Tuning of magnetic exchange interactions between organic radicals through bond and space

The dissertation entitled "Tuning of magnetic exchange interactions between organic radicals through bond and space" comprises eight chapters. In the initial part of chapter 1, an overview of organic radicals and their applications were discussed and in the latter part motivation and objective of thesis was described. As the EPR spectroscopy is a necessary tool to study organic radicals, the basic principles of EPR spectroscopy were discussed in chapter 2. rnAntiferromagnetically coupled species can be considered as a source of interacting bosons. Consequently, such biradicals can serve as molecular models of a gas of magnetic excitations which can be used for quantum computing or quantum information processing. Notably, initial small triplet state population in weakly AF coupled biradicals can be switched into larger in the presence of applied magnetic field. Such biradical systems are promising molecular models for studying the phenomena of magnetic field-induced Bose-Einstein condensation in the solid state. To observe such phenomena it is very important to control the intra- as well as inter-molecular magnetic exchange interactions. Chapters 3 to 5 deals with the tuning of intra- and inter-molecular exchange interactions utilizing different approaches. Some of which include changing the length of π-spacer, introduction of functional groups, metal complex formation with diamagnetic metal ion, variation of radical moieties etc. During this study I came across two very interesting molecules 2,7-TMPNO and BPNO, which exist in semi-quinoid form and exhibits characteristic of the biradical and quinoid form simultaneously. The 2,7-TMPNO possesses the singlet-triplet energy gap of ΔEST = –1185 K. So it is nearly unrealistic to observe the magnetic field induced spin switching. So we studied the spin switching of this molecule by photo-excitation which was discussed in chapter 6. The structural similarity of BPNO with Tschitschibabin’s HC allowed us to dig the discrepancies related to ground state of Tschitschibabin’s hydrocarbon(Discussed in chapter 7). Finally, in chapter 8 the synthesis and characterization of a neutral paramagnetic HBC derivative (HBCNO) is discussed. The magneto liquid crystalline properties of HBCNO were studied by DSC and EPR spectroscopy.rn

Structure of the Hsp110:Hsc70 nucleotide exchange machine.

Hsp70s mediate protein folding, translocation, and macromolecular complex remodeling reactions. Their activities are regulated by proteins that exchange ADP for ATP from the nucleotide-binding domain (NBD) of the Hsp70. These nucleotide exchange factors (NEFs) include the Hsp110s, which are themselves members of the Hsp70 family. We report the structure of an Hsp110:Hsc70 nucleotide exchange complex. The complex is characterized by extensive protein:protein interactions and symmetric bridging interactions between the nucleotides bound in each partner protein's NBD. An electropositive pore allows nucleotides to enter and exit the complex. The role of nucleotides in complex formation and dissociation, and the effects of the protein:protein interactions on nucleotide exchange, can be understood in terms of the coupled effects of the nucleotides and protein:protein interactions on the open-closed isomerization of the NBDs. The symmetrical interactions in the complex may model other Hsp70 family heterodimers in which two Hsp70s reciprocally act as NEFs.

Arsenic speciation in edible alga samples by microwave-assisted extraction and high performance liquid chromatography coupled to atomic fluorescence spectrometry

Twelve commercially available edible marine algae from France, Japan and Spain and the certified reference material (CRM) NIES No. 9 Sargassum fulvellum were analyzed for total arsenic and arsenic species. Total arsenic concentrations were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) after microwave digestion and ranged from 23 to 126 μg g−1. Arsenic species in alga samples were extracted with deionized water by microwave-assisted extraction and showed extraction efficiencies from 49 to 98%, in terms of total arsenic. The presence of eleven arsenic species was studied by high performance liquid chromatography–ultraviolet photo-oxidation–hydride generation atomic–fluorescence spectrometry (HPLC–(UV)–HG–AFS) developed methods, using both anion and cation exchange chromatography. Glycerol and phosphate sugars were found in all alga samples analyzed, at concentrations between 0.11 and 22 μg g−1, whereas sulfonate and sulfate sugars were only detected in three of them (0.6-7.2 μg g−1). Regarding arsenic toxic species, low concentration levels of dimethylarsinic acid (DMA) (<0.9 μg g−1) and generally high arsenate (As(V)) concentrations (up to 77 μg g−1) were found in most of the algae studied. The results obtained are of interest to highlight the need to perform speciation analysis and to introduce appropriate legislation to limit toxic arsenic species content in these food products.

Direct interaction of Gβγ with a C-terminal Gβγ-binding domain of the Ca2+ channel α1 subunit is responsible for channel inhibition by G protein-coupled receptors

Several classes of voltage-gated Ca2+ channels (VGCCs) are inhibited by G proteins activated by receptors for neurotransmitters and neuromodulatory peptides. Evidence has accumulated to indicate that for non-L-type Ca2+ channels the executing arm of the activated G protein is its βγ dimer (Gβγ). We report below the existence of two Gβγ-binding sites on the A-, B-, and E-type α1 subunits that form non-L-type Ca2+ channels. One, reported previously, is in loop 1 connecting transmembrane domains I and II. The second is located approximately in the middle of the ca. 600-aa-long C-terminal tails. Both Gβγ-binding regions also bind the Ca2+ channel β subunit (CCβ), which, when overexpressed, interferes with inhibition by activated G proteins. Replacement in α1E of loop 1 with that of the G protein-insensitive and Gβγ-binding-negative loop 1 of α1C did not abolish inhibition by G proteins, but the exchange of the α1E C terminus with that of α1C did. This and properties of α1E C-terminal truncations indicated that the Gβγ-binding site mediating the inhibition of Ca2+ channel activity is the one in the C terminus. Binding of Gβγ to this site was inhibited by an α1-binding domain of CCβ, thus providing an explanation for the functional antagonism existing between CCβ and G protein inhibition. The data do not support proposals that Gβγ inhibits α1 function by interacting with the site located in the loop I–II linker. These results define the molecular mechanism by which presynaptic G protein-coupled receptors inhibit neurotransmission.

Efficient exchange of the primary quinone acceptor QA in isolated reaction centers of Rhodopseudomonas viridis

A key step in the conversion of solar energy into chemical energy by photosynthetic reaction centers (RCs) occurs at the level of the two quinones, QA and QB, where electron transfer couples to proton transfer. A great deal of our understanding of the mechanisms of these coupled reactions relies on the seminal work of Okamura et al. [Okamura, M. Y., Isaacson, R. A., & Feher, G. (1975) Proc. Natl. Acad. Sci. USA 88, 3491–3495], who were able to extract with detergents the firmly bound ubiquinone QA from the RC of Rhodobacter sphaeroides and reconstitute the site with extraneous quinones. Up to now a comparable protocol was lacking for the RC of Rhodopseudomonas viridis despite the fact that its QA site, which contains 2-methyl-3-nonaprenyl-1,4-naphthoquinone (menaquinone-9), has provided the best x-ray structure available. Fourier transform infrared difference spectroscopy, together with the use of isotopically labeled quinones, can probe the interaction of QA with the RC protein. We establish that a simple incubation procedure of isolated RCs of Rp. viridis with an excess of extraneous quinone allows the menaquinone-9 in the QA site to be almost quantitatively replaced either by vitamin K1, a close analogue of menaquinone-9, or by ubiquinone. To our knowledge, this is the first report of quinone exchange in bacterial photosynthesis. The Fourier transform infrared data on the quinone and semiquinone vibrations show a close similarity in the bonding interactions of vitamin K1 with the protein at the QA site of Rp. viridis and Rb. sphaeroides, whereas for ubiquinone these interactions are significantly different. The results are interpreted in terms of slightly inequivalent quinone–protein interactions by comparison with the crystallographic data available for the QA site of the two RCs.

Coupling of histamine H3 receptors to neuronal Na+/H+ exchange: A novel protective mechanism in myocardial ischemia

In myocardial ischemia, adrenergic nerves release excessive amounts of norepinephrine (NE), causing dysfunction and arrhythmias. With anoxia and the concomitant ATP depletion, vesicular storage of NE is impaired, resulting in accumulation of free NE in the axoplasm of sympathetic nerves. Intraneuronal acidosis activates the Na+/H+ exchanger (NHE), leading to increased Na+ entry in the nerve terminals. These conditions favor availability of the NE transporter to the axoplasmic side of the membrane, causing massive carrier-mediated efflux of free NE. Neuronal NHE activation is pivotal in this process; NHE inhibitors attenuate carrier-mediated NE release. We previously reported that activation of histamine H3 receptors (H3R) on cardiac sympathetic nerves also reduces carrier-mediated NE release and alleviates arrhythmias. Thus, H3R activation may be negatively coupled to NHE. We tested this hypothesis in individual human SKNMC neuroblastoma cells stably transfected with H3R cDNA, loaded with the intracellular pH (pHi) indicator BCECF. These cells possess amiloride-sensitive NHE. NHE activity was measured as the rate of Na+-dependent pHi recovery in response to an acute acid pulse (NH4Cl). We found that the selective H3R-agonist imetit markedly diminished NHE activity, and so did the amiloride derivative EIPA. The selective H3R antagonist thioperamide abolished the imetit-induced NHE attenuation. Thus, our results provide a link between H3R and NHE, which may limit the excessive release of NE during protracted myocardial ischemia. Our previous and present findings uncover a novel mechanism of cardioprotection: NHE inhibition in cardiac adrenergic neurons as a means to prevent ischemic arrhythmias associated with carrier-mediated NE release.

Anisotropic exchange interaction induced by a single photon in semiconductor microcavities

We investigate coupling of localized spins in a semiconductor quantum dot embedded in a microcavity. The lowest cavity mode and the quantum dot exciton are coupled and close in energy, forming a polariton. The fermions forming the exciton interact with localized spins via exchange. Exact diagonalization of a Hamiltonian in which photons, spins, and excitons are treated quantum mechanically shows that a single polariton induces a sizable indirect anisotropic exchange interaction between spins. At sufficiently low temperatures strong ferromagnetic correlations show up without an appreciable increase in exciton population. In the case of a (Cd,Mn)Te quantum dot, Mn-Mn ferromagnetic coupling is still significant at 1 K: spin-spin correlation around 3 for exciton occupation smaller than 0.3. We find that the interaction mediated by photon-polaritons is 10 times stronger than the one induced by a classical field for equal Rabi splitting.

Screen-printed electrode-based electrochemical detector coupled with in-situ ionic-liquid-assisted dispersive liquid–liquid microextraction for determination of 2,4,6-trinitrotoluene

A novel method is reported, whereby screen-printed electrodes (SPELs) are combined with dispersive liquid–liquid microextraction. In-situ ionic liquid (IL) formation was used as an extractant phase in the microextraction technique and proved to be a simple, fast and inexpensive analytical method. This approach uses miniaturized systems both in sample preparation and in the detection stage, helping to develop environmentally friendly analytical methods and portable devices to enable rapid and onsite measurement. The microextraction method is based on a simple metathesis reaction, in which a water-immiscible IL (1-hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, [Hmim][NTf2]) is formed from a water-miscible IL (1-hexyl-3-methylimidazolium chloride, [Hmim][Cl]) and an ion-exchange reagent (lithium bis[(trifluoromethyl)sulfonyl]imide, LiNTf2) in sample solutions. The explosive 2,4,6-trinitrotoluene (TNT) was used as a model analyte to develop the method. The electrochemical behavior of TNT in [Hmim][NTf2] has been studied in SPELs. The extraction method was first optimized by use of a two-step multivariate optimization strategy, using Plackett–Burman and central composite designs. The method was then evaluated under optimum conditions and a good level of linearity was obtained, with a correlation coefficient of 0.9990. Limits of detection and quantification were 7 μg L−1 and 9 μg L−1, respectively. The repeatability of the proposed method was evaluated at two different spiking levels (20 and 50 μg L−1), and coefficients of variation of 7 % and 5 % (n = 5) were obtained. Tap water and industrial wastewater were selected as real-world water samples to assess the applicability of the method.

Consequences of Kondo exchange on quantum spins

When individual quantum spins are placed in close proximity to conducting substrates, the localized spin is coupled to the nearby itinerant conduction electrons via Kondo exchange. In the strong coupling limit this can result in the Kondo effect — the formation of a correlated, many body singlet state — and a resulting renormalization of the density of states near the Fermi energy. However, even when Kondo screening does not occur, Kondo exchange can give rise to a wide variety of other phenomena. In addition to the well known renormalization of the g factor and the finite spin decoherence and relaxation times, Kondo exchange has recently been found to give rise to a newly discovered effect: the renormalization of the single ion magnetic anisotropy. Here we put these apparently different phenomena on equal footing by treating the effect of Kondo exchange perturbatively. In this formalism, the central quantity is ρJ, the product of the density of states at the Fermi energy ρ and the Kondo exchange constant J. We show that perturbation theory correctly describes the experimentally observed exchange induced shifts of the single spin excitation energies, demonstrating that Kondo exchange can be used to tune the effective magnetic anisotropy of a single spin.

Quantum anomalous Hall effect in graphene coupled to skyrmions

Skyrmions are topologically protected spin textures, characterized by a topological winding number N, that occur spontaneously in some magnetic materials. Recent experiments have demonstrated the capability to grow graphene on top Fe/Ir, a system that exhibits a two-dimensional skyrmion lattice. Here we show that a weak exchange coupling between the Dirac electrons in graphene and a two-dimensional skyrmion lattice withN = ±1 drives graphene into a quantum anomalous Hall phase, with a band gap in bulk, a Chern number C = 2N, and chiral edge states with perfect quantization of conductance G = 2N e2 h . Our findings imply that the topological properties of the skyrmion lattice can be imprinted in the Dirac electrons of graphene.

Growth and gas exchange responses of Brazilian pepper (Schinus terebinthifolius) and native South Florida species to salinity

Schinus terebinthifolius Raddi (Schinus) is an invasive exotic species widely found in disturbed and native communities of Florida. This species has been shown to displace native species as well as alter community structure and function. The purpose of this study was to determine if the growth and gas exchange patterns of Schinus, under differing salinity conditions, were different from native species. Two native upland glycophytic species (Rapanea punctata and Randia aculeata) and two native mangrove species (Rhizophora mangle and Laguncularia racemosa) were compared with the exotic. Overall, the exotics morphologic changes and gas exchange patterns were most similar to R. mangle. Across treatments, increasing salinity decreased relative growth rate (RGR), leaf area ratio (LAR) and specific leaf area (SLA) but did not affect root/shoot ratios (R:S). Allocation patterns were however significantly different among species. The largest proportion of Schinus biomass was allocated to stems (47%), resulting in plants that were generally taller than the other species. Schinus also had the highest SLA and largest total leaf area of all species. This meant that the exotic, which was taller and had thinner leaves, was potentially able to maintain photosynthetic area comparable to native species. Schinus response patterns show that this exotic exhibits some physiological tolerance for saline conditions. Coupled with its biomass allocation patterns (more stem biomass and large area of thin leaves), the growth traits of this exotic potentially provide this species an advantage over native plants in terms of light acquisition in a brackish forested ecosystem.

Numerical Analysis on a Dual-Loop Waste Heat Recovery System Coupled with an ORC for Vehicle Applications

The internal combustion (IC) engines exploits only about 30% of the chemical energy ejected through combustion, whereas the remaining part is rejected by means of cooling system and exhausted gas. Nowadays, a major global concern is finding sustainable solutions for better fuel economy which in turn results in a decrease of carbon dioxide (CO2) emissions. The Waste Heat Recovery (WHR) is one of the most promising techniques to increase the overall efficiency of a vehicle system, allowing the recovery of the heat rejected by the exhaust and cooling systems. In this context, Organic Rankine Cycles (ORCs) are widely recognized as a potential technology to exploit the heat rejected by engines to produce electricity. The aim of the present paper is to investigate a WHR system, designed to collect both coolant and exhausted gas heats, coupled with an ORC cycle for vehicle applications. In particular, a coolant heat exchanger (CLT) allows the heat exchange between the water coolant and the ORC working fluid, whereas the exhausted gas heat is recovered by using a secondary circuit with diathermic oil. By using an in-house numerical model, a wide range of working conditions and ORC design parameters are investigated. In particular, the analyses are focused on the regenerator location inside the ORC circuits. Five organic fluids, working in both subcritical and supercritical conditions, have been selected in order to detect the most suitable configuration in terms of energy and exergy efficiencies.

Speciation analysis of Arsenic in fish and rice samples using liquid chromatography-inductively coupled plasma mass spectrometry

Chemical speciation in foodstuffs is of uttermost importance since it is nowadays recognized that both toxicity and bioavailability of an element depend on the chemical form in which the element is present. Regarding arsenic, inorganic species are classified as carcinogenic while organic arsenic, such as arsenobetaine (AsB) or arsenocholine (AsC), is considered less toxic or even non-toxic. Coupling a High Performance Liquid Chromatographer (HPLC) with an Inductively Coupled Plasma Mass Spectrometer (ICP-MS) combines the power of separation of the first with the selectivity and sensitivity of the second. The present work aims at developing a method, using HPLC-ICP-MS technique, to identify and quantify the chemical species of arsenic present in two food matrices, rice and fish. Two extraction methods, ultrasound and microwave, and different settings were studied. The best method was chosen based on recovery percentages. To ensure that no interconversion of species was occurring, individual spikes of each species of arsenic were made in both matrices and recovery rates were calculated. To guaranty accurate results reference material BCR-627 TUNA FISH, containing certified values for AsB and DMA, was analyzed. Chromatographic separation was achieved using an anion exchange column, HAMILTON-PRP X-100, which allowed to separate the four arsenic species for which standards were available (AsB, dimethylarsenic (DMA), arsenite (AsIII), arsenate (AsV). The mobile phase was chosen based on scientific literature and adjusted to laboratory conditions. Different gradients were studied. As a result we verified that the arsenic species present in both matrices were not the same. While in fish 90% of the arsenic present was in the form of arsenobetaine, in rice 80% of arsenic was present as DMA and 20% as inorganic arsenic.

Environmental assessment of proton exchange membrane fuel cell platinum catalyst recycling

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Hybrid Monte Carlo algorithm for the double exchange model

The Hybrid Monte Carlo algorithm is adapted to the simulation of a system of classical degrees of freedom coupled to non self-interacting lattices fermions. The diagonalization of the Hamiltonian matrix is avoided by introducing a path-integral formulation of the problem, in d + 1 Euclidean space–time. A perfect action formulation allows to work on the continuum Euclidean time, without need for a Trotter–Suzuki extrapolation. To demonstrate the feasibility of the method we study the Double Exchange Model in three dimensions. The complexity of the algorithm grows only as the system volume, allowing to simulate in lattices as large as 163 on a personal computer. We conclude that the second order paramagnetic–ferromagnetic phase transition of Double Exchange Materials close to half-filling belongs to the Universality Class of the three-dimensional classical Heisenberg model.