74 research outputs found
Art+Politics
For the exhibition Art + Politics, students worked closely with the holdings of Gettysburg College\u27s Special Collections and College Archives to curate an exhibition in Schmucker Art Gallery that engages with issues of public policy, activism, war, propaganda, and other critical socio-political themes. Each of the students worked diligently to contextualize the objects historically, politically, and art-historically. The art and artifacts presented in this exhibition reveal how various political events and social issues have been interpreted through various visual and printed materials, including posters, pins, illustrations, song sheets, as well as a Chinese shoe for bound feet. The students\u27 essays that follow demonstrate careful research and thoughtful reflection on the American Civil War, nineteenth-century politics, the First and Second World Wars, World\u27s Fairs, Dwight D. Eisenhower\u27s campaign, Vietnam-War era protests, and the Cultural Revolution in China. [excerpt]https://cupola.gettysburg.edu/artcatalogs/1009/thumbnail.jp
The Nature of the Long-Lived Excited State in a Ni^(II) Phthalocyanine Complex Investigated by X-Ray Transient Absorption Spectroscopy
The nature of the photoexcited state of octabutoxy nickel(II) phthalocyanine (NiPcOBuâ) with a 500â
ps lifetime was investigated by Xâray transient absorption (XTA) spectroscopy. Previous optical, vibrational, and computational studies have suggested that this photoexcited state has a ligandâtoâmetal charge transfer (LMCT) nature. By using XTA, which provides unambiguous information on the local electronic and nuclear configuration around the Ni center, the nature of the excited state of NiPcOBuâ was reassessed. Using Xâray probe pulses from a synchrotron source, the groundâ and excitedâstate Xâray absorption spectra of NiPcOBu8 were measured. Based on the results, we identified that the excited state exhibits spectral features that are characteristic of a Ni^(1,â3)(3d_(zÂČ), 3d_(xÂČ-yÂČ)) state rather than a LMCT state with a transiently reduced Ni center. This state resembles the (d,d) state of nickel(II) tetramesitylphorphyrin. The XTA features are rationalized based on the inherent cavity sizes of the macrocycles. These results may provide useful guidance for the design of photocatalysts in the future
Imaging ultrafast excited state pathways in transition metal complexes by X-ray transient absorption and scattering using X-ray free electron laser source
This report will describe our recent studies of transition metal complex structural dynamics on the fs and ps time scales using an X-ray free electron laser source, Linac Coherent Light Source (LCLS). Ultrafast XANES spectra at the Ni K-edge of nickel(II) tetramesitylporphyrin (NiTMP) were successfully measured for optically excited state at a timescale from 100 fs to 50 ps, providing insight into its sub-ps electronic and structural relaxation processes. Importantly, a transient reduced state Ni(I) (Ï, 3d(x2ây2)) electronic state is captured through the interpretation of a short-lived excited state absorption on the low-energy shoulder of the edge, which is aided by the computation of X-ray transitions for postulated excited electronic states. The observed and computed inner shell to valence orbital transition energies demonstrate and quantify the influence of electronic configuration on specific metal orbital energies. A strong influence of the valence orbital occupation on the inner shell orbital energies indicates that one should not use the transition energy from 1s to other orbitals to draw conclusions about the d-orbital energies. For photocatalysis, a transient electronic configuration could influence d-orbital energies up to a few eV and any attempt to steer the reaction pathway should account for this to ensure that external energies can be used optimally in driving desirable processes. NiTMP structural evolution and the influence of the porphyrin macrocycle conformation on relaxation kinetics can be likewise inferred from this study
Electronic and nuclear contributions to time-resolved optical and X-ray absorption spectra of hematite and insights into photoelectrochemical performance
Ultrafast time-resolved studies of photocatalytic thin films can provide a wealth of information crucial for understanding and thereby improving the performance of these materials by directly probing electronic structure, reaction intermediates, and charge carrier dynamics. The interpretation of transient spectra, however, can be complicated by thermally induced structural distortions, which appear within the first few picoseconds following excitation due to carrierâphonon scattering. Here we present a comparison of ex situ steady-state thermal difference spectra and transient absorption spectra spanning from NIR to hard X-ray energies of hematite thin films grown by atomic layer deposition. We find that beyond the first 100 picoseconds, the transient spectra measured for all excitation wavelengths and probe energies are almost entirely due to thermal effects as the lattice expands in response to the ultrafast temperature jump and then cools to room temperature on the microsecond timescale. At earlier times, a broad excited state absorption band that is assigned to free carriers appears at 675 nm, and the lifetime and shape of this feature also appear to be mostly independent of excitation wavelength. The combined spectroscopic data, which are modeled with density functional theory and full multiple scattering calculations, support an assignment of the optical absorption spectrum of hematite that involves two LMCT bands that nearly span the visible spectrum. Our results also suggest a framework for shifting the ligand-to-metal charge transfer absorption bands of ferric oxide films from the near-UV further into the visible part of the solar spectrum to improve solar conversion efficiency
Rats bred for low and high running capacity display alterations in peripheral tissues and nerves relevant to neuropathy and pain
IntroductionDiet and activity are recognized as modulators of nervous system disease, including pain. Studies of exercise consistently reveal a benefit on pain. This study focused on female rats to understand differences related to metabolic status and peripheral nerve function in females.MethodsHere, we investigated parameters of peripheral nerve function relevant to pain in rats selectively bred for high (highâcapacity runners; HCR) or low endurance exercise capacity (lowâcapacity runners; LCR) resulting in divergent intrinsic aerobic capacities and susceptibility for metabolic conditions.ResultsLCR female rats have reduced mechanical sensitivity, higher intraepidermal nerve fiber density and TrkAâpositive epidermal axons, increased numbers of Langerhans and mast cells in cutaneous tissues, and a higher fat content despite similar overall body weights compared to female HCR rats. Sensory and motor nerve conduction velocities, thermal sensitivity, and mRNA expression of selected genes relevant to peripheral sensation were not different.ConclusionsThese results suggest that aerobic capacity and metabolic status influence sensory sensitivity and aspects of inflammation in peripheral tissues that could lead to poor responses to tissue damage and painful stimuli. The LCR and HCR rats should prove useful as models to assess how the metabolic status impacts pain.These results suggest that aerobic capacity and metabolic status influence sensory sensitivity and aspects of inflammation in peripheral tissues that could lead to poor responses to tissue damage and painful stimuli. The LCR and HCR rats should prove useful as models to assess how the metabolic status impacts pain.Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/139060/1/brb3780.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/139060/2/brb3780_am.pd
Ultrafast Excited State Relaxation of a Metalloporphyrin Revealed by Femtosecond X-ray Absorption Spectroscopy
Photoexcited NickelÂ(II) tetramesitylporphyrin
(NiTMP), like many
open-shell metalloporphyrins, relaxes rapidly through multiple electronic
states following an initial porphyrin-based excitation, some involving
metal centered electronic configuration changes that could be harnessed
catalytically before excited state relaxation. While a NiTMP excited
state present at 100 ps was previously identified by X-ray transient
absorption (XTA) spectroscopy at a synchrotron source as a relaxed
(d,d) state, the lowest energy excited state (<i>J. Am. Chem.
Soc.</i>, <b>2007</b>, <i>129</i>, 9616 and <i>Chem. Sci.</i>, <b>2010</b>, <i>1</i>, 642),
structural dynamics before thermalization were not resolved due to
the âŒ100 ps duration of the available X-ray probe pulse. Using
the femtosecond (fs) X-ray pulses of the Linac Coherent Light Source
(LCLS), the Ni center electronic configuration from the initial excited
state to the relaxed (d,d) state has been obtained via ultrafast Ni
K-edge XANES (X-ray absorption near edge structure) on a time scale
from hundreds of femtoseconds to 100 ps. This enabled the identification
of a short-lived NiÂ(I) species aided by time-dependent density functional
theory (TDDFT) methods. Computed electronic and nuclear structure
for critical excited electronic states in the relaxation pathway characterize
the dependence of the complexâs geometry on the electron occupation
of the 3d orbitals. Calculated XANES transitions for these excited
states assign a short-lived transient signal to the spectroscopic
signature of the NiÂ(I) species, resulting from intramolecular charge
transfer on a time scale that has eluded previous synchrotron studies.
These combined results enable us to examine the excited state structural
dynamics of NiTMP prior to thermal relaxation and to capture intermediates
of potential photocatalytic significance
Electronic and nuclear contributions to time-resolved optical and X-ray absorption spectra of hematite and insights into photoelectrochemical performance
Ultrafast time-resolved studies of photocatalytic thin films can provide a wealth of information crucial for understanding and thereby improving the performance of these materials by directly probing electronic structure, reaction intermediates, and charge carrier dynamics. The interpretation of transient spectra, however, can be complicated by thermally induced structural distortions, which appear within the first few picoseconds following excitation due to carrierâphonon scattering. Here we present a comparison of ex situ steady-state thermal difference spectra and transient absorption spectra spanning from NIR to hard X-ray energies of hematite thin films grown by atomic layer deposition. We find that beyond the first 100 picoseconds, the transient spectra measured for all excitation wavelengths and probe energies are almost entirely due to thermal effects as the lattice expands in response to the ultrafast temperature jump and then cools to room temperature on the microsecond timescale. At earlier times, a broad excited state absorption band that is assigned to free carriers appears at 675 nm, and the lifetime and shape of this feature also appear to be mostly independent of excitation wavelength. The combined spectroscopic data, which are modeled with density functional theory and full multiple scattering calculations, support an assignment of the optical absorption spectrum of hematite that involves two LMCT bands that nearly span the visible spectrum. Our results also suggest a framework for shifting the ligand-to-metal charge transfer absorption bands of ferric oxide films from the near-UV further into the visible part of the solar spectrum to improve solar conversion efficiency
Implementation and results of an integrated data quality assurance protocol in a randomized controlled trial in Uttar Pradesh, India
A many-analysts approach to the relation between religiosity and well-being
The relation between religiosity and well-being is one of the most researched topics in the psychology of religion, yet the directionality and robustness of the effect remains debated. Here, we adopted a many-analysts approach to assess the robustness of this relation based on a new cross-cultural dataset (N=10,535 participants from 24 countries). We recruited 120 analysis teams to investigate (1) whether religious people self-report higher well-being, and (2) whether the relation between religiosity and self-reported well-being depends on perceived cultural norms of religion (i.e., whether it is considered normal and desirable to be religious in a given country). In a two-stage procedure, the teams first created an analysis plan and then executed their planned analysis on the data. For the first research question, all but 3 teams reported positive effect sizes with credible/confidence intervals excluding zero (median reported ÎČ=0.120). For the second research question, this was the case for 65% of the teams (median reported ÎČ=0.039). While most teams applied (multilevel) linear regression models, there was considerable variability in the choice of items used to construct the independent variables, the dependent variable, and the included covariates
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