from comparisons between simulations and experiments. If vapor wall loss in the Caltech chamber is of order 10^-5 s^-1, GECKO-A greatly overpredicts SOA during high UV experiments, likely due to an overprediction of second-generation products. However, if instead vapor wall loss in the Caltech chamber is of order 10^-3 s^-1, GECKO-A greatly underpredicts SOA during low UV experiments, possibly due to missing autoxidation pathways in the α-pinene mechanism.

Drug development:the cell wall as a drug target

The complex and essential cell wall of Mycobacterium tuberculosis represents a plethora of new and old drug targets that collectively form an apparent mycobacterial “Achilles’ heel”. The mycolic acids are long-chain α-alkyl-β-hydroxy fatty acids (C70–90), which are unique to mycobacterial species, forming an integral component of the mycolyl–arabinogalactan–peptidoglycan complex. Their apparent uniqueness to the M. tuberculosis complex has rendered components of mycolic acid biosynthesis as powerful drug targets for specific tuberculosis (TB) chemotherapy. Here, I will discuss a contribution to TB drug discovery by deconvolution of the inhibitory mechanisms of a number of antitubercular compounds targeting mycolic acid biosynthesis. I will begin with the early days, elucidating the mode of action of ethionamide [1] and thiolactomycin [2], each targeting two separate components of the fatty acid synthase II (FAS-II) pathway. I will further discuss the recently discovered tetrahydropyrazo[1,5-a]pyrimidine-3-carboxamide compounds [3] which selectively target the essential, catalytically silent M. tuberculosis EchA6, providing a crucial lipid shunt between β-oxidation and FAS-II and supplying lipid precursors for essential mycolate biosynthesis. Finally, I will discuss the recent discovery of the mode of action of the indazole sulfonamides [4], inhibiting M. tuberculosis KasA by, a completely novel inhibitory mechanism.

Numerical simulation of fresh SCC flow in wall and beam elements using flow dynamics models

Abstract : Recently, there is a great interest to study the flow characteristics of suspensions in different environmental and industrial applications, such as snow avalanches, debris flows, hydrotransport systems, and material casting processes. Regarding rheological aspects, the majority of these suspensions, such as fresh concrete, behave mostly as non-Newtonian fluids. Concrete is the most widely used construction material in the world. Due to the limitations that exist in terms of workability and formwork filling abilities of normal concrete, a new class of concrete that is able to flow under its own weight, especially through narrow gaps in the congested areas of the formwork was developed. Accordingly, self-consolidating concrete (SCC) is a novel construction material that is gaining market acceptance in various applications. Higher fluidity characteristics of SCC enable it to be used in a number of special applications, such as densely reinforced sections. However, higher flowability of SCC makes it more sensitive to segregation of coarse particles during flow (i.e., dynamic segregation) and thereafter at rest (i.e., static segregation). Dynamic segregation can increase when SCC flows over a long distance or in the presence of obstacles. Therefore, there is always a need to establish a trade-off between the flowability, passing ability, and stability properties of SCC suspensions. This should be taken into consideration to design the casting process and the mixture proportioning of SCC. This is called “workability design” of SCC. An efficient and non-expensive workability design approach consists of the prediction and optimization of the workability of the concrete mixtures for the selected construction processes, such as transportation, pumping, casting, compaction, and finishing. Indeed, the mixture proportioning of SCC should ensure the construction quality demands, such as demanded levels of flowability, passing ability, filling ability, and stability (dynamic and static). This is necessary to develop some theoretical tools to assess under what conditions the construction quality demands are satisfied. Accordingly, this thesis is dedicated to carry out analytical and numerical simulations to predict flow performance of SCC under different casting processes, such as pumping and tremie applications, or casting using buckets. The L-Box and T-Box set-ups can evaluate flow performance properties of SCC (e.g., flowability, passing ability, filling ability, shear-induced and gravitational dynamic segregation) in casting process of wall and beam elements. The specific objective of the study consists of relating numerical results of flow simulation of SCC in L-Box and T-Box test set-ups, reported in this thesis, to the flow performance properties of SCC during casting. Accordingly, the SCC is modeled as a heterogeneous material. Furthermore, an analytical model is proposed to predict flow performance of SCC in L-Box set-up using the Dam Break Theory. On the other hand, results of the numerical simulation of SCC casting in a reinforced beam are verified by experimental free surface profiles. The results of numerical simulations of SCC casting (modeled as a single homogeneous fluid), are used to determine the critical zones corresponding to the higher risks of segregation and blocking. The effects of rheological parameters, density, particle contents, distribution of reinforcing bars, and particle-bar interactions on flow performance of SCC are evaluated using CFD simulations of SCC flow in L-Box and T-box test set-ups (modeled as a heterogeneous material). Two new approaches are proposed to classify the SCC mixtures based on filling ability and performability properties, as a contribution of flowability, passing ability, and dynamic stability of SCC.

Superposition relations of microfabrics in the northern hanging-wall block

This study reports alternation of D2 extension-related and D3 contraction-related microfabrics in the northern hanging wall block of a gneiss dome-like structure recognized in the Évora Massif (Ossa-Morena Zone). In the Arraiolos – Santo Antonio de Alcorrego traverse high- to low-grade mylonites are dominant. Microfabrics related to D2 ductile deformation and M2 high-amphibolite to greenschist facies characterize an extensional shear zone with telescoping metamorphic isograds. D2 microstructures indicate shear sense with top-to-SE. Superposition of D3 contraction developed under greenschist facies (M3) producing folding of D2 microfabrics, mylonitization of granites along strike-slip shear zones and retrogression of M2 mineral assemblages.

Secretome analysis of the mycoparasitic fungus Trichoderma harzianum ALL 42 cultivated in different media supplemented with Fusarium solani cell wall or glucose.

2016

Development of numerical methodologies to predict the liquid fuel sprays - wall interaction to optimize the mixing process of direct injection spark ignition engines

Nowadays the development of new Internal Combustion Engines is mainly driven by the need to reduce tailpipe emissions of pollutants, Green-House Gases and avoid the fossil fuels wasting. The design of dimension and shape of the combustion chamber together with the implementation of different injection strategies e.g., injection timing, spray targeting, higher injection pressure, play a key role in the accomplishment of the aforementioned targets. As far as the match between the fuel injection and evaporation and the combustion chamber shape is concerned, the assessment of the interaction between the liquid fuel spray and the engine walls in gasoline direct injection engines is crucial. The use of numerical simulations is an acknowledged technique to support the study of new technological solutions such as the design of new gasoline blends and of tailored injection strategies to pursue the target mixture formation. The current simulation framework lacks a well-defined best practice for the liquid fuel spray interaction simulation, which is a complex multi-physics problem. This thesis deals with the development of robust methodologies to approach the numerical simulation of the liquid fuel spray interaction with walls and lubricants. The accomplishment of this task was divided into three tasks: i) setup and validation of spray-wall impingement three-dimensional CFD spray simulations; ii) development of a one-dimensional model describing the liquid fuel – lubricant oil interaction; iii) development of a machine learning based algorithm aimed to define which mixture of known pure components mimics the physical behaviour of the real gasoline for the simulation of the liquid fuel spray interaction.

Advanced imaging study in cerebrovascular pathology for the personalization of therapy: from the capillary microcirculation to the vessel wall

Objectives: To investigate the use of intravascular optical coherence tomography (IVOCT) for carotid artery stenting (CAS) procedures in patients with atherosclerotic stenosis. Examine possible markers that might identify the onset of new cerebral ischemic lesions on MRI. Specifically, attention was drawn to the morphological features of the used dual layer stent, which could be underestimated during traditional CAS procedures. Secondary goals are to compare the safety and efficacy of different CAS techniques and the accuracy of the vessel analysis software’s on pre-operative CTA examination used to quantify ICA stenosis with the gold standard IVOCT. Material and Methods: Ten patients underwent CAS procedure with flow-arrest technique and IVOCT evaluations prior to and following stent deployment, while five matched patients underwent CAS procedure with distal embolic protection device (EPD) technique. All patients underwent 24-hours 3T MRI examination to check for ischemic lesions; all patients were treated with the same dual-layer stent. Results: Patients with new ischemic lesions demonstrated peculiar stent configuration in the distal end, and a strong Spearman’s rank order correlation was found among the volume of new DWI lesions and the stent configuration in its distal end (Rs: 0.81; p <0.001). No statistically significant differences were observed in the total burden of new ischemic lesions for each technique. The vessel analysis software's on CTA comparison demonstrated a higher diagnostic accuracy in the degree of ICA stenosis compared to the gold standard of IVOCT of the specialized software (ROC curve = 0.63; p = 0.06) compared to the general software (ROC curve = 0.57, p = 0.31). Conclusions: Study’s results support the use of IVOCT to allow recognition of potential features that can predict the onset of new cerebral ischemic lesions. Additionally, IVOCT made it possible to evaluate specialized software's increased accuracy in the pre-operative evaluation of ICA atherosclerotic stenosis.

Multiple Desmoid Tumors In A Patient With Gardner's Syndrome - Report Of A Case.

Desmoid tumor (DT) is a common manifestation of Gardner's Syndrome (GS), although it is a rare condition in the general population. DT in patients with GS is usually located in the abdominal wall and/or intra-abdominal cavity. We report a case of a 32 years-old female patient with familial adenomatous polyposis (FAP), who was already submitted to total colectomy and developed multiple DT, located in the abdominal wall and in the left breast. The patient underwent several surgical procedures, with a multidisciplinary team of surgeons. Wide surgical resections of the left breast and the abdominal wall tumors were performed in separate steps. Polypropylene mesh reconstruction and muscle flaps were needed to cover the defects of the thoracic and abdominal walls. After partial necrosis of the adipose-cutaneous flap in the abdomen that required a new skin graft, she had a satisfactory outcome with complete healing of the surgical incisions. DT is frequent in GS, however, breast localization is very rare, with few cases reported in the literature. Recurrence of DT is not negligible, even after a wide surgical resection. GS patients must be followed up closely, and clinical examination, associated with imaging studies, should be performed to detect any signs of tumor. DT represents one of the most significant causes of the morbidity and mortality that affects FAP patients following colectomy. In general, the surgical procedures to excise DT are highly complex, requiring a multidisciplinary team.

Intensification Of Bioactive Compounds Extraction From Medicinal Plants Using Ultrasonic Irradiation.

Extraction processes are largely used in many chemical, biotechnological and pharmaceutical industries for recovery of bioactive compounds from medicinal plants. To replace the conventional extraction techniques, new techniques as high-pressure extraction processes that use environment friendly solvents have been developed. However, these techniques, sometimes, are associated with low extraction rate. The ultrasound can be effectively used to improve the extraction rate by the increasing the mass transfer and possible rupture of cell wall due the formation of microcavities leading to higher product yields with reduced processing time and solvent consumption. This review presents a brief survey about the mechanism and aspects that affecting the ultrasound assisted extraction focusing on the use of ultrasound irradiation for high-pressure extraction processes intensification.

Interplay Between Cell Growth And Cell Cycle In Plants.

The growth of organs and whole plants depends on both cell growth and cell-cycle progression, but the interaction between both processes is poorly understood. In plants, the balance between growth and cell-cycle progression requires coordinated regulation of four different processes: macromolecular synthesis (cytoplasmic growth), turgor-driven cell-wall extension, mitotic cycle, and endocycle. Potential feedbacks between these processes include a cell-size checkpoint operating before DNA synthesis and a link between DNA contents and maximum cell size. In addition, key intercellular signals and growth regulatory genes appear to target at the same time cell-cycle and cell-growth functions. For example, auxin, gibberellin, and brassinosteroid all have parallel links to cell-cycle progression (through S-phase Cyclin D-CDK and the anaphase-promoting complex) and cell-wall functions (through cell-wall extensibility or microtubule dynamics). Another intercellular signal mediated by microtubule dynamics is the mechanical stress caused by growth of interconnected cells. Superimposed on developmental controls, sugar signalling through the TOR pathway has recently emerged as a central control point linking cytoplasmic growth, cell-cycle and cell-wall functions. Recent progress in quantitative imaging and computational modelling will facilitate analysis of the multiple interconnections between plant cell growth and cell cycle and ultimately will be required for the predictive manipulation of plant growth.

Taurine Supplementation Reduces Blood Pressure And Prevents Endothelial Dysfunction And Oxidative Stress In Post-weaning Protein-restricted Rats.

Taurine is a sulfur-containing amino acid that exerts protective effects on vascular function and structure in several models of cardiovascular diseases through its antioxidant and anti-inflammatory properties. Early protein malnutrition reprograms the cardiovascular system and is linked to hypertension in adulthood. This study assessed the effects of taurine supplementation in vascular alterations induced by protein restriction in post-weaning rats. Weaned male Wistar rats were fed normal- (12%, NP) or low-protein (6%, LP) diets for 90 days. Half of the NP and LP rats concomitantly received 2.5% taurine supplementation in the drinking water (NPT and LPT, respectively). LP rats showed elevated systolic, diastolic and mean arterial blood pressure versus NP rats; taurine supplementation partially prevented this increase. There was a reduced relaxation response to acetylcholine in isolated thoracic aortic rings from the LP group that was reversed by superoxide dismutase (SOD) or apocynin incubation. Protein expression of p47phox NADPH oxidase subunit was enhanced, whereas extracellular (EC)-SOD and endothelial nitric oxide synthase phosphorylation at Ser 1177 (p-eNOS) were reduced in aortas from LP rats. Furthermore, ROS production was enhanced while acetylcholine-induced NO release was reduced in aortas from the LP group. Taurine supplementation improved the relaxation response to acetylcholine and eNOS-derived NO production, increased EC-SOD and p-eNOS protein expression, as well as reduced ROS generation and p47phox expression in the aortas from LPT rats. LP rats showed an increased aortic wall/lumen ratio and taurine prevented this remodeling through a reduction in wall media thickness. Our data indicate a protective role of taurine supplementation on the high blood pressure, endothelial dysfunction and vascular remodeling induced by post-weaning protein restriction. The beneficial vascular effect of taurine was associated with restoration of vascular redox homeostasis and improvement of NO bioavailability.

Two-component System Vicrk Regulates Functions Associated With Establishment Of Streptococcus Sanguinis In Biofilms.

Streptococcus sanguinis is a commensal pioneer colonizer of teeth and an opportunistic pathogen of infectious endocarditis. The establishment of S. sanguinis in host sites likely requires dynamic fitting of the cell wall in response to local stimuli. In this study, we investigated the two-component system (TCS) VicRK in S. sanguinis (VicRKSs), which regulates genes of cell wall biogenesis, biofilm formation, and virulence in opportunistic pathogens. A vicK knockout mutant obtained from strain SK36 (SKvic) showed slight reductions in aerobic growth and resistance to oxidative stress but an impaired ability to form biofilms, a phenotype restored in the complemented mutant. The biofilm-defective phenotype was associated with reduced amounts of extracellular DNA during aerobic growth, with reduced production of H2O2, a metabolic product associated with DNA release, and with inhibitory capacity of S. sanguinis competitor species. No changes in autolysis or cell surface hydrophobicity were detected in SKvic. Reverse transcription-quantitative PCR (RT-qPCR), electrophoretic mobility shift assays (EMSA), and promoter sequence analyses revealed that VicR directly regulates genes encoding murein hydrolases (SSA_0094, cwdP, and gbpB) and spxB, which encodes pyruvate oxidase for H2O2 production. Genes previously associated with spxB expression (spxR, ccpA, ackA, and tpK) were not transcriptionally affected in SKvic. RT-qPCR analyses of S. sanguinis biofilm cells further showed upregulation of VicRK targets (spxB, gbpB, and SSA_0094) and other genes for biofilm formation (gtfP and comE) compared to expression in planktonic cells. This study provides evidence that VicRKSs regulates functions crucial for S. sanguinis establishment in biofilms and identifies novel VicRK targets potentially involved in hydrolytic activities of the cell wall required for these functions.

All Green, But Equal? Morphological Traits And Ecological Implications On Spores Of Three Species Of Mosses In The Brazilian Atlantic Forest.

Spores of the tropical mosses Pyrrhobryum spiniforme, Neckeropsis undulata and N. disticha were characterized regarding size, number per capsule and viability. Chemical substances were analyzed for P. spiniforme and N. undulata spores. Length of sporophyte seta (spore dispersal ability) was analyzed for P. spiniforme. Four to six colonies per species in each site (lowland and highland areas of an Atlantic Forest; Serra do Mar State Park, Brazil) were visited for the collection of capsules (2008 - 2009). Neckeropsis undulata in the highland area produced the largest spores (ca. 19 µm) with the highest viability. The smallest spores were found in N. disticha in the lowland (ca. 13 µm). Pyrrhobryum spiniforme produced more spores per capsule in the highland (ca. 150,000) than in lowland (ca. 40,000); longer sporophytic setae in the lowland (ca. 64 mm) than in the highland (ca. 43 mm); and similar sized spores in both areas (ca. 16 µm). Spores of N. undulata and P. spiniforme contained lipids and proteins in the cytoplasm, and acid/neutral lipids and pectins in the wall. Lipid bodies were larger in N. undulata than in P. spiniforme. No starch was recorded for spores. Pyrrhobryum spiniforme in the highland area, different from lowland, was characterized by low reproductive effort, but presented many spores per capsule.

Management Of Severe Thoracic Impalement Trauma Against Two-wheeled Horse Carriage: A Case Report And Literature Review.

Thoracic injuries in general are of great importance due to their high incidence and high mortality. Thoracic impalement injuries are rare but severe due to the combination of cause, effect and result. This study's primary objective is to report the case of a young man who was impaled by a two-wheeled horse carriage shaft while crashing his motorcycle in a rural zone. An EMT-B ferry was called at the crash scene and a conscious patient was found, sustaining a severe impalement injury to the left hemithorax, suspended over the floor by the axial skeleton with the carriage shaft coming across his left chest. As a secondary objective, a literature review of thoracic impalement injuries is performed. Cases of thoracic impalement injury require unique and individualized care based on injury severity and affected organs. Reported protocols for managing impalement injuries are entirely anecdotal, with no uniformity on impaled patient's approach and management. In penetrating trauma, it is essential not to remove the impaled object, so that possible vascular lesions remain buffered by the object, avoiding major bleeding and exsanguination haemorrhage. Severed impaled thoracic patients should be transferred to a specialist centre for trauma care, as these lesions typically require complex multidisciplinary treatment. High-energy thoracic impalement injuries are rare and hold a high mortality rate, due to the complexity of trauma and associated injuries such as thoracic wall and lung lesions. Modern medicine still seems limited in cases of such seriousness, not always with satisfactory results.

Oligomerization, Membrane Association, And In Vivo Phosphorylation Of Sugarcane Udp-glucose Pyrophosphorylase.

Sugarcane is a monocot plant that accumulates sucrose to levels of up to 50% of dry weight in the stalk. The mechanisms that are involved in sucrose accumulation in sugarcane are not well understood, and little is known with regard to factors that control the extent of sucrose storage in the stalks. UDP-glucose pyrophosphorylase (UGPase; EC 2.7.7.9) is an enzyme that produces UDP-glucose, a key precursor for sucrose metabolism and cell wall biosynthesis. The objective of this work was to gain insights into the ScUGPase-1 expression pattern and regulatory mechanisms that control protein activity. ScUGPase-1 expression was negatively correlated with the sucrose content in the internodes during development, and only slight differences in the expression patterns were observed between two cultivars that differ in sucrose content. The intracellular localization of ScUGPase-1 indicated partial membrane association of this soluble protein in both the leaves and internodes. Using a phospho-specific antibody, we observed that ScUGPase-1 was phosphorylated in vivo at the Ser-419 site in the soluble and membrane fractions from the leaves but not from the internodes. The purified recombinant enzyme was kinetically characterized in the direction of UDP-glucose formation, and the enzyme activity was affected by redox modification. Preincubation with H2O2 strongly inhibited this activity, which could be reversed by DTT. Small angle x-ray scattering analysis indicated that the dimer interface is located at the C terminus and provided the first structural model of the dimer of sugarcane UGPase in solution.