NMR study of the dissolution of laser-polarized xenon

NMR of laser-polarized xenon is used to probe the dissolution behaviour of the noble gas in different liquids. The dissolution and self-relaxation rates are extracted via a macroscopic model, and comparison of the decay rate of the xenon magnetization in deuterated and non-deuterated solvent pairs allows the determination of the pure dipole-dipole contribution to relaxation. A transient convective effect, tentatively assigned to the xenon concentration gradient, is observed and characterized by diffusion encoding MRI experiments. The flow of xenon penetrates inside the solvent near the walls of the NMR tube, the longitudinal images showing a “” shape, the transverse ones a “O” shape. This convection effect has implications for delivery conditions of laser-polarized xenon in continuous flow experiments and magnetic resonance imaging. Received 29 April 2002 / Received in final form 26 July 2002 Published online 22 October 2002 RID="a" ID="a"e-mail: hdesvaux@cea.fr RID="b" ID="b"URA CNRS/CEA 331     

Perturbative and nonperturbative processes in adiabatic population transfer

With the help of superadiabatic techniques for quantum systems depending slowly on time, we demonstrate how the total transition amplitude, tracked in time in the usual adiabatic basis, can be decomposed into a perturbative part consisting of terms proportional to powers of the adiabaticity parameter, and a nonperturbative component. The interference of both components underlies the oscillations that accompany transitions in the adiabatic basis. Whereas for traditionally considered systems the final nonadiabatic transition probability is determined by the nonperturbative part alone, this is no longer correct for models describing stimulated Raman adiabatic passage (STIRAP). We explain the recently discovered breakdown of the Dykhne-Davis-Pechukas formula on general grounds, and provide simple, but accurate approximations for transition amplitudes in STIRAP systems. Received: 22 January 1998 / Revised: 17 March 1998 / Accepted: 31 March 1998     

Investigation of magneto-optical effect in transverse magnetic field in He

The non-linear Voigt effect has been studied in He discharge under resonance laser interaction with the He transition. The range of non-linear signal existence was determined. The contribution of the lower and upper states to the overall signal was analyzed. The cross-section for depolarizing collisions with ground state He atoms was estimated for the 3³ D _2,3 He state. Received: 16 June 1998 / Received in final form: 14 December 1998     

Adiabatic population transfer in multistate chains via dressed intermediate states

The well-known process of stimulated Raman adiabatic passage (STIRAP) provides a robust technique for achieving complete population transfer between the first and last state of a three-state chain, with little population, even transiently, in the intermediate state. The extension of STIRAP to general N-state chainwise-linked systems continues to generate interest. Recently Malinovsky and Tannor (Phys. Rev. A 56, 4929 (1997)) have shown with numerical simulation that a resonant pulse sequence, which they term “straddle STIRAP”, can produce (under appropriate conditions, including specific pulse areas) complete population transfer with very little population in intermediate states. Their proposal supplements a pair of counterintuitively ordered delayed laser pulses, driving the first and last transition of the chain and corresponding to the pump and Stokes pulses in STIRAP, with one or more additional strong pulses of longer duration which couple the intermediate transition(s) and overlap both the pump and the Stokes pulses. In this paper, we modify the “straddling” Malinovsky-Tannor pulse sequence so that the intermediate couplings are constant (and strong), at least during the times when the pump and Stokes pulses are present, and the intermediate states therefore act as a strongly coupled subsystem with constant eigenvalues. Under this condition, we show that the original N-state chain is mathematically equivalent to a system comprising N-2 parallel -transitions, in which the initial state is coupled simultaneously to N-2 dressed intermediate states, which in turn are coupled to the final state. The population transfer is optimized by suitably tuning the pump and Stokes frequencies to resonance with one of these dressed intermediate states, which effectively acts as the single intermediate state in a three-state STIRAP-like process. We show that tuning to a dressed intermediate state turns the system (for both odd N and even N) into a three-state system - with all of the properties of conventional STIRAP (complete population transfer, little transient population in the intermediate states, insensitivity to variations in the laser parameters, such as pulse area). The success of the tuning-to-dressed-state idea is explained by using simple analytic approaches and illustrated with numerical simulations for four-, five-, six- and seven-state systems. Received: 17 April 1998 / Accepted: 15 June 1998     

Slow nucleic acid unzipping kinetics from sequence-defined barriers

Recent experiments on unzipping of RNA helix-loop structures by force have shown that ≈40-base molecules can undergo kinetic transitions between two well-defined “open” and “closed” states, on a timescale ≈1 sec [Liphardt et al., Science 297, 733-737 (2001)]. Using a simple dynamical model, we show that these phenomena result from the slow kinetics of crossing large free energy barriers which separate the open and closed conformations. The dependence of barriers on sequence along the helix, and on the size of the loop(s) is analyzed. Some DNA and RNA sequences that could show dynamics on different time scales, or three(or more)-state unzipping, are proposed. Our dynamical model is also applied to the unzipping of long (kilo-basepair) DNA molecules at constant force. Received 29 July 2002 / Received in final form 5 February 2003 Published online: 16 April 2003 RID="a" ID="a"e-mail: cocco@ldfc.u-strasbg.fr RID="b" ID="b"e-mail: jmarko@uic.edu RID="c" ID="c"e-mail: monasson@lpt.ens.fr     

Log-periodic oscillations for biased diffusion of a polymer chain in a porous medium

A coarse-grained off-lattice bead-spring model is used to reveal the complex dynamics of a polymer chain in a quenched porous medium in the presence of an external field B. The behavior of the mean square displacement (MSD) of the center chain bead and that of the center of mass of the chain as a function of time is studied at different values of the barrier concentration C, the field strength B and the chain length N. In a field, important information on the way in which chains move between obstacles and overcome them is gained from the MSD vs. time analysis in the directions parallel and perpendicular to the flow. Instead of a steady approach to uniform drift-like motion at low C, for sufficiently strong field B we observe logarithmic oscillations in the effective exponents describing the time dependence of the MSD along and perpendicular to field. A common nature of this phenomenon with oscillatory behavior, observed earlier for biased diffusion of tracers on random lattices, is suggested. Received 7 August 1998     

Route to and from the NMR chaos in diamagnets

The route to and from the chaos via period doubling bifurcations in nuclear spin system with dipole-dipole interactions is investigated. The transition points are found. It is shown that route from the chaos proceeds according the Feigenbaum scenario. Received 19 August 1998 and Received in final form 15 December 1998     

Mechanical detection of nuclear spin relaxation in a micron-size crystal

A room temperature nuclear magnetic resonance force microscope (MRFM), fitted in a 1 tesla electromagnet, has been used to measure the nuclear spin relaxation of ¹H in a micron-size (70 ng) crystal of ammonium sulfate. NMR sequences, combining both pulsed and continuous wave radio-frequency fields, have allowed us to measure mechanically T₂ and T₁, the transverse and longitudinal spin relaxation times. Because two spin species with different T₁ values are measured in our 7 μm thick crystal, magnetic resonance imaging of their spatial distribution inside the sample section have been performed. To understand quantitatively the measured signal, we carefully study the influence of spin-lattice relaxation and non-adiabaticity of the continuous-wave sequence on the intensity and time dependence of the detected signal. Received 23 February 2000     

Localization properties of electronic states in a polaron model of poly(dG)-poly(dC) and poly(dA)-poly(dT) DNA polymers

We numerically investigate localization properties of electronic states in a static model of poly(dG)-poly(dC) and poly(dA)-poly(dT) DNA polymers with realistic parameters obtained by quantum-chemical calculation. The randomness in the on-site energies caused by the electron-phonon coupling is completely correlated to the off-diagonal parts. In the single electron model, the effect of the hydrogen-bond stretchings, the twist angles between the base pairs and the finite system size effects on the energy dependence of the localization length and on the Lyapunov exponent are given. The localization length is reduced by the influence of the fluctuations in the hydrogen bond stretchings. It is also shown that the helical twist angle affects the localization length in the poly(dG)-poly(dC) DNA polymer more strongly than in the poly(dA)-poly(dT) one. Furthermore, we show resonance structures in the energy dependence of the localization length when the system size is relatively small.     

A DFT study of electron or hole localization in a peptide containing asparagin

The mechanisms of protein degradation induced by ionisation are of great interest for radiobiology, improvement of mass spectroscopy and industrial processes such as radio sterilisation. Sequences containing asparagin are very sensitive especially if surrounded by glycine. Very few techniques allow a satisfying understanding of the processes induced by creation of an anionic or cationic site in a peptide. We used the methods of quantum chemistry (DFT/B3LYP with 6-31G^* basis set) to characterise the geometry modifications induced in the cations or in the anions derived from peptide Gly Asn Gly. The cationic sites are localised mostly close to the first peptidic bond and induce a lengthening of the Ca-C(O) bond. Conversely the anionic sites are localised on a carbonyl function. Implications are discussed considering the radiolytic products and the proposed mechanisms. Received 21 January 2002 Published online 13 September 2002     

Quantum diffusion in polaron model of poly(dG)-poly(dC) and poly(dA)-poly(dT) DNA polymers

We numerically investigate quantum diffusion of an electron in a model of poly(dG)-poly(dC) and poly(dA)-poly(dT) DNA polymers with fluctuation of the parameters due to the impact of colored noise. The randomness is introduced by fluctuations of distance between two consecutive bases along the stacked base pairs. We demonstrate that in the model the decay time of the correlation can control the spread of the electronic wavepacket. Furthermore it is shown that in a motional narrowing regime the averaging over fluctuation causes ballistic propagation of the wavepacket, and in the adiabatic regime the electronic states are affected by localization.     

Sphere packing, helices and the polytope {3, 3, 5}

The packing of tetrahedra in face contact is well-known to be relevant to atomic clustering in many complex alloys. We briefly review some of the structures that can arise in this way, and introduce methods of dealing with the geometry of the polytope {3, 3, 5}, which is highly relevant to an understanding of these structures. Finally, we present a method of projection from S₃ to E₃ that enables coordinates for the key vertices of the collagen model of Sadoc and Rivier to be calculated. Received 27 March 2001     

Is there a universality of the helix-coil transition in protein models?

The similarity in the thermodynamic properties of two completely different theoretical models for the helix-coil transition is examined critically. The first model is an all-atomic representation for a poly-alanine chain, while the second model is a minimal helix-forming model that contains no system specifics. Key characteristics of the helix-coil transition, in particular, the effective critical exponents of these two models agree with each other, within a finite-size scaling analysis. Received 8 December 1999     

Modelling of dynamical processes in a molecular crystal by NMR

In this contribution we report on the plastic crystal 1-chloroadamantane dynamics via conventional frequency dependent (¹H and ¹³C) and field cycling NMR measurements. A suitable microscopic dynamical model, worked out from from X-ray analysis is developed and the molecular motions are interpreted in terms of: self diffusion and dipolar molecular axis combined with uniaxial rotation. In the rotator phase the molecules execute a bimodal reorientation process whereas the uniaxial rotation solely persists in the low temperature phase. In both phases, the residence times exhibit an Arrhenius temperature dependence. The results confirm the existence of a dynamic crossover transition predicted by molecular dynamics simulation.     

Electrodeposited cobalt films: hcp versus fcc nanostructuring and magnetic properties

The crystallographic structure and morphology of electrodeposited cobalt films on Au(111) is found to be very sensitive on the electrolyte pH value and on the overpotential applied during deposition. The samples, 2 to 500 nm thick, where characterized by nuclear magnetic resonance (NMR), atomic force microscopy (AFM) and electron diffraction. The latter technique shows that the Co films grow in registry with the gold underlayer, reproducing the Au(111) texture. During the first stage of growth and depending on overpotential and pH value, either continuous hcp Co films or hcp Co islands are formed. Only the latter growth mode leads to an out of plane magnetization with 100% of remanence. Increasing the thickness, fcc Co becomes the prevailing phase. Eventually the fcc to hcp ratio saturates at the same value regardless the overpotential. The thickness for which the equilibrium fcc to hcp ratio is obtained as well as the sample structure and morphology before saturation, depend strongly on the overpotential value. In any case, the predominance of the fcc Co phase leads to an in plane magnetization of the thick samples. This study opens up new opportunities of engineering the properties of electrodeposited cobalt films. Received 29 February 2000 and Received in final form 3 July 2000     

Spin-wave contributions to nuclear magnetic relaxation in magnetic metals

The longitudinal and transverse nuclear magnetic relaxation rates 1/T ₁(T) and 1/T ₂(T) are calculated for three- and two-dimensional (3D and 2D) metallic ferro- and antiferromagnets (FM and AFM) with localized magnetic moments in the spin-wave temperature region. The contribution of the one-magnon decay processes is strongly enhanced in comparison with the standard T-linear Korringa term, especially for the FM case. For the 3D AFM case this contribution diverges logarithmically, the divergence being cut at the magnon gap ω due to magnetic anisotropy, and for the 2D AFM case as ω^-1. The electron-magnon scattering processes yield T ²ln(T/ω) and T ²/ω^1/2-terms in 1/T ₁ for the 3D AFM and 2D FM cases, respectively. The two-magnon (“Raman”) contributions are investigated and demonstrated to be large in the 2D FM case. Peculiarities of the isotropic 2D limit (where the correlation length is very large) are analyzed. Received 29 November 1999 and Received in final form 6 June 2000     

Fibril stability in solutions of twisted -sheet peptides: a new kind of micellization in chiral systems

The problem of fibril (fibre) formation in chiral systems is explored theoretically being supported by experiments on synthetic de novo 11-mer peptide forming self-assembled -sheet tapes. Experimental data unambiguously indicate that the tapes form fibrils of nearly monodisperse thickness ca . 8-10 nm. Fibril formation and stabilisation are attributed to inter-tape face-to-face attraction and their intrinsic twist, correspondingly. The proposed theory is capable of predicting the fibril aggregation number and its equilibrium twist in terms of molecular parameters of the primary tapes. The suggested novel mechanism of twist stabilisation of finite aggregates (fibrils) is different to the well-known stabilisation of micelles in amphiphilic systems, and it is likely to explain the formation and stability of fibrils in a wide variety of systems including proteinaceous amyloid fibres, sickle-cell hemoglobin fibres responsible for HbS anemia, corkscrew threads found in chromonics in the presence of chiral additives and native cellulose microfibrillar crystallites. The theory also makes it possible to extract the basic molecular parameters of primary tapes (inter-tape attraction energy, helical twist step, elastic moduli) from the experimental data. Received 7 May 1999 and Received in final form 15 February 2000     

Force spectroscopy of single multidomain biopolymers: A master equation approach

Experiments using atomic force microscopy for unfolding single multidomain biopolymers cover a broad range of time scales from equilibrium to non-equilibrium. A master equation approach allows to identify and treat coherently three dynamical regimes for increasing linear ramp velocity: i) an equilibrium regime, ii) a transient regime where refolding events still occur, and iii) a saw-tooth regime without any refolding events. For each regime, analytical approximations are derived and compared to numerically investigated examples. We analyze in the framework of this model also a periodic experimental protocol instead of a linear ramp. In this case, a major simplification arises if the dynamics can be restricted to an effectively two-dimensional subspace. For transitions with an intermediate meta-stable state, like Immunoglobulin27, a refined model allows to extract previously unknown molecular parameters related to this meta-stable state.     

Precise measurement of hyperfine coupling in CH F based on nuclear spin conversion

A new method is proposed for the experimental determination of the hyperfine coupling in molecules. The method is based on the level-crossing effect in the spin isomer conversion in alternating electric fields. An experiment performed with the ¹³CH₃F molecules has revealed the strength of the off-diagonal in K () nuclear spin-spin coupling kHz, which is only by kHz larger than the theoretical value calculated on the basis of the molecular structure. Received 25 January 2000 and Received in final form 11 May 2000     

Electric dipole moments and conformations of isolated peptides

The electric dipole moments of the isolated amino acid tryptophan and small glycine-based peptides (WG_n, n = 1-5, W = tryptophan, G = glycine) have been measured by deflection of a molecular beam in an inhomogeneous electric field. The measurements are compared to the results of ab initio calculations and Monte-Carlo simulations. The conformation and the flexibility of the peptides, at different temperatures, are discussed. The WG_n peptides are much more floppy than an isolated tryptophan, even a single glycine is enough to make the peptide floppy on the timescale of the electric deflection measurements. Received 4 January 2002 Published online 13 September 2002