On the use of rotational splitting asymmetries to probe the internal rotation profile of stars: Application to beta Cephei stars

Rotationally-split modes can provide valuable information about the internal rotation profile of stars. This has been used for years to infer the internal rotation behavior of the Sun. The present work discusses the potential additional information that rotationally splitting asymmetries may provide when studying the internal rotation profile of stars. We present here some preliminary results of a method, currently under development, which intends: 1) to understand the variation of the rotational splitting asymmetries in terms of physical processes acting on the angular momentum distribution in the stellar interior, and 2) how this information can be used to better constrain the internal rotation profile of the stars. The accomplishment of these two objectives should allow us to better use asteroseismology as a test-bench of the different theories describing the angular momentum distribution and evolution in the stellar interiors. (C) 2010 WILEY-VCH Verlag GmbH&Co. KGaA, Weinheim

Directed self-assembly of quantum structures by nanomechanical stamping using probe tips

We demonstrate that nanomechanically stamped substrates can be used as templates to pattern and direct the self-assembly of epitaxial quantum structures such as quantum dots. Diamond probe tips are used to indent or stamp the surface of GaAs( 100) to create nanoscale volumes of dislocation-mediated deformation, which alter the growth surface strain. These strained sites act to bias nucleation, hence allowing for selective growth of InAs quantum dots. Patterns of quantum dots are observed to form above the underlying nanostamped template. The strain state of the patterned structures is characterized by micro-Raman spectroscopy. The potential of using nanoprobe tips as a quantum dot nanofabrication technology are discussed.

Detection and Characterization of Cholesterol-Oxidized Products Using HPLC Coupled to Dopant Assisted Atmospheric Pressure Photoionization Tandem Mass Spectrometry

Oxidation of cholesterol (Ch) by a variety of reactive oxygen species gives rise mainly to hydroperoxides and aldehydes. Despite the growing interest in Ch-oxidized products, the detection and characterization of these products is still a matter of concern. In this work, the main Ch-oxidized products, namely, 3 beta-hydroxycholest-5-ene-7 alpha-hydroperoxide (7 alpha-OOH), 3 beta-5 alpha-cholest-6-ene-5-hydroperoxide (5 alpha-OOH), 3 beta-hydroxycholest-4-ene-6 alpha-hydroperoxide (6 alpha-OOH), 3 beta-hydroxycholest-4-ene-6 beta-hydroperoxide (6 beta-OOH), and 3 beta-hydroxy-5 beta-hydroxy-B-norcholestane-6 beta-carboxaldehyde (ChAld), were detected in the same analysis using high-performance liquid chromatography (HPLC) coupled to dopant assisted atmospheric pressure photoionization tandem mass spectrometry. The use of selected reaction monitoring mode (SRM) allowed a sensitive detection of each oxidized product, while the enhanced product ion mode (EPI) helped to improve the confidence of the analyses. Isotopic labeling experiments enabled one to elucidate mechanistic features during fragmentation processes. The characteristic fragmentation pattern of Ch-oxidized products is the consecutive loss of 1120 molecules, yielding cationic fragments at m/z 401, 383, and 365. Homolytic scissions of the peroxide bond are also seen. With (18)O-labeling approach, it was possible to establish a fragmentation order for each isomer. The SRM transitions ratio along with EPI and (18)O-labeled experiments give detailed information about differences for water elimination, allowing a proper discrimination between the isomers:Phis is of special interest considering the emerging role of Ch-oxidized products in the development of diseases.

Thermo-solvatochromism of merocyanine polarity probes - What are the consequences of increasing probe lipophilicity through annelation?

The question raised in the title has been answered by comparing the solvatochromism of two series of polarity probes, the lipophilicities of which were increased either by increasing the length of an alkyl group (R) attached to a fixed pyridine-based structure or through annelation (i.e., by fusing benzene rings onto a central pyridine-based structure). The following novel solvatochromic probes were synthesized: 2,6-dibromo-4-[(E)-2-(1-methylquinolinium-4-yl)ethenyl]-phenolate (MeQMBr(2)) and 2,6-dibromo-4-[(E)-2-(1-methyl-acridinium-4- yl) ethenyl)]phenolate (MeAMBr(2) The solvatochromic behavior of these probes, along with that of 2,6dibromo-4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl]phenol-ate(MePMBr(2)) was analyzed in terms of increasing probe lipophilicity, through annelation. Values of the empirical solvent polarity scale [E(T)(MePMBr(2))] in kcalmol(-1) correlated linearly with ET(30), the corresponding values for the extensively employed probe 2,6-diphenyl-4-(2,4,6-triphenylpyridinium-1-yl)phenolate (RB). On the other hand, the nonlinear correlations of ET(MeQMBr(2)) or ET(MeAMBr(2)) with E(T)(30) are described by second-order polynomials. Possible reasons for this behavior include: i) self-aggregation of the probe, ii) photoinduced cis/trans isomerization of the dye, and iii) probe structure- and solvent-dependent contributions of the quinonoid and zwitterionic limiting formulas to the ground and excited states of the probe. We show that mechanisms (i) and (ii) are not operative under the experimental conditions employed; experimental evidence (NMR) and theoretical calculations are presented to support the conjecture that the length of the central ethenylic bond in the dye increases in the order MeAMBr(2) > MeQMBr(2) > MePMBr(2), That is, the contribution of the zwitterionic limiting formula predominates for the latter probe, as is also the case for RB, this being the reason for the observed linear correlation between the ET(MePMBr2) and the ET(30) scales. The effect of increasing probe lipophilicity on solvatochromic behavior therefore depends on the strategy employed. Increasing the length of R affects solvatochromism much less than annelation, because the former structural change hardly perturbs the energy of the intramolecular charge-transfer transition responsible for solvatochromism. The thermo-solvatochromic behavior (effect of temperature on solvatochromism) of the three probes was studied in mixtures of water with propanol and/or with DMSO. The solvation model used explicitly considers the presence of three ""species"" in the system: bulk solution and probe solvation shell [namely, water (W), organic solvent (Solv)], and solvent-water hydrogen-bonded aggregate (Solv-W). For aqueous propanol, the probe is efficiently solvated by Solv-W; the strong interaction of DMSO with W drastically decreases the efficiency of Solv-W in solvating the probe, relative to its precursor solvents. Temperature increases resulted in desolvation of the probes, due to the concomitant reduction in the structured characters of the components of the binary mixtures.

Atmospheric pressure photoionization mass spectrometry as a tool for the investigation of the hydrolysis reaction mechanisms of phosphite antioxidants

The hydrolysis reaction mechanism of phosphite antioxidants is investigated by liquid chromatography-mass spectrometry (LC/MS). The phosphites were chosen because they differed in chemical structure and phosphorus content. Dopant assisted-atmospheric pressure photoionization (DA-APPI) is chosen as the ion source for (lie ionization of the compounds. [it our previous work, DA-APPI was shown to offer an attractive alternative to atmospheric pressure chemical ionization (APCI) since it provided background-ion free mass spectra and higher sensitivity [M. Papanastasiou, et al., Polymer Degradation and Stability 91 (11) (2006) 2675-2682]. In positive ion mode, the molecules are generally detected in their protonated form. In negative ion mode, the phosphites are unstable and only fragment ions are observed: these however, are characteristic of each phosphite and may be used for the identification of the analytes in complex mixtures. The analytes under investigation are exposed to accelerated humid ageing conditions and their hydrolytic pathway and stability is investigated. Different substituents around the phosphorus atom are shown to have a significant effect on the stability of the phosphites, with phenol substituents producing very hydrolytically stable structures. Alkanox P24 and PEP-36 follow a similar hydrolytic pathway via the scission of the first and then the second P-O-phenol bonds, eventually leading to the formation of phenol, Phosphorous acid and pentaerythritol as end products. HP-10 exhibits a rather different Structure and the products detected suggest scission of either the P-O-hydrocarbon or one of the P-O-phenol bonds. A phenomenon similar to that of autocatalysis is observed for all phosphites and is attributed to the formation of dialkyl phosphites as intermediate products. (C) 2008 Elsevier B.V. All rights reserved.

On the interaction of bovine serum albumin with ionic surfactants: Temperature induced EPR changes of a maleimide nitroxide reflect local protein dynamics and probe solvent accessibility

The interaction of bovine serum albumin (BSA) with the ionic surfactants sodium dodecylsulfate (SDS, anionic), cetyltrimethylammonium chloride (CTAC, cationic) and N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS, zwitterionic) was studied by electron paramagnetic resonance (EPR) spectroscopy of spin label covalently bound to the single free thiol group of the protein. EPR spectra simulation allows to monitor the protein dynamics at the labeling site and to estimate the changes in standard Gibbs free energy, enthalpy and entropy for transferring the nitroxide side chain from the more motionally restricted to the less restricted component. Whereas SDS and CTAC showed similar increases in the dynamics of the protein backbone for all measured concentrations. HPS presented a smaller effect at concentrations above 1.5 mM. At 10 mM of surfactants and 0.15 mM BSA, the standard Gibbs free energy change was consistent with protein backbone conformations more expanded and exposed to the solvent as compared to the native protein, but with a less pronounced effect for HPS. In the presence of the surfactants, the enthalpy change, related to the energy required to dissociate the nitroxide side chain from the protein, was greater, suggesting a lower water activity. The nitroxide side chain also detected a higher viscosity environment in the vicinity of the paramagnetic probe induced by the addition of the surfactants. The results suggest that the surfactant-BSA interaction, at higher surfactant concentration, is affected by the affinities of the surfactant to its own micelles and micelle-like aggregates. Complementary DLS data suggests that the temperature induced changes monitored by the nitroxide probe reflects local changes in the vicinity of the single thiol group of Cys-34 BSA residue. (C) 2011 Elsevier B.V. All rights reserved.

Multimilligram enantioresolution of sulfoxide proton pump inhibitors by liquid chromatography on polysaccharide-based chiral stationary phase

The enantiomers of sulfoxide proton pump inhibitors - omeprazole, lansoprazole, rabeprazole and Ro 18-5364 - were enantiomerically separated by liquid chromatography at multimilligram scale on a poly saccharide-based chiral stationary phase using normal and polar organic conditions as mobile phase. The values of the recovery and production rate were significant for each enantiomer; better results were achieved using a solid-phase injection system. However, this system was applied just for the enantionteric separation of omeprazole to demonstrate the applicability of this injection mode at milligram scale. The chiroptical characterization of the compounds was performed using a polarimeter and a circular dichroism detector. The higher enantiomeric purity obtained for the isolated enantiomers suggests that the methods here described should be considered as a simple and rapid way to obtain enantiomeric pure standards for analytical purpose. (C) 2007 Elsevier B.V. All rights reserved.

Simulation of Photovoltaic Panel Production as Complement to Ground Source Heat Pump System

This master thesis presents a new technological combination of two environmentally friendly sources of energy in order to provide DHW, and space heating. Solar energy is used for space heating, and DHW production using PV modules which supply direct current directly to electrical heating elements inside a water storage tank. On the other hand a GSHP system as another source of renewable energy provides heat in the water storage tank of the system in order to provide DHW and space heating. These two sources of renewable energy have been combined in this case-study in order to obtain a more efficient system, which will reduce the amount of electricity consumed by the GSHP system.The key aim of this study is to make simulations, and calculations of the amount ofelectrical energy that can be expected to be produced by a certain amount of PV modules that are already assembled on a house in Vantaa, southern Finland. This energy is then intended to be used as a complement to produce hot water in the heating system of the house beside the original GSHP system. Thus the amount of electrical energy purchased from the grid should be reduced and the compressor in the GSHP would need fewer starts which would reduce the heating cost of the GSHP system for space heating and providing hot water.The produced energy by the PV arrays in three different circuits will be charged directly to three electrical heating elements in the water storage tank of the existing system to satisfy the demand of the heating elements. The excess energy can be used to heat the water in the water storage tank to some extent which leads to a reduction of electricity consumption by the different components of the GSHP system.To increase the efficiency of the existing hybrid system, optimization of different PV configurations have been accomplished, and the results are compared. Optimization of the arrays in southern and western walls shows a DC power increase of 298 kWh/year compared with the existing PV configurations. Comparing the results from the optimization of the arrays on the western roof if the intention is to feed AC power to the components of the GSHP system shows a yearly AC power production of 1,646 kWh.This is with the consideration of no overproduction by the PV modules during the summer months. This means the optimized PV systems will be able to cover a larger part of summer demand compared with the existing system.

Simulation study of cascade heat pump for solar combisystems

This paper focuses on the study of cascade heat pump systems in combination with solar thermal for the production of hot water and space heating in single family houses with relatively high heating demand. The system concept was developed by Ratiotherm GmbH and simulated with TRNSYS 17. The basic cascade system uses the heat pump and solar collectors in parallel operation while a further development is the inclusion of an intermediate store that enables the possibility of serial/parallel operation and the use of low temperature solar heat. Parametric studies in terms of compressor size, refrigerant pair and size of intermediate heat exchanger were carried out for the optimization of the basic system. The system configurations were simulated for the complete year and compared to a reference of a solar thermal system combined with an air source heat pump. The results show ~13% savings in electricity use for all three cascade systems compared to the reference. However, the complexity of the systems is different and thus higher capital costs are expected.

Final report on heat pump developments in WP 4 - MacSheep Deliverable 4.4 : MacSheep -New Materials and Control for a next generation of compact combined Solar and heat pump systems with boosted energetic and exergetic performance

FP7- MacSheep

Influence of hydraulics and control of thermal storage in solar assisted heat pump combisystems

This paper studies the influence of hydraulics and control of thermal storage in systems combined with solar thermal and heat pump for the production of warm water and space heating in dwellings. A reference air source heat pump system with flat plate collectors connected to a combistore was defined and modeled together with the IEA SHC Task 44 / HPP Annex 38 (T44A38) “Solar and Heat Pump Systems” boundary conditions of Strasbourg climate and SFH45 building. Three and four pipe connections as well as use of internal and external heat exchangers for DHW preparation were investigated as well as sensor height for charging of the DHW zone in the store. The temperature in this zone was varied to ensure the same DHW comfort was achieved in all cases. The results show that the four pipe connection results in 9% improvement in SPF compared to three pipe and that the external heat exchanger for DHW preparation leads to a 2% improvement compared to the reference case. Additionally the sensor height for charging the DHW zone of the store should not be too low, otherwise system performance is adversely affected

Evaluation of a thermally driven heat pump for solar heating and cooling applications

Exploiting solar energy technology for both heating and cooling purposes has the potential of meeting an appreciable portion of the energy demand in buildings throughout the year. By developing an integrated, multi-purpose solar energy system, that can operate all twelve months of the year, a high utilisation factor can be achieved which translates to more economical systems. However, there are still some techno-economic barriers to the general commercialisation and market penetration of such technologies. These are associated with high system and installation costs, significant system complexity, and lack of knowledge of system implementation and expected performance. A sorption heat pump module that can be integrated directly into a solar thermal collector has thus been developed in order to tackle the aforementioned market barriers. This has been designed for the development of cost-effective pre-engineered solar energy system kits that can provide both heating and cooling. This thesis summarises the characterisation studies of the operation of individual sorption modules, sorption module integrated solar collectors and a full solar heating and cooling system employing sorption module integrated collectors. Key performance indicators for the individual sorption modules showed cooling delivery for 6 hours at an average power of 40 W and a temperature lift of 21°C. Upon integration of the sorption modules into a solar collector, measured solar radiation energy to cooling energy conversion efficiencies (solar cooling COP) were between 0.10 and 0.25 with average cooling powers between 90 and 200 W/m2 collector aperture area. Further investigations of the sorption module integrated collectors implementation in a full solar heating and cooling system yielded electrical cooling COP ranging from 1.7 to 12.6 with an average of 10.6 for the test period. Additionally, simulations were performed to determine system energy and cost saving potential for various system sizes over a full year of operation for a 140 m2 single-family dwelling located in Madrid, Spain. Simulations yielded an annual solar fraction of 42% and potential cost savings of €386 per annum for a solar heating and cooling installation employing 20m2 of sorption integrated collectors.

A simplified heat pump model for use in solar plus heat pump system simulation studies

Solar plus heat pump systems are often very complex in design, with sometimes special heat pump arrangements and control. Therefore detailed heat pump models can give very slow system simulations and still not so accurate results compared to real heat pump performance in a system. The idea here is to start from a standard measured performance map of test points for a heat pump according to EN 14825 and then determine characteristic parameters for a simplified correlation based model of the heat pump. By plotting heat pump test data in different ways including power input and output form and not only as COP, a simplified relation could be seen. By using the same methodology as in the EN 12975 QDT part in the collector test standard it could be shown that a very simple model could describe the heat pump test data very accurately, by identifying 4 parameters in the correlation equation found. © 2012 The Authors.