Synthetic studies of azulenyl and pseudoazulenyl nitrones

Free radicals have been implicated in various pathological conditions such as, stroke, aging and ischemic heart disease (IHD), as well as neurodegenerative diseases like Alzheimer’s, Parkinson’s, and Huntington’s disease. The role of antioxidants in protection from the harmful effects of free radicals has long been recognized. Trapping extremely reactive free radicals and eliminating them from circulation has been shown to be effective in animal models. Nitrone-based free radical traps have been extensively explored in biological systems. Examples include nitrones such as PBN, NXY-059, MDL-101,002, DMPO and EMPO. However, these nitrones have extremely high oxidation potentials as compared to natural antioxidants such as Vitamin E (α-tocopherol), and glutathione. Becker et al. (1995) synthesized novel azulenyl nitrones, which were shown to have oxidation potentials much lower than that of any of the previously reported nitrone based spin traps. Another azulenyl nitrone derivative, stilbazulenyl nitrone (STAZN), was shown to have an even lower oxidation potential within the range of natural antioxidants. STAZN, a second generation free radical trap, was found to be markedly superior than the two most studied nitrones, PBN and NXY-059, in animal models of cerebral ischemia and in an in vitro assay of lipid peroxidation. In this study, a third generation azulenyl nitrone was synthesized with an electron donating group on the previously synthesized STAZN derivative with the aim to lower the oxidation potential even more. Pseudoazulenes, because of the presence of an annular heteroatom, have been reported to possess even lower oxidation potential than that of the azulenyl counterpart. Therefore, pseudoazulenyl nitrones were synthesized for the first time by extracting and elaborating valtrate from the roots of Centranthus ruber (Red valerian or Jupiter’s beard). Several pseudoazulenyl nitrones were synthesized by using a facile experimental protocol. The physical and biological properties of these pseudoazulenyl nitrones can be easily modified by simply changing the substituent on the heteroatom. Cyclic voltammetry experiments have shown that these pseudoazulenyl nitrones do indeed have low oxidation potentials. The oxidation potential of these nitrones was lowered even more by preparing derivatives bearing an electron donating group at the 3-position of the five membered ring of the pseudoazulenyl nitrone.

Synthetic Studies of Azulenyl and Pseudoazulenyl Nitrones

Free radicals have been implicated in various pathological conditions such as, stroke, aging and ischemic heart disease (IHD), as well as neurodegenerative diseases like Alzheimer’s, Parkinson’s, and Huntington’s disease. The role of antioxidants in protection from the harmful effects of free radicals has long been recognized. Trapping extremely reactive free radicals and eliminating them from circulation has been shown to be effective in animal models. Nitrone-based free radical traps have been extensively explored in biological systems. Examples include nitrones such as PBN, NXY-059, MDL-101,002, DMPO and EMPO. However, these nitrones have extremely high oxidation potentials as compared to natural antioxidants such as Vitamin E (á-tocopherol), and glutathione. Becker et al. (1995) synthesized novel azulenyl nitrones, which were shown to have oxidation potentials much lower than that of any of the previously reported nitrone based spin traps. Another azulenyl nitrone derivative, stilbazulenyl nitrone (STAZN), was shown to have an even lower oxidation potential within the range of natural antioxidants. STAZN, a second generation free radical trap, was found to be markedly superior than the two most studied nitrones, PBN and NXY-059, in animal models of cerebral ischemia and in an in vitro assay of lipid peroxidation. In this study, a third generation azulenyl nitrone was synthesized with an electron donating group on the previously synthesized STAZN derivative with the aim to lower the oxidation potential even more. Pseudoazulenes, because of the presence of an annular heteroatom, have been reported to possess even lower oxidation potential than that of the azulenyl counterpart. Therefore, pseudoazulenyl nitrones were synthesized for the first time by extracting and elaborating valtrate from the roots of Centranthus ruber (Red valerian or Jupiter’s beard). Several pseudoazulenyl nitrones were synthesized by using a facile experimental protocol. The physical and biological properties of these pseudoazulenyl nitrones can be easily modified by simply changing the substituent on the heteroatom. Cyclic voltammetry experiments have shown that these pseudoazulenyl nitrones do indeed have low oxidation potentials. The oxidation potential of these nitrones was lowered even more by preparing derivatives bearing an electron donating group at the 3-position of the five membered ring of the pseudoazulenyl nitrone.

Resource allocation in multi-user telecommunication networks

This dissertation discussed resource allocation mechanisms in several network topologies including infrastructure wireless network, non-infrastructure wireless network and wire-cum-wireless network. Different networks may have different resource constrains. Based on actual technologies and implementation models, utility function, game theory and a modern control algorithm have been introduced to balance power, bandwidth and customers' satisfaction in the system. ^ In infrastructure wireless networks, utility function was used in the Third Generation (3G) cellular network and the network was trying to maximize the total utility. In this dissertation, revenue maximization was set as an objective. Compared with the previous work on utility maximization, it is more practical to implement revenue maximization by the cellular network operators. The pricing strategies were studied and the algorithms were given to find the optimal price combination of power and rate to maximize the profit without degrading the Quality of Service (QoS) performance. ^ In non-infrastructure wireless networks, power capacity is limited by the small size of the nodes. In such a network, nodes need to transmit traffic not only for themselves but also for their neighbors, so power management become the most important issue for the network overall performance. Our innovative routing algorithm based on utility function, sets up a flexible framework for different users with different concerns in the same network. This algorithm allows users to make trade offs between multiple resource parameters. Its flexibility makes it a suitable solution for the large scale non-infrastructure network. This dissertation also covers non-cooperation problems. Through combining game theory and utility function, equilibrium points could be found among rational users which can enhance the cooperation in the network. ^ Finally, a wire-cum-wireless network architecture was introduced. This network architecture can support multiple services over multiple networks with smart resource allocation methods. Although a SONET-to-WiMAX case was used for the analysis, the mathematic procedure and resource allocation scheme could be universal solutions for all infrastructure, non-infrastructure and combined networks. ^

Geospatial Data Indexing Analysis and Visualization via Web Services with Autonomic Resource Management

With the exponential growth of the usage of web-based map services, the web GIS application has become more and more popular. Spatial data index, search, analysis, visualization and the resource management of such services are becoming increasingly important to deliver user-desired Quality of Service. First, spatial indexing is typically time-consuming and is not available to end-users. To address this, we introduce TerraFly sksOpen, an open-sourced an Online Indexing and Querying System for Big Geospatial Data. Integrated with the TerraFly Geospatial database [1-9], sksOpen is an efficient indexing and query engine for processing Top-k Spatial Boolean Queries. Further, we provide ergonomic visualization of query results on interactive maps to facilitate the user’s data analysis. Second, due to the highly complex and dynamic nature of GIS systems, it is quite challenging for the end users to quickly understand and analyze the spatial data, and to efficiently share their own data and analysis results with others. Built on the TerraFly Geo spatial database, TerraFly GeoCloud is an extra layer running upon the TerraFly map and can efficiently support many different visualization functions and spatial data analysis models. Furthermore, users can create unique URLs to visualize and share the analysis results. TerraFly GeoCloud also enables the MapQL technology to customize map visualization using SQL-like statements [10]. Third, map systems often serve dynamic web workloads and involve multiple CPU and I/O intensive tiers, which make it challenging to meet the response time targets of map requests while using the resources efficiently. Virtualization facilitates the deployment of web map services and improves their resource utilization through encapsulation and consolidation. Autonomic resource management allows resources to be automatically provisioned to a map service and its internal tiers on demand. v-TerraFly are techniques to predict the demand of map workloads online and optimize resource allocations, considering both response time and data freshness as the QoS target. The proposed v-TerraFly system is prototyped on TerraFly, a production web map service, and evaluated using real TerraFly workloads. The results show that v-TerraFly can accurately predict the workload demands: 18.91% more accurate; and efficiently allocate resources to meet the QoS target: improves the QoS by 26.19% and saves resource usages by 20.83% compared to traditional peak load-based resource allocation.

Next generation of recommender systems: Algorithms and applications

Personalized recommender systems aim to assist users in retrieving and accessing interesting items by automatically acquiring user preferences from the historical data and matching items with the preferences. In the last decade, recommendation services have gained great attention due to the problem of information overload. However, despite recent advances of personalization techniques, several critical issues in modern recommender systems have not been well studied. These issues include: (1) understanding the accessing patterns of users (i.e., how to effectively model users' accessing behaviors); (2) understanding the relations between users and other objects (i.e., how to comprehensively assess the complex correlations between users and entities in recommender systems); and (3) understanding the interest change of users (i.e., how to adaptively capture users' preference drift over time). To meet the needs of users in modern recommender systems, it is imperative to provide solutions to address the aforementioned issues and apply the solutions to real-world applications. ^ The major goal of this dissertation is to provide integrated recommendation approaches to tackle the challenges of the current generation of recommender systems. In particular, three user-oriented aspects of recommendation techniques were studied, including understanding accessing patterns, understanding complex relations and understanding temporal dynamics. To this end, we made three research contributions. First, we presented various personalized user profiling algorithms to capture click behaviors of users from both coarse- and fine-grained granularities; second, we proposed graph-based recommendation models to describe the complex correlations in a recommender system; third, we studied temporal recommendation approaches in order to capture the preference changes of users, by considering both long-term and short-term user profiles. In addition, a versatile recommendation framework was proposed, in which the proposed recommendation techniques were seamlessly integrated. Different evaluation criteria were implemented in this framework for evaluating recommendation techniques in real-world recommendation applications. ^ In summary, the frequent changes of user interests and item repository lead to a series of user-centric challenges that are not well addressed in the current generation of recommender systems. My work proposed reasonable solutions to these challenges and provided insights on how to address these challenges using a simple yet effective recommendation framework.^

Next generation high density three-dimensional magnetic recording systems

This work is the first work using patterned soft underlayers in multilevel three-dimensional vertical magnetic data storage systems. The motivation stems from an exponentially growing information stockpile, and a corresponding need for more efficient storage devices with higher density. The world information stockpile currently exceeds 150EB (ExaByte=1x1018Bytes); most of which is in analog form. Among the storage technologies (semiconductor, optical and magnetic), magnetic hard disk drives are posed to occupy a big role in personal, network as well as corporate storage. However; this mode suffers from a limit known as the Superparamagnetic limit; which limits achievable areal density due to fundamental quantum mechanical stability requirements. There are many viable techniques considered to defer superparamagnetism into the 100's of Gbit/in2 such as: patterned media, Heat-Assisted Magnetic Recording (HAMR), Self Organized Magnetic Arrays (SOMA), antiferromagnetically coupled structures (AFC), and perpendicular magnetic recording. Nonetheless, these techniques utilize a single magnetic layer; and can thusly be viewed as two-dimensional in nature. In this work a novel three-dimensional vertical magnetic recording approach is proposed. This approach utilizes the entire thickness of a magnetic multilayer structure to store information; with potential areal density well into the Tbit/in2 regime. ^ There are several possible implementations for 3D magnetic recording; each presenting its own set of requirements, merits and challenges. The issues and considerations pertaining to the development of such systems will be examined, and analyzed using empirical and numerical analysis techniques. Two novel key approaches are proposed and developed: (1) Patterned soft underlayer (SUL) which allows for enhanced recording of thicker media, (2) A combinatorial approach for 3D media development that facilitates concurrent investigation of various film parameters on a predefined performance metric. A case study is presented using combinatorial overcoats of Tantalum and Zirconium Oxides for corrosion protection in magnetic media. ^ Feasibility of 3D recording is demonstrated, and an emphasis on 3D media development is emphasized as a key prerequisite. Patterned SUL shows significant enhancement over conventional "un-patterned" SUL, and shows that geometry can be used as a design tool to achieve favorable field distribution where magnetic storage and magnetic phenomena are involved. ^

Orthogonal frequency division multiplexing based air interfaces and multiple input multiple output techniques in cooperative satellite communications for 4th generation mobile systems

Recently, wireless network technology has grown at such a pace that scientific research has become a practical reality in a very short time span. Mobile wireless communications have witnessed the adoption of several generations, each of them complementing and improving the former. One mobile system that features high data rates and open network architecture is 4G. Currently, the research community and industry, in the field of wireless networks, are working on possible choices for solutions in the 4G system. 4G is a collection of technologies and standards that will allow a range of ubiquitous computing and wireless communication architectures. The researcher considers one of the most important characteristics of future 4G mobile systems the ability to guarantee reliable communications from 100 Mbps, in high mobility links, to as high as 1 Gbps for low mobility users, in addition to high efficiency in the spectrum usage. On mobile wireless communications networks, one important factor is the coverage of large geographical areas. In 4G systems, a hybrid satellite/terrestrial network is crucial to providing users with coverage wherever needed. Subscribers thus require a reliable satellite link to access their services when they are in remote locations, where a terrestrial infrastructure is unavailable. Thus, they must rely upon satellite coverage. Good modulation and access technique are also required in order to transmit high data rates over satellite links to mobile users. This technique must adapt to the characteristics of the satellite channel and also be efficient in the use of allocated bandwidth. Satellite links are fading channels, when used by mobile users. Some measures designed to approach these fading environments make use of: (1) spatial diversity (two receive antenna configuration); (2) time diversity (channel interleaver/spreading techniques); and (3) upper layer FEC. The author proposes the use of OFDM (Orthogonal Frequency Multiple Access) for the satellite link by increasing the time diversity. This technique will allow for an increase of the data rate, as primarily required by multimedia applications, and will also optimally use the available bandwidth. In addition, this dissertation approaches the use of Cooperative Satellite Communications for hybrid satellite/terrestrial networks. By using this technique, the satellite coverage can be extended to areas where there is no direct link to the satellite. For this purpose, a good channel model is necessary.

Orthogonal Frequency Division Multiplexing Based Air Interfaces and Multiple Input Multiple Output Techniques in Cooperative Satellite Communications for 4th Generation Mobile Systems

Recently, wireless network technology has grown at such a pace that scientific research has become a practical reality in a very short time span. One mobile system that features high data rates and open network architecture is 4G. Currently, the research community and industry, in the field of wireless networks, are working on possible choices for solutions in the 4G system. The researcher considers one of the most important characteristics of future 4G mobile systems the ability to guarantee reliable communications at high data rates, in addition to high efficiency in the spectrum usage. On mobile wireless communication networks, one important factor is the coverage of large geographical areas. In 4G systems, a hybrid satellite/terrestrial network is crucial to providing users with coverage wherever needed. Subscribers thus require a reliable satellite link to access their services when they are in remote locations where a terrestrial infrastructure is unavailable. The results show that good modulation and access technique are also required in order to transmit high data rates over satellite links to mobile users. The dissertation proposes the use of OFDM (Orthogonal Frequency Multiple Access) for the satellite link by increasing the time diversity. This technique will allow for an increase of the data rate, as primarily required by multimedia applications, and will also optimally use the available bandwidth. In addition, this dissertation approaches the use of Cooperative Satellite Communications for hybrid satellite/terrestrial networks. By using this technique, the satellite coverage can be extended to areas where there is no direct link to the satellite. The issue of Cooperative Satellite Communications is solved through a new algorithm that forwards the received data from the fixed node to the mobile node. This algorithm is very efficient because it does not allow unnecessary transmissions and is based on signal to noise ratio (SNR) measures.

Development of distributed generation infrastructure for microgrid connectivity to operational power systems

Distributed Generation (DG) from alternate sources and smart grid technologies represent good solutions for the increase in energy demands. Employment of these DG assets requires solutions for the new technical challenges that are accompanied by the integration and interconnection into operational power systems. A DG infrastructure comprised of alternate energy sources in addition to conventional sources, is developed as a test bed. The test bed is operated by synchronizing, wind, photovoltaic, fuel cell, micro generator and energy storage assets, in addition to standard AC generators. Connectivity of these DG assets is tested for viability and for their operational characteristics. The control and communication layers for dynamic operations are developed to improve the connectivity of alternates to the power system. A real time application for the operation of alternate sources in microgrids is developed. Multi agent approach is utilized to improve stability and sequences of actions for black start are implemented. Experiments for control and stability issues related to dynamic operation under load conditions have been conducted and verified.