Relative basicities of free base porphyrins : understanding the role of macrocyclic distortion

Porphyrins have been the center of numerous investigations in different areas of chemistry, geochemistry, and the life sciences. In nature the conformation of the porphyrin macrocycle varies, depending on the function of its apoenzyme. It is believed that the conformation of the porphyrin ring is necessary for the enzyme to achieve its function and modify its reactivity. It is important to understand how the conformation of the porphyrin ring will influence its properties. In synthetic porphyrins particular conformations and ring deformations can be achieved by peripheral substitution, metallation, core substitution, and core protonation among other alterations of the macrocycle. The macrocyclic distortions will affect the ring current, the ability of pyrroles to intramolecularly hydrogen bond and the relative basicity of each of the porphyrins. To understand these effects different theoretical models are used. The ground state structure of each of 19 free base porphyrins is determined using molecular mechanics (MM+) and semiempirical methods (PM3). The energetics of deformation of the macrocyclic core is calculated by carrying out single point energy calculations for the conformation achieved by each synthetic compound. Enthalpies of solution and enthalpies of protonation of 10 porphyrins with varying degrees of macrocyclic deformation and varying electron withdrawing groups in the periphery are determined using solution calorimetry. Using Hess's Law, the relative basicity of each of the different free base porphyrins is calculated. NMR results are described, including the determination of free energies of activation of ring tautomerization and hydrogen bonding for several compounds. It was found that in the absence of electronic effects, the greater macrocyclic deformation, the greater the basicity of the porphyrins. This basicity is attenuated by the presence of electron withdrawing groups and ability to of the macrocycle to intramolecularly hydrogen bond.

Immunocytes of the Atlantic bottlenose dolphin (Tursiops truncatus) and West Indian manatee (Trichechus manatus latirostris) : morphologic characterizations and correlations between healthy and disease states under free-ranging and captive conditions

Interest in the health of marine mammals has increased due, in part, to the attention given to human impact on the marine environment. Recent mass strandings of the Atlantic bottlenose dolphin (Tursiops truncatus) and rising mortalities of the endangered Florida manatee (Trichechus manatus latirostris) have raised questions on the extent to which pollution, infectious disease, "stress," and captivity influence the immune system of these animals. This study has provided the first in-depth characterization of immunocytes in the peripheral blood of dolphins (n=180) and manatees (n=56). Immunocyte morphology and baseline values were determined in clinically normal animals under free-ranging, stranded and captive living conditions as well as by age and sex. Additionally, immuocyte population dynamics were characterized in sick animals. This was accomplished with traditional cytochemical techniques and new lymphocyte phenotyping methodology which was validated in this study. Traditional cytochemical techniques demonstrated that blood immunocyte morphology and cell numbers are similar to terrestrial mammals with some notable exceptions. The manatee heterophilic granulocyte is a morphologically unique cell and probably functions similarly to the typical mammalian neutrophil. Eosinophils were rarely found in manatees but were uncommonly high in healthy and sick dolphins. Basophils were not identified. Manatees had higher total lymphocyte numbers compared to dolphins and most terrestrial mammals. Lymphocyte subsets identified in healthy animals included Th, Tes, B and NK cells. Dolphin and manatee T and B cell values were higher than those reported in man and most terrestrial mammals. The manatee has extraordinarily high absolute numbers of circulating Th cells which suggests an enhanced immunological response capability. With few exceptions, immunocyte types and absolute numbers were not significantly different between free-ranging, stranded and captive categories or between sex and age categories. The evaluation of immunocyte dynamics in various disease states demonstrated a wide variation in cellular responses which provided new insights into innate, humoral and cell-mediated immunity in these species. Additionally, this study demonstrated that lymphocyte phenotyping has diagnostic significance and could be developed into a potential indicator of immunocompetence in both free-ranging and captive dolphin and manatee populations.

Modeling of a Heat-Induced Buckling of Plates Using the Mesh-free Method

In the process of engineering design of structural shapes, the flat plate analysis results can be generalized to predict behaviors of complete structural shapes. In this case, the purpose of this project is to analyze a thin flat plate under conductive heat transfer and to simulate the temperature distribution, thermal stresses, total displacements, and buckling deformations. The current approach in these cases has been using the Finite Element Method (FEM), whose basis is the construction of a conforming mesh. In contrast, this project uses the mesh-free Scan Solve Method. This method eliminates the meshing limitation using a non-conforming mesh. I implemented this modeling process developing numerical algorithms and software tools to model thermally induced buckling. In addition, convergence analysis was achieved, and the results were compared with FEM. In conclusion, the results demonstrate that the method gives similar solutions to FEM in quality, but it is computationally less time consuming.

Development of a New Client-Server Architecture for Context Aware Mobile Computing

This dissertation studies the context-aware application with its proposed algorithms at client side. The required context-aware infrastructure is discussed in depth to illustrate that such an infrastructure collects the mobile user’s context information, registers service providers, derives mobile user’s current context, distributes user context among context-aware applications, and provides tailored services. The approach proposed tries to strike a balance between the context server and mobile devices. The context acquisition is centralized at the server to ensure the usability of context information among mobile devices, while context reasoning remains at the application level. Hence, a centralized context acquisition and distributed context reasoning are viewed as a better solution overall. The context-aware search application is designed and implemented at the server side. A new algorithm is proposed to take into consideration the user context profiles. By promoting feedback on the dynamics of the system, any prior user selection is now saved for further analysis such that it may contribute to help the results of a subsequent search. On the basis of these developments at the server side, various solutions are consequently provided at the client side. A proxy software-based component is set up for the purpose of data collection. This research endorses the belief that the proxy at the client side should contain the context reasoning component. Implementation of such a component provides credence to this belief in that the context applications are able to derive the user context profiles. Furthermore, a context cache scheme is implemented to manage the cache on the client device in order to minimize processing requirements and other resources (bandwidth, CPU cycle, power). Java and MySQL platforms are used to implement the proposed architecture and to test scenarios derived from user’s daily activities. To meet the practical demands required of a testing environment without the impositions of a heavy cost for establishing such a comprehensive infrastructure, a software simulation using a free Yahoo search API is provided as a means to evaluate the effectiveness of the design approach in a most realistic way. The integration of Yahoo search engine into the context-aware architecture design proves how context aware application can meet user demands for tailored services and products in and around the user’s environment. The test results show that the overall design is highly effective,providing new features and enriching the mobile user’s experience through a broad scope of potential applications.

Free Drink or Free Mug? Managing Service Experience with Experiential vs. Material Complimentary Gifts

In the marketplace, complimentary gifts can take the form of experiential elements (e.g., a meal) or material items (e.g., tangible objects such as a mug). We identify these free gifts as a meaningful service design choice that helps service providers innovate service. Specifically, we examine the circumstances under which experiential or material gifts are preferred and generate greater consumer satisfaction, enhancing the overall service experience. Across three experiments, we demonstrate that consumers are generally happier with experiential offerings, and they prefer (and are more satisfied with) experiential offerings on ordinary consumption occasions; experiential elements are believed to further enrich otherwise mundane experiences. However, this experiential advantage disappears for consumers on meaningful and special occasions because of a strong desire to obtain a memory cue that will help them recall the experience. Indeed, the preference for a material item holds only when the gift has the quality to serve as a salient memory marker, but not when it lacks this quality. This research provides insight for managers to take into account consumption occasions or type of consumers (e.g., special occasions, repeat customers) to effectively design service bundles with complimentary gifts and thus better manage overall service experience.

Viewing biofilms within the larger context of bacterial aggregations

The ‘Microbial Cities’ vision of bacterial biofilms has dominated our understanding of the development and functioning of bacterial aggregations for the past 20 years, during which active sludge, clumps, colonies, flocs, mats, pellicles, rafts, slimes, zooglea, etc. have been largely forgotten or ignored. Although the medically inspired developmental model of human pathogen biofilms has merits including providing a rationale for the development of anti-biofilm therapeutics, it fails to provide links to other types of bacterial aggregation that are commonly found in a wide range of natural and man-made environments. Possibly as a result, applied and environmental microbiologists tend to avoid the term ‘biofilm’ and use others such as ‘microbial mats’ instead. Here we challenge the simplistic planktonic (independent and free-swimming bacteria)-biofilm (sessile and co-operative bacteria) dichotomy, and consider biofilms within the larger context of bacterial aggregations. By placing biofilms into context, which we see as a continuum of aggregations or communities with varying abiotic and biotic properties, fundamental physical, biological, and evolutionary ecological processes that effect community development and function can no longer be considered unique to biofilms, but may also be important in other aggregations that develop over time and change in nature depending on prevailing conditions. By doing this, we will be better able to distinguish those processes which govern bacterial colonisation and ecological success in a wider sense from those that are unique to particular environments and specialised strategies.

University Reforms in the Context of the Bologna Process

Georgia, a former Soviet Union state, has undergone a lot of political, social, economic and of course educational changes. This article shows how Georgia’s higher education system has developed after the collapse of the Soviet Union. As an independent country, Georgia has started developing a free nation with a new type of the education system. The government of Georgia chose the European system of higher education and their major aim was to become a part of the Bologna process. Reforms made in Georgian higher education system have been essential for the country and indeed a lot has changed since the starting period. Georgia managed to hold unified national entry exams and has implemented the ECTS system; there are modern curricula that meet the requirements of European standards. etc. But still, even though a lot is being done, a lack of funding, outdated teaching methods and old facilities in some universities are still unresolved problems.

Utilization of free and microencapsulated Rosmarinus oficinalis L. extracts as bioactives ingredientes for new functional foods developmen

Currently, many consumers search for food with functional characteristics beyond their nutritional properties. Thus, the concept of functional food becomes a hot topic, allowing the obtaining of health benefits, including disease prevention. In this context, plants are recognized as sources of a wide range of bioactives, mainly phenolic compounds. In particular, the Rosmarinus officina/is L., commonly referred as rosemary, has several phenolic compounds with different bioactive properties such as antioxidant, antiinflammatory and antimicrobial activities, among others [!]. Hence, this plant has great potential for incorporation into foods in order to confer bioactivity to the final products. However, it should be highlighted that the bioactive compounds if exposed to adverse environments, for example: light, moisture, extreme pH, storage, food processing conditions, can be degraded leading to the consequent loss of bioactivity [2]. The microencapsulation is an alternative to overcome this problematic of bioactive compounds, as also to ensure controlled release, or target deliver to a specific site [3]. In this work, lyophilized rosemary aqueous extract prepared by in:'usion was used as a functional ingredient for cottage cheeses, after proving that it possesses, both higher content in phenolic compounds and higher antioxidant activity, comparatively with the corresponding hydroethanolic extract. The rosemary aqueous extract revealed, for example, a DPPH scavenging activity with an EC50 value of 73.44±0.54j!g/mL and presented as main phenolic compound the caffeic acid dimer, commonly named as rosmarinic acid. For the functionalized cottage cheeses, a decrease of bioactivity was observed after seven days under storage in fridge, when the extracts were incorporated in its free form. Therefore, to preserve the antioxidant activity, the rosemary aqueous extract was efficiently microencapsulated by using an atomization/coagulation technique and alginate as the matrix material and thereafter incorporated into the cottage cheeses. The final microspheres showed a size, estimated by OM using a magnification of I OOx, ranging between 51.1 and 122.6 J!m and an encapsulation efficiency, estimated through an indirect method, approaching 100%. Overall, the introduction of both free and microencapsulated extracts did not change the nutritional value of cottage cheeses, providing bioactivity that was more preserved with microencapsulated extracts putting in evidence the importance of using microencapsulation to develop effective functional foods.

A non-contrast self-navigated 3-dimensional MR technique for aortic root and vascular access route assessment in the context of transcatheter aortic valve replacement: proof of concept.

OBJECTIVES: Due to the high prevalence of renal failure in transcatheter aortic valve replacement (TAVR) candidates, a non-contrast MR technique is desirable for pre-procedural planning. We sought to evaluate the feasibility of a novel, non-contrast, free-breathing, self-navigated three-dimensional (SN3D) MR sequence for imaging the aorta from its root to the iliofemoral run-off in comparison to non-contrast two-dimensional-balanced steady-state free-precession (2D-bSSFP) imaging. METHODS: SN3D [field of view (FOV), 220-370 mm(3); slice thickness, 1.15 mm; repetition/echo time (TR/TE), 3.1/1.5 ms; and flip angle, 115°] and 2D-bSSFP acquisitions (FOV, 340 mm; slice thickness, 6 mm; TR/TE, 2.3/1.1 ms; flip angle, 77°) were performed in 10 healthy subjects (all male; mean age, 30.3 ± 4.3 yrs) using a 1.5-T MRI system. Aortic root measurements and qualitative image ratings (four-point Likert-scale) were compared. RESULTS: The mean effective aortic annulus diameter was similar for 2D-bSSFP and SN3D (26.7 ± 0.7 vs. 26.1 ± 0.9 mm, p = 0.23). The mean image quality of 2D-bSSFP (4; IQR 3-4) was rated slightly higher (p = 0.03) than SN3D (3; IQR 2-4). The mean total acquisition time for SN3D imaging was 12.8 ± 2.4 min. CONCLUSIONS: Our results suggest that a novel SN3D sequence allows rapid, free-breathing assessment of the aortic root and the aortoiliofemoral system without administration of contrast medium. KEY POINTS: • The prevalence of renal failure is high among TAVR candidates. • Non-contrast 3D MR angiography allows for TAVR procedure planning. • The self-navigated sequence provides a significantly reduced scanning time.

Free Troposphere Ozone and Carbon Monoxide over the North Atlantic for 2001-2011

Carbon Monoxide (CO) and Ozone (O3) are considered to be one of the most important atmospheric pollutants in the troposphere with both having significant effects on human health. Both are included in the U.S. E.P.A list of criteria pollutants. CO is primarily emitted in the source region whereas O3 can be formed near the source, during transport of the pollution plumes containing O3 precursors or in a receptor region as the plumes subside. The long chemical lifetimes of both CO and O3 enable them to be transported over long distances. This transport is important on continental scales as well, commonly referred to as inter-continental transport and affects the concentrations of both CO and O3 in downwind receptor regions, thereby having significant implications for their air quality standards. Over the period 2001-2011, there have been decreases in the anthropogenic emissions of CO and NOx in North America and Europe whereas the emissions over Asia have increased. How these emission trends have affected concentrations at remote sites located downwind of these continents is an important question. The PICO-NARE observatory located on the Pico Mountain in Azores, Portugal is frequently impacted by North American pollution outflow (both anthropogenic and biomass burning) and is a unique site to investigate long range transport from North America. This study uses in-situ observations of CO and O3 for the period 2001-2011 at PICO-NARE coupled with output from the full chemistry (with normal and fixed anthropogenic emissions) and tagged CO simulations in GEOS-Chem, a global 3-D chemical transport model of atmospheric composition driven by meteorological input from the Goddard Earth Observing System (GEOS) of the NASA Global Modeling and Assimilation Office, to determine and interpret the trends in CO and O3 concentrations over the past decade. These trends would be useful in ascertaining the impacts emission reductions in the United States have had over Pico and in general over the North Atlantic. A regression model with sinusoidal functions and a linear trend term was fit to the in-situ observations and the GEOS-Chem output for CO and O3 at Pico respectively. The regression model yielded decreasing trends for CO and O3 with the observations (-0.314 ppbv/year & -0.208 ppbv/year respectively) and the full chemistry simulation with normal emissions (-0.343 ppbv/year & -0.526 ppbv/year respectively). Based on analysis of the results from the full chemistry simulation with fixed anthropogenic emissions and the tagged CO simulation it was concluded that the decreasing trends in CO were a consequence of the anthropogenic emission changes in regions such as USA and Asia. The emission reductions in USA are countered by Asian increases but the former have a greater impact resulting in decreasing trends for CO at PICO-NARE. For O3 however, it is the increase in water vapor content (which increases O3 destruction) along the pathways of transport from North America to PICO-NARE as well as around the site that has resulted in decreasing trends over this period. This decrease is offset by increase in O3 concentrations due to anthropogenic influence which could be due to increasing Asian emissions of O3 precursors as these emissions have decreased over the US. However, the anthropogenic influence does not change the final direction of the trend. It can thus be concluded that CO and O3 concentrations at PICO-NARE have decreased over 2001-2011.

Development of a Coupling Model for Fluid-Structure Interaction using the Mesh-free Finite Element Method and the Lattice Boltzmann Method

In the presented thesis work, the meshfree method with distance fields was coupled with the lattice Boltzmann method to obtain solutions of fluid-structure interaction problems. The thesis work involved development and implementation of numerical algorithms, data structure, and software. Numerical and computational properties of the coupling algorithm combining the meshfree method with distance fields and the lattice Boltzmann method were investigated. Convergence and accuracy of the methodology was validated by analytical solutions. The research was focused on fluid-structure interaction solutions in complex, mesh-resistant domains as both the lattice Boltzmann method and the meshfree method with distance fields are particularly adept in these situations. Furthermore, the fluid solution provided by the lattice Boltzmann method is massively scalable, allowing extensive use of cutting edge parallel computing resources to accelerate this phase of the solution process. The meshfree method with distance fields allows for exact satisfaction of boundary conditions making it possible to exactly capture the effects of the fluid field on the solid structure.

What Is a Firm’s Life Expectancy? Empirical Evidence in the Context of Portuguese Companies

It is a fact that the uncertainty about a firm’s future has to be measured and incorporated into a company’s valuation throughout the explicit analysis period – in the continuing or terminal value within valuation models. One of the concerns that can influence the continuing value of enterprises, which is not explicitly considered in traditional valuation models, is a firm’s average life expectancy. Although the literature has studied the life cycle of a firm, there is still a considerable lack of references on this topic. If we ignore the period during which a company has the ability to produce future cash flows, the valuations can fall into irreversible errors, leading to results markedly different from market values. This paper aims to provide a contribution in this area. Its main objective is to construct a mortality table for non-listed Portuguese enterprises, showing that the use of a terminal value through a mathematical expression of perpetuity of free cash flows is not adequate. We provide the use of an appropriate coefficient to perceive the number of years in which the company will continue to operate until its theoretical extinction. If well addressed regarding valuation models, this issue can be used to reduce or even to eliminate one of the main problems that cause distortions in contemporary enterprise valuation models: the premise of an enterprise’s unlimited existence in time. Besides studying the companies involved in it, from their existence to their demise, our study intends to push knowledge forward by providing a consistent life and mortality expectancy table for each age of the company, presenting models with an explicitly and different survival rate for each year. Moreover, we show that, after reaching a certain age, firms can reinvent their business, acquiring maturity and consequently postponing their mortality through an additional life period.

Determinants of Terminal Value in the Evaluation of Companies: A Panel Data Approach to the Context of European Companies.

The uncertainty of the future of a firm has to be modelled and incorporated into the evaluation of companies outside their explicit period of analysis, i.e., in the continuing or terminal value considered within valuation models. However, there is a multiplicity of factors that influence the continuing value of businesses which are not currently being considered within valuation models. In fact, ignoring these factors may cause significant errors of judgment, which can lead models to values of goodwill or badwill, far from the substantial value of the inherent assets. Consequently, these results provided will be markedly different from market values. So, why not consider alternative models incorporating life expectancy of companies, as well as the influence of other attributes of the company in order to get a smoother adjustment between market price and valuation methods? This study aims to provide a contribution towards this area, having as its main objective the analysis of potential determinants of firm value in the long term. Using a sample of 714 listed companies, belonging to 15 European countries, and a panel data for the period between 1992 and 2011, our results show that continuing value cannot be regarded as the current value of a constant or growth perpetuity of a particular attribute of the company, but instead be according to a set of attributes such as free cash flow, net income, the average life expectancy of the company, investment in R&D, capabilities and quality of management, liquidity and financing structure.

Grant-free protocols for massive multiple access

In next generation Internet-of-Things, the overhead introduced by grant-based multiple access protocols may engulf the access network as a consequence of the proliferation of connected devices. Grant-free access protocols are therefore gaining an increasing interest to support massive multiple access. In addition to scalability requirements, new demands have emerged for massive multiple access, including latency and reliability. The challenges envisaged for future wireless communication networks, particularly in the context of massive access, include: i) a very large population size of low power devices transmitting short packets; ii) an ever-increasing scalability requirement; iii) a mild fixed maximum latency requirement; iv) a non-trivial requirement on reliability. To this aim, we suggest the joint utilization of grant-free access protocols, massive MIMO at the base station side, framed schemes to let the contention start and end within a frame, and succesive interference cancellation techniques at the base station side. In essence, this approach is encapsulated in the concept of coded random access with massive MIMO processing. These schemes can be explored from various angles, spanning the protocol stack from the physical (PHY) to the medium access control (MAC) layer. In this thesis, we delve into both of these layers, examining topics ranging from symbol-level signal processing to succesive interference cancellation-based scheduling strategies. In parallel with proposing new schemes, our work includes a theoretical analysis aimed at providing valuable system design guidelines. As a main theoretical outcome, we propose a novel joint PHY and MAC layer design based on density evolution on sparse graphs.

An Efficient Protocol For The Generation Of Monocyte Derived Dendritic Cells Using Serum-free Media For Clinical Applications In Post Remission Aml Patients.

Protocols for the generation of dendritic cells (DCs) using serum as a supplementation of culture media leads to reactions due to animal proteins and disease transmissions. Several types of serum-free media (SFM), based on good manufacture practices (GMP), have recently been used and seem to be a viable option. The aim of this study was to evaluate the results of the differentiation, maturation, and function of DCs from Acute Myeloid Leukemia patients (AML), generated in SFM and medium supplemented with autologous serum (AS). DCs were analyzed by phenotype characteristics, viability, and functionality. The results showed the possibility of generating viable DCs in all the conditions tested. In patients, the X-VIVO 15 medium was more efficient than the other media tested in the generation of DCs producing IL-12p70 (p=0.05). Moreover, the presence of AS led to a significant increase of IL-10 by DCs as compared with CellGro (p=0.05) and X-Vivo15 (p=0.05) media, both in patients and donors. We concluded that SFM was efficient in the production of DCs for immunotherapy in AML patients. However, the use of AS appears to interfere with the functional capacity of the generated DCs.