Exciton Plasmon Coupling in Hybrid Semiconductor - Metal Nanoparticle Monolayers

Hybrid semiconductor-metal nanoparticles monolayer of Cadmium Sclenide and gold nanoparticles has been prepared, using Langmuir – Blodgett technique. The near field photoluminescence spectra from such monolayer films, shows red shift similar to 75 meV with respect to CdSe QDs monolayer film and splitting similar to 57 meV. The composite spectra are much broader similar to 330 meV compared to the corresponding emission spectra of CdSe monolayer similar to 165 meV. The possible explanation for the observed features are provided in terms of exciton - Plasmon interaction.

Benthic-pelagic coupling in the northern Baltic Sea: importance of bioturbation and benthic predation

Benthic-pelagic coupling describes processes that operate across and between the seafloor and open-water ecosystems. In soft-sediment communities, bioturbation by sediment-dwelling and epibenthic organisms may strongly shape habitat characteristics and influence processes, e.g. biogeochemical cycling, which supplies bioavailable nutrients to pelagic primary producers. In addition, benthic fauna may mediate benthic-pelagic coupling by affecting the survival and hatching of zooplankton dormant eggs in the sediment. In the shallow waters and seasonally fluctuating environment of the Baltic Sea, emergence from the seafloor essentially contributes to the dynamics of zooplankton pelagic populations. In this thesis, I examine how benthic organisms with different functional traits affect the link between the benthic and pelagic systems in the northern Baltic Sea. By means of experimental laboratory studies, the effects of sediment-dwelling (Monoporeia affinis, Macoma balthica and Marenzelleria spp.) and nectobenthic (Mysis spp.) taxa on the survival and hatching of zooplankton benthic eggs and on benthic nutrient fluxes and sediment structure were investigated. In the predation studies, the nectobenthic mysids Mysis spp. preyed upon benthic eggs of the cladoceran Bosmina longispina maritima (syn. B. coregoni maritima), both in pelagic and benthic environments. Of the sediment-dwelling species, the amphipod M. affinis and the bivalve M. balthica reduced the number of cladoceran eggs in the sediment, whereas the polychaetes Marenzelleria spp. had no effects on cladoceran eggs. Both M. balthica and M. affinis also increased the mortality rates of benthic eggs of copepods and rotifers. It was estimated that zooplankton eggs provide an additional carbon source for food-limited benthic communities. The results indicate that predation pressure on zooplankton benthic eggs may be strong, but varies widely depending on the season and the functional characteristics of the macrofauna. Macoma balthica buried cladoceran eggs and a fluorescent tracer from the sediment surface to a depth of 3 4 cm, indicating efficient sediment mixing. In contrast, the other taxa had fewer effects on particle distributions. In addition to organic matter mineralization, particle mixing is crucial to the success of benthic recruitment of zooplankton, since only eggs close to the sediment surface may hatch. Macoma balthica and M. affinis altered the patterns of zooplankton emergence from the sediment. In general, the highest emergence rates were observed in the absence of macroscopic fauna, and M. balthica exerted a stronger suppressive effect than M. affinis. Moreover, copepods were less severely affected than cladocerans, while only one species (Temora longicornis) clearly benefited from the presence of the macrofauna. These differences probably result from species-specific differences in the resistance of eggs to disturbances. The results show that benthic fauna may considerably alter the patterns of zooplankton emergence from the seafloor, thereby shaping zooplankton pelagic populations. The semi-motile M. balthica and Marenzelleria spp. increased the fluxes of phosphate and ammonium from the sediment to the water, whereas the motile M. affinis and Mysis mixta had a contrasting effect. In the eutrophied Baltic Sea, efficient internal cycling of bioavailable nutrients forms a strong feedback inhibiting the recovery of the ecosystem. Based on the results, a change in species dominance from the two motile taxa, susceptible to oxygen deficiency, to the more tolerant semi-motile taxa provides additional feedback, strengthening internal nutrient cycling and accelerating eutrophication, with deteriorating near-bottom oxygen conditions and changes in the benthic communities. In shallow-water ecosystems, benthic nutrient regeneration plays a key role in determining the overall productivity of the ecosystem. In addition, the results of this study show that the communities in the benthos may essentially contribute to the structure of those in the plankton.

Toward the Discovery of Vaccine Adjuvants: Coupling In Silico Screening and In Vitro Analysis of Antagonist Binding to Human and Mouse CCR4 Receptors

Background: Adjuvants enhance or modify an immune response that is made to an antigen. An antagonist of the chemokine CCR4 receptor can display adjuvant-like properties by diminishing the ability of CD4+CD25+ regulatory T cells (Tregs) to down-regulate immune responses. Methodology: Here, we have used protein modelling to create a plausible chemokine receptor model with the aim of using virtual screening to identify potential small molecule chemokine antagonists. A combination of homology modelling and molecular docking was used to create a model of the CCR4 receptor in order to investigate potential lead compounds that display antagonistic properties. Three-dimensional structure-based virtual screening of the CCR4 receptor identified 116 small molecules that were calculated to have a high affinity for the receptor; these were tested experimentally for CCR4 antagonism. Fifteen of these small molecules were shown to inhibit specifically CCR4-mediated cellmigration, including that of CCR4(+) Tregs. Significance: Our CCR4 antagonists act as adjuvants augmenting human T cell proliferation in an in vitro immune response model and compound SP50 increases T cell and antibody responses in vivo when combined with vaccine antigens of Mycobacterium tuberculosis and Plasmodium yoelii in mice.

Transient NEMP Field Coupling With Buried Shielded Cables

The interaction of transient electromagnetic field due to an NEMP with buried cables has been studied in this paper. The cables studied were of two types: shielded as well as unshielded cables. Using transmission line analysis, the induced voltage and current are computed at the load end of the cable for different soil conductivities, different depths of burial of cable and for different lengths of the cable. Effect of shielding on the induced voltage on the cable inner conductor as well as the dependence of the induced voltage on the shield thickness are also studied.

Electronic coupling and catalytic effect on H2 evolution of MoS2/graphene nanocatalyst

Inorganic nano-graphene hybrid materials that are strongly coupled via chemical bonding usually present superior electrochemical performance. However, how the chemical bond forms and the synergistic catalytic mechanism remain fundamental questions. In this study, the chemical bonding of the MoS2 nanolayer supported on vacancy mediated graphene and the hydrogen evolution reaction of this nanocatalyst system were investigated. An obvious reduction of the metallic state of the MoS2 nanolayer is noticed as electrons are transferred to form a strong contact with the reduced graphene support. The missing metallic state associated with the unsaturated atoms at the peripheral sites in turn modifies the hydrogen evolution activity. The easiest evolution path is from the Mo edge sites, with the presence of the graphene resulting in a decrease in the energy barrier from 0.17 to 0.11 eV. Evolution of H2 from the S edge becomes more difficult due to an increase in the energy barrier from 0.43 to 0.84 eV. The clarification of the chemical bonding and catalytic mechanisms for hydrogen evolution using this strongly coupled MoS2/graphene nanocatalyst provide a valuable source of reference and motivation for further investigation for improved hydrogen evolution using chemically active nanocoupled systems.

Temperature-dependent infrared reflectivity studies of multiferroic TbMnO3: Evidence for spin-phonon coupling

We have measured near normal incidence far-infrared (FIR) reflectivity spectra of a single crystal of TbMnO3 from 10 K to 300 K in the spectral range of 50 cm(-1)-700 cm(-1). Fifteen transverse optic (TO) and longitudinal optic (LO) modes are identified in the imaginary part of the dielectric function epsilon(2)(omega) and energy loss function Im(-1/epsilon(omega)), respectively. Some of the observed phonon modes show anomalous softening below the magnetic transition temperature T-N (similar to 46 K). We attribute this anomalous softening to the spin-phonon coupling caused by phonon modulation of the superexchange integral between the Mn3+ spins. The effective charge of oxygen (Z(O)) calculated using the measured LO-TO splitting increases below TN.

Observations of the solar wind-magnetosphere-ionosphere coupling

In this thesis, the solar wind-magnetosphere-ionosphere coupling is studied observationally, with the main focus on the ionospheric currents in the auroral region. The thesis consists of five research articles and an introductory part that summarises the most important results reached in the articles and places them in a wider context within the field of space physics. Ionospheric measurements are provided by the International Monitor for Auroral Geomagnetic Effects (IMAGE) magnetometer network, by the low-orbit CHAllenging Minisatellite Payload (CHAMP) satellite, by the European Incoherent SCATter (EISCAT) radar, and by the Imager for Magnetopause-to-Aurora Global Exploration (IMAGE) satellite. Magnetospheric observations, on the other hand, are acquired from the four spacecraft of the Cluster mission, and solar wind observations from the Advanced Composition Explorer (ACE) and Wind spacecraft. Within the framework of this study, a new method for determining the ionospheric currents from low-orbit satellite-based magnetic field data is developed. In contrast to previous techniques, all three current density components can be determined on a matching spatial scale, and the validity of the necessary one-dimensionality approximation, and thus, the quality of the results, can be estimated directly from the data. The new method is applied to derive an empirical model for estimating the Hall-to-Pedersen conductance ratio from ground-based magnetic field data, and to investigate the statistical dependence of the large-scale ionospheric currents on solar wind and geomagnetic parameters. Equations describing the amount of field-aligned current in the auroral region, as well as the location of the auroral electrojets, as a function of these parameters are derived. Moreover, the mesoscale (10-1000 km) ionospheric equivalent currents related to two magnetotail plasma sheet phenomena, bursty bulk flows and flux ropes, are studied. Based on the analysis of 22 events, the typical equivalent current pattern related to bursty bulk flows is established. For the flux ropes, on the other hand, only two conjugate events are found. As the equivalent current patterns during these two events are not similar, it is suggested that the ionospheric signatures of a flux rope depend on the orientation and the length of the structure, but analysis of additional events is required to determine the possible ionospheric connection of flux ropes.

Disk-Outflow Coupling: Energetics Around Spinning BlacK Holes

The mechanism by which outflows and plausible jets are driven from black hole systems still remains observationally elusive. This notwithstanding, several observational evidences and deeper theoretical insights reveal that accretion and outflow/jet are strongly correlated. We model an advective disk-outflow coupled dynamics, incorporating explicitly the vertical flux. Inter-connecting dynamics of outflow andaccretion essentially upholds the conservation laws. We investigate the properties of the disk-outflow surface and its strong dependence on the rotation parameter of the black hole. The energetics of the disk outflow strongly depend on the mass, accretion rate, and spin of the black holes. The model clearly shows that the outflow power extracted from the disk increases strongly with the spin of the black hole, inferring that the power of the observed astrophysical jets has a proportional correspondence with the spin of the central object. In the case of blazars (BL Lacs and flat spectrum radio quasars, FSRQs), most of their emission are believed to be originated from their jets. It is observed that BL Lacs are relatively low luminous than FSRQs. The luminosity might be linked to the power of the jet, which in turn reflects that the nuclear regions of the BL Lac objects have a relatively low spinning black hole compared to that in the case of FSRQs. If extreme gravity is the source that powers strong outflows and jets, then the spin of the black hole, perhaps, might be the fundamental parameter to account for the observed astrophysical processes in an accretion powered system.

Nickel(II) meso-hydroxyporphyrin complexes revisited: Palladium-catalysed synthesis, electronic structures of derived oxy radicals, and oxidative coupling to a dioxoporphodimethene dyad

We report the synthesis and characterisation of new examples of meso-hydroxynickel(II) porphyrins with 5,15-diphenyl and 10-phenyl-5,15-diphenyl/diaryl substitu- tion. The OH group was introduced by using carbonate or hydroxide as nucleophile by using palladium/phosphine cat- alysis. The NiPor OHs exist in solution in equilibrium with the corresponding oxy radicals NiPor OC. The 15-phenyl group stabilises the radicals, so that the 1H NMR spectra of {NiPor OH} are extremely broad due to chemical exchange with the paramagnetic species. The radical concentration for the diphenylporphyrin analogue is only 1%, and its NMR line-broadening was able to be studied by variable-tempera- ture NMR spectroscopy. The EPR signals of NiPor OC are con- sistent with somewhat delocalised porphyrinyloxy radicals, and the spin distributions calculated by using density func- tional theory match the EPR and NMR spectroscopic obser- vations. Nickel(II) meso-hydroxy-10,20-diphenylporphyrin was oxidatively coupled to a dioxo-terminated porphodimethene dyad, the strongly red-shifted electronic spectrum of which was successfully modelled by using time-dependent DFT calculations.

Interfacial coupling and its size dependence in PbTiO3 and PbMg1/3Nb2/3O3 multilayers

Multilayers of Pb(Mg1/3Nb2/3)O-3 (PMN)-PbTiO3 (PT) were deposited through pulsed laser ablation deposition with different periodicities (d=10, 20, 30, 40, 50, 60, and 70 nm) for a constant total thickness of the film. The presence of superlattice reflections in the x-ray diffraction pattern clearly showed the superlattice behavior of the fabricated structures over a periodicity range of 20-50 nm. Polarization hysteresis and the capacitance-voltage characteristics of these films show clear size dependent ferroelectric and antiferroelectric (AFE) characteristics. Presence of long-range coupling and strain in multilayers with lower periodicity (similar to 10 nm) exhibited a clear ferroelectric behavior similar to a solid solution of PMN and PT. Multilayers with higher periodicities (20-50 nm) exhibited antiferroelectric behavior, which could be understood from the energy arguments. On further increase of periodicity, they again exhibit ferroelectric behavior. The polarization studies were carried out beyond the Curie temperature T-c of PMN to understand the interlayer interaction. The interaction is changed to a ferroelectric-paraelectric interlayer and tends to lose its antiferroelectric behavior. The behavior of remnant polarization P-r and dP(r)/dT with temperature clearly proves that the AFE coupling of these superlattices is due to the extrinsic interfacial coupling and not an intrinsic interaction as in a homogeneous conventional AFE material. The evidence of an averaged behavior at a periodicity of similar to 10 nm, and the behavior of individual materials at larger periodicities were further confirmed through dielectric phase transition studies. The presence of AFE interfacial coupling was insignificant over the dielectric phase transition of the multilayers.

Observation of a large coupling of a bound dihydrogen ligand to phosphorus ligands in trans-[(dppe)(2)Ru(eta(2)-H-2) (PF(OMe)(2))][BF4](2) complex

A new dicationic dihydrogen complex of the type trans-[(dppe)(2)Ru(eta (2)-H-2)(PF(OMe)(2))]BF4](2) has been prepared and characterized. A large coupling of about 50 Hz between the H-2 and trans-phosphorus ligand in this complex has been observed.

Non-resonant microwave absorption evidence for intrinsic Josephson coupling in Tl2Ba2CaCu2O8 single crystals

We report the results of our non-resonant microwave absorption (NRMA) studies on single crystals of Tl2Ba2CaCu2O8 (Tl 2212) which reflect the occurrence of intrinsic Josephson coupling in these crystals. We have studied the magnetic field induced microwave absorption at various temperatures from 4.2K to T-c (similar to 104K) using a standard CW EPR spectrometer (H-dc parallel to c). We observe the appearance of a characteristic feature in the NRMA signals similar to the ones observed earlier by us in Bi2Sr2CaCu2O8 (Bi 2212) starting a few degrees below T-c, which on cooling passes through a maximum in intensity before disappearing at a further low temperature. This behaviour is attributed to the appearance, strengthening and disappearance of Josephson response consequent to the temperature dependence of the viscosity of the Josephson medium between the CuO2 superconducting sheets.

Scaling behavior of plasmon coupling in Au and ReO3 nanoparticles incorporated in polymer matrices

Polymer nanocomposites containing different concentrations of Au nanoparticles have been investigated by small angle X-ray scattering and electronic absorption spectroscopy. The variation in the surface plasmon resonance (SPR) band of Au nanoparticles with concentration is described by a scaling law. The variation in the plasmon band of ReO3 nanoparticles embedded in polymers also follows a similar scaling law. Sistance dependence of plasmon coupling in polymer composites f metal nanoparticles. (C) 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of lattice distortion on the Curie temperature and spin-phonon coupling in LaMn0.5Co0.5O3

Two distinct ferromagnetic phases of LaMn0.5Co0.5O3 having monoclinic structure with distinct physical properties have been studied. The ferromagnetic ordering temperature T-c is found to be different for both the phases. The origin of such contrasting characteristics is assigned to the changes in the distance(s) and angle(s) between Mn-O-Co resulting from distortions observed from neutron diffraction studies. Investigations on the temperature dependent Raman spectroscopy provide evidence for such structural characteristics, which affects the exchange interaction. The difference in B-site ordering which is evident from the neutron diffraction is also responsible for the difference in T-c. Raman scattering suggests the presence of spin-phonon coupling for both the phases around the T-c. Electrical transport properties of both the phases have been investigated based on the lattice distortion.