Structure and physical properties of [µ-Tris(1,4-bis(tetrazol-1-yl)butane-N4,N4‘')iron(II)] Bis(hexafluorophosphate), a new Fe(II) spin-crossover compound with a three-dimensional threefold interlocked crystal lattice

[μ-Tris(1,4-bis(tetrazol-1-yl)butane-N4,N4‘)iron(II)] bis(hexafluorophosphate), [Fe(btzb)3](PF6)2, crystallizes in a three-dimensional 3-fold interlocked structure featuring a sharp two-step spin-crossover behavior. The spin conversion takes place between 164 and 182 K showing a discontinuity at about T1/2 = 174 K and a hysteresis of about 4 K between T1/2 and the low-spin state. The spin transition has been independently followed by magnetic susceptibility measurements, 57Fe-Mössbauer spectroscopy, and variable temperature far and midrange FTIR spectroscopy. The title compound crystallizes in the trigonal space group P30¯(No. 147) with a unit cell content of one formula unit plus a small amount of disordered solvent. The lattice parameters were determined by X-ray diffraction at several temperatures between 100 and 300 K. Complete crystal structures were resolved for 9 of these temperatures between 100 (only low spin, LS) and 300 K (only high spin, HS), Z = 1 [Fe(btzb)3](PF  6)2:  300 K (HS), a = 11.258(6) Å, c = 8.948(6) Å, V = 982.2(10) Å3; 100 K (LS), a = 10.989(3) Å, c = 8.702(2) Å, V = 910.1(4) Å3. The molecular structure consists of octahedral coordinated iron(II) centers bridged by six N4,N4‘ coordinating bis(tetrazole) ligands to form three 3-dimensional networks. Each of these three networks is symmetry related and interpenetrates each other within a unit cell to form the interlocked structure. The Fe−N bond lengths change between 1.993(1) Å at 100 K in the LS state and 2.193(2) Å at 300 K in the HS state. The nearest Fe separation is along the c-axis and identical with the lattice parameter c.

Improving resource management in virtualized data centers using application performance models

The rapid growth of virtualized data centers and cloud hosting services is making the management of physical resources such as CPU, memory, and I/O bandwidth in data center servers increasingly important. Server management now involves dealing with multiple dissimilar applications with varying Service-Level-Agreements (SLAs) and multiple resource dimensions. The multiplicity and diversity of resources and applications are rendering administrative tasks more complex and challenging. This thesis aimed to develop a framework and techniques that would help substantially reduce data center management complexity.^ We specifically addressed two crucial data center operations. First, we precisely estimated capacity requirements of client virtual machines (VMs) while renting server space in cloud environment. Second, we proposed a systematic process to efficiently allocate physical resources to hosted VMs in a data center. To realize these dual objectives, accurately capturing the effects of resource allocations on application performance is vital. The benefits of accurate application performance modeling are multifold. Cloud users can size their VMs appropriately and pay only for the resources that they need; service providers can also offer a new charging model based on the VMs performance instead of their configured sizes. As a result, clients will pay exactly for the performance they are actually experiencing; on the other hand, administrators will be able to maximize their total revenue by utilizing application performance models and SLAs. ^ This thesis made the following contributions. First, we identified resource control parameters crucial for distributing physical resources and characterizing contention for virtualized applications in a shared hosting environment. Second, we explored several modeling techniques and confirmed the suitability of two machine learning tools, Artificial Neural Network and Support Vector Machine, to accurately model the performance of virtualized applications. Moreover, we suggested and evaluated modeling optimizations necessary to improve prediction accuracy when using these modeling tools. Third, we presented an approach to optimal VM sizing by employing the performance models we created. Finally, we proposed a revenue-driven resource allocation algorithm which maximizes the SLA-generated revenue for a data center.^

"New" Social Movements: Alternative Modernities, (Trans)local Nationalisms, and Solidarity Economies

My dissertation is the first project on the Haitian Platform for Advocacy for an Alternative Development- PAPDA, a nation-building coalition founded by activists from varying sectors to coordinate one comprehensive nationalist movement against what they are calling an Occupation. My work not only provides information on this under-theorized popular movement but also situates it within the broader literature on the postcolonial nation-state as well as Latin American and Caribbean social movements. The dissertation analyzes the contentious relationship between local and global discourses and practices of citizenship. Furthermore, the research draws on transnational feminist theory to underline the scattered hegemonies that intersect to produce varied spaces and practices of sovereignty within the Haitian postcolonial nation-state. The dissertation highlights how race and class, gender and sexuality, education and language, and religion have been imagined and co-constituted by Haitian social movements in constructing ‘new’ collective identities that collapse the private and the public, the rural and the urban, the traditional and the modern. My project complements the scholarship on social movements and the postcolonial nation-state and pushes it forward by emphasizing its spatial dimensions. Moreover, the dissertation de-centers the state to underline the movement of capital, goods, resources, and populations that shape the postcolonial experience. I re-define the postcolonial nation-state as a network of local, regional, international, and transnational arrangements between different political agents, including social movement actors. To conduct this interdisciplinary research project, I employed ethnographic methods, discourse and textual analysis, as well as basic mapping and statistical descriptions in order to present a historically-rooted interpretation of individual and organizational negotiations for community-based autonomy and regional development.

A study of the top executive conference centers in the United States and an examination of the corresponding corporate meetings market

Introduction: The United States today has become "meeting-conscious." The complexity of conducting business has led to the need for sophisticated coordination of decision-making processes on all levels of the organization. Company meetings have played an increasingly important role in the success and future of many companies. Strategies and decisions are developed at meetings that can determine future policies of crucial importance. Executive training can mean the difference in whether the company will even survive. Large and growing companies have increased their off-premise meeting budgets annually in spite of the state of the economy. however, the rising costs of travel and lodging have made management monitor these budgets more closely than ever. Thus, the need to use every dollar efficiently has compelled companies to examine newer methods of running meetings and alternatives to the usage of typical off-premise meeting facilities. The importance of off-premise meetings in the United States economy has greatly increased due to the billions of dollars spent annually. These factors make it vital to explore the effectiveness of time and monetary expenditures. Up until the mid-1960's, company meetings were held in facilities of various design and purpose, none of which were specifically designed for the small to medium corporate meeting. Upon gathering information concerning the meetings market and the corporate meeting planner, certain individuals endeavored to change the situation. This study is designed to investigate this new concept, which will hereafter be referred to as "conference center." For the purpose of this study, the following two definitions will be used. 1. Conference center - that meeting facility primarily marketing its facilities for the small to medium-sized corporate meeting. The center is operated by specialists aware of market needs in as much detail as are those people working for the company involved. On-premise sleeping rooms are not mandatory provided such facilities are within easy access. 2. Meeting planner - that person within an organization who has primary responsibility for arranging off-premise meetings and all other related items necessary for meeting effectiveness. This person may spend anywhere from 10 to 100l of his time in this capacity. The conference center has effectively satisfied the need for specialized corporate meeting facilities. This study will show the depth of the corporate meetings market and trace the growth and development of this relatively new conference center concept. Information will also be compiled on the top centers in the country. It is hoped that by presenting this research meeting planners will become more aware of the nature and location of these centers, especially for use by the small to medium-sized company. Such exposure of the centers will hopefully increase existing demand and enable the construction of new, innovative centers.

Impact of Rapid Transit on the Residential Market in Hudson County, New Jersey

The New York Metropolitan region is one of the most populous urban agglomerations in the world, and the single largest in North America.[1] It is also one of the most prominent economic centers, with New York City at the epicenter of its growth. With the entire region growing rapidly over the last decade, it is essential to analyze the socio-economic changes in order to understand the impact it has on commercial real estate. With its focus on housing rentals, this study aims to highlight housing costs as a function of rapid transit over time.

New tools for cognitive and motor rehabilitation: development and clinical validation

Nervous system disorders are associated with cognitive and motor deficits, and are responsible for the highest disability rates and global burden of disease. Their recovery paths are vulnerable and dependent on the effective combination of plastic brain tissue properties, with complex, lengthy and expensive neurorehabilitation programs. This work explores two lines of research, envisioning sustainable solutions to improve treatment of cognitive and motor deficits. Both projects were developed in parallel and shared a new sensible approach, where low-cost technologies were integrated with common clinical operative procedures. The aim was to achieve more intensive treatments under specialized monitoring, improve clinical decision-making and increase access to healthcare. The first project (articles I – III) concerned the development and evaluation of a web-based cognitive training platform (COGWEB), suitable for intensive use, either at home or at institutions, and across a wide spectrum of ages and diseases that impair cognitive functioning. It was tested for usability in a memory clinic setting and implemented in a collaborative network, comprising 41 centers and 60 professionals. An adherence and intensity study revealed a compliance of 82.8% at six months and an average of six hours/week of continued online cognitive training activities. The second project (articles IV – VI) was designed to create and validate an intelligent rehabilitation device to administer proprioceptive stimuli on the hemiparetic side of stroke patients while performing ambulatory movement characterization (SWORD). Targeted vibratory stimulation was found to be well tolerated and an automatic motor characterization system retrieved results comparable to the first items of the Wolf Motor Function Test. The global system was tested in a randomized placebo controlled trial to assess its impact on a common motor rehabilitation task in a relevant clinical environment (early post-stroke). The number of correct movements on a hand-to-mouth task was increased by an average of 7.2/minute while the probability to perform an error decreased from 1:3 to 1:9. Neurorehabilitation and neuroplasticity are shifting to more neuroscience driven approaches. Simultaneously, their final utility for patients and society is largely dependent on the development of more effective technologies that facilitate the dissemination of knowledge produced during the process. The results attained through this work represent a step forward in that direction. Their impact on the quality of rehabilitation services and public health is discussed according to clinical, technological and organizational perspectives. Such a process of thinking and oriented speculation has led to the debate of subsequent hypotheses, already being explored in novel research paths.

Absorption and luminescent excitation spectra of F and M centers in Kcl and NaF

Luminescent excitation spectra were measured for the F and M centers in KCl; in particular, for the F band, M band, and the M2 transition. In all 3 cases, the spectra were nearly double-Gaussian in shape, and the efficiency for luminescence was nearly independent of the wavelength of the exciting light. A comparison of the absorption spectrum with the excitation spectrum of the F-band region of crystals with M centers present and oriented provided further evidence for the existence of the M2 transition of van Doorn and Haven and of Okamoto, and against the energy transfer theory of Lambe and Compton. The efficiency for luminescence of the M center upon M-band excitation was equal to the efficiency for F centers in pulse-annealed crystals of low F-center concentrations. The ratio of the efficiencies of the Ml to M2 transitions was 1.2 ± .25. The oscillator strengths of 3 of the M-center transitions in KCl relative to the oscillator strength for the F center were found to be in better agreement with the results reported by Okamoto, than with the results reported by Delbecq. The polarization of luminescence of M centers in KCl was measured at right angles to the exciting light, and was found to agree with the predictions of the van Doorn-Haven model of the M center. In NaF crystals having no absorption bands to the red side of the M band, the absorption and excitation spectra of the M band were accurately double-Gaussian over a wide range of wavelengths; the efficiency of luminescence of the M center was independent of the wavelength of the exciting light in that range; and the polarization of luminescence upon M-band excitation agreed well with the calculations based on the van DoornHaven model of the M center, In crystals in which the F band was bleached sufficiently to make it smaller in absorption height than the M band, several new color centers appeared on the red side of the M band, in contrast to the results reported by Blum; in these crystals, the polarization of luminescence of the M center upon M-band excitation disagreed strongly with theory, even though the absorptions for the new color centers were small compared to the M-band absorption.

New Jersey Coastal Heritage Trail /

Shows trail-related region, subregions, and welcome centers.

New Jersey Coastal Heritage Trail /

Shows trail-related region, subregions, and welcome centers.

New Jersey Coastal Heritage Trail /

Also shows project area, subregions, and welcome centers.

New Jersey Coastal Heritage Trail /

Also shows project area, subregions, and welcome centers.

New Jersey Coastal Heritage Trail /

Also shows project area, subregions, and welcome centers.

New Catalysts for the Renewable Production of Monomers for Bioplastics

Terephthalic acid (PTA) is one of the monomers used for the synthesis of the polyester, polyethylene terephthalate (PET), that is used for the large-scale manufacture of synthetic fibers and plastic bottles. PTA is largely produced from the liquid-phase oxidation of petroleum-derived p-xylene (PX). However, there are now ongoing worldwide efforts exploring alternative routes for producing PTA from renewable, biomass resources.

In this thesis, I present a new route to PTA starting from the biomass-derived platform chemical, 5-hydroxymethylfurfural (HMF). This route utilizes new, selective Diels-Alder-dehydration reactions involving ethylene and is advantageous over the previously proposed Diels-Alder-dehydration route to PTA from HMF via 2,5-dimethylfuran (DMF) since the H₂ reduction of HMF to DMF is avoided. Specifically, oxidized derivatives of HMF are reacted as is, or after etherification-esterification with methanol, with ethylene over solid Lewis acid catalysts that do not contain strong Brønsted acids in order to synthesize intermediates of PTA and its equally important diester, dimethyl terephthalate (DMT). The partially oxidized HMF, 5-(hydroxymethyl)furoic acid (HMFA) is reacted with high pressure ethylene over a pure-silica molecular sieve catalyst containing framework tin (Sn-Beta) to produce the Diels-Alder-dehydration product, 4-(hydroxymethyl)benzoic acid (HMBA), with ~30% selectivity at ~20% yield. If HMFA is protected with methanol to form methyl 5-(methoxymethyl)furan-2-carboxylate (MMFC), MMFC can react with ethylene in the presence of a pure-silica molecular sieve containing framework zirconium (Zr-Beta) to produce methyl 4-(methoxymethyl)benzenecarboxylate (MMBC) with >70% selectivity at >20% yield. HMBA and MMBC can then be oxidized to produce PTA and DMT, respectively. When Lewis acid containing mesoporous silica (MCM-41) and amorphous silica, or Brønsted acid containing zeolites (Al-Beta), are used as catalysts, a significant decrease in selectivity/yield of the Diels-Alder-dehydration product is observed.

An investigation to elucidate the reaction network and side products in the conversion of MMFC to MMBC was performed, and the main side products are found to be methyl 4-formylcyclohexa-1,3-diene-1-carboxylate and the ethylene Diels-Alder adduct of this cyclohexadiene. These products presumably form by a different dehydration pathway of the MMFC/ethylene Diels-Alder adduct and should be included when determining the overall selectivity to PTA or DMT since, like MMBC, these compounds are precursors to PTA or DMT.

Fundamental physical and chemical information on the ethylene Diels-Alder-dehydration reactions catalyzed by the Lewis acid-containing molecular sieves was obtained. Madon-Boudart experiments using Zr-Beta as catalyst show that the reaction rates are limited by chemical kinetics only (physical transport limitations are not present), all the Zr⁴⁺ centers are incorporated into the framework of the molecular sieve, and the whole molecular sieve crystal is accessible for catalysis. Apparent activation energies using Zr-Beta are low, suggesting that the overall activation energy of the system may be determined by a collection of terms and is not the true activation energy of a single chemical step.

A REVIEW OF THE SMALL BUSINESS DEVELOPMENT CENTERS PROGRAM

Members of the General Assembly requested that we conduct an audit of the Small Business Development Centers program. We planned to review the accuracy of the program’s reporting of its effectiveness, expenditures, and structure. The audit objectives were listed as follows: Determine if the SBDC program’s reporting, including the program’s effectiveness, is in compliance with the U.S. Small Business Administration’s guidelines and is accurate and complete ; Determine if the current structure of the SBDC is the most beneficial to the small business clients, provides appropriate oversight to SBDC staff, and allows for necessary sharing of best practices throughout all SBDC offices ; Review a sample of SBDC’s use of funding to ensure that the program is efficiently handling federal, state, and other funds for expenditures, including technology upgrades and training conferences.

New Haitian social movements: Alternative modernities, (trans)local nationalisms, and solidarity economies

My dissertation is the first project on the Haitian Platform for Advocacy for an Alternative Development- PAPDA, a nation-building coalition founded by activists from varying sectors to coordinate one comprehensive nationalist movement against what they are calling an Occupation. My work not only provides information on this under-theorized popular movement but also situates it within the broader literature on the postcolonial nation-state as well as Latin American and Caribbean social movements. The dissertation analyzes the contentious relationship between local and global discourses and practices of citizenship. Furthermore, the research draws on transnational feminist theory to underline the scattered hegemonies that intersect to produce varied spaces and practices of sovereignty within the Haitian postcolonial nation-state. The dissertation highlights how race and class, gender and sexuality, education and language, and religion have been imagined and co-constituted by Haitian social movements in constructing ‘new’ collective identities that collapse the private and the public, the rural and the urban, the traditional and the modern. My project complements the scholarship on social movements and the postcolonial nation-state and pushes it forward by emphasizing its spatial dimensions. Moreover, the dissertation de-centers the state to underline the movement of capital, goods, resources, and populations that shape the postcolonial experience. I re-define the postcolonial nation-state as a network of local, regional, international, and transnational arrangements between different political agents, including social movement actors. To conduct this interdisciplinary research project, I employed ethnographic methods, discourse and textual analysis, as well as basic mapping and statistical descriptions in order to present a historically-rooted interpretation of individual and organizational negotiations for community-based autonomy and regional development. ^