Photo-CIDNP study of the splitting of the dinucleotidecis,syn-thymine dimer with reduced flavin as a sensitizer: Evidence for a thymine radical anion intermediate

Photochemically induced dynamic nuclear polarization (photo-CIDNP) studies were performed on the splitting ofcis,syn 2′-deoxythymidylyl-(3′→5′)-2′-deoxythymidine cyclobutane dimer (cs-dTp dT), using reduced flavin as a sensitizer. This system serves as a model for the light-induced repair mechanism of thymine dimers in DNA by the enzyme photolyase. The CIDNP spectrum shows enhanced absorption of the two C6-H protons of the corresponding monomer dTpdT, which demonstrates that a thymine radical anion is involved in the splitting of the dimer. This is supported by a similar CIDNP spectrum that is obtained with the electron-donorN _α-acetyl tryptophan as a sensitizer. This result suggests that the light-induced splitting of thymine dimers in DNA by photolyase also proceedsvia the thymine radical anion. The small difference in intensity of the two CIDNP signals belonging to the C6-H protons shows that the unpaired electron in the monomer radical has a slight preference for the thymine moiety at the 5′ terminus.     

Baryonium, tetraquark state and glueball in large-Nc QCD

From the large- QCD point of view, baryonia, tetraquark states, hybrids, and glueballs are studied. The existence of these states is argued for. They are constructed from baryons. In large- QCD, a baryonium is always identical to a glueball with valence gluons. The ground state glueball has a mass of about 2450 MeV. is identified as the lowest glueball. The lowest four-quark nonet should be , , and . Combining with the heavy quark effective theory, spectra of heavy baryonia and heavy tetraquark states are predicted. corrections are discussed. PACS 12.39.Mk; 14.20.-c; 12.38.Lg     

Relative coarse-graining

The problem of statistical inference based on a partial measurement (coarse-graining) requires the specification of an a priori distribution. We reformulate the ordinary theory such as to encompass systematically a wide range of a priori distributions (relative coarse-graining). This is done in a mathematical setting which admits an interpretation in both classical probability and quantum mechanics. The formalism is illustrated in a few simple examples, such as the die whose geometrical shape is known, the spin in thermal equilibrium with an unknown reservoir, and the position measurement of a one-dimensional particle. It is shown that some of the limitations of the usual theory are a consequence of the fact that it is restricted to equidistributed (symmetric) a priori states.     

Statistical analysis of DNA duplex structures in solution derived by high resolution NMR

An initial statistical analysis has been performed on the helical parameters for the solution structures of three DNA duplexes recently solved in this laboratory by proton NMR. Local conformations in these structures belong to the B family of forms; nevertheless they display a strong sequence-dependent heterogeneity akin to that found in single crystals and by theoretical calculations. However, average helical parameters as well as their variations are quite different for short DNA fragments in solution and in crystal. Average helical twist in three NMR-refined oligonucleotides is 34.6°, in remarkable agreement with independent solution-state data, while helical twist is 36° for DNA in crystals. Other characteristic features of solution DNA conformations are negative slide, systematically open minor groove (for almost all sequences), and decreased helical rise. The latter, rather unexpected finding, is correlated with a surprisingly strong non-flatness of Watson-Crick base pairs. Deviations of base pairs from planarity proved to be a significant source of conformational variability; of particular importance is base stagger, which is often missed in structural analysis of DNA. Several new structural parameters have been introduced for dinucleotide steps, characterizing non-planar geometries of constituent base pairs; these parameters show a significant degree of correlation with traditional step parameters (twist, tillt roll, shift, slide, rise). Many sequence-dependent features are observed in solution structures; variation of roll and slide parameters occurs according to “Calladine’s rules”, while variation of helical twist appears to oppose them. However, a larger set of solution structures is needed to complete the analysis of sequence dependence of DNA conformation.     

Observation of broad EPR spectra of transient free radicals by FT-EPR

Application of electron spin echo Fourier transform EPR (ESE-FT-EPR) to photo-induced chemical reactions is presented. Main purpose of this study is to observe broad EPR spectra of free radicals having very shortT ₂ ^* by means of the ESE-FT-EPR technique. Details of the experimental procedures are described. In ESE experiments design of the resonator is important to obtain sufficient spectral bandwidth because of use of multiple pulses which decrease the bandwidth. We designed and constructed Loop-Gap-Resonantors (LGR) for light irradiation experiments and their specifications were examined. The phase cycling method is essential to obtain pure ESE signals and proper time resolution by eliminating unwanted FID signals which result from imperfect pulse angles. We applied this technique to observe the photo-induced electron transfer reaction between tetraphenylporphinato zinc(II) (ZnTPP) and duroquinone (DQ) in an ethanol solution, and successfully observed the time resolved EPR spectra of the both Zn(TPP) cation and DQ anion radicals by ESE-FT-EPR of the Hahn echo. The half-height full-width of envelope of EPR spectrum of Zn(TPP)⁺, which is never observed in ordinary FT-EPR, is about 16 MHz. Specificity of spectra and the time resolution are compared among the ESE-FT-, FT- and cw-Time-Resolved-EPR (cw-TREPR) techniques.     

Nucleic acid spin labeling study of interaction between polyadenylic acid: Polyuridilic acid duplex and egg phosphatidylcholine vesicles. Involvement of terminal and internal nucleotides and sugar-phosphate backbone

Model DNA-membrane contacts were studied in the system containing polyadenylic acid (polyA): polyuridilic acid (polyU) duplex and egg phosphatidylcholine (PC) vesicles without or in the presence of MgCl₂. PolyU containing O-(1-oxyl-2,2,5,5-tetramethylpyrroline-3-carbonyl) spin label at 2′-OH moiety was used for spin labeling study of nucleic acid-phospholipid interactions. For polyA labeled with the same nitroxyl radical EPR spectra from spin labels attached at terminal and at internal nucleotide units contribute into the EPR spectrum of d.s. polynucleotide without or in the presence of egg PC vesicles and Mg ions. Internal spin labels are more sensitive to the interaction with PC-MLV than terminal ones. The complexation between s.s. polynucleotide and PC-MLV was shown. The values of spin labels’ melting temperature of polyA: SL-polyU duplex at 1 mM MgCl₂ reflect the changes in rotational mobility of terminal spin labels connected with duplex→triplex transition. Arrhenius plots of temperature dependence of EPR spectra parameters prove that ribose moieties of sugarphosphate backbone are involved into the interaction between polynucleotide duplex and phospholipid bilayer. Egg PC vesicles demonstrate stabilizing effect on polyA: polyU duplex at 1 mM of Mg²⁺ and destabilizing effect at 5 mM Mg²⁺.     

Axiomatic unsharp quantum theory (From Mackey to Ludwig and Piron)

On the basis of Mackey's axiomatic approach to quantum physics or, equivalently, of a state-event-probability (SEVP) structure, using a quite standard fuzzification procedure, a set of unsharp events (or effects) is constructed and the corresponding state-effect-probability (SEFP) structure is introduced. The introduction of some suitable axioms gives rise to a partially ordered structure of quantum Brouwer-Zadeh (BZ) poset; i.e., a poset endowed with two nonusual orthocomplementation mappings, a fuzzy-like orthocomplementation, and an intuitionistic-like orthocomplementation, whose set of sharp elements is an orthomodular complete lattice. As customary, by these orthocomplementations the two modal-like necessity and possibility operators are introduced, and it is shown that Ludwig's and Jauch-Piron's approaches to quantum physics are interpreted in complete SEFP. As a marginal result, a standard procedure to construct a lot of unsharp realizations starting from any sharp realization of a fixed observable is given, and the relationship among sharp and corresponding unsharp realizations is studied.     

Inosine — Adenosine base pairing in d-GGTACIAGTACC: Duplex and hairpin with a two-base loop

An oligonucleotide dodecamer d-GGTACIAGTACC containing two inosine-adenosine mismatched base-pairs has been studied by¹H and³¹P NMR spectroscopy. Unique assignments of¹H and³¹P spins have been achieved by using a recently proposed two-dimensionalheteronuclearlong rangecorrelation (2D-HELCO) technique. The 2D nuclear Overhauser enhancement spectroscopy (NOESY) spectrum recorded in a mixed solvent of 90% H₂O+10%²H₂O has been used to assign all the exchangeable imino and amino proton resonances. NMR results indicate that at concentrations above 5 mM, the molecule adopts a duplex structure where the inosine imino protons are hydrogen bonded. Cross-strand NOEs between the imino proton of I6 and H2 proton of A7 and that between H2 of I6 and H2 of A7 provide evidence for inosine-adenosine base-pairing, with both bases I6 and A7 inanti conformation. The observed NOE connectivitiesd1,d2 andd3 from almost the middle of the molecule to the two ends are consistent with a right handed B-DNA conformation. However, the molecule adopts a more extended conformation in the mismatch region to accomodate the bulky purine-purine (IA) base pairs. NMR experiments at lower concentrations indicate the coexistence of a monomeric hairpin with a two base loop, consisting of I6 and A7 units, in equilibrium with the duplex. 2D-ROESY experiment at such a concentration shows that the conformation of the stem of the hairpin does not deviate much from the corresponding region of the duplex and four nucleotides C5, I6, A7 and G8 undergo significant structural changes during the formation of hairpin loop.     

Interactions between polyamines and nucleotides studied by31P and1H NMR

The formation of complexes between poly- and mono-amines and some polyphosphate molecules such as ATP, ADP and tripolyphosphate was studied by³¹P and¹H NMR. Evidence for formation of complexes was obtained by¹H NMR, while the values of dissociation constants of the complexes between nucleotides and spermine and spermidine, calculated from the shift of the³¹P NMR, were in mM range.     

Nano-structured oriented carbon films grown by PLD and CVD methods

PLD and CVD methods, plasma or bias assisted, have been used to prepare thin films of nano-clustered graphite. The experimental conditions (vz. deposition apparatus, substrate temperature, working pressure, inert sustaining gases, parent species, and applied voltage) have been changed with the final aim of obtaining small graphene particles with the basal planes oriented along the growth vector and perpendicular to the n-Si100 substrate. Pulsed laser ablation (Nd:YAG, 2nd harmonic: =532 nm, h=2.33 eV, =7 ns, =10 Hz, 7 J/cm²), assisted by an RF-plasma, of a pyrolytic graphite target gave good results for nano-structure formation, provided high substrate temperature and high inert gas pressure are maintained. CVD methods, in the presence of high substrate temperature and a DC bias, showed a good attitude to drive a longitudinal growth of graphene layers and nano-wires from a reactive gas flow of Argon/Hydrogen and Methane. The morphology of the films grown at different conditions have been characterised by scanning electron microscopy (SEM). Film quality and nano-particle dimensions have been estimated by Raman spectroscopy. PACS 81.07.-b; 81.15.-z; 78.30.-j; 68.37.-d     

Electron spin polarization of doublet state species due to interaction with excited triplet states in single crystals

Doublet states species trapped in crystalline solids show transient spin polarized EPR spectra if the crystal is illuminated by visible or UV light. The spin polarization is accounted for by the interaction of the doublet species with photoexcited triplet states. The mechanism of the process producing the spin polarization is examined and some experimental examples are discussed. The analysis of the time evolution of the transient variation of the EPR signal allows the measurements of the spin lattice relaxation time and in some cases of the diffusion rate of mobile triplet excitations in the crystal lattice.     

ESR and ESR microscopy in geosciences and radiation dosimetry

ESR and its microscopic imaging (microscopy) have found new applications in interdisciplinary fields related with geosciences and with radiation dosimetry. Geological, archaeological and forensic dating has been made through paleo-dosimetry of natural radiation and chemical reactions of both radical formation and valency changes. ESR microscopy, especially the simple scanning method has a potentiality to be used in various fields. New applications of ESR are briefly reviewed with some examples.     

Critical (Φ4)3,ε

The Euclidean (⁴)_3, model in R³ corresponds to a perturbation by a ⁴ interaction of a Gaussian measure on scalar fields with a covariance depending on a real parameter in the range 01. For =1 one recovers the covariance of a massless scalar field in R³. For =0, ⁴ is a marginal interaction. For 0<1 the covariance continues to be Osterwalder-Schrader and pointwise positive. We consider the infinite volume critical theory with a fixed ultraviolet cutoff at the unit length scale and we prove that for >0, sufficiently small, there exists a non-gaussian fixed point (with one unstable direction) of the Renormalization Group iterations. We construct the stable critical manifold near this fixed point and prove that under Renormalization Group iterations the critical theories converge to the fixed point. Partially supported by NSERC of CanadaLaboratoire Associé au CNRS. UMR 5825Partially supported by CNR, G.N.F.M. and MURST     

Transquantum Dynamics

Segal proposed transquantum commutation relations with two transquantum constants , besides Planck's quantum constant and with a variable i. The Heisenberg quantum algebra is a contraction—in a more general sense than that of Inönü and Wigner—of the Segal transquantum algebra. The usual constant i arises as a vacuum order-parameter in the quantum limit ,0. One physical consequence is a discrete spectrum for canonical variables and space-time coordinates. Another is an interconversion of time and energy accompanying space-time meltdown (disorder), with a fundamental conversion factor of some kilograms of energy per second.     

Atomic versus ionized states in many-particle systems and the spectra of reduced density matrices: A model study

We study the spectrum of appropriate reduced density matrices for a model consisting of one quantum particle (electron) in a classical fluid (of protons) at thermal equilibrium. The quantum and classical particles interact by a shortrange, attractive potential such that the quantum particle can form atomic bound states with a single classical particle. We consider two models for the classical component: an ideal gas and the cell model of a fluid. We find that when the system is at low density the spectrum of the electron-proton pair density matrix has, in addition to a continuous part, a discrete part that is associated with atomic bound states. In the high-density limit the discrete eigenvalues disappear in the case of the cell model, indicating the existence of pressure ionization or a Mott effect according to a general criterion for characterizing bound and ionized electron-proton pairs in a plasma proposed recently by M. Girardeau. For the ideal gas model, on the other hand, eigenvalues remain even at high density.     

Phonon assisted quantum diffusion in a periodic potential

We study the diffusion of a quantum heavy particle moving in a one dimensional strongly corrugated periodic potential, and interacting with a phonon bath.By integrating out the phonons degrees of freedom we derive an effective action functional for the particle, which includes a non-local self-interacting term whose strength is proved to be the classical friction coefficient .Using an instanton approach we express the velocity-velocity correlation function, and thus the mobility, of the brownian particle in terms of the charge density-density correlation function of a classical Coulomb gas, which in the strong corrugation limit has a very low fugacity.By making a virial expansion in the gas fugacity we evaluate the static mobility of the brownian particle as a function of the temperature, and we find two different behaviours: a diffusive behaviour at low friction, where decreases withT, and a localised behaviour at high friction, where increases withT.The cross-over between the two régimes takes place at a critical friction ₀, corresponding to the Kosterlitz-Thouless transition for the Coulomb gas.     

Where Is a Singer''s Voice if It Is Placed “Forward”?

Singing teachers sometimes characterize voice quality in terms of "forward" and "backward" placement. In view of our traditional knowledge about voice production it is hard to explain any possible acoustic or articulatory differences between the voices so "placed." The analysis of the teachers' expert opinions demonstrates that, in general, a voice placed "forward" indicates a desirable quality that students should attain by the end of their studies. Productions that were perceived as "forward" and "backward" were selected from the listening test. The acoustic analysis of those productions reveals that the voice quality in the case of "forward" placement correlates with higher frequencies of the second (F2) and third (F3) formants, as well as with a more salient "singer's formant" in the voice. The five basic vowels were included in the investigation.     

c = 2 Rational Toroidal Conformal Field Theories via the Gauss Product

We find a concise relation between the moduli , of a rational Narain lattice (,) and the corresponding momentum lattices of left and right chiral algebras via the Gauss product. As a byproduct, we find an identity which counts the cardinality of a certain double coset space defined for isometries between the discriminant forms of rank two lattices.     

A dimension formula for Bernoulli convolutions

We present a dynamical approach to the study of the singularity of infinitely convolved Bernoulli measuresv , for the golden section. We introducev as the transverse measure of the maximum entropy measure on the repelling set invariant for contracting maps of the square, the fat baker's transformation. Our approach strongly relies on the Markov structure of the underlying dynamical system. Indeed, if =golden mean, the fat baker's transformation has a very simple Markov coding. The ambiguity (of order two) of this coding, which appears when projecting on the line, due to passages for the central, overlapping zone, can be expressed by means of products of matrices (of order two). This product has a Markov distribution inherited by the Markov structure of the map. The dimension of the projected measure is therefore associated to the growth of this product; our dimension formula appears in a natural way as a version of the Furstenberg-Guivarch formula. Our technique provides an explicit dimension formula and, most important, provides a formalism well suited for the multifractal analysis of this measure, as we will show in a forthcoming paper.     

Stationary solutions of the bogoliubov hierarchy equations in classical statistical mechanics. 3

We continue the analysis of the conjugate equation for the generating function of a Gibbs random point field corresponding to a stationary solution of the classical BBGKY hierarchy. This equation was established and partially investigated in the preceding papers under the same title. In the present paper we reduce a general theorem about the form of solutions of the conjugate equation to a statement which relates to a special case where the interacting particles constitute a quasi—one dimensional configuration.