Ribonucleotide Reductases (RNRs) are crucial enzymes that catalyze reduction of ribonucleotides to deoxyribonucleotides, required for the biosynthesis of DNA. Vital role played by RNR in the biosynthesis of DNA and its control on cell growth made it one of the main targets for anticancer therapy. Several laboratories clarified the aspects of reaction cascades at active site of RNR. Biochemical studies of RNR by Stubbe for the inactivation of RDPR by 2'-chloro-2'-deoxyuridine-5'-diphosphate emphasizes departure of chlorine as an anion, while biomimetic studies by Robins with 6'-O-nitro-2'-chloro-homonucleosides emphasizes the elimination of chlorine substituent from 2'-position as a radical. To clarify the ambiguity in the mechanism of inhibition of RNR by 2'-chloro-2'-deoxyuridine, biomimetic reactions with model 6-O-nitro-1,5-dideoxyhomosugar derivatives were investigated. The study includes several modes: (i) synthesis of 6-O-nitro-1,5-dideoxyhomosugar derivatives with chlorine, bromine or tosyl substituent at the C2 position with ribo and arabino configurations, (ii) biomimetic studies of 6-O-nitro-1,5-dideoxyhomosugar derivatives with Bu3SnH/AIBN to provide chemical evidences to distinguish the nature of elimination of chlorine from 2'-chloro-2'-deoxyuridine upon its incubation with enzyme, and (iii) kinetic studies to differentiate between heterolytic or homolytic C2'-chlorine bond cleavage. In the second half of this dissertation, azido and sulfenamide modified nucleosides and 2-azidolyxofuranoside derivatives have been synthesized with the azido or sulfenamide substitution at a specific site in the sugar or in the base moiety. The electron-induced site specific formation of neutral aminyl radicals (RNH●) and their subsequent reactions have been investigated using ESR spectroscopy. In 2'-AZdC the RNH● site is attached to a 2o C-atom, where as in 4'-AZdC, the RNH● site is attached to a 3o C-atom, respectively. These studies elucidated how stereo and electronic environment affect formation and subsequent reactivity of various types of RNH● generated from azidonucleosides. To avoid the interaction of transient radical with nucleoside heterocyclic bases, 2-azidolyxofuranoside derivatives as a simpler abasic model were synthesized and studied with ESR spectroscopy. Aminyl radical generated from 2-azidolyxofuranoside derivatives subsequently abstracted hydrogen from C5 intramolecularly. These studies were designed to understand the mechanism of damage in various DNA model structures.

Orientador: Pascoal José Giglio Pagliuso / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-14T11:11:25Z (GMT). No. of bitstreams: 1 HolandaJunior_LinoMartinsde_M.pdf: 2170608 bytes, checksum: 3abed7533be911b023d90094d4aa28f4 (MD5) Previous issue date: 2009 / Resumo: Nesta Dissertação desenvolvemos estudos de Ressonância de Spin Eletrônico (ESR) em monocristais dos compostos tipo férmions pesados YbR h2Si2 e YbAlB4. No caso do sistem YbRh2Si2, exploraramos os experimentos de ESR para três bandas de frequência existentes em nosso laboratório (n = 4,1 GHz (Banda-S), n = 9,4 GHz (Banda-X) e n = 34,0 GHz (Banda-Q)), o que situa o campo de ressonância da linha de ESR em diferentes regimes do diagrama de fase do YbRh2Si2, onde as fases antiferromagnética (AFM), líquido de Fermi (FL) e não-líquido de Fermi (NFL) podem ser encontradas. Foram investigados efeitos de campo cristalino e mudanças da dinâmica de spin dos elétrons 4¦ do Yb, para as diferentes bandas, e também para monocristais de YbR h2Si2 dopados com Lu e crescidos em uxo de Zn. Nossos resultados sugerem que o sinal de ESR observado em YbRh2Si2 consiste em um modo acoplado entre os 4f do Yb3+ e os elétrons de condução, em um regime tipo bottleneck com presença de interações antiferromagnéticas. Para o sistema YbAlB4, realizamos experimentos de ESR em banda-X nas duas fases iso-estequiométricas b -YbAl B4 e - a -YbAlB4. Para as amostras de b - YbAlB4 encontramos um comportamento interessante do sinal de ESR que apresenta características de uma ressonância de elétrons de condução (CESR) a altas temperaturas e adquire propriedades do íon de Yb3+ a baixas temperaturas. Tal dualidade não foi observada na fase a - YbAlB4. Nós discutiremos uma possível correlação entre o espectro de ESR observado nos dois sistemas férmions pesados que se situam em lados opostos de um ponto crítico quântico (Quantum Critical Point - QCP) em seus diagramas de fase. Essa correlação permitiu uma especulação sobre origem desse sinal de ESR em compostos férmions pesados, na qual a proximidade ao QCP desenvolve um papel crucial para o comportamento do espectro de ESR observado nessa classe de compostos. / Abstract: In this work we have performed Electron Spin Resonance (ESR) experiments on single crystals of YbR h2Si2 and YbAlB4 heavy fermion compounds. For YbRh2Si2, we explore the ESR measurements at three frequency bands (n = 4,1 GHz (S-Band), n = 9,4 GHz (X-Band) e n = 34,0 GHz (Q-Band)) which places the ESR resonance field within different regimes in the phase diagram of YbRh2Si2 where antiferromagnetic (AFM), Fermi liquid (FL) and non Fermi liquid (NFL) phases could be found. We have also explored the effects of crystal field and spin dynamics of Yb3+ for these different bands and also as a function of Lu-doping and single crystal growth methods. Our results indicate that the ESR signal found YbRh2Si2 behave such a Kondo coupled mode in a bottleneck-like regime with the presence of antiferromagnetic interactions. For YbAlB4, we have performed X-band experiments for single crystals the two different phases b -YbAl B4 and a -YbAlB4. For b -YbAlB4, we found a remarkable ESR signal that behaves as a conduction electron spin resonance (CESR) at high temperatures and acquires characteristics of the Yb3+ local moment ESR at low temperature. This behavior was not found in the a -YbAlB4. The striking and unique dual behavior observed in the same ESR spectra of b -YbAl B4 - a -YbAlB4 associated to the ESR results found for a -YbAlB4, YbRh2Si2 allow us to propose a qualitative scenario that may explain the origin of the ESR signal in HF systems. We speculate that for HF systems a strongly coupled 4¦ and ce give origin to Kondo coupled ESR modes with may behave as CESR or LM ESR, depending on the strength of Jfs. Moreover, HF systems near a QCP may have propitious conditions to present such a signal. / Mestrado / Física da Matéria Condensada / Mestre em Física

ESR, OSL and TT-OSL dating methods were applied to samples collected from six of the Ancient Coastal Deposits (ACDs) along the southern Georgia Coastline. Samples were collected from the Princess Anne (the youngest and most seaward ACD), Pamlico, Talbot, Penholoway, Wicomico, and Okefenokee ACDs with the goal of determining the age of formation of these features. Ground Penetrating Radar (GPR) was used to determine the subsurface morphology and target lithologies for age determination. OSL and TT-OSL dating was attempted on samples collected from the youngest two ACDs, the Pamlico and Princess Anne, at McMaster Universities AGE Lab. ESR samples collected from all of the ACDs studied were measured at Florida State University as well as Osaka University. ESR analysis measured the Al signal, the Ti-Li signal, measured using two different methods, as well as the Ti-H signal. A number of low additive dose points were added to the ESR dose plan to attempt to create a better dose response curve for the low saturating Ti-H signal in attempt to better utilize the signal. While the geochronological methodology did not prove useful for determining the age of all of the ACDs it did result in depositional age estimates for the Cypresshead Formation at 433-2978 ka and Satilla Formations at 243-417 ka using the Ti-Li ESR signal as a maximum age estimate. The GPR, ESR, and core data all point to the conclusion that the ACDs of the Georgia Coast are geomorphic modifications and not the result of a unique depositional process. Based on the discrepancy between the depositional age of the Cypresshead and Satilla Formations as determined by ESR in this study and the ages of the ACDs published by others from Georgia (Markewich et.al., 2013) or other areas of the Atlantic Coast (Wehmiller, 2004; Willis, 2006) it can be concluded that paleo sea-levels modified the Cypresshead and Satilla Formations in to the morphology seen today at some point after their initial deposition. / Dissertation / Doctor of Philosophy (PhD) / ESR, OSL and TT-OSL dating methods were applied to samples collected from six of the Ancient Coastal Deposits (ACDs) along the southern Georgia Coastline with the goal of determining the age of formation of these features. Ground Penetrating Radar (GPR) was used to determine the subsurface morphology and target lithologies for age determination. A number of low additive dose points were added to the ESR dose plan to attempt to create a better dose response curve for the low-dose saturation of the Ti-H signal in attempt to better utilize the signal. While the geochronological methodology did not prove useful for determining the age of all of the ACDs, it did result in depositional age estimates for the Cypresshead Formation at 433-2978 ka and Satilla Formations at 243-417 ka. The GPR, ESR, and core data all point to the conclusion that the ACDs of the Georgia Coast are geomorphic features without unique depositional events.

<p> The recent urban sprawl in the tectonically active region of California has prompted palaeoseismologists, to find ways of forecasting potentially hazardous earthquakes on existing faults. Electron spin resonance (ESR) can be used to date fault gouge from different regions in a fault zone thereby providing a history of fault movements in a particular region. Therefore, an earthquake frequency pattern can be established and the faults can be rated as to their potential danger. </p> <p> ESR dating of fault gouge is based on the premise that the ESR signals of quartz grains in the gouge have been completely reset by movements on the fault. The elapsed time since faulting is recorded by a gradual charge build up in the quartz corresponding to radioactive decay of radionuclides in the fault gouge matrix. The mechanism of zeroing of the ESR signals in quartz during fault activity is not well understood. In order to better comprehend the zeroing process, the variation of ESR signals, AD and age, with respect to quartz grains size were studied. These parameters are affected by induced stress to a greater extent in the smaller grain sizes. Therefore, with sufficient stress, the smallest grain sizes (smaller than a critical size) will be totally reset and define a "plateau" of equal age. This plateau criteria is used to define total resetting in a fault gouge sample and only these portions of the samples are used for dating. The establishment of an equal age plateau is confirmed for one of the fault samples collected from Southern California. </p> / Thesis / Master of Science (MS)

Quantum mechanics has a long history of helping computer science. For a long time, it provided help only at the hardware level by giving a better understanding of the properties of matter and thus allowing the design of ever smaller and ever more efficient components. For the last few decades, much research has been dedicated to finding whether one can change computer science even more radically by using the principles of quantum mechanics at both the hardware and algorithm levels. This field of research called Quantum Information Processing (QIP) has rapidly seen interesting theoretical developments: it was in particular shown that using superposition of states leads to computers that could outperform classical ones. The experimental side of QIP however lags far behind as it requires an unprecedented amount of control and understanding of quantum systems. Much effort is spent on finding which particular systems would provide the best physical implementation of QIP concepts. Because of their nearly endless versatility and the high degree of control over their synthesis, organic materials deserve to be assessed as a possible route to quantum computers. This thesis studies the QIP potential of spin degrees of freedom in several such organic compounds. Firstly, a study on low-spin antiferromagnetic rings is presented. It is shown that in this class of molecular nanomagnets the relaxation times are much longer than previously expected and are in particular long enough for up to a few hundred quantum operations to be performed. A detailed study of the relaxation mechanisms is presented and, with it, routes to increasing the phase coherence time further by choosing the suitable temperature, isotopic and chemical substitution or solvent. A study of higher-spin systems is also presented and it is shown that the relaxation mechanisms are essentially the same as in low-spin compounds. The route to multi-qubit system is also investigated: the magnetic properties of several supermolecular assemblies, in particular dimers, are investigated. Coupling between neighbouring nanomagnets is demonstrated and experimental issues are raised concerning the study of the coherent dynamics of dimers. Finally a study of the purely organic compound phenanthrene is reported. In this molecule the magnetic moment does not result from the interactions between several transition metal ions as in molecular nanomagnets but from the photoexcitation of an otherwise diamagnetic molecule. The interest of such a system in terms of QIP is presented and relaxation times and coupling to relevant nuclei are identified.

Condensed matter systems exhibit a variety of dynamical phenomena at low energy scales, from gigahertz (GHz) to terahertz (THz) frequencies in particular, arising from complex interplay between charge, spin, and lattice. A large number of collective and elementary excitations in solids occur in this frequency range, which are further modified and enriched by scattering, interactions, and disorder. Recent advancements in spectroscopic methods for probing low-energy dynamics allow us to investigate novel aspects of charge and spin dynamics in solids. In this dissertation work, we used direct current (DC) conductivity, GHz, THz, and mid-infrared (MIR) techniques to provide significant new insights into interaction and disorder effects in low-dimensional systems. Specifically, we have studied temperature-dependent magnetoresistance (MR) and electron spin resonance (ESR) in single-wall carbon nanotubes (SWCNTs), intra-exciton scattering in InGaAs quantum wells, and high-field MIR-induced band gaps in graphene. Temperature-dependent resistance and MR were measured in an ensemble of SWCNTs from 0.3 to 350 K. The resistance temperature behavior followed a 3D variable range hopping (VRH) behavior from 0.3 to ~100 K. A positive MR was observed at temperatures above 25 K and could be fit with a spin-dependent VRH model; negative MR was seen at low temperatures. In the GHz regime, the ESR linewidth for SWCNTs was observed to narrow by as much as ~50% as the temperature was increased from 3 to 300 K, a phenomenon known as motional narrowing, suggesting that we are detecting the ESR of hopping spins. From the linewidth change versus temperature, we find the hopping frequency to be 285 GHz. For excitons in InGaAs quantum wells, we demonstrate the manipulation of intra-excitonic populations using intense, narrow-band THz pulses. The THz radiation temporarily quenches the 1s emission, which is then followed by an enhancement and subsequent decay of 2s emission. After the quenching, the 1s emission recovers and then eventually becomes enhanced, a demonstration of energy storage in intra-exciton states known as excitonic shelving. We show that the diffusive Coulomb scattering between the 2p and 2s states produces a symmetry breaking, leading to a THz-field-induced 1s-to-2s exciton population transfer.

Thesis (Ph. D.)--West Virginia University, 2002. / Title from document title page. Document formatted into pages; contains xi, 121 p. : ill. (some col.). Includes abstract. Includes bibliographical references (p. 113-115).

Electron spin resonance (ESR) experiments are used to assess the possibilities for processing quantum information in the electronic and nuclear spins of endohedral fullerenes. It is shown that ¹⁵N@C₆₀ can be used for universal two-qubit quantum computing. The first step in this scheme is to initialize the nuclear and electron spins that each store one qubit. This was achieved with a magnetic field of 8.6 T at 3 K, by applying resonant RF and microwave radiation. This dynamic nuclear polarization technique made it possible to show that the nuclear T₁ time of ¹⁵N@C₆₀ is on the order of twelve hours at 4.2 K. The electronic T₂ is the limiting decoherence time for the system. At 3.7 K, this can be extended to 215 μs by using amorphous sulphur as the solvent. Pulse sequences are described that could perform all single-qubit gates to the two qubits independently, as well as CNOT gates. After these manipulations, the value of the qubits should be measured. Two techniques are demonstrated for this, by measuring the nuclear spin. Sc@C₈₂ could also be useful for quantum computation. By comparing ESR measurements with density functional theory calculations, it is shown how the orientation of a Sc@C₈₂ molecule in an applied magnetic field affects the molecule's Zeeman and hyperfine coupling. Hence the g- and A-tensors are written in the coordinate frame of the molecule. Pulsed ESR measurements show that the decoherence time at 20 K is 13 μs, which is 20 times longer than had been previously reported. Carbon nanotubes have been filled with endohedral fullerenes, forming 1D arrays that could lead to a scalable quantum computer. N@C₀₆ and Sc@C₈₂ have been used for this filling in various concentrations. ESR measurements of these samples are consistent with simulations of the dipolar coupling.

The research in low-dimensional (low-D) quantum spin systems has become an arduous challenge for the condensed matter physics community during the last years. In systems with low dimensional magnetic interactions the exchange coupling is restricted to dimensions lower than the full three-D exhibited by the bulk real material. The remarkable interest in this field is fueled by a continuous stream of striking discoveries like superconductivity, quantum liquid and spin gap states, chiral phases, etc, derived from the strong effect of quantum fluctuations on the macroscopic properties of the system and the competition between electronic and magnetic degrees of freedom. The main goal of the current studies is to reach a broad understanding of the mechanisms that participate in the formation of those novel ground states as well as the characteristic dependence with respect to relevant physical parameters. In this thesis we present the results of an Electron Spin Resonance (ESR)-based study on different quasi-1D spin systems, exemplifying the realization of 1D-magnetic spin-chains typically containing transition metal oxides such as Cu2+ or V4+. The local sensitivity of the ESR technique has been considered useful in exploring magnetic excitation energies, dominant mechanisms of exchange interactions, spin fluctuations and the dimensionality of the electron spin system, among others. Aside from ESR other experimental results, e.g., magnetization and nuclear magnetic resonance besides some theoretical approaches were especially helpful in achieving a proper understanding and modeling of those low-D spin systems. This thesis is organized into two parts: The first three chapters are devoted to the basic knowledge of the subject. The first chapter is about magnetic exchange interactions between spin moments and the effect of the crystal field potential and the external magnetic field. The second chapter is a short introduction on exchange interactions in a 1D-spin chain, and the third chapter is devoted to ESR basics and the elucidation of dynamic magnetic properties from the absorption spectrum parameters. The second part deals with the experimental results. In the fourth chapter we start with the magnetization results from the zero-dimensional endohedral fullerene Dy3N@C80. This system is seemingly ESR “silent” at the frequency of X-band experiments. The fifth chapter shows an unexpected temperature dependence of the anisotropy in the homometallic ferrimagnet Na2Cu5Si4O14 containing alternating dimer-trimer units in the zig-zag Cu-O chains. In the sixth chapter different magnetic species in the layer structure of vanadium oxide nanotubes (VOx-NT) have been identified, confirming earlier magnetization measurements. Moreover the superparamagnetic-like nature of the Li-doped VOx-NT samples was found to justify its ferromagnetic character at particular Li concentration on the room temperature scale. In the seventh chapter the Li2ZrCuO4 system is presented as a unique model to study the influence of additional interactions on frustrated magnetism. The eighth chapter highlights the magnetic properties of the pyrocompound Cu2As2O7. The results suggest significant spin fluctuations below TN. The thesis closes with the summary and the list of references.

Orientador: Prof. Dr. Marcos Abreu Avila / Tese (doutorado) - Universidade Federal do ABC, Programa de Pós-Graduação em Física, 2017. / The electronic correlations originated from the Coulomb interactions between electrons play a fundamental role in the establishment of the physical properties of a wide range of materials. For the case of weak correlations, the material can be described within a simplied non-interacting point of view, as in the case of standard metals. Unexpected and intriguing properties are revealed when strong correlations are involved, due to a large number of degrees of freedom in the electronic correlations. As a result of this electronic correlation, it is possible to go from conventional forms of magnetism, passing through superconducting systems and reaching heavy fermion behavior. Members within a single family of compounds can provide all those very dierent ground states, and the opportunity to study and try to understand some of the electronic and magnetic fundamental interactions involved. This thesis is a result of exploring these dierent behaviors that arise from electron-electron correlations, specically in the family of cage compounds RT2Zn20 (R=Y,Gd,Yb and T=Fe,Co). A detailed combination of quantitative macroscopic and microscopic descriptions of the electronic, thermodynamic and magnetic properties of some members of this family were developed. The rst part of this thesis presents a study on Gd3+- doped YCo2Zn20 single crystals (Y1..xGdxCo2Zn20: (0.002 . x 1.00) through a combination of temperature-dependent Electron Spin Resonance (ESR), heat capacity and dc magnetic susceptibility experiments, plus collaborative rst-principles Density Functional Theory (DFT) calculations. The combination of experimental and electronic structure data establish GdCo2Zn20 as a model Ruderman-Kittel-Kasuya-Yosida (RKKY) system by predicting a Curie-Weiss temperature C = ..1:2(2) K directly from microscopic parameters, in very good agreement with the bulk value from magnetization data. The second part involves an exploration of the unconventional ferromagnetic behaviors that have been found in GdFe2Zn20, which has a relatively high ferromagnetic ordering temperature (TC = 86 K) despite being a system with wide separation between Gd3+ ions in a matrix with strong electron-electron correlation. Taking into account those correlations and itinerant molecular eld eects, analysis of our ESR results indicate that the exchange interaction between the Gd3+ is processed via the d-type of electrons at the Fermi level and becomes an exchange interaction of covalent nature (J(0)fd < 0). Our results shows that the RKKY model cannot explain the ferromagnetic behavior of this compound, and a super-exchange-like mechanism is proposed for this magnetic interaction. Increasing a little bit the level of complexity, the third part of this thesis is on the tuning of the electronic properties of the heavy fermion compound YbFe2Zn20 by chemical substitution (Cd doping). With increasing amount of Cd, the hybridization between Yb 4f electrons and the conduction electrons is weakened, which should be accompanied by a valence shift of the Yb3+ due to the negative chemical pressure eect. The combined results demonstrate excellent complementarity between positive physical pressure and negative chemical pressure, and point to a rich playground for exploring the physics of strongly correlated electron systems. Finally, this thesis ends with a general set of conclusions of the explored quantum materials.