Electrochemistry and Spectroscopy of Sulfate and Thiosulfate Complexes of Iron Porphyrins

The electrochemical and spectroscopic properties of the complex formed by the addition of thiosulfate to ferric porphyrins were examined. The NMR spectrum of the thiosulfate–ferric porphyrin complex was consistent with a high-spin ferric complex, while the EPR spectrum at liquid nitrogen temperatures indicated that the complex under these conditions was low-spin. Such behavior has been previously observed for other ferric porphyrin complexes. The visible spectra were characterized by a shift in the Soret band to higher energies, with smaller changes in the longer wavelength region. The complex was reasonably stable in DMF, but slowly reduced over several hours to FeII(TPP) and S4O6 2−. The voltammetric behavior of the thiosulfate complex in DMF consists of two waves, the first of which was irreversible. The ferric/ferrous reduction in the presence of thiosulfate was shifted negatively about 400 mV, compared to the Fe(TPP)(Cl) reduction. The visible, NMR and EPR spectra were most consistent with a Fe–S bonded ferric porphyrin–thiosulfate complex, Fe(P)(SSO3)−. The kinetics of the reduction of ferric porphyrin by thiosulfate in DMSO indicated an autocatalytic mechanism, where the first step is the formation of the catalyst. The identity of the catalyst could not be determined because it must be present at low concentrations, but it is formed from the reaction of the ferric complex with thiosulfate. Coordination of thiosulfate to the porphyrin was not necessary for the reduction to occur, and the reduction of Fe(TPP)(Cl) by thiosulfate was accelerated by the addition of sulfate. Under these conditions, sulfate had replaced thiosulfate as the axial ligand for the ferric porphyrin. In the presence of sulfate, the reduction occurred in a single kinetic pseudo-first order step. The voltammetry, spectroelectrochemistry and kinetics for the reaction of thiosulfate with ferric porphyrins were examined. A rapid reaction between ferric porphyrins and thiosulfate was observed in DMF. The reaction was complex, involving the formation of a catalytic intermediate. Window factor analysis and multivariate curve resolution were used to deconvolute the kinetic data

Concept paper on a curriculum initiative for energy, climate change, and sustainability at Boston University

[Summary] Boston University has made important contributions to the interconnected challenges of energy, climate change, and sustainability (ECS) through its research, teaching, and campus operations. This work reveals new opportunities to expand the scope of teaching and research and place the University at the forefront of ECS in higher education. This paper describes the framework for a University-wide curriculum initiative that moves us in that direction and that complements the University’s strategic plan. The central curricular objectives are to provide every undergraduate the opportunity be touched in some way in their educational program by exposure to some aspect of the ECS challenge, and to increase opportunities for every graduate student to achieve a focused competence in ECS. The initiative has six cornerstone initiatives. The first is the Campus as a Living Lab (CALL) program in which students, faculty and staff work together and use our urban campus and its community to study and implement ECS solutions. The second is a university-wide minor degree that helps students develop an integrated perspective of the economic, environmental, and social dimensions of sustainability. The third is one or more graduate certificate programs open to all graduate students. The fourth is an annual summer faculty workshop that develops new ECS curriculum and CALL opportunities. The fifth is web-based resource that underpins the construction of a vibrant knowledge network for the BU community and beyond. Finally, an enhanced sustainability alumni network will augment professional opportunities and generate other benefits. The learning outcomes of this initiative will be realized through the collaborative work of faculty, students, and staff from all 17 colleges and schools. The initiative will leverage existing BU student resources such as the Thurman Center, Build Lab, and Innovate@BU. Benefits of this initiative, beyond the curriculum, include acceleration towards the goals of our Climate Action Plan; improving the “sustainability brand” of BU; enhancing the ability to attract students and new faculty; strengthening our alumni and campus communities; deepening our ties with the city of Boston; and the potential to spin off new social and technological innovations.Published versio

Into the Looking Glass: The Mirror of Old Age in Beauvoir and Améry

Although the pandemic's early months were witness to a nearly unprecedented level of public concern for the plight of the old, such attention did not lead to much sustained analysis into either the concrete experience of old age or the many ways in which a greater knowledge of aging might prove instructive for rethinking the possibilities of contemporary philosophy and social change. The present paper seeks to pursue this otherwise neglected line of inquiry by recovering a previously unexplored episode from the history of social theory in which Simone de Beauvoir and Jean Améry set themselves before the mirror of old age in order to there explore reflections as inimical to their time as our own. For what this intertextual scene of contestation so clearly demonstrates is that the aging body is itself a body of knowledge capable of transforming the very ideologies and social systems that continue to deform the lives of old and young alike

The Possible Interstellar Anion CH2CN-: Spectroscopic Constants, Vibrational Frequencies, and Other Considerations

It is hypothesized that the A ^1B_1 <- X ^1A' excitation into the dipole-bound state of the cyanomethyl anion (CH2CN-) is proposed as the carrier for one diffuse interstellar band. However, this particular molecular system has not been detected in the interstellar medium even though the related cyanomethyl radical and the isoelectronic ketenimine molecule have been found. In this study we are employing the use of proven quartic force fields and second-order vibrational perturbation theory to compute accurate spectroscopic constants and fundamental vibrational frequencies for ^1A' CH2CN- in order to assist in laboratory studies and astronomical observations

Quantitatively Assessed Blood Loss Compared to Visually Estimated Blood Loss in the Early Identification and Treatment of Post-partum Hemorrhage

Nearly one-quarter of all maternal pregnancy-related deaths worldwide are a result of post-partum hemorrhage (PPH) [1]. In the Joint Commission’s Sentinel Event Database, hemorrhage was a causal factor in over half of the cases leading to maternal death or severe morbidity [3]. Between 1993 and 2014, the rate of PPH per 10,000 delivery hospitalizations increased by almost five times, from 4.3 to 21.2 [3]. Using visualization to estimate blood loss is currently the primary method for assessment. However, a new, alternative assessment technique is using quantitative measurement. These two techniques were compared through a literature review. The literature review was conducted using MEDLINE Complete and CINAHL Complete, and five studies were identified. These studies were appraised and synthesized to answer the PICO question: in post-partum mothers, is the use of quantitative blood loss assessment or visually estimated blood loss effective in the early identification of PPH? The literature indicated that using a quantitative method to estimate postpartum blood loss early is more effective than using a visual estimation method and may reduce the number of PPHs. These findings can be implemented into nursing practice by incorporating a quantitative blood loss assessment protocol for post-partum mothers. Annual simulation-based training on this new method may be an appropriate means of educating point-of-care healthcare providers. With these changes, health care facilities should collect morbidity and mortality rates, incidence rates, treatment rates, and the time-to-treat rate to measure the effectiveness of the quantitative blood loss method

What's the best treatment for cradle cap?

Ketoconazole (Nizoral) shampoo appears to be a safe and efficacious treatment for infants with cradle cap (strength of recommendation [SOR]: C, consensus, usual practice, opinion, disease-oriented evidence, and case series). Limit topical corticosteroids to severe cases because of possible systemic absorption (SOR: C). Overnight application of emollients followed by gentle brushing and washing with baby shampoo helps to remove the scale associated with cradle cap (SOR: C)

Vibrational Frequencies and Spectroscopic Constants for 1(sup 3)A' HNC and 1(sup 3)A' HOC+ from High-Accuracy Quartic Force Fields

The spectroscopic constants and vibrational frequencies for the 1(sup 3)A' states of HNC, DNC, HOC+, and DOC+ are computed and discussed in this work. The reliable CcCR quartic force field based on high-level coupled cluster ab initio quantum chemical computations is exclusively utilized to provide the anharmonic potential. Then, second order vibrational perturbation theory and vibrational configuration interaction methods are employed to treat the nuclear Schroedinger equation. Second-order perturbation theory is also employed to provide spectroscopic data for all molecules examined. The relationship between these molecules and the corresponding 1(sup 3)A' HCN and HCO+ isomers is further developed here. These data are applicable to laboratory studies involving formation of HNC and HOC+ as well as astronomical observations of chemically active astrophysical environments