Synthesis, characterization and chemical vapor deposition of transition metal di(tert-butyl)amido compounds

Although the transition metal chemistry of many dialkylamido ligands has been well studied, the chemistry of the bulky di(tert-butyl)amido ligand has been largely overlooked. The di(tert-butyl)amido ligand is well suited for synthesizing transition metal compounds with low coordination numbers; such compounds may exhibit interesting structural, physical, and chemical properties. Di(tert-butyl)amido complexes of transition metals are expected to exhibit high volatilities and low decomposition temperatures, thus making them well suited for the chemical vapor deposition of metals and metal nitrides. Treatment of MnBr₂(THF)₂, FeI₂, CoBr₂(DME), or NiBr₂(DME) with two equivalents of LiN(t-Bu)2 in benzene affords the two-coordinate complex M[N(t-Bu)₂]₂, where M is Mn, Fe, Co, or Ni. Crystallographic studies show that the M-N distances decrease across the series: 1.9365 (Mn), 1.8790 (Fe), 1.845 (Co), 1.798 Å (Ni). The N-M- N angles are very close to linear for Mn and Fe (179.30 and 179.45°, respectively), but bent for Co and Ni (159.2 and 160.90°, respectively). As expected, the d⁵ Mn complex has a magnetic moment of 5.53 μΒ that is very close to the spin only value. The EPR spectrum is nearly axial with a low E/D ratio of 0.014. The d⁶ Fe compound has a room temperature magnetic moment of 5.55 μΒ indicative of a large orbital angular momentum contribution. It does not exhibit a Jahn-Teller distortion despite the expected doubly degenerate ground state. Applied field Mössbauer spectroscopy shows that the effective internal hyperfine field is unusually large, Hint = 105 T. The magnetic moments of Co[N(t-Bu)₂]₂ and Ni[N(t-Bu)₂]₂ are 5.24 and 3.02 μΒ respectively. Both are EPR silent at 4.2 K. Treatment of TiCl₄ with three equivalents of LiN(t-Bu)2 in pentane affords the briding imido compound Ti₂[μ-N(t-Bu)]₂Cl₂[N(t-Bu)₂]₂ via a dealkylation reaction. Rotation around the bis(tert-butyl)amido groups is hindered, with activation parameters of ΔH‡ = 12.8 ± 0.6 kcal mol-1 and ΔS‡ = -8 ± 2 cal K-1 ·mol-1, as evidenced by variable temperature 1H NMR spectroscopy. Treatment of TiCl₄ with two equivalents of HN(t-Bu)₂ affords Ti₂Cl₆[N(t-Bu)₂]₂. This complex shows a close-contact of 2.634(3) Å between Ti and the carbon atom of one of the CH₃ substituents on the tert-butyl groups. Theoretical considerations and detailed structural comparisons suggest this interaction is not agostic in nature, but rather is a consequence of interligand repulsions. Treatment of NiI₂(PPh3)₂ and PdCl₂(PPh₃)₂ with LiN(t-Bu)₂in benzene affords Ni[N(t-Bu)₂](PPh₃)I and Pd₃(μ₂-NBut₂)2(μ₂-PPh₂)Ph(PPh₃) respectively. The compound Ni[N(t-Bu)₂](PPh₃)I has distorted T-shape in geometry, whereas Pd₃(μ₂-NBut₂)₂(μ₂-PPh₂)Ph(PPh₃) contains a triangular palladium core. Manganese nitride films were grown from Mn[N(t-Bu)₂]₂ in the presence of anhydrous ammonia. The growth rate was several nanometers per minute even at the remarkably low temperature of 80⁰C. As grown, the films are carbon- and oxygen-free, and have a columnar morphology. The spacings between the columns become smaller and the films become smoother as the growth temperature is increased. The composition of the films is consistent with a stoichiometry of Mn₅N₂.

A Soft Computing Approach to Quality Evaluation of General Chemistry Learning in Higher Education

In contemporary societies higher education must shape individuals able to solve problems in a workable and simpler manner and, therefore, a multidisciplinary view of the problems, with insights in disciplines like psychology, mathematics or computer science becomes mandatory. Undeniably, the great challenge for teachers is to provide a comprehensive training in General Chemistry with high standards of quality, and aiming not only at the promotion of the student’s academic success, but also at the understanding of the competences/skills required to their future doings. Thus, this work will be focused on the development of an intelligent system to assess the Quality-of-General-Chemistry-Learning, based on factors related with subject, teachers and students.

Assessing the Role of General Chemistry Learning in Higher Education

The inclusion of General Chemistry (GC) in the curricula of higher education courses in science and technology aims, on the one hand, to develop students' skills necessary for further studies and, on the other hand, to respond to the need of endowing future professionals of knowledge to analyze and solve multidisciplinary problems in a sustainable way. The participation of students in the evaluation of the role played by the GC in their training is crucial, and the analysis of the results can be an essential tool to increase success in the education of students and improving practices in various professions. Undeniably, this work will be focused on the development of an intelligent system to assess the role of GC. The computational framework is built on top of a Logic Programming approach to Knowledge Representation and Reasoning, complemented with a problem solving methodology moored on Artificial Neural Networks. The results so far obtained show that the proposed model stands for a good start, being its overall accuracy higher than 95%.

Green synthesis of polypyrrole-supported metal catalysts: application to nitrate removal in water

Pt and Pt/Sn catalysts supported on polypyrrole (PPy) have been prepared using Ar plasma to reduce the metal precursors dispersed on the polymer. The PPy support was synthesized by chemical polymerization of pyrrole with FeCl3·6H2O, this leading to the conducting form of the polymer (conductimetric measurements). The Ar plasma treatment produced a partial reduction of platinum ions, anchored as platinum chloro-complexes to the PPy chain, into metallic platinum. A homogeneous distribution of Pt and Sn nanoparticles was observed by TEM. Activity of the PPy-supported catalysts was evaluated in the reduction of aqueous nitrate with H2 at room temperature. Nitrate concentration in water below the maximum acceptable level of 50 mg L−1 was achieved with all catalysts. However, considering not only efficiency in nitrate reduction, but also minimized concentrations of undesired nitrite and ammonium, the monometallic Pt catalyst seems to be the most promising one.

Problema di Cauchy-Dirichlet per l'equazione del calore

In quest'elaborato si risolve il problema di Cauchy-Dirichlet per l'equazione del calore, prendendo come oggetto d'esame una sbarra omogenea. Nel primo capitolo si studiano le serie di Fourier reali a partire dalle serie trigonometriche; vengono dati, poi, i principali risultati di convergenza puntuale, uniforme ed in L^2 e si discute l'integrabilità termine a termine di una serie di Fourier. Il secondo capitolo tratta la convergenza secondo Cesàro, le serie di Fejèr ed i principali risultati di convergenza di queste ultime. Nel terzo, ed ultimo, capitolo si risolve il Problema di Cauchy-Dirichlet, distinguendo i casi in cui il dato iniziale sia di classe C^1 o solo continuo; nel secondo caso si propone una risoluzione basata sulle serie di Fejér e sul concetto di barriera ed una utilizzando il nucleo di Green per l'equazione del calore.

Densita con la proprieta di media per i sub-Laplaciani

Nella tesi studiamo le densità con la proprietà di media per i sub-Laplaciani. In particolare determiniamo un’espressione generale per una densità positiva con la proprietà di media, su un insieme Ω generico che soddisfi certe prorpietà di regolarità. Troviamo inoltre delle stime della funzione di Green e del nucleo di Poisson per un qualsiasi sub-Laplaciano su un generico gruppo di Carnot e tramite queste stime troviamo delle condizioni sufficienti affinchè, con la densità precedentemente trovata, si possa avere una struttura di Γ-tripla sull’insieme Ω. Studiamo infine un problema inverso per il quale sarà fondamentale avere una struttura di Γ-tripla.

Brucite Microbialites in Living Coral Skeletons: Indicators of Extreme Microenvironments in Shallow-Marine Settings

Brucite [Mg(OH)2] microbialites occur in vacated interseptal spaces of living scleractinian coral colonies (Acropora, Pocillopora, Porites) from subtidal and intertidal settings in the Great Barrier Reef, Australia, and subtidal Montastraea from the Florida Keys, United States. Brucite encrusts microbial filaments of endobionts (i.e., fungi, green algae, cyanobacteria) growing under organic biofilms; the brucite distribution is patchy both within interseptal spaces and within coralla. Although brucite is undersaturated in seawater, its precipitation was apparently induced in the corals by lowered pCO2 and increased pH within microenvironments protected by microbial biofilms. The occurrence of brucite in shallow-marine settings highlights the importance of microenvironments in the formation and early diagenesis of marine carbonates. Significantly, the brucite precipitates discovered in microenvironments in these corals show that early diagenetic products do not necessarily reflect ambient seawater chemistry. Errors in environmental interpretation may arise where unidentified precipitates occur in microenvironments in skeletal carbonates that are subsequently utilized as geochemical seawater proxies.

Time-Dependent Density Functional Molecular Orbital and Excited State Calculations on Bis(porphyrinyl)butadiynes in the Monocationic, Neutral, Monoanionic, and Dianionic Oxidation States

We report a theoretical study of the multiple oxidation states (1+, 0, 1−, and 2−) of a meso,meso-linked diporphyrin, namely bis[10,15,20-triphenylporphyrinatozinc(II)-5-yl]butadiyne (4), using Time-Dependent Density Functional Theory (TDDFT). The origin of electronic transitions of singlet excited states is discussed in comparison to experimental spectra for the corresponding oxidation states of the close analogue bis{10,15,20-tris[3‘,5‘-di-tert-butylphenyl]porphyrinatozinc(II)-5-yl}butadiyne (3). The latter were measured in previous work under in situ spectroelectrochemical conditions. Excitation energies and orbital compositions of the excited states were obtained for these large delocalized aromatic radicals, which are unique examples of organic mixed-valence systems. The radical cations and anions of butadiyne-bridged diporphyrins such as 3 display characteristic electronic absorption bands in the near-IR region, which have been successfully predicted with use of these computational methods. The radicals are clearly of the “fully delocalized” or Class III type. The key spectral features of the neutral and dianionic states were also reproduced, although due to the large size of these molecules, quantitative agreement of energies with observations is not as good in the blue end of the visible region. The TDDFT calculations are largely in accord with a previous empirical model for the spectra, which was based simplistically on one-electron transitions among the eight key frontier orbitals of the C4 (1,4-butadiyne) linked diporphyrins.

Capability green

Tract consultants are a landscape architecture practice, founded in 1973 as an offshoot to the highly innovative, interdisciplinary design and build company Merchant Builders, and was perhaps the first truly corporate practice of this type in Australia. Founding directors Rodney Wulff and Steve Calhoun were both instrumental in establishing the undergraduate landscape architecture course at RMIT University, and bringing our Jim Sinatra, who had taught Calhoun at the University of Iowa. Wulff remained for many years the holder of the only doctorate in landscape architecture in the country. This combination of an academic, design and professional agenda was a rich one for Tract in their early days. This founding generosity and interest in the intellectual aspects of landscape architecture continues in relation to the university in a number of ways, including information ones, such as the regular employment of applicants who fail to get into the course at RMIT. In preparing them for re-applying, he has given a number of individuals a way into the profession that the university could not allow.

Village green

For a communal garden in Copenhagen, Stig L. Andersson uses grasses of varying texture and height, creating a new view or spatial experience from every angle. The idea of vegetation texture being an important constituent of planting design is pervasive. Gardening books tell aspiring designers that "colour, texture and form" are the central aspects of planting arrangements. While these elements contribute to this language, they have tended to limit the language of planting to a singular, two dimensional paradigm, where planting is designed in static elevation. This has developed from a perennial-border approach demonstrated by the early 20th century garden designer Gertrude Jekyll, where the viewer is parallel to the bed, and the planting is layered to address this view. If one were to characterise the difference between a garden design and a landscape architectural approach, the latter would seem self-conscious in its use of space, movement and vision.

Living walls - a way to green the built environment

Actions Towards Sustainable Outcomes Environmental Issues/Principal Impacts The increasing urbanisation of cities brings with it several detrimental consequences, such as: • Significant energy use for heating and cooling many more buildings has led to urban heat islands and increased greenhouse gas emissions. • Increased amount of hard surfaces, which not only contributes to higher temperatures in cities, but also to increased stormwater runoff. • Degraded air quality and noise. • Health and general well-being of people is frequently compromised, by inadequate indoor air quality. • Reduced urban biodiversity. Basic Strategies In many design situations, boundaries and constraints limit the application of cutting EDGe actions. In these circumstances, designers should at least consider the following: • Living walls are an emerging technology, and many Australian examples function more as internal feature walls. However,as understanding of the benefits and construction of living walls develops this technology could be part of an exterior facade that enhances a building’s thermal performance. • Living walls should be designed to function with an irrigation system using non-potable water. Cutting EDGe Strategies • Living walls can be part of a design strategy that effectively improves the thermal performance of a building, thereby contributing to lower energy use and greenhouse gas emissions. • Including living walls in the initial stages of design would provide greater flexibility to the design, especially of the facade, structural supports, mechanical ventilation and watering systems, thus lowering costs. • Designing a building with an early understanding of living walls can greatly reduce maintenance costs. • Including plant species and planting media that would be able to remove air impurities could contribute to improved indoor air quality, workplace productivity and well-being. Synergies and References • Living walls are a key research topic at the Centre for Subtropical Design, Queensland University of Technology: http://www.subtropicaldesign.bee.qut.edu.au • BEDP Environment Design Guide: DES 53: Roof and Facade Gardens • BEDP Environment Design Guide: GEN 4: Positive Development – Designing for Net Positive Impacts (see green scaffolding and green space frame walls). • Green Roofs Australia: www.greenroofs.wordpress.com • Green Roofs for Healthy Cities USA: www.greenroofs.org