ASU Scholarship Showcase

Does school participatory budgeting (SPB) increase students’ political efficacy? SPB, which is implemented in thousands of schools around the world, is a democratic process of deliberation and decision-making in which students determine how to spend a portion of the school’s budget. We examined the impact of SPB on political efficacy in one middle school in Arizona. Our participants’ (n = 28) responses on survey items designed to measure self-perceived growth in political efficacy indicated a large effect size (Cohen’s d = 1.46), suggesting that SPB is an effective approach to civic pedagogy, with promising prospects for developing students’ political efficacy.

S-cysteinylated albumin and methionine-oxidized apolipoprotein A-I (apoA-I) have been posed as candidate markers of diseases associated with oxidative stress. Here, a dilute-and-shoot form of LC–electrospray ionization–MS requiring half a microliter of blood plasma was employed to simultaneously quantify the relative abundance of these oxidized proteoforms in samples stored at −80 °C, −20 °C, and room temperature and exposed to multiple freeze-thaw cycles and other adverse conditions in order to assess the possibility that protein oxidation may occur as a result of poor sample storage or handling. Samples from a healthy donor and a participant with poorly controlled type 2 diabetes started at the same low level of protein oxidation and behaved similarly; significant increases in albumin oxidation via S-cysteinylation were found to occur within hours at room temperature and days at −20 °C. Methionine oxidation of apoA-I took place on a longer time scale, setting in after albumin oxidation reached a plateau. Freeze–thaw cycles had a minimal effect on protein oxidation. In matched collections, protein oxidation in serum was the same as that in plasma. Albumin and apoA-I oxidation were not affected by sample headspace or the degree to which vials were sealed. ApoA-I, however, was unexpectedly found to oxidize faster in samples with lower surface-area-to-volume ratios. An initial survey of samples from patients with inflammatory conditions normally associated with elevated oxidative stress-including acute myocardial infarction and prostate cancer—demonstrated a lack of detectable apoA-I oxidation. Albumin S-cysteinylation in these samples was consistent with known but relatively brief exposures to temperatures above −30 °C (the freezing point of blood plasma). Given their properties and ease of analysis, these oxidized proteoforms, once fully validated, may represent the first markers of blood plasma specimen integrity based on direct measurement of oxidative molecular damage that can occur under suboptimal storage conditions.

In recent years, a substantial amount of research has been focused on identifying suitable interfacial layers in organic light-emitting diodes and organic solar cells which has efficient charge transport properties. In this work, a very thin layer of AgOx is deposited on top of the ITO layer along with PEDOT:PSS and is observed that the solar cells having the AgOx interfacial layer showed a 28% increase in power conversion efficiency in comparison to that of the control cell. The enhancement in efficiency has been ascribed to improvements in fill factor as well as the increase in shunt resistance and decrease in the series resistance of the solar cells. An equivalent circuit model is also provided to understand the changes in the series and shunt resistances in the AgOx modified devices.

Signatures of nonlinear and non-Gaussian dynamics in time-resolved linear and nonlinear (correlation) 2D spectra are analyzed in a model considering a linear plus quadratic dependence of the spectroscopic transition frequency on a Gaussian nuclear coordinate of the thermal bath (quadratic coupling). This new model is contrasted to the commonly assumed linear dependence of the transition frequency on the medium nuclear coordinates (linear coupling). The linear coupling model predicts equality between the Stokes shift and equilibrium correlation functions of the transition frequency and time-independent spectral width. Both predictions are often violated, and we are asking here the question of whether a nonlinear solvent response and/or non-Gaussian dynamics are required to explain these observations. We find that correlation functions of spectroscopic observables calculated in the quadratic coupling model depend on the chromophore’s electronic state and the spectral width gains time dependence, all in violation of the predictions of the linear coupling models. Lineshape functions of 2D spectra are derived assuming Ornstein–Uhlenbeck dynamics of the bath nuclear modes. The model predicts asymmetry of 2D correlation plots and bending of the center line. The latter is often used to extract two-point correlation functions from 2D spectra. The dynamics of the transition frequency are non-Gaussian. However, the effect of non-Gaussian dynamics is limited to the third-order (skewness) time correlation function, without affecting the time correlation functions of higher order. The theory is tested against molecular dynamics simulations of a model polar–polarizable chromophore dissolved in a force field water.

The dopamine-TiO₂ system shows a specific spectroscopic response, surface enhanced Raman scattering (SERS), whose mechanism is not fully understood. In this study, the goal is to reveal the key role of the molecule–nanoparticle interface in the electronic structure by means of ab initio modeling. The dopamine adsorption energy on anatase surfaces is computed and related to changes in the electronic structure. Two features are observed: the appearance of a state in the material band gap, and charge transfer between molecule and surface upon electronic excitation. The analysis of the energetics of the systems would point to a selective adsorption of dopamine on the (001) and (100) terminations, with much less affinity for the (101) plane.

Two pentacoordinate mononuclear iron carbonyls of the form (bdt)Fe(CO)P₂ [bdt = benzene-1,2-dithiolate; P₂ = 1,1′-diphenylphosphinoferrocene (1) or methyl-2-{bis(diphenylphosphinomethyl)amino}acetate (2)] were prepared as functional, biomimetic models for the distal iron (Fe_d) of the active site of [FeFe]-hydrogenase. X-ray crystal structures of the complexes reveal that, despite similar ν(CO) stretching band frequencies, the two complexes have different coordination geometries. In X-ray crystal structures, the iron center of 1 is in a distorted trigonal bipyramidal arrangement, and that of 2 is in a distorted square pyramidal geometry. Electrochemical investigation shows that both complexes catalyze electrochemical proton reduction from acetic acid at mild overpotential, 0.17 and 0.38 V for 1 and 2, respectively. Although coordinatively unsaturated, the complexes display only weak, reversible binding affinity toward CO (1 bar). However, ligand centered protonation by the strong acid, HBF₄·OEt₂, triggers quantitative CO uptake by 1 to form a dicarbonyl analogue [1(H)-CO]⁺ that can be reversibly converted back to 1 by deprotonation using NEt₃. Both crystallographically determined distances within the bdt ligand and density functional theory calculations suggest that the iron centers in both 1 and 2 are partially reduced at the expense of partial oxidation of the bdt ligand. Ligand protonation interrupts this extensive electronic delocalization between the Fe and bdt making 1(H)⁺ susceptible to external CO binding.

Novel hydride chemistries are employed to deposit light-emitting Ge_1-y Sn_yalloys with y ≤ 0.1 by Ultra-High Vacuum Chemical Vapor Deposition (UHV-CVD) on Ge-buffered Si wafers. The properties of the resultant materials are systematically compared with similar alloys grown directly on Si wafers. The fundamental difference between the two systems is a fivefold (and higher) decrease in lattice mismatch between film and virtual substrate, allowing direct integration of bulk-like crystals with planar surfaces and relatively low dislocation densities. For y ≤ 0.06, the CVD precursors used were digermane Ge₂H₆ and deuterated stannane SnD₄. For y ≥ 0.06, the Ge precursor was changed to trigermane Ge₃H₈, whose higher reactivity enabled the fabrication of supersaturated samples with the target film parameters. In all cases, the Ge wafers were produced using tetragermane Ge₄H₁₀ as the Ge source. The photoluminescence intensity from Ge_1-y Sn_y /Ge films is expected to increase relative to Ge_1-y Sn_y /Si due to the less defected interface with the virtual substrate. However, while Ge_1-y Sn_y /Si films are largely relaxed, a significant amount of compressive strain may be present in the Ge_1-y Sn_y /Ge case. This compressive strain can reduce the emission intensity by increasing the separation between the direct and indirect edges. In this context, it is shown here that the proposed CVD approach to Ge_1-y Sn_y /Ge makes it possible to approach film thicknesses of about 1  μm, for which the strain is mostly relaxed and the photoluminescence intensity increases by one order of magnitude relative to Ge_1-y Sn_y /Si films. The observed strain relaxation is shown to be consistent with predictions from strain-relaxation models first developed for the Si_1-x Ge_x /Si system. The defect structure and atomic distributions in the films are studied in detail using advanced electron-microscopy techniques, including aberration corrected STEM imaging and EELS mapping of the average diamond–cubic lattice.

Telomerase RNA (TER) is an essential component of the telomerase ribonucleoprotein complex. The mechanism for TER 3′-end processing is highly divergent among different organisms. Here we report a unique spliceosome-mediated TER 3′-end cleavage mechanism in Neurospora crassa that is distinct from that found specifically in the fission yeast Schizosaccharomyces pombe. While the S. pombe TER intron contains the canonical 5′-splice site GUAUGU, the N. crassa TER intron contains a non-canonical 5′-splice site AUAAGU that alone prevents the second step of splicing and promotes spliceosomal cleavage. The unique N. crassa TER 5′-splice site sequence is evolutionarily conserved in TERs from Pezizomycotina and early branching Taphrinomycotina species. This suggests that the widespread and basal N. crassa-type spliceosomal cleavage mechanism is more ancestral than the S. pombe-type. The discovery of a prevalent, yet distinct, spliceosomal cleavage mechanism throughout diverse fungal clades furthers our understanding of TER evolution and non-coding RNA processing.

Explosive extrusion of cold material from the interior of icy bodies, or cryovolcanism, has been observed on Enceladus and, perhaps, Europa, Triton, and Ceres. It may explain the observed evidence for a young surface on Charon (Pluto’s surface is masked by frosts). Here, we evaluate prerequisites for cryovolcanism on dwarf planet-class Kuiper belt objects (KBOs). We first review the likely spatial and temporal extent of subsurface liquid, proposed mechanisms to overcome the negative buoyancy of liquid water in ice, and the volatile inventory of KBOs. We then present a new geochemical equilibrium model for volatile exsolution and its ability to drive upward crack propagation. This novel approach bridges geophysics and geochemistry, and extends geochemical modeling to the seldom-explored realm of liquid water at subzero temperatures. We show that carbon monoxide (CO) is a key volatile for gas-driven fluid ascent; whereas CO₂ and sulfur gases only play a minor role. N₂, CH₄, and H₂ exsolution may also drive explosive cryovolcanism if hydrothermal activity produces these species in large amounts (a few percent with respect to water). Another important control on crack propagation is the internal structure: a hydrated core makes explosive cryovolcanism easier, but an undifferentiated crust does not. We briefly discuss other controls on ascent such as fluid freezing on crack walls, and outline theoretical advances necessary to better understand cryovolcanic processes. Finally, we make testable predictions for the 2015 New Horizons flyby of the Pluto-Charon system.

Formally zerovalent (κ³-phosphine)Fe(η⁴-COT) complexes supported by either Triphos (PhP(CH₂CH₂PPh₂)₂) or Triphos* (H₃CC(CH₂PPh₂)₃) have been prepared following chelate addition to (COT)₂Fe (COT = 1,3,5,7-cyclooctatetraene) and by reduction of the respective dibromide complexes in the presence of excess COT. The solid-state structure of each complex was determined by single-crystal X-ray diffraction, and close inspection of the metrical parameters revealed significant COT ligand reduction, independent of the coordination geometry about iron. While the neutral and dianionic forms of the redox-active COT ligand have historically received a great deal of attention, a dearth of information regarding the often-evoked radical monoanion form of this ligand prompted the full electronic structure investigation of these complexes using a range of techniques. Comparison of the Mössbauer spectroscopic data collected for both (Triphos)Fe(η⁴-COT) complexes with data obtained for two appropriate reference compounds indicated that they possess a low-spin Fe(I) center that is antiferromagnetically coupled to a COT radical monoanion. Further evidence for this electronic structure determination by EPR spectroscopy and cyclic voltammetry is presented. A comparison of the solid-state metrical parameters determined in this study to those of related first-row transition-metal complexes has provided insight into the electronic structure analysis of related organometallic complexes.