Unimolecular reaction rates in solution and in the isolated molecule: Comparison of diphenyl butadiene nonradiative decay in solutions and supersonic jets

The recent study of diphenyl butadiene (DPB) in supersonic jets and in solution by Shepanski et al.(1) and by Courtney and Felming(2), respectively, provides an opportunity to compare the isomerization rates measured in the isolated molecule (jet) with those measured at very low viscosity in solution. These comparisons should shed light on the vibrational energy flows between “optical” and “reactive” modes in the isolated molecule and on the connection between activated, friction dependent, models of barrier crossing in solution,(3-5) and statistical RRK (or RRKM) theories of gas phase unimolecular reactions(6)

Edaq530: a transparent, open-end and open-source measurement solution in natural science education

We present Edaq530, a low-cost, compact and easy-to-use digital measurement solution consisting of a thumb-sized USB-to-sensor interface and a measurement software. The solution is fully open-source, our aim being to provide a viable alternative to professional solutions. Our main focus in designing Edaq530 has been versatility and transparency. In this paper, we shall introduce the capabilities of Edaq530, complement it by showing a few sample experiments, and discuss the feedback we have received in the course of a teacher training workshop in which the participants received personal copies of Edaq530 and later made reports on how they could utilise Edaq530 in their teaching

Using Multiple-hierarchy Stratification and Life Course Approaches to Understand Health Inequalities: The Intersecting Consequences of Race, Gender, SES, and Age

This study examines how the intersecting consequences of race-ethnicity, gender, socioeconomics status (SES), and age influence health inequality. We draw on multiple-hierarchy stratification and life course perspectives to address two main research questions. First, does racial-ethnic stratification of health vary by gender and/or SES? More specifically, are the joint health consequences of racial-ethnic, gender, and socioeconomic stratification additive or multiplicative? Second, does this combined inequality in health decrease, remain stable, or increase between middle and late life? We use panel data from the Health and Retirement Study (N = 12,976) to investigate between- and within-group differences in in self-rated health among whites, blacks, and Mexican Americans. Findings indicate that the effects of racial-ethnic, gender, and SES stratification are interactive, resulting in the greatest racial-ethnic inequalities in health among women and those with higher levels of SES. Furthermore, racial-ethnic/gender/SES inequalities in health tend to decline with age. These results are broadly consistent with intersectionality and aging-as-leveler hypotheses

Utility of Pop-Up Satellite Archival Tags to Study the Summer Dispersal and Habitat Occupancy of Dolly Varden in Arctic Alaska

In Arctic Alaska, Dolly Varden Salvelinus malma is highly valued as a subsistence fish; however, little is known about its marine ecology. New advances in electronic tagging, such as pop-up satellite archival tags (PSATs), provide scientists with a fishery-independent means of studying several aspects of this species’ movement and ecology. To evaluate the usefulness of this technology, we attached 52 PSATs to Dolly Varden in the Wulik River, which flows from northwestern Alaska into the Chukchi Sea, to study several characteristics of the marine habits of this species. Overall, PSATs provided unprecedented information about summer dispersal of Dolly Varden, including the first evidence of offshore dispersal in the Chukchi Sea, as well as previously documented dispersal types such as movement to other rivers and southerly nearshore movements in northwestern Alaska. On the basis of minimal observable evidence of tag-induced behavioral effects, as well as movements of more than 450 km by fish at liberty (i.e., between tag deployment and release or recapture), we conclude that PSATs offer an effective alternative method for studying several aspects of Dolly Varden dispersal and ecology in areas where it is not practical or feasible to capture these fish, such as coastal and offshore regions of Arctic AlaskaDans l’Alaska de l’Arctique, l’omble du Pacifique, Salvelinus malma revêt une grande importance en tant que poisson de subsistance. Toutefois, on en sait peu sur son écologie marine. Les progrès réalisés en matière de traçabilité électronique, notamment en ce qui a trait aux étiquettes de collecte de données par satellite (PSAT) permettent aux scientifiques d’étudier plusieurs aspects des déplacements et de l’écologie de cette espèce sans dépendre de la pêche. Afin d’évaluer l’utilité de cette technologie, nous avons fixé 52 PSAT à des ombles du Pacifique de la rivière Wulik, qui s’écoule depuis le nord-ouest de l’Alaska jusqu’à la mer des Tchouktches, pour étudier plusieurs caractéristiques des habitudes aquatiques de cette espèce. Dans l’ensemble, les PSAT ont permis de recueillir des renseignements sans précédent au sujet de la dispersion estivale de l’omble du Pacifique, y compris la première preuve de dispersion extracôtière dans la mer des Tchouktches et d’autres types de dispersion anciennement documentés, comme les déplacements vers d’autres cours d’eau et les déplacements sublittoraux en direction sud, dans le nord-ouest de l’Alaska. D’après un minimum d’éléments de preuve observables quant aux effets découlant de la présence d’étiquettes sur le comportement ainsi que d’après les déplacements de plus de 450 kilomètres des poissons en liberté (c’est-à-dire entre l’installation des étiquettes et le relâchement ou la recapture), nous concluons que les PSAT présentent une méthode de rechange efficace pour étudier plusieurs aspects de la dispersion et de l’écologie de l’omble du Pacifique dans des endroits où il n’est pas pratique ou réalisable de prendre ces poissons, comme dans les régions côtières et extracôtières de l’Alaska de l’Arctique

Molecules in external fields: a semiclassical analysis

We undertake a semiclassical analysis of the spectral properties (modulations of photoabsorption spectra, energy level statistics) of a simple Rydberg molecule in static fields within the framework of Closed-Orbit/Periodic-Orbit theories. We conclude that in addition to the usual classically allowed orbits one must consider classically forbidden diffractive paths. Further, the molecule brings in a new type of 'inelastic' diffractive trajectory, different from the usual 'elastic' diffractive orbits encountered in previous studies of atomic and analogous systems such as billiards with point-scatterers. The relative importance of inelastic versus elastic diffraction is quantified by merging the usual Closed Orbit theory framework with molecular quantum defect theory.Comment: 4 pages, 3 figure

Symmetry breaking in crossed magnetic and electric fields

We present the first observations of cylindrical symmetry breaking in highly excited diamagnetic hydrogen with a small crossed electric field, and we give a semiclassical interpretation of this effect. As the small perpendicular electric field is added, the recurrence strengths of closed orbits decrease smoothly to a minimum, and revive again. This phenomenon, caused by interference among the electron waves that return to the nucleus, can be computed from the azimuthal dependence of the classical closed orbits.Comment: 4 page REVTeX file including 5 postscript files (using psfig) Accepted for publication in Physical Review Letters. Difference from earlier preprint: we have discovered the cause of the earlier apparent discrepancy between experiment and theory and now achieve excellent agreemen

Sis1 potentiates the stress response to protein aggregation and elevated temperature

Cells adapt to conditions that compromise protein conformational stability by activating various stress response pathways, but the mechanisms used in sensing misfolded proteins remain unclear. Moreover, aggregates of disease proteins often fail to induce a productive stress response. Here, using a yeast model of polyQ protein aggregation, we identified Sis1, an essential Hsp40 co-chaperone of Hsp70, as a critical sensor of proteotoxic stress. At elevated levels, Sis1 prevented the formation of dense polyQ inclusions and directed soluble polyQ oligomers towards the formation of permeable condensates. Hsp70 accumulated in a liquid-like state within this polyQ meshwork, resulting in a potent activation of the HSF1 dependent stress response. Sis1, and the homologous DnaJB6 in mammalian cells, also regulated the magnitude of the cellular heat stress response, suggesting a general role in sensing protein misfolding. Sis1/DnaJB6 functions as a limiting regulator to enable a dynamic stress response and avoid hypersensitivity to environmental changes. Identifying factors that enable cells to induce a potent stress response to amyloid-like aggregation can provide further insight into the mechanism of stress regulation. Here, the authors express polyglutamine-expanded Huntingtin as a model disease protein in yeast cells and perform a genetic screen for chaperone factors that allow yeast cells to activate a potent stress response. They identify Sis1, an essential Hsp40 co-chaperone of Hsp70, as a critical sensor of proteotoxic stress and further show that both Sis1 and its mammalian homolog DnaJB6 regulate the magnitude of the cellular heat stress response, indicating that this mechanism is conserved

Implementation of Continuous Capnography Is Associated With a Decreased Utilization of Blood Gases

Background Capnography provides a continuous, non-invasive monitoring of the CO2 to assess adequacy of ventilation and provide added safety features in mechanically ventilated patients by allowing for quick identification of unplanned extubation. These monitors may allow for decreased utilization of blood gases. The objective was to determine if implementation of continuous capnography monitoring decreases the utilization of blood gases resulting in decreased charges. Methods This is a retrospective review of a quality improvement project that compares the utilization of blood gases before and after the implementation of standard continuous capnography. The time period of April 2010 to September 2010 was compared to April 2011 to September 2011. Parameters collected included total number of blood gases analyzed, cost of blood gas analysis, ventilator and patient days. Results The total number of blood gases after the institution of end tidal CO2 monitoring decreased from 12,937 in 2009 and 13,171 in 2010 to 8,070 in 2011. The average number of blood gases per encounter decreased from 20.8 in 2009 and 21.6 in 2010 to 13.8 post intervention. The blood gases per ventilator day decreased from 4.94 in 2009 and 4.76 in 2010 to 3.30 post intervention. The total charge savings over a 6-month period was $880,496. Conclusions Continuous capnography resulted in a significant savings over a 6-month period by decreasing the utilization of blood gas measurements

Composition Operators and Endomorphisms

If $b$ is an inner function, then composition with $b$ induces an endomorphism, $\beta$, of $L^\infty(\mathbb{T})$ that leaves $H^\infty(\mathbb{T})$ invariant. We investigate the structure of the endomorphisms of $B(L^2(\mathbb{T}))$ and $B(H^2(\mathbb{T}))$ that implement $\beta$ through the representations of $L^\infty(\mathbb{T})$ and $H^\infty(\mathbb{T})$ in terms of multiplication operators on $L^2(\mathbb{T})$ and $H^2(\mathbb{T})$. Our analysis, which is based on work of R. Rochberg and J. McDonald, will wind its way through the theory of composition operators on spaces of analytic functions to recent work on Cuntz families of isometries and Hilbert $C^*$-modules