ASU Scholarship Showcase

Shade plays an important role in designing pedestrian-friendly outdoor spaces in hot desert cities. This study investigates the impact of photovoltaic canopy shade and tree shade on thermal comfort through meteorological observations and field surveys at a pedestrian mall on Arizona State University's Tempe campus. During the course of 1 year, on selected clear calm days representative of each season, we conducted hourly meteorological transects from 7:00 a.m. to 6:00 p.m. and surveyed 1284 people about their thermal perception, comfort, and preferences. Shade lowered thermal sensation votes by approximately 1 point on a semantic differential 9-point scale, increasing thermal comfort in all seasons except winter. Shade type (tree or solar canopy) did not significantly impact perceived comfort, suggesting that artificial and natural shades are equally efficient in hot dry climates. Globe temperature explained 51 % of the variance in thermal sensation votes and was the only statistically significant meteorological predictor. Important non-meteorological factors included adaptation, thermal comfort vote, thermal preference, gender, season, and time of day. A regression of subjective thermal sensation on physiological equivalent temperature yielded a neutral temperature of 28.6 °C. The acceptable comfort range was 19.1 °C-38.1 °C with a preferred temperature of 20.8 °C. Respondents exposed to above neutral temperature felt more comfortable if they had been in air-conditioning 5 min prior to the survey, indicating a lagged response to outdoor conditions. Our study highlights the importance of active solar access management in hot urban areas to reduce thermal stress.

This study investigates the impact of urban form and landscaping type on the mid-afternoon microclimate in semi-arid Phoenix, Arizona. The goal is to find effective urban form and design strategies to ameliorate temperatures during the summer months. We simulated near-ground air temperatures for typical residential neighborhoods in Phoenix using the three-dimensional microclimate model ENVI-met. The model was validated using weather observations from the North Desert Village (NDV) landscape experiment, located on the Arizona State University's Polytechnic campus. The NDV is an ideal site to determine the model's input parameters, since it is a controlled environment recreating three prevailing residential landscape types in the Phoenix metropolitan area (mesic, oasis, and xeric). After validation, we designed five neighborhoods with different urban forms that represent a realistic cross-section of typical residential neighborhoods in Phoenix. The scenarios follow the Local Climate Zone (LCZ) classification scheme after Stewart and Oke. We then combined the neighborhoods with three landscape designs and, using ENVI-met, simulated microclimate conditions for these neighborhoods for a typical summer day. Results were analyzed in terms of mid-afternoon air temperature distribution and variation, ventilation, surface temperatures, and shading. Findings show that advection is important for the distribution of within-design temperatures and that spatial differences in cooling are strongly related to solar radiation and local shading patterns. In mid-afternoon, dense urban forms can create local cool islands. Our approach suggests that the LCZ concept is useful for planning and design purposes.

The electronic structure of eight zinc-centered porphyrin macrocyclic molecules are investigated using density functional theory for ground-state properties, time-dependent density functional theory (TDDFT) for excited states, and Franck-Condon (FC) analysis for further characterization of the UV-vis spectrum. Symmetry breaking was utilized to find the lowest energy of the excited states for many states in the spectra. To confirm the theoretical modeling, the spectroscopic result from zinc phthalocyanine (ZnPc) is used to compare to the TDDFT and FC result. After confirmation of the modeling, five more planar molecules are investigated: zinc tetrabenzoporphyrin (ZnTBP), zinc tetrabenzomonoazaporphyrin (ZnTBMAP), zinc tetrabenzocisdiazaporphyrin (ZnTBcisDAP), zinc tetrabenzotransdiazaporphyrin (ZnTBtransDAP), and zinc tetrabenzotriazaporphyrin (ZnTBTrAP). The two latter molecules are then compared to their phenylated sister molecules: zinc monophenyltetrabenzotriazaporphyrin (ZnMPTBTrAP) and zinc diphenyltetrabenzotransdiazaporphyrin (ZnDPTBtransDAP). The spectroscopic results from the synthesis of ZnMPTBTrAP and ZnDPTBtransDAP are then compared to their theoretical models and non-phenylated pairs. While the Franck-Condon results were not as illuminating for every B-band, the Q-band results were successful in all eight molecules, with a considerable amount of spectral analysis in the range of interest between 300 and 750 nm. The π-π^* transitions are evident in the results for all of the Q bands, while satellite vibrations are also visible in the spectra. In particular, this investigation finds that, while ZnPc has a D_4h symmetry at ground state, a C_4v symmetry is predicted in the excited-state Q band region. The theoretical results for ZnPc found an excitation energy at the Q-band 0-0 transition of 1.88 eV in vacuum, which is in remarkable agreement with published gas-phase spectroscopy, as well as our own results of ZnPc in solution with Tetrahydrofuran that are provided in this paper.

A structurally and compositionally well-defined and spectrally tunable artificial light-harvesting system has been constructed in which multiple organic dyes attached to a three-arm-DNA nanostructure serve as an antenna conjugated to a photosynthetic reaction center isolated from Rhodobacter sphaeroides 2.4.1. The light energy absorbed by the dye molecules is transferred to the reaction center, where charge separation takes place. The average number of DNA three-arm junctions per reaction center was tuned from 0.75 to 2.35. This DNA-templated multichromophore system serves as a modular light-harvesting antenna that is capable of being optimized for its spectral properties, energy transfer efficiency, and photostability, allowing one to adjust both the size and spectrum of the resulting structures. This may serve as a useful test bed for developing nanostructured photonic systems.

Time-resolved fluorescence spectroscopy was used to explore the pathway and kinetics of energy transfer in photosynthetic membrane vesicles (chromatophores) isolated from Rhodobacter (Rba.) sphaeroides cells harvested 2, 4, 6 or 24 hours after a transition from growth in high to low level illumination. As previously observed, this light intensity transition initiates the remodeling of the photosynthetic apparatus and an increase in the number of light harvesting 2 (LH2) complexes relative to light harvesting 1 (LH1) and reaction center (RC) complexes. It has generally been thought that the increase in LH2 complexes served the purpose of increasing the overall energy transmission to the RC. However, fluorescence lifetime measurements and analysis in terms of energy transfer within LH2 and between LH2 and LH1 indicate that, during the remodeling time period measured, only a portion of the additional LH2 generated are well connected to LH1 and the reaction center. The majority of the additional LH2 fluorescence decays with a lifetime comparable to that of free, unconnected LH2 complexes. The presence of large LH2-only domains has been observed by atomic force microscopy in Rba. sphaeroides chromatophores (Bahatyrova et al., Nature, 2004, 430, 1058), providing structural support for the existence of pools of partially connected LH2 complexes. These LH2-only domains represent the light-responsive antenna complement formed after a switch in growth conditions from high to low illumination, while the remaining LH2 complexes occupy membrane regions containing mixtures of LH2 and LH1–RC core complexes. The current study utilized a multi-parameter approach to explore the fluorescence spectroscopic properties related to the remodeling process, shedding light on the structure-function relationship of the photosynthetic assembles. Possible reasons for the accumulation of these largely disconnected LH2-only pools are discussed.

There are an increasing variety of applications in which peptides are both synthesized and used attached to solid surfaces. This has created a need for high throughput sequence analysis directly on surfaces. However, common sequencing approaches that can be adapted to surface bound peptides lack the throughput often needed in library-based applications. Here we describe a simple approach for sequence analysis directly on solid surfaces that is both high speed and high throughput, utilizing equipment available in most protein analysis facilities. In this approach, surface bound peptides, selectively labeled at their N-termini with a positive charge-bearing group, are subjected to controlled degradation in ammonia gas, resulting in a set of fragments differing by a single amino acid that remain spatially confined on the surface they were bound to. These fragments can then be analyzed by MALDI mass spectrometry, and the peptide sequences read directly from the resulting spectra.

Persistent currents (PCs), one of the most intriguing manifestations of the Aharonov-Bohm (AB) effect, are known to vanish for Schrödinger particles in the presence of random scatterings, e.g., due to classical chaos. But would this still be the case for Dirac fermions? Addressing this question is of significant value due to the tremendous recent interest in two-dimensional Dirac materials. We investigate relativistic quantum AB rings threaded by a magnetic flux and find that PCs are extremely robust. Even for highly asymmetric rings that host fully developed classical chaos, the amplitudes of PCs are of the same order of magnitude as those for integrable rings, henceforth the term superpersistent currents (SPCs). A striking finding is that the SPCs can be attributed to a robust type of relativistic quantum states, i.e., Dirac whispering gallery modes (WGMs) that carry large angular momenta and travel along the boundaries. We propose an experimental scheme using topological insulators to observe and characterize Dirac WGMs and SPCs, and speculate that these features can potentially be the base for a new class of relativistic qubit systems. Our discovery of WGMs in relativistic quantum systems is remarkable because, although WGMs are common in photonic systems, they are relatively rare in electronic systems.

The phenomenon of Fano resonance is ubiquitous in a large variety of wave scattering systems, where the resonance profile is typically asymmetric. Whether the parameter characterizing the asymmetry should be complex or real is an issue of great experimental interest. Using coherent quantum transport as a paradigm and taking into account of the collective contribution from all available scattering channels, we derive a universal formula for the Fano-resonance profile. We show that our formula bridges naturally the traditional Fano formulas with complex and real asymmetry parameters, indicating that the two types of formulas are fundamentally equivalent (except for an offset). The connection also reveals a clear footprint for the conductance resonance during a dephasing process. Therefore, the emergence of complex asymmetric parameter when fitting with experimental data needs to be properly interpreted. Furthermore, we have provided a theory for the width of the resonance, which relates explicitly the width to the degree of localization of the close-by eigenstates and the corresponding coupling matrices or the self-energies caused by the leads. Our work not only resolves the issue about the nature of the asymmetry parameter, but also provides deeper physical insights into the origin of Fano resonance. Since the only assumption in our treatment is that the transport can be described by the Green’s function formalism, our results are also valid for broad disciplines including scattering problems of electromagnetic waves, acoustics, and seismology.

Background: Chemistry and particularly enzymology at surfaces is a topic of rapidly growing interest, both in terms of its role in biological systems and its application in biocatalysis. Existing protein immobilization approaches, including noncovalent or covalent attachments to solid supports, have difficulties in controlling protein orientation, reducing nonspecific absorption and preventing protein denaturation. New strategies for enzyme immobilization are needed that allow the precise control over orientation and position and thereby provide optimized activity.

Methodology/Principal Findings: A method is presented for utilizing peptide ligands to immobilize enzymes on surfaces with improved enzyme activity and stability. The appropriate peptide ligands have been rapidly selected from high-density arrays and when desirable, the peptide sequences were further optimized by single-point variant screening to enhance both the affinity and activity of the bound enzyme. For proof of concept, the peptides that bound to β-galactosidase and optimized its activity were covalently attached to surfaces for the purpose of capturing target enzymes. Compared to conventional methods, enzymes immobilized on peptide-modified surfaces exhibited higher specific activity and stability, as well as controlled protein orientation.

Conclusions/Significance: A simple method for immobilizing enzymes through specific interactions with peptides anchored on surfaces has been developed. This approach will be applicable to the immobilization of a wide variety of enzymes on surfaces with optimized orientation, location and performance, and provides a potential mechanism for the patterned self-assembly of multiple enzymes on surfaces.

The City of Phoenix (Arizona, USA) developed a Tree and Shade Master Plan and a Cool Roofs initiative to ameliorate extreme heat during the summer months in their arid city. This study investigates the impact of the City's heat mitigation strategies on daytime microclimate for a pre-monsoon summer day under current climate conditions and two climate change scenarios. We assessed the cooling effect of trees and cool roofs in a Phoenix residential neighborhood using the microclimate model ENVI-met. First, using xeric landscaping as a base, we created eight tree planting scenarios (from 0% canopy cover to 30% canopy cover) for the neighborhood to characterize the relationship between canopy cover and daytime cooling benefit of trees. In a second set of simulations, we ran ENVI-met for nine combined tree planting and landscaping scenarios (mesic, oasis, and xeric) with regular roofs and cool roofs under current climate conditions and two climate change projections. For each of the 54 scenarios, we compared average neighborhood mid-afternoon air temperatures and assessed the benefits of each heat mitigation measure under current and projected climate conditions. Findings suggest that the relationship between percent canopy cover and air temperature reduction is linear, with 0.14 °C cooling per percent increase in tree cover for the neighborhood under investigation. An increase in tree canopy cover from the current 10% to a targeted 25% resulted in an average daytime cooling benefit of up to 2.0 °C in residential neighborhoods at the local scale. Cool roofs reduced neighborhood air temperatures by 0.3 °C when implemented on residential homes. The results from this city-specific mitigation project will inform messaging campaigns aimed at engaging the city decision makers, industry, and the public in the green building and urban forestry initiatives.