The Morita-Baylis-Hillman (MBH) reaction is a very versatile synthetic protocol to synthesize various useful compounds containing several functional groups. MBH acetates and carbonates are highly valued compounds as they have good potential to be precursors for organic synthesis reactions due to their ease of modification and synthesis. This thesis utilizes Density Functional Theory (DFT) calculations to understand the mechanism and selectivity of an unexpected tandem conjugate addition-elimination (CA-E) reaction of allylic alkylated Morita-Baylis-Hillman C- adducts. This synthetic protocol was developed by Prof. Zhi-Yong Jiang and co-workers from Henan University, China. The reaction required the use of sub-stoichiometric amounts of an organic or inorganic Brøndst base as a catalyst and was achieved with excellent yields (96%) in neat conditions. TBD gave the highest yield amongst the organocatalysts and Cs2CO3 gave the highest yield amongst all screened bases. A possible mechanistic pathway was proposed and three different energy profiles were modeled using 1,5,7-triaza-bicyclo-[4.4.0]-dec-5-ene (TBD), Cs2CO3 and CO32- as catalysts. All three models were able to explain the experimental observations, revealing both kinetic and thermodynamic factors influencing the selectivity of the CA-E reaction. CO32- model gave the most promising result, revealing a significant energy difference of 17.9 kcal/mol between the transition states of the two differing pathways and an energy difference of 20.9 kcal/mol between the two possible products. Although TBD modeling did not show significant difference in the transition states of the differing pathways, it revealed an unexpected secondary non-covalent electrostatic interaction, involving the electron deficient C atom of the triaza CN3 moiety of the TBD catalyst and the O atom of a neighboring NO2- group in the intermediate. Subsequent modeling using a similar substrate proved the possibility of this non-covalent electrostatic interaction, as there was significant overlap of the orbital cloud present in both the Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) of the molecule between the C atom of the triaza moiety belonging to the TBD catalyst and the O atom of the nitro group of the substrate. The Mayer bond order was of the C-O interaction was determined to be 0.138.

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ITC/USA 2015 Conference Proceedings / The Fifty-First Annual International Telemetering Conference and Technical Exhibition / October 26-29, 2015 / Bally's Hotel & Convention Center, Las Vegas, NV / Data security is becoming increasingly important in all areas of storage. The news services frequently have stories about lost or stolen storage devices and the panic it causes. Data security in an SSD usually involves two components: data protection and data elimination. Data protection includes passwords to protect against unauthorized access and encryption to protect against recovering data from the flash chips. Data elimination includes erasing the encryption key and erasing the flash. Telemetry applications frequently add requirements such as write protection, external erase triggers, and overwriting the flash after the erase. This presentation will review these data security features.

We describe contributions to algorithmic proof techniques for deciding the satisfiability of boolean combinations of many-variable nonlinear polynomial equations and inequalities over the real and complex numbers. In the first half, we present an abstract theory of Grobner basis construction algorithms for algebraically closed fields of characteristic zero and use it to introduce and prove the correctness of Grobner basis methods tailored to the needs of modern satisfiability modulo theories (SMT) solvers. In the process, we use the technique of proof orders to derive a generalisation of S-polynomial superfluousness in terms of transfinite induction along an ordinal parameterised by a monomial order. We use this generalisation to prove the abstract (“strategy-independent”) admissibility of a number of superfluous S-polynomial criteria important for efficient basis construction. Finally, we consider local notions of proof minimality for weak Nullstellensatz proofs and give ideal-theoretic methods for computing complex “unsatisfiable cores” which contribute to efficient SMT solving in the context of nonlinear complex arithmetic. In the second half, we consider the problem of effectively combining a heterogeneous collection of decision techniques for fragments of the existential theory of real closed fields. We propose and investigate a number of novel combined decision methods and implement them in our proof tool RAHD (Real Algebra in High Dimensions). We build a hierarchy of increasingly powerful combined decision methods, culminating in a generalisation of partial cylindrical algebraic decomposition (CAD) which we call Abstract Partial CAD. This generalisation incorporates the use of arbitrary sound but possibly incomplete proof procedures for the existential theory of real closed fields as first-class functional parameters for “short-circuiting” expensive computations during the lifting phase of CAD. Identifying these proof procedure parameters formally with RAHD proof strategies, we implement the method in RAHD for the case of full-dimensional cell decompositions and investigate its efficacy with respect to the Brown-McCallum projection operator. We end with some wishes for the future.

Thesis advisor: James P. Morken / This dissertation describes the development of two enantioselective methods of carbon-carbon bond formation. Chapter one discusses the development of an enantioselective Pd(0)-catalyzed conjugate addition of allylboronic acid pinacol ester to α,β-unsaturated methylidene ketones. Utilizing the same rationale for regio- and enantiocontrol as in the related enantioselective conjugate allylation of arylidene ketones, this method addresses the gap in technology by expanding the scope of the reaction to include alkyl-substituted enones. Chapter two examines the coupling of allyl electrophiles and allyl metal reagents. With computational insight into the reaction mechanism, a catalyst system was designed to control regioselectivity and enantioselectivity. Isotope labeling studies were carried out to probe the mechanism of the transformation. The reaction also proves to be diastereoselective when a substituted allyl boron reagent is employed. / Thesis (PhD) — Boston College, 2011. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Thesis advisor: James A. Russell / Prior research showing that children recognize emotional expressions has used a choice-from-array style task; for example, children are asked to find the fear face in an array of several expressions. However, these choice-from-array tasks allow for the use of a process of elimination strategy in which children could select an expression they are unfamiliar with when presented a label that does not apply to other expressions in the array. Across six studies (N = 144), 80% of 2- to 4-year-olds selected a novel expression when presented a target label and performed similarly when the label was novel (such as <italic>pax</italic>) or familiar (such as <italic>fear</italic>). In addition, 46% of children went on to freely label the expression with the target label in a subsequent task. These data are the first to show that children extend the process of elimination strategy to facial expressions and also call into question the findings of prior choice-from-array studies. / Thesis (PhD) — Boston College, 2011. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Psychology.

Work injury is one of the major obstacles in manufacturing industries especially in production assembly systems all over the world. Work injuries reduce production efficiency and threat human health. Among various types of work injuries, repetitive work injuries are the one that can be easily neglected. This thesis is about the application of computing technology to analysis and synthesis of repetitive work injuries in production assembly systems for the purpose of reduction or elimination of these injuries.<p> A production assembly system consists of the assembly machines, products, tools, humans (workers), and particular environments. Injuries of the worker are basically caused by over stress, strain, and fatigue, which are further related to the workers posture.<p> This research proposed a general methodology for constructing a software system for analysis and simulation of a workers postures in a virtual environment. The implementation of such a computer system was discussed. This research also proposed methods to compute work injury cost. Finally, this research proposed a more systematic method for the synthesis or re-design of worker postures to reduce or eliminate work injuries. The major contribution of this thesis work is to advance computing to work injury analysis and synthesis in production systems. <p> This thesis study concludes that the computer technology is matured enough to highly automate the process of work injury analysis and synthesis. It is possible that a complete design of production systems with consideration of work injuries can be done in a much more efficient manner perhaps reduction of the ramp-up process in the automobile industry from 6 months (typically) to one month in addition to the removal of wasted materials and potential injuries in the ramp-up process.

Aluminum- and gallium-bridged ansa-zirconocene compounds (Pytsi)Al[1]ZCP (31a) and (Pytsi)Ga[1]ZCP (31b) containing a bulky trisyl-based ligand with a pyridyl donor group [Pytsi = -C(SiMe3)2SiMe2(2-C5H4N)] were synthesized in 31% and 40% yield, respectively, by the reaction of (Pytsi)ECp2 [E = Al (29a), Ga (29b)] with Zr(NMe2)4 followed by reaction with Me3SiCl. Compounds 29a and 29b were prepared by the reaction of (Pytsi)ECl2 [E = Al (28a), E = Ga (28b)] with two equivalents of NaCp. The molecular structures of 29a and 29b were elucidated in solution by 1H and 13C NMR spectroscopy. Species 31a was characterized by multinuclear NMR spectroscopy while 31b was characterized by CHN elemental analysis, 1H and 13C NMR spectroscopy and mass spectrometry. Both species are the only known examples of aluminum- and gallium-bridged ansa-zirconocenes. Compound 31b in combination with MAO was applied and shown to be highly active for ethylene polymerization at room temperature. The activity of 31b was compared to that obtained for Cp2ZrCl2 using a glass reactor system and was found to be comparable. The influence of precatalyst concentration and ethylene pressure on activity of 31b was studied.

This report presents an algorithm for locating the cut points for and separatingvertically attached traffic signs in Sweden. This algorithm provides severaladvanced digital image processing features: binary image which representsvisual object and its complex rectangle background with number one and zerorespectively, improved cross correlation which shows the similarity of 2Dobjects and filters traffic sign candidates, simplified shape decompositionwhich smoothes contour of visual object iteratively in order to reduce whitenoises, flipping point detection which locates black noises candidates, chasmfilling algorithm which eliminates black noises, determines the final cut pointsand separates originally attached traffic signs into individual ones. At each step,the mediate results as well as the efficiency in practice would be presented toshow the advantages and disadvantages of the developed algorithm. Thisreport concentrates on contour-based recognition of Swedish traffic signs. Thegeneral shapes cover upward triangle, downward triangle, circle, rectangle andoctagon. At last, a demonstration program would be presented to show howthe algorithm works in real-time environment.

Work injury is one of the major obstacles in manufacturing industries especially in production assembly systems all over the world. Work injuries reduce production efficiency and threat human health. Among various types of work injuries, repetitive work injuries are the one that can be easily neglected. This thesis is about the application of computing technology to analysis and synthesis of repetitive work injuries in production assembly systems for the purpose of reduction or elimination of these injuries.<p> A production assembly system consists of the assembly machines, products, tools, humans (workers), and particular environments. Injuries of the worker are basically caused by over stress, strain, and fatigue, which are further related to the workers posture.<p> This research proposed a general methodology for constructing a software system for analysis and simulation of a workers postures in a virtual environment. The implementation of such a computer system was discussed. This research also proposed methods to compute work injury cost. Finally, this research proposed a more systematic method for the synthesis or re-design of worker postures to reduce or eliminate work injuries. The major contribution of this thesis work is to advance computing to work injury analysis and synthesis in production systems. <p> This thesis study concludes that the computer technology is matured enough to highly automate the process of work injury analysis and synthesis. It is possible that a complete design of production systems with consideration of work injuries can be done in a much more efficient manner perhaps reduction of the ramp-up process in the automobile industry from 6 months (typically) to one month in addition to the removal of wasted materials and potential injuries in the ramp-up process.