This study evaluated how well energy savings persisted over time in ten university buildings that had undergone retro-commissioning in 1996. The savings achieved immediately following retro-commissioning and in three subsequent years were documented in a previous study (Cho 2002). The current study expanded on this previous study by evaluating the performance of each building over nine additional years. Follow up retro-commissioning work performed in each building during that time was documented, as well as changes to the energy management control system. Savings were determined in accordance with the methodology outlined in the International Performance Measurement and Verification Protocol (IPMVP 2007), with ASHRAE Guideline 14 also serving as a reference. Total annualized savings for all buildings in 1997 (the year just after retro-commissioning) were 45(plus or minus 2)% for chilled water, 67(plus or minue 2)% for hot water, and 12% for electricity. Combining consumption from the most recent year for each building with valid energy consumption data showed a total savings of 39(plus or minus 1)% for chilled water, 64(plus or minus 2)% for heating water, and 22% for electricity. Uncertainty values were calculated in accordance with methodology in the IPMVP and ASHRAE Guideline 14, and were reported at the 90% confidence interval. The most recent year of data for most of the buildings was 2008-2009, although a few of the buildings did not have valid consumption data for that year. Follow up work performed in the buildings, lighting retrofits, and building metering changes beginning in 2005 were the major issues believed to have contributed to the high level of savings persistence in later years. When persistence trends were evaluated with adjustment for these factors, average savings for the buildings studied were found to degrade over time, and exponential models were developed to describe this degradation. The study concluded that on average energy savings after retro-commissioning will degrade over time in a way that can be modeled exponentially. It was also concluded that high levels of savings persistence can be achieved through performing retro-commissioning follow up, particularly when significant increases are observed in metered energy consumption data, but also at other times as retro-commissioning procedures and technology continually improve.

Traffic signs, which transportation agencies must inventory and manage, are one of the most important roadway assets because they are used to ensure roadway safety and provide important travel guidance/information. Traffic sign inventory and condition assessment are two important components that are essential for establishing a cost-effective and sustainable traffic sign management system. Traditionally, state departments of transportation (DOTs) have conducted traffic sign inventory and condition assessment manually, a process that is labor-intensive, time-consuming, and sometimes hazardous to field engineers in the roadway environment. Methods have been developed to automate sign inventory and condition assessment using video log images in previous studies. However, the performance of these methods still needs to be improved. Based on the need to inventory signs and manage them more effectively, this study has two focuses. The first focus is to develop an enhanced traffic sign detection methodology to improve the productivity of an image-based sign inventory for state DOTs. The proposed methodology includes two enhanced algorithms: a) a lighting dependent statistical color model (LD-SCM)-based color segmentation algorithm that is robust to different image lighting conditions, especially adverse lighting and b) an ordinary/partial differential equation (ODE/PDE)-based shape detection algorithm that is immune to discontinuous sign boundaries in a cluttered background. The second focus of the study is to explore a new traffic sign retroreflectivity condition assessment methodology to develop a mobile method that uses emerging computer vision and mobile light detection and ranging (LiDAR) technologies to assess traffic sign retroreflectivity conditions. The proposed methodology includes a) an image-LiDAR registration method employing camera calibration and point co-planarity to register the 3D LiDAR point cloud with 2D video log images, b) a theoretical-empirical normalization scheme to adjust the magnitude of the LiDAR retro-intensity values with respect to LiDAR beam distance and incidence angle based on the radiometric responses, and c) a population-based retroreflectivity condition assessment method to evaluate the adequacy of a traffic sign retroreflectivity condition based on the correlation between the normalized LiDAR retro-intensity and the retroreflectivity values. For the proposed traffic sign detection methodology, comprehensive tests using representative datasets (e.g. with different road functions, data collection sources, and data qualities) were conducted to validate the performance of the two enhanced algorithms and the complete methodology. For the proposed retroreflectivity condition assessment methodology, the fundamental behavior of LiDAR retro-intensity was comprehensively tested and simulated under a controlled lab and roadway environment to quantify the impact of beam distance and incidence angle. A preliminary test on Type 1 engineer grade stop signs was conducted in the field to validate the performance of the proposed sign retroreflectivity condition assessment method. The results from both of the proposed methodologies are promising.

In the Ward Group, stereoselective aldol reactions of thiopyran derived templates play an important role in polypropionate natural product syntheses. Central to this approach is the diastereo- and enantioselective synthesis of all possible aldol adducts 3 arising from tetrahydro-4H-thiopyran-4-one (1) and 1,4-dioxa-8-thiaspiro[4.5] decane-6- carboxaldehyde (2). There are four possible diastereomers of 3 indicated by the relative configurations at positions 3 and 1’ (syn or anti) and positions 1’ and 6’ (syn or anti). Up to date, the asymmetric aldol reaction of 1 with 2 catalyzed by L-proline or its tetrazole analogue 12 provides efficient access to 3,1’-anti-1’,6’-syn-3 (3-AS) without need for chromatography (>40 g scale; 75% yield, >98% ee) and 3,1’-syn-1’,6’-syn-3(3-SS) (via isomerization of 3-AS; >75% yield, 2 cycles); however, the preparation of enantiopure 3,1’-anti-1’,6’-anti-3 (3-AA) and 3,1’-anti-1’,6’-syn-3 (3-SA) still requires the use of enantiopure aldehyde 2 in a diastereoselective synthesis. Without a simple and scalable route, access to enantioenriched iterative aldol adducts and polypropionate natural products that are based on 3-AA and 3-SA skeletons are hindered. It was observed that conducting the asymmetric aldol synthesis of 3-AS on large scale gave enantioenriched 3-AA as a very minor product. This observation triggered the hypothesis of using L-proline to resolve racemic 3-AA via a retro-aldol reaction.In this thesis, the development, optimization, and application of an unprecedented L-proline catalyzed enantioselective retro-aldol reaction is described. Interesting mechanistic insights were uncovered. An unexpected isomerization process between 3-AA and 3-SA occurs in parallel with the retro-aldol process. The method was demonstrated to be a robust, flexible, and readily scalable process to access highly enantioenriched 3-AA (ee > 95%) and 3-SA (ee > 95%). To the best of our knowledge, this reaction represents the only reported enantioselective retro-aldol reaction catalyzed by L-proline.

Light as a “green” source of energy has become increasingly attractive throughout the past century and has shown versatility for the application of activating chemical reactions. Compared with traditional energy sources, it provides a more direct, selective and controllable method. My PhD study was focused on the study of photochemistry of organic materials in two different systems. The first system is regarding reversible photoacids which generate protons on irradiation. With the aim of systematically studying these novel types of long lived photoacids, a series of photoacids was designed, synthesized and whose chemical mechanism was thoroughly investigated. This type of photoacid changes from a weak acid to a strong acid with a pH change of several units, which achieves nearly complete proton dissociation upon visible light irradiation. The whole process is reversible and the half-life of the proton-dissociation state is long enough to be used in many applications. Besides fundamental studies, different applications based on this type of photoacids were also completed. An esterification reaction was catalyzed and the volume of a pH-sensitive polymer was altered due to the large amount of photo generated protons from this photoacid. A reversible electrical conductivity change of polyaniline (PANI) was also achieved by doping with this reversible photoacid. In order to induce a large conductivity increase, an irreversible photoacid generator (PAG) was embedded in a novel PANI/PAG/PVA novel composition. In this system, Poly (vinyl alcohol) (PVA) forms a hydrogen-bonding network to facilitate proton transfer between the PAG and PANI. A final electrical conductivity of 10-1 S cm-1 was successfully achieved after irradiation. The second system in which I explored photochemistry of organic molecules concerns Photoretro-Diels-Alder (PrDA) reactions and a variety of Diels-Alder (DA) adducts were designed for these studies. UV light was used to trigger the retro-Diels-Alder reactions. Quantum yield of iv each DA adducts was investigated. This revealed that the photo-reactivity of this process depends on the electron-donating ability of the diene and the electron-withdrawing ability of the dienophile component. Mechanistic studies of this PrDA reaction reveal that a charge-separated intermediate is generated from a singlet excited state. This was applied to an unsaturated cyclic α-diketones (DKs), which underwent PrDA reactions and generated anthracene derivatives and carbon monoxide (CO), which itself plays profound and important roles in biological systems. These unsaturated cyclic α-diketones (DKs) encapsulated in micelles are effective CO-releasing molecules (CORMs) and are capable of carrying and releasing CO in cellular systems. This novel type of organic CORMs has potentially low toxicity and generates fluorescence, which provides a useful tool for the study of the biological functions of CO.

The creation of artificial enzymes to catalyze desired reactions is a major goal of computational protein design. However, de novo enzymes display low catalytic efficiencies, requiring the introduction of activity-enhancing active site and distal mutations through directed evolution. A better understanding of how mutations introduced by directed evolution contribute to increased enzymatic activity will guide the development of design methods such that efficient enzymes can be designed de novo. Here, we evaluate the structural, functional, and dynamical impacts of active site and distal mutations introduced by directed evolution of the de novo retro-aldolase RA95, an enzyme that presents an important case study in enzyme design due to the significant structural remodelling that was observed during evolution. We observe that the variant RA95-Core, containing only active site mutations introduced by directed evolution, displays activity within one order of magnitude of the fully evolved variant. This suggests that computational enzyme design methods can be improved to create much more efficient enzymes than what was previously achieved in RA95. However, structural changes induced by distal mutations prevent computational recapitulation of the evolved active site on the original design template, indicating that the optimized active site identified through directed evolution could not have been designed de novo using current design methodologies. We suggest strategies for the incorporation of backbone remodelling into design procedures that would allow recapitulation of the evolved retro-aldolase active site, as well as the de novo design of highly efficient enzymes without the need for optimization by directed evolution.