Photosynthetic reaction center complexes from heliobacteria

The goal of this project is to understand the early evolutionary development of photosynthesis by examining the properties of reaction centers isolated from certain contemporary organisms that appear to contain the simplest photosynthetic reaction centers. The major focus of this project is the family of newly discovered strictly anaerobic photosynthetic organisms known as Heliobacteria. These organisms are the only known photosynthetic organisms that are grouped with the gram-positive phylum of bacteria. The properties of these reaction centers suggest that they might be the decendants of an ancestor that also gave rise to Photosystem 1 found in oxygen-evolving photosynthetic organisms. Photoactive reaction center-core antenna complexes have been isolated from the photosynthetic bacteria Heliobacillus mobilis and Heliobacterium gestii. The absorption and fluorescence properties of membranes and reaction centers are almost identical, suggesting that a single pigment-protein complex serves as both antenna and reaction center. Experiments in progress include sequence determination of the 48,000 Mr reaction center protein, and evolutionary comparisons with other reaction center proteins

Tests of Transfer Reaction Determinations of Astrophysical S-Factors

The ${}^{16}O ({}^{3}He,d) {}^{17}F$ reaction has been used to determine asymptotic normalization coefficients for transitions to the ground and first excited states of ${}^{17}F$. The coefficients provide the normalization for the tails of the overlap functions for ${}^{17}F \to{}^{16}O + p$ and allow us to calculate the S-factors for ${}^{16}O (p,\gamma){}^{17}F$ at astrophysical energies. The calculated S-factors are compared to measurements and found to be in very good agreement. This provides the first test of this indirect method to determine astrophysical direct capture rates using transfer reactions. In addition, our results yield S(0) for capture to the ground and first excited states in $^{17}F$, without the uncertainty associated with extrapolation from higher energies.Comment: 6 pages, 2 figure

A Study of Cosmic Ray Composition in the Knee Region using Multiple Muon Events in the Soudan 2 Detector

Deep underground muon events recorded by the Soudan 2 detector, located at a depth of 2100 meters of water equivalent, have been used to infer the nuclear composition of cosmic rays in the "knee" region of the cosmic ray energy spectrum. The observed muon multiplicity distribution favors a composition model with a substantial proton content in the energy region 800,000 - 13,000,000 GeV/nucleus.Comment: 38 pages including 11 figures, Latex, submitted to Physical Review

Preparation of amino-substituted indenes and 1,4-dihydronaphthalenes using a one-pot multireaction approach: total synthesis of oxybenzo[c]phenanthridine alkaloids

Allylic trichloroacetimidates bearing a 2-vinyl or 2-allylaryl group have been designed as substrates for a one-pot, two-step multi-bond-forming process leading to the general preparation of aminoindenes and amino-substituted 1,4-dihydronaphthalenes. The synthetic utility of the privileged structures formed from this one-pot process was demonstrated with the total synthesis of four oxybenzo[c]phenanthridine alkaloids, oxychelerythrine, oxysanguinarine, oxynitidine, and oxyavicine. An intramolecular biaryl Heck coupling reaction, catalyzed using the Hermann–Beller palladacycle was used to effect the key step during the synthesis of the natural products

Investigating optimal accelerometer placement for energy expenditure prediction in children using a machine learning approach

Accurate measurement of energy expenditure (EE) is imperative for identifying and targeting health-associated implications. Whilst numerous accelerometer-based regression equations to predict EE have been developed, there remains little consensus regarding optimal accelerometer placement. Therefore, the purpose of the present study was to validate and compare artificial neural networks (ANNs) developed from accelerometers worn on various anatomical positions, and combinations thereof, to predict EE.Twenty-seven children (15 boys; 10.8  ±  1.1 years) participated in an incremental treadmill test and 30 min exergaming session wearing a portable gas analyser and nine ActiGraph GT3X+  accelerometers (chest and left and right wrists, hips, knees, and ankles). Age and sex-specific resting EE equations (Schofield) were used to estimate METs from the oxygen uptake measures. Using all the data from both exergames, incremental treadmill test and the transition period in between, ANNs were created and tested separately for each accelerometer and for combinations of two or more using a leave-one-out approach to predict EE compared to measured EE. Six features (mean and variance of the three accelerometer axes) were extracted within each 15 s window as inputs in the ANN. Correlations and root mean square error (RMSE) were calculated to evaluate prediction accuracy of each ANN, and repeated measures ANOVA was used to statistically compare accuracy of the ANNs.All single-accelerometer ANNs and combinations of two-, three-, and four-accelerometers performed equally (r  =  0.77–0.82), demonstrating higher correlations than the 9-accelerometer ANN (r  =  0.69) or the Freedson linear regression equation (r  =  0.75). RMSE did not differ between single-accelerometer ANNs or combinations of two, three, or four accelerometers (1.21–1.31 METs), demonstrating lower RMSEs than the 9-accelerometer ANN (1.46 METs) or Freedson equation (1.74 METs).These findings provide preliminary evidence that ANNs developed from single accelerometers mounted on various anatomical positions demonstrate equivalency in the accuracy to predict EE in a semi-structured setting, supporting the use of ANNs in improving EE prediction accuracy compared with linear regression

A systems perspective on the interactions between urban green infrastructure and the built environment

This research addresses the intricate dynamics between urban green infrastructure (UGI) and the built environment, focusing on the effects of urban heat islands, building energy demand, and human health. Following the idea of the Socio-Ecological-Technological Systems framework, we investigate key indicators related to green and grey infrastructure and their interactions at the urban scale. We construct a comprehensive causal-loop diagram through an iterative approach involving literature analysis and expert consultation. The outcomes highlight the significance of urban form and green infrastructure in connecting indoor and outdoor spaces. This research enhances the understanding of systemic behavior in the urban fabric and offers insights into the complex interactions between UGI and the built environment. The approach underscores the value of iterative modeling, fostering collaborative efforts and providing a foundation for further system modeling. Future research should focus on quantitative validation of the identified connections. Additionally, connection strengths and spatial elements would be valuable extensions of the presented system model

Alpha scattering and capture reactions in the A = 7 system at low energies

Differential cross sections for $^3$He-$\alpha$ scattering were measured in the energy range up to 3 MeV. These data together with other available experimental results for $^3$He $+ \alpha$ and $^3$H $+ \alpha$ scattering were analyzed in the framework of the optical model using double-folded potentials. The optical potentials obtained were used to calculate the astrophysical S-factors of the capture reactions $^3$He$(\alpha,\gamma)^7$Be and $^3$H$(\alpha,\gamma)^7$Li, and the branching ratios for the transitions into the two final $^7$Be and $^7$Li bound states, respectively. For $^3$He$(\alpha,\gamma)^7$Be excellent agreement between calculated and experimental data is obtained. For $^3$H$(\alpha,\gamma)^7$Li a $S(0)$ value has been found which is a factor of about 1.5 larger than the adopted value. For both capture reactions a similar branching ratio of $R = \sigma(\gamma_1)/\sigma(\gamma_0) \approx 0.43$ has been obtained.Comment: submitted to Phys.Rev.C, 34 pages, figures available from one of the authors, LaTeX with RevTeX, IK-TUW-Preprint 930540

Scope and Mechanistic Study of the Coupling Reaction of α,β-Unsaturated Carbonyl Compounds with Alkenes: Uncovering Electronic Effects on Alkene Insertion vs Oxidative Coupling Pathways

The cationic ruthenium-hydride complex [(C6H6)(PCy3)(CO)RuH]+BF4– (1) was found to be a highly effective catalyst for the intermolecular conjugate addition of simple alkenes to α,β-unsaturated carbonyl compounds to give (Z)-selective tetrasubstituted olefin products. The analogous coupling reaction of cinnamides with electron-deficient olefins led to the oxidative coupling of two olefinic C–H bonds in forming (E)-selective diene products. The intramolecular version of the coupling reaction efficiently produced indene and bicyclic fulvene derivatives. The empirical rate law for the coupling reaction of ethyl cinnamate with propene was determined as follows: rate = k[1]1[propene]0[cinnamate]−1. A negligible deuterium kinetic isotope effect (kH/kD = 1.1 ± 0.1) was measured from both (E)-C6H5CH═C(CH3)CONHCH3 and (E)-C6H5CD═C(CH3)CONHCH3 with styrene. In contrast, a significant normal isotope effect (kH/kD = 1.7 ± 0.1) was observed from the reaction of (E)-C6H5CH═C(CH3)CONHCH3 with styrene and styrene-d8. A pronounced carbon isotope effect was measured from the coupling reaction of (E)-C6H5CH═CHCO2Et with propene (13C(recovered)/13C(virgin) at Cβ = 1.019(6)), while a negligible carbon isotope effect (13C(recovered)/13C(virgin) at Cβ = 0.999(4)) was obtained from the reaction of (E)-C6H5CH═C(CH3)CONHCH3 with styrene. Hammett plots from the correlation of para-substituted p-X-C6H4CH═CHCO2Et (X = OCH3, CH3, H, F, Cl, CO2Me, CF3) with propene and from the treatment of (E)-C6H5CH═CHCO2Et with a series of para-substituted styrenes p-Y-C6H4CH═CH2 (Y = OCH3, CH3, H, F, Cl, CF3) gave the positive slopes for both cases (ρ = +1.1 ± 0.1 and +1.5 ± 0.1, respectively). Eyring analysis of the coupling reaction led to the thermodynamic parameters, ΔH⧧ = 20 ± 2 kcal mol–1 and ΔS⧧ = −42 ± 5 eu. Two separate mechanistic pathways for the coupling reaction have been proposed on the basis of these kinetic and spectroscopic studies