Atmospheric radiative transfer in multiple scattering conditions. Application to NWP models.

High spectral resolution radiative transfer (RT) codes are essential tools in the study of the radiative energy transfer in the Earth atmosphere and a support for the development of parameterizations for fast RT codes used in climate and weather prediction models. Cirrus clouds cover permanently 30% of the Earth's surface, representing an important contribution to the Earth-atmosphere radiation balance. The work has been focussed on the development of the RT model LBLMS. The model, widely tested in the infra-red spectral range, has been extended to the short wave spectrum and it has been used in comparison with airborne and satellite measurements to study the optical properties of cirrus clouds. A new database of single scattering properties has been developed for mid latitude cirrus clouds. Ice clouds are treated as a mixture of ice crystals with various habits. The optical properties of the mixture are tested in comparison to radiometric measurements in selected case studies. Finally, a parameterization of the mixture for application to weather prediction and global circulation models has been developed. The bulk optical properties of ice crystals are parameterized as functions of the effective dimension of measured particle size distributions that are representative of mid latitude cirrus clouds. Tests with the Limited Area Weather Prediction model COSMO have shown the impact of the new parameterization with respect to cirrus cloud optical properties based on ice spheres.

Alpha, Omega end group functionalization of RAFT polymers based on pentafluorophenyl esters and methane thiosulfonates

While polymers with different functional groups along the backbone have intensively been investigated, there is still a challenge in orthogonal functionalization of the end groups. Such well-defined systems are interesting for the preparation of multiblock (co) polymers or polymer networks, for bio-conjugation or as model systems for examining the end group separation of isolated polymer chains. rnHere, Reversible Addition Fragmentation Chain Transfer (RAFT) polymerization was employed as method to investigate improved techniques for an a, w end group functionalization. RAFT produces polymers terminated in an R group and a dithioester-Z group, where R and Z stem from a suitable chain transfer agent (CTA). rnFor alpha end group functionalization, a CTA with an activated pentafluorophenyl (PFP) ester R group was designed and used for the polymerization of various methacrylate monomers, N-isopropylacrylamide and styrene yielding polymers with a PFP ester as a end group. This allowed the introduction of inert propyl amides, of light responsive diazo compounds, of the dyes NBD, Texas Red, or Oregon Green, of the hormone thyroxin and allowed the formation of multiblocks or peptide conjugates. rnFor w end group functionalization, problems of other techniques were overcome through an aminolysis of the dithioester in the presence of a functional methane thiosulfonate (MTS), yielding functional disulfides. These disulfides were stable under ambient conditions and could be cleaved on demand. Using MTS chemistry, terminal methyl disulfides (enabling self-assembly on planar gold surfaces and ligand substitution on gold and semiconductor nanoparticles), butynyl disulfide end groups (allowing the “clicking” of the polymers onto azide functionalized surfaces and the selective removal through reduction), the bio-target biotin, and the fluorescent dye Texas Red were introduced into polymers. rnThe alpha PFP amidation could be performed under mild conditions, without substantial loss of DTE. This way, a step-wise synthesis produced polymers with two functional end groups in very high yields. rnAs examples, polymers with an anchor group for both gold nanoparticles (AuNP) and CdSe / ZnS semi-conductor nanoparticles (QD) and with a fluorescent dye end group were synthesized. They allowed a NP decoration and enabled an energy transfer from QD to dye or from dye to AuNP. Water-soluble polymers were prepared with two different bio-target end groups, each capable of selectively recognizing and binding a certain protein. The immobilization of protein-polymer-protein layers on planar gold surfaces was monitored by surface plasmon resonance.Introducing two different fluorescent dye end groups enabled an energy transfer between the end groups of isolated polymer chains and created the possibility to monitor the behavior of single polymer chains during a chain collapse. rnThe versatility of the synthetic technique is very promising for applications beyond this work.

Factors improving the vibration transfer of the floating mass transducer at the round window

With the placement of a floating mass transducer (FMT) at the round window, a new approach of coupling an implantable hearing system to the cochlea has been introduced. The aim of the present experimental study is to examine the influence of different ways of FMT placement at the round window on the vibration energy transfer to the cochlea.

Enhanced (1)G(4) emission in NaLaF4: Pr3+, Yb3+ and charge transfer in NaLaF4: Ce3+, Yb3+ studied by fourier transform luminescence spectroscopy

A high resolution luminescence study of NaLaF4: 1%Pr3+, 5%Yb3+ and NaLaF4: 1%Ce3+, 5%Yb3+ in the UV to NIR spectral range using a InGaAs detector and a fourier transform interferometer is reported. Although the Pr3+(P-3(0) -> (1)G(4), Yb3+(F-2(7/2) -> F-2(5/2)) energy transfer step takes place, significant Pr3+ (1)G(4) emission around 993, 1330 and 1850 nm is observed. No experimental proof for the second energy transfer step in the down-conversion process between Pr3+ and Yb3+ can be given. In the case of NaLaF4: Ce3+, Yb3+ it is concluded that the observed Yb3+ emission upon Ce3+ 5d excitation is the result of a charge transfer process instead of down-conversion. (C) 2010 Elsevier B.V. All rights reserved.

Determination of Maximum Mechanical Energy Efficiency in Energy Galloping Systems

Transverse galloping is a type of aeroelastic instability characterized by large amplitude, low frequency, normal to wind oscillations that appear in some elastic two-dimensional bluff bodies when subjected to a fluid flow, provided that the flow velocity exceeds a threshold critical value. Such an oscillatory motion is explained because of the energy transfer from the flow to the two-dimensional bluff body. The 7 amount of energy that can be extracted depends on the cross section of the galloping prism. Assuming that the Glauert-Den Hartog quasistatic criterion for galloping instability is satisfied in a first approximation, the suitability of a given cross section for energy harvesting is evaluated by analyzing the lateral aerodynamic force coefficient, fitting a function with a power series in tan a (a being the angle of attack) to 10 available experimental data. In this paper, a fairly large number of simple prisms (triangle, ellipse, biconvex, and rhombus cross sections, as well 11 as D-shaped bodies) is analyzed for suitability as energy harvesters. The influence of the fitting process in the energy harvesting efficiency evaluation is also demonstrated. The analysis shows that the more promising bodies are those with isosceles or approximate isosceles cross sections.

Vehicle to vehicle energy exchange in smart grid applications

This paper presents a novel vehicle to vehicle energy exchange market (V2VEE) between electric vehicles (EVs) for decreasing the energy cost to be paid by some users whose EVs must be recharged during the day to fulfil their daily scheduled trips and also reducing the impact of charging on the electric grid. EVs with excess of energy in their batteries can transfer this energy among other EVs which need charge during their daily trips. These second type of owners can buy the energy directly to the electric grid or they can buy the energy from other EV at lower price. An aggregator is responsible for collecting all information among vehicles located in the same area at the same time and make possible this energy transfer.

An unusual pathway of excitation energy deactivation in carotenoids: Singlet-to-triplet conversion on an ultrafast timescale in a photosynthetic antenna

Carotenoids are important biomolecules that are ubiquitous in nature and find widespread application in medicine. In photosynthesis, they have a large role in light harvesting (LH) and photoprotection. They exert their LH function by donating their excited singlet state to nearby (bacterio)chlorophyll molecules. In photosynthetic bacteria, the efficiency of this energy transfer process can be as low as 30%. Here, we present evidence that an unusual pathway of excited state relaxation in carotenoids underlies this poor LH function, by which carotenoid triplet states are generated directly from carotenoid singlet states. This pathway, operative on a femtosecond and picosecond timescale, involves an intermediate state, which we identify as a new, hitherto uncharacterized carotenoid singlet excited state. In LH complex-bound carotenoids, this state is the precursor on the reaction pathway to the triplet state, whereas in extracted carotenoids in solution, this state returns to the singlet ground state without forming any triplets. We discuss the possible identity of this excited state and argue that fission of the singlet state into a pair of triplet states on individual carotenoid molecules constitutes the mechanism by which the triplets are generated. This is, to our knowledge, the first ever direct observation of a singlet-to-triplet conversion process on an ultrafast timescale in a photosynthetic antenna.

Intra- vs intermolecular photoinduced electron transfer reactions of a macrocyclic donor-acceptor dyad

The synthesis, structural characterization, and photophysical behavior of a 14-membered tetraazamacrocycle with pendant 4-dimethylaminobenzyl (DMAB) and 9-anthracenylmethyl groups is reported (L-3, 6-((9-anthracenylmethyl)amino)-trans-6,13-dimethyl-13-((4-dimethylaminobenzyl)amino)-1,4,8,11-tetraaza-cyclotetradecane). In its free base form, this compound displays rapid intramolecular photoinduced electron transfer (PET) quenching of the anthracene emission, with both the secondary amines and the DMAB group capable of acting as electron donors. When complexed with Zn(II), the characteristic fluorescence of the anthracene chromophore is restored as the former of these pathways is deactivated by coordination. Importantly, it is shown that the DMAB group, which remains uncoordinated and PET active, acts only very weakly to quench emission, by comparison to the behavior of a model Zn complex lacking the pendant DMAB group, [ZnL2](2+) (Chart 1). By contrast, Stern-Volmer analysis of intermolecular quenching of [ZnL2](2+) by N,N-dimethylaniline (DMA) has shown that this reaction is diffusion limited. Hence, the pivotal role of the bridge in influencing intramolecular PET is highlighted.

Criteria for quantum coherent transfer of excitations between chromophores in a polar solvent

We show that the quantum decoherence of Forster resonant energy transfer between two optically active molecules can be described by a spin-boson model. This allows us to give quantitative criteria that are necessary for coherent quantum oscillations of excitations between the chromophores. Experimental tests of our results should be possible with flourescent resonant energy transfer (FRET) spectroscopy. Although we focus on the case of protein-pigment complexes our results are also relevant to quantum dots and organic molecules in a dielectric medium. (c) 2006 Elsevier B.V. All rights reserved.

Determination of the orientational distribution and orientation factor for transfer between membrane-bound fluorophores using a confocal microscope

Orientational fluorophores have been a useful tool in physical chemistry, biochemistry, and more recently structural biology due to the polarized nature of the light they emit and that fact that energy can be transferred between them. We present a practical scheme in which measurements of the intensity of emitted fluorescence can be used to determine limits on the mean and distribution of orientation of the absorption transition moment of membrane-bound. uorophores. We demonstrate how information about the orientation of. uorophores can be used to calculate the orientation factor k(2) required for use in FRET spectroscopy. We illustrate the method using images of AlexaFluor probes bound to MscL mechanosensitive transmembrane channel proteins in spherical liposomes.

Some aspects of the interaction of humic substances with metal ions

Humic substances are the major organic constituents of soils and sediments. They are heterogeneous, polyfunctional, polydisperse, macromolecular and have no accurately known chemical structure. Their interactions with radionuclides are particularly important since they provide leaching mechanisms from disposal sites. The central theme to this research is the interaction of heavy metal actinide analogues with humic materials. Studies described focus on selected aspects of the characteristics and properties of humic substances. Some novel approaches to experiments and data analysis are pursued. Several humic substances are studied; all but one are humic acids, and those used most extensively were obtained commercially. Some routine characterisation techniques are applied to samples in the first instance. Humic substances are coloured, but their ultra-violet and visible absorption spectra are featureless. Yet, they fluoresce over a wide range of wavelengths. Enhanced fluorescence in the presence of luminescent europium(III) ions is explained by energy transfer from irradiated humic acid to the metal ion in a photophysical model. Nuclear magnetic resonance spectroscopy is applied to the study of humic acids and their complexes with heavy metals. Proton and carbon-13 NMR provides some structural and functionality information; Paramagnetic lanthanide ions affect these spectra. Some heavy metals are studied as NMR nuclei, but measurements are restricted by their sensitivity. A humic acid is fractionated yielding a broad molecular weight distribution. Electrophoretic mobilities and particle radii determined by Laser Doppler Electrophoretic Light Scattering are sensitive to the conditions of the supporting media, and the concentration and particle size distribution of humic substances. In potentiometric titrations of humate dispersions, the organic matter responds slowly and the mineral acid addition is buffered. Proton concentration data is modelled and a mechanism is proposed involving two key stages, both resulting in proton release after some conformational changes.

High energy three -body breakup of three -nucleon systems

The main goal of this dissertation was to study two- and three-nucleon Short Range Correlations (SRCs) in high energy three-body breakup of 3He nucleus in 3He(e, e'NN) N reaction. SRCs are characterized by quantum fluctuations in nuclei during which constituent nucleons partially overlap with each other. ^ A theoretical framework is developed within the Generalized Eikonal Approximation (GEA) which upgrades existing medium-energy methods that are inapplicable for high momentum and energy transfer reactions. High momentum and energy transfer is required to provide sufficient resolution for probing SRCs. GEA is a covariant theory which is formulated through the effective Feynman diagrammatic rules. It allows self-consistent calculation of single and double re-scatterings amplitudes which are present in three-body breakup processes. The calculations were carried out in detail and the analytical result for the differential cross section of 3He(e, e'NN)N reaction was derived in a form applicable for programming and numerical calculations. The corresponding computer code has been developed and the results of computation were compared to the published experimental data, showing satisfactory agreement for a wide range of values of missing momenta. ^ In addition to the high energy approximation this study exploited the exclusive nature of the process under investigation to gain more information about the SRCs. The description of the exclusive 3He( e, e'NN)N reaction has been done using the formalism of the nuclear decay function, which is a practically unexplored quantity and is related to the conventional spectral function through the integration of the phase space of the recoil nucleons. Detailed investigation showed that the decay function clearly exhibits the main features of two- and three-nucleon correlations. Four highly practical types of SRCs in 3He nucleus were discussed in great detail for different orders of the final state re-interactions using the decay function as an unique identifying tool. ^ The overall conclusion in this dissertation suggests that the investigation of the decay function opens up a completely new venue in studies of short range nuclear properties. ^

High energy three-body breakup of three-nucleon systems

The main goal of this dissertation was to study two- and three-nucleon Short Range Correlations (SRCs) in high energy three-body breakup of 3He nucleus in 3He(e, e'NN)N reaction. SRCs are characterized by quantum fluctuations in nuclei during which constituent nucleons partially overlap with each other. A theoretical framework is developed within the Generalized Eikonal Approximation (GEA) which upgrades existing medium-energy methods that are inapplicable for high momentum and energy transfer reactions. High momentum and energy transfer is required to provide sufficient resolution for probing SRCs. GEA is a covariant theory which is formulated through the effective Feynman diagrammatic rules. It allows self-consistent calculation of single and double re-scatterings amplitudes which are present in three-body breakup processes. The calculations were carried out in detail and the analytical result for the differential cross section of 3He(e, e'NN)Nreaction was derived in a form applicable for programming and numerical calculations. The corresponding computer code has been developed and the results of computation were compared to the published experimental data, showing satisfactory agreement for a wide range of values of missing momenta. In addition to the high energy approximation this study exploited the exclusive nature of the process under investigation to gain more information about the SRCs. The description of the exclusive 3He(e, e'NN)N reaction has been done using the formalism of the nuclear decay function, which is a practically unexplored quantity and is related to the conventional spectral function through the integration of the phase space of the recoil nucleons. Detailed investigation showed that the decay function clearly exhibits the main features of two- and three-nucleon correlations. Four highly practical types of SRCs in 3He nucleus were discussed in great detail for different orders of the final state re-interactions using the decay function as an unique identifying tool. The overall conclusion in this dissertation suggests that the investigation of the decay function opens up a completely new venue in studies of short range nuclear properties.

RF energy harvesting two-way cognitive DF relaying with transceiver impairments

This paper analyzes the impact of transceiver impairments on outage probability (OP) and throughput of decode-and-forward two-way cognitive relay (TWCR) networks, where the relay is self-powered by harvesting energy from the transmitted signals. We consider two bidirectional relaying protocols namely, multiple access broadcast (MABC) protocol and time division broadcast (TDBC) protocol, as well as, two power transfer policies namely, dual-source (DS) energy transfer and single-fixed-source (SFS) energy transfer. Closed-form expressions for OP and throughput of the network are derived in the context of delay-limited transmission. Numerical results corroborate our analysis, thereby we can quantify the degradation of OP and throughput of TWCR networks due to transceiver hardware impairments. Under the specific parameters, our results indicate that the MABC protocol achieves asymptotically a higher throughput by 0.65 [bits/s/Hz] than the TDBC protocol, while the DS energy transfer scheme offers better performance than the SFS policy for both relaying protocols.

Energy level decay and excited state absorption processes in erbium-doped tellurium glass

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)