Picosecond time-resolved energy transfer within C-phycocyanin aggregates of Mastigocladus laminosus

We have investigated by picosecond absorption experiments how the size of C-phycocyanin aggregates from Mastigocladus laminosus influences the excitation energy transfer kinetics. Going from C-phycocyanin monomers to trimers the lifetime of the faster energy transfer component decreased from 57 ± 4 to 27 ± 4 ps over most of the wavelength range (580–645 nm) studied. This change was interpreted as the opening of fast transfer channels (α-84 → β-84 and/or β-84 → β-84) between two adjacent monomers in the trimeric unit. The 57 ps lifetime is probably due mainly to the β-155 → β-84 energy transfer step. The intermediate lifetime decreased from about 300 ps in the monomer to 100–120 ps in the trimer. The former is believed to be dominated by the equilibration process α-84 a3 β-84, while the latter probably represents the time required for the excitation energy to reach thermodynamic equilibrium within the trimer. The lifetime of the longest components was about 1 ns in both systems. This indicates that the chromophores in these C-phycocyanin complexes are more exposed to non-radiative processes (like, for instance, isomerization) compared to the chromophores in intact phycobilisomes, where this lifetime typically is about 1.8 ns. The anisotropy relaxation closely followed the isotropic lifetimes in both systems. The anisotropy after the initial fast relaxation, r(∞), was 0.29 ± 0.04 in monomers and decreased to 0.15 ± 0.03 in trimers. Measurements of the steady-state fluorescence excitation anisotropy gave the same results within the experimental error

A parallel multistate framework for atomistic non-equilibrium reaction dynamics of solutes in strongly interacting organic solvents

We describe a parallel linear-scaling computational framework developed to implement arbitrarily large multi-state empirical valence bond (MS-EVB) calculations within CHARMM. Forces are obtained using the Hellman-Feynmann relationship, giving continuous gradients, and excellent energy conservation. Utilizing multi-dimensional Gaussian coupling elements fit to CCSD(T)-F12 electronic structure theory, we built a 64-state MS-EVB model designed to study the F + CD3CN -> DF + CD2CN reaction in CD3CN solvent. This approach allows us to build a reactive potential energy surface (PES) whose balanced accuracy and efficiency considerably surpass what we could achieve otherwise. We use our PES to run MD simulations, and examine a range of transient observables which follow in the wake of reaction, including transient spectra of the DF vibrational band, time dependent profiles of vibrationally excited DF in CD3CN solvent, and relaxation rates for energy flow from DF into the solvent, all of which agree well with experimental observations. Immediately following deuterium abstraction, the nascent DF is in a non-equilibrium regime in two different respects: (1) it is highly excited, with ~23 kcal mol-1 localized in the stretch; and (2) not yet Hydrogen bonded to the CD3CN solvent, its microsolvation environment is intermediate between the non-interacting gas-phase limit and the solution-phase equilibrium limit. Vibrational relaxation of the nascent DF results in a spectral blue shift, while relaxation of its microsolvation environment results in a red shift. These two competing effects result in a post-reaction relaxation profile distinct from that observed when DF vibration excitation occurs within an equilibrium microsolvation environment. The parallel software framework presented in this paper should be more broadly applicable to a range of complex reactive systems.Comment: 58 pages and 29 Figure

A comparison of the nutritional qualities of supermarket's own and regular brands of bread in Sweden

Processed food is associated with unhealthy qualities such as higher content of harmful fats, sugars and salt. The aim of our study was to compare the nutritional qualities of supermarket's own brands and regular brands of bread sold in Sweden. Additionally, we compared the nutritional qualities of gluten-free and gluten-containing bread. We collected information from the labels of 332 bread products available in the largest grocery store chains. The Australian Health Star Rating (HSR) system was used to quantify the nutritional quality of each bread product. We compared all supermarket's own brand products to regular brand products, and gluten-free to gluten-containing bread. The mean HSR for the supermarket's own brands was lower than the regular brands (3.6 vs. 3.7; p = 0.046). For the regular brand products, the fibre, sugar and total fat content were greater (p < 0.001, p = 0.002 and p = 0.021, respectively), while less protein (p = 0.009) compared to regular bread products. Gluten-free bread had a lower HSR than gluten-containing bread (mean 3.5 vs. 3.8, respectively; p < 0.001). The regular brand products were slightly healthier than the supermarket's own brands, primarily as a result of a higher fibre content. Gluten-free bread products were slightly unhealthier due to a lower protein content

Spatial distributions and seasonal cycles of aerosols in India and China seen in global climate-aerosol model

Peer reviewe

Simulation of the radiative effect of haze on the urban hydrological cycle using reanalysis data in Beijing

Although increased aerosol concentration modifies local air temperatures and boundary layer structure in urban areas, little is known about its effects on the urban hydrological cycle. Changes in the hydrological cycle modify surface runoff and flooding. Furthermore, as runoff commonly transports pollutants to soil and water, any changes impact urban soil and aquatic environments. To explore the radiative effect of haze on changes in the urban surface water balance in Beijing, different haze levels are modelled using the Surface Urban Energy and Water Balance Scheme (SUEWS), forced by reanalysis data. The pollution levels are classified using aerosol optical depth observations. The secondary aims are to examine the usability of a global reanalysis dataset in a highly polluted environment and the SUEWS model performance. We show that the reanalysis data do not include the attenuating effect of haze on incoming solar radiation and develop a correction method. Using these corrected data, SUEWS simulates measured eddy covariance heat fluxes well. Both surface runoff and drainage increase with severe haze levels, particularly with low precipitation rates: runoff from 0.06 to 0.18 mm d−1 and drainage from 0.43 to 0.62 mm d−1 during fairly clean to extremely polluted conditions, respectively. Considering all precipitation events, runoff rates are higher during extremely polluted conditions than cleaner conditions, but as the cleanest conditions have high precipitation rates, they induce the largest runoff. Thus, the haze radiative effect is unlikely to modify flash flooding likelihood. However, flushing pollutants from surfaces may increase pollutant loads in urban water bodies.Peer reviewe

Left ventricular geometric patterns and adaptations to hemodynamics are similar in elderly men and women

<p>Abstract</p> <p>Background</p> <p>Common conditions such as obesity and hypertension result in hemodynamic alterations that will induce remodeling of the left ventricle (LV). However, differences between the genders in the relationship of hemodynamics to LV geometry are not well known.</p> <p>The present study aims to investigate differences between the genders in this respect, in a sample of elderly persons.</p> <p>Methods</p> <p>Echocardiography and Doppler was performed in a population-based sample aged 70 - The Prospective Investigation of the Vasculature in Uppsala Seniors (PIVUS) study (n = 922).</p> <p>Hemodynamic patterns obtained by echocardiography and Doppler were evaluated in relation to four LV geometric groups (normal, concentric remodeling, eccentric hypertrophy and concentric hypertrophy).</p> <p>Results</p> <p>No significant difference between the genders was observed regarding the prevalence of the LV geometric groups.</p> <p>Mean values of most evaluated echocardiography and Doppler variables differed between men and women, such as LA, IVS, LVEDD and IVRT, but the relationship of hemodynamic variables to LV geometric groups did not differ between the genders.</p> <p>Conclusions</p> <p>Although mean values of many echocardiographic variables differed between men and women, the LV geometric adaptations to a given hemodynamic load appear similar in both genders.</p

Interchain effects in the ultrafast photophysics of a semiconducting polymer: THz time-domain spectroscopy of thin films and isolated chains in solution

Euan Hendry, Mattijs Koeberg, Juleon M. Schins, H. K. Nienhuys, V. Sundström, L. D. A. Siebbeles, and Mischa Bonn, Physical Review B, Vol. 71, article 125201 (2005). "Copyright © 2005 by the American Physical Society."We compare the generation and decay dynamics of charges and excitons in a model polymer semiconductor (MEH-PPV) in solution and drop-cast thin films, by recording the sub-ps transient complex conductivity using THz time-domain spectroscopy. The results show that the quantum efficiency of charge generation is two orders of magnitude smaller in solution (~10–5) than in the solid film (~10–3). The proximity of neighboring chains in the films apparently facilitates (hot) exciton dissociation, presumably by allowing the electron and hole to separate on different polymer strands. For both samples, photoexcitation leads to the predominant formation of bound charge pairs (excitons) that can be detected through their polarizability. Surprisingly, the polarizability per absorbed photon is a factor of 3 larger in solution than in the film, suggesting that interchain interactions in the film do not result in a substantial delocalization of the exciton wave function

Development of an Industry 4.0 Demonstrator Using Sequence Planner and ROS2

In many modern automation solutions, manual off-line programming is being replaced by online algorithms that dynamically perform tasks based on the state of the environment. Complexities of such systems are pushed even further with collaboration among robots and humans, where intelligent machines and learning algorithms are replacing more traditional automation solutions. This chapter describes the development of an industrial demonstrator using a control infrastructure called Sequence Planner (SP), and presents some lessons learned during development. SP is based on ROS2 and it is designed to aid in handling the increased complexity of these new systems using formal models and online planning algorithms to coordinate the actions of robots and other devices. During development, SP can auto generate ROS nodes and message types as well as support continuous validation and testing. SP is also designed with the aim to handle traditional challenges of automation software development such as safety, reliability and efficiency. In this chapter, it is argued that ROS2 together with SP could be an enabler of intelligent automation for the next industrial revolution

Two-Dimensional Spectroscopy of Extended Molecular Systems: Applications to Energy Transport and Relaxation in an α-Helix

A simulation study of the coupled dynamics of amide I and amide II vibrations in an α-helix dissolved in water shows that two-dimensional (2D) infrared spectroscopy may be used to disentangle the energy transport along the helix through each of these modes from the energy relaxation between them. Time scales for both types of processes are obtained. Using polarization-dependent 2D spectroscopy is an important ingredient in the method we propose. The method may also be applied to other two-band systems, both in the infrared (collective vibrations) and the visible (excitons) parts of the spectrum.