Shrinking of anionic polyacrylate coils induced by Ca2+, Sr2+ and Ba2+: A combined light scattering and ASAXS study

Anionic polyacrylate chains (NaPA) form precipitates if alkaline earth cations are added in stoichiometric amounts. Accordingly, precipitation thresholds were established for three different alkaline earth cations Ca²⁺, Sr²⁺ and Ba²⁺. Close to the precipitation threshold, the NaPA chains significantly decrease in size. This shrinking process was followed by means of combined static and dynamic light scattering. Intermediates were generated by varying the ratio [MCl₂]/[NaPA] with M denoting the respective alkaline earth cation. All experiments were performed at an inert salt level of 0.01M NaCl. Similar coil-to-sphere transitions could be observed with all three alkaline earth cations Ca²⁺, Sr²⁺ and Ba²⁺. Based on these findings, supplementary conventional and anomalous small-angle X-ray scattering experiments using selected intermediates close to the precipitation threshold of SrPA were performed. The distribution of Sr counterions around the polyacrylate chains in aqueous solution provided the desired scattering contrast. Energy-dependent scattering experiments enabled successful separation of the pure-resonant terms, which solely stem from the counterions. The Sr²⁺ scattering roughly reflects the monomer distribution of the polyacrylate chains. Different ratios of the concentrations of [ SrCl₂]/[NaPA] revealed dramatic changes in the scattering curves. The scattering curve at the lowest ratio indicated an almost coil-like behaviour, while at the higher ratios the scattering curves supported the model of highly contracted polymer chains. Most of X-ray scattering experiments on intermediate states revealed compact structural elements which were significantly smaller than the respective overall size of the NaPA particles.     

Crystal and magnetic structures of the oxyphosphates MFePO 5 (M = Fe, Co, Ni, Cu). Analysis of the magnetic ground state in terms of superexchange interactions

We have studied in detail the crystal and magnetic structures of the oxyphosphates MFePO₅ (M: divalent transition metal) using neutron powder diffraction as a function of temperature. All of them are isomorphic to the mixed valence compound α-Fe₂PO₅ with space-group Pnma. No disorder exists between the two metallic sites. The M²⁺O₆ octahedra share edges between them and faces with Fe³⁺O₆ octahedra building zigzag chains running parallel to the b-axis that are connected by PO₄ tetrahedra. The topology of this structure gives rise to a complex pattern of super-exchange interactions responsible of the observed antiferromagnetic order. The magnetic structures are all collinear with the spin directed along the b-axis except for M = Co. The experimental magnetic moments of Cu⁺² and Ni²⁺ correspond to the expected ionic value, on the contrary the magnetic moment of Fe³⁺ is reduced, probably due to covalence effects, and that of Co²⁺ is greater than the spin-only value indicating a non negligible orbital contribution. Using numerical calculations we have established a magnetic phase diagram adapted for this type of crystal structure and determined the constraints to be satisfied by the values of the exchange interactions in order to obtain the observed magnetic structure as the ground state. Received 15 December 2000 and Received in final form 25 June 2001     

Flexible linear polyelectrolytes in multivalent salt solutions: Solubility conditions

Single- and double-stranded DNA and many biological and synthetic polyelectrolytes undergo two structural transitions upon increasing the concentration of multivalent salt or molecules. First, the expanded-stretched chains in low monovalent salt solutions collapse into nearly neutral compact structures when the density of multivalent salt approaches that of the monomers. With further addition of multivalent salt the chains redissolve acquiring expanded-coiled conformations. We study the redissolution transition using a two-state model (F.J. Solis, M. Olvera de la Cruz, J. Chem. Phys. 112, 2030 (2000)). The redissolution occurs when there is a high degree of screening of the electrostatic interactions between monomers, thus reducing the energy of the expanded state. The transition is determined by the chemical potential of the multivalent ions in the solution, μ and the inverse screening length, κ. The transition point also depends on the charge distribution along the chain but is nearly independent of the molecular weight and degree of flexibility of the polyelectrolytes. We generate a diagram of μversusκ² where we find two regions of expanded conformations, one with charged chains and the other with overcharged (inverted charge) chains, separated by a collapsed nearly neutral conformation region. The collapse and redissolution transitions occur when the trajectory of the properties of the salt crosses the boundaries between these regions. We find that in most cases the redissolution occurs within the same expanded branch from which the chain precipitates. Received 15 May 2000 and Received in final form 28 June 2000     

Stratification of foam films made from polyelectrolyte solutions

Studies of thin liquid films, made from semidilute polyelectrolyte solutions, are presented. The disjoining pressure variation with film thickness exhibits oscillations, corresponding to film stratification. The oscillations become sharper as the polymer concentration c increases, and disappear when salt is added. The period of the oscillations scales as c ^-1/2. The observed stratification is related to the polymer network and the size of the steps to the mesh size ξ. Received 25 April 2000 and Received in final form 3 October 2000     

The association of octadecyl-end-capped poly-(sodium 2-acrylamido-2-methylpropanesulfonates) in water and salt solutions: A study by fluorescence spectroscopy and isothermal titration calorimetry

Steady-state fluorescence spectroscopy and isothermal titration calorimetry (ITC) have been used to study the aggregation in aqueous solutions of poly-(2-acrylamido)-2-methylpropanesulfonic acids, sodium salt mono-endcapped with either N,N-di-n-octadecyl or N-4-[(1-pyrenyl)butyl]-N-n-octadecyl which were prepared by free radical polymerization of 2-(acrylamido)-2-methylpropane sulfonic acid (AMPS) initiated with the azo compounds, 4,4'-azobis{cyano-N,N-di-n-octadecyl}pentanamide and 4,4'-azobis{cyano-N,N-[4-(1-pyrenyl)butyl]-n-octadecyl}pentanamide, respectively. Both techniques indicate the occurrence of multimolecular aggregates in solutions of the polymers in water and in 0.2 M NaCl. The concentration range for aggregation is about 1-14 mmol AMPS l^-1 (0.5-2.7 g l^-1) in 0.2 M NaCl and the enthalpy of micellization, estimated from ITC data, is ∼100 J [mol AMPS]^-1. The accessibility of the chromophores to neutral molecules and to cationic species was assessed by quenching of fluorescence with nitromethane and thallium nitrate, respectively. The association of the mono-endcapped polymers is compared to that of PAMPS derivatives carrying hydrophobic groups randomly attached along the chain. Received 7 August 2000 and Received in final form 26 October 2000     

Cellular oscillator with a small number of particles

To illustrate complex spatio-temporal effects which are possible in cellular reactions with a small number of particles, we present Monte Carlo simulations of the formation of oscillatory spark-like patterns in a model completely stochastic Ca⁺² oscillator. Our analysis shows that in order to observe such patterns the minimum average number of Ca⁺² ions in the cytosol may be as low as about 50. Received 21 April 2002 / Received in final form 19 June 2002 Published online 14 October 2002 RID="a" ID="a"e-mail: zhdanov@catalysis.nsk.su     

Characterization of a miniature Paul-Straubel trap

Frequency standard applications and ultra-high resolution spectroscopy of a confined single ion require traps of drastically reduced dimensions (about or below 1 mm). These small dimensions increase the sensitivity of the trapping behavior to imperfections in the trap geometry and to patch potentials. For the aim of the metrological laser interrogation of a single Ca⁺ ion, a miniature cylindrical ring trap was built. In order to optimize the laser cooling process and to reach strong binding conditions, the boundaries of the stability diagram and the zones of low confinement as well as the ion motion properties were characterized. Received 14 November 2000 and Received in final form 1st February 2001     

X-ray scattering study of the phase transitions in crystalline fullerene-biphenyl C 60 [(C 6 H 5 ) 2 ]

The phase diagram of the newly synthesized mixed crystal C₆₀-biphenyl is investigated as a function of temperature by single-crystal X-ray scattering. Diffuse scattering investigations evidencing complex disorder and local order effects are presented. Two phase transitions leading to two different doublings of the high temperature unit cell are observed, at 212 K and 147 K. The first transition is attributed to the ordering of twisted biphenyls, which couples to the orientational ordering of the C₆₀ molecules as the temperature decreases. Full ordering of the C₆₀ molecules is achieved below 100 K only, in the low temperature phase. The rich phase diagram of C₆₀-biphenyl is due to the interplay between fullerene and biphenyl ordering phenomena. Received 31 August 2001 and Received in final form 4 December 2001     

Polyelectrolyte chains in poor solvent. A variational description of necklace formation

We study the properties of polyelectrolyte chains under different solvent conditions, using a variational technique. The free energy and the conformational properties of a polyelectrolyte chain are studied by minimizing the free energy F_N, depending on N(N - 1)/2 trial probabilities that characterize the conformation of the chain. The Gaussian approximation is considered for a ring of length 2⁴ < N < 2⁸ and for an open chain of length 50 < N < 200 in poor- and theta-solvent conditions, including a Coulomb repulsion between the monomers. In theta-solvent conditions the blob size is measured and found in agreement with scaling theory, including charge depletion effects, expected for the case of an open chain. In poor-solvent conditions, a globule instability, driven by electrostatic repulsion, is observed. We notice also inhomogeneous behavior of the monomer-monomer correlation function, reminiscence of necklace formation in poor-solvent polyelectrolyte solutions. A global phase diagram in terms of solvent quality and inverse Bjerrum length is presented. Received 7 June 2001 and Received in final form 17 October 2001     

On polarization of strange baryons in reactions p + p↦p + Λ0 + K+ and p + p↦p + Σ0 + K+ near thresholds

Polarization properties of strange baryons produced in pp reactions, p + p↦p + Λ⁰ + K⁺ and p + p↦p + Σ⁰ + K⁺, near thresholds of the final states pΛ⁰K⁺ and pΣ⁰K⁺ are analysed relative to polarizations of colliding protons. The cross-sections for pp reactions are calculated within the effective Lagrangian approach accounting for strong pp rescattering in the initial state of colliding protons with a dominant contribution of the one-pion exchange and strong final-state interaction of daughter hadrons (Eur. Phys. J. A 9, 425 (2000)). Received: 22 October 2001 / Accepted: 14 November 2001     

Magnetization and resistivity steps in the phase separated PrCaMn NiO manganites

The low temperature magnetic and transport properties of the Pr_0.5Ca_0.5Mn_1-xNi_xO₃ manganites ( 0≤ x ≤0.1) have been investigated. The presence of Ni hinders the charge and orbital ordering observed in Pr_0.5Ca_0.5MnO₃ and favors the creation of ferromagnetic regions, leading to phase separation. The ferromagnetic fractions induced by the Ni substitution have been estimated from magnetization measurements, they are large and reach 40% for 4% of Ni. Steps are observed in the M ( H ) and ρ( H ) curves of all the samples at T < 5 K. They are similar to the steps observed in Pr_0.5Ca_0.5Mn_1-xM_xO₃, where M is a non magnetic cation (Mg²⁺, Ga³⁺,...), and for which the ferromagnetic fractions are very small (less than 2%), however, their appearance is restricted to lower temperatures (T < 5 K) with Ni dopant than with non magnetic cations. This study shows that steps can be observed in a wide range of phase-separated systems, even when the ferromagnetic fraction is very large. Received 5 April 2002 / Received in final form 8 July 2002 Published online 14 October 2002 RID="a" ID="a"e-mail: antoine.maignan@ismra.fr     

Radiative transitions in highly ionised silicon-like ions

Transition energies, oscillator strengths and transition probability values for radiative transitions have been calculated for the highly ionised atoms of Si isoelectronic sequence from Mn¹¹⁺ to Kr²²⁺ for the singly excited states up to principal quantum number n = 7. Time-dependent coupled Hartree-Fock (TDCHF) theory has been used to estimate such transition properties. Most of the results for the oscillator strengths and transition probabilities are new. Transition energies agree reasonably well with available spectroscopic values. Received 25 January 2000 and Received in final form 24 October 2000     

Early stages of phase separation from polydisperse polymer mixtures

We study the early stages of phase separation in a mixture of a polydisperse and a monodisperse polymer within the Cahn-Hilliard framework. We model the polydisperse component using a finite, but arbitrarily large, number of components, and show that the number of components required for convergent behaviour to be achieved is computationally undemanding. We study the growth rate of fluctuations following a quench into the two-phase region of the phase diagram. The q-dependence of the growth rate is shown to be commensurate with the behaviour of a monodisperse-monodisperse mixture, with the major difference being an effective mobility that is dependent on the quench depth. We also study the deviation of the time dependence of the scattering function from single exponential behaviour. Received 29 June 2000 and Received in final form 20 November 2000     

Solubility of highly charged anionic polyelectrolytes in presence of multivalent cations: Specific interaction effect

Studies performed on strong polyelectrolytes and on a weak polyelectrolyte, sodium poly(acrylate), show that their stability in presence of multivalent cations depends on the chemical nature of the charged side groups of the polymer. For sulfonate groups (SO₃ ^-) or sulfate groups (OSO₃ ^-) phase separation generally occurs in presence of inorganic cations of valency 3 (as La³⁺) or larger and a resolubilization takes place at high salt concentration. The interactions of the polyelectrolyte with multivalent cations are of electrostatic origin and the phase diagrams are weakly dependent on the chemical nature of the polymer backbone and on the specificity of the counterions. For acrylate groups, (COO^-), the phase separation was observed with inorganic cations of valency 2 (as Ca²⁺) or larger without resolubilization at high salt concentration. The phase separation is due to a chemical association between cations and acrylate groups of two neighboring monomers of the same chain. This chemical association creates a hydrophobic complex by dehydrating both monomer and cation. With organic trivalent cation, as spermidine ⁺H₃N(CH₂)₄NH₂ ⁺(CH₂)₃NH₃ ⁺, where no chemical association occurs with the charged side groups COO^- or SO₃ ^- of the polyelectrolyte, similar phase diagrams were observed whatever was the polyelectrolyte with a resolubilization at high trivalent cation concentration. Received 3 March 1999 and Received in final form 2 September 1999     

Macroscopic and local magnetic moments in Si-doped CuGeO 3 as determined by neutron and μSR studies

The temperature-concentration phase diagram of the Si-doped spin-Peierls compound CuGeO₃ is investigated by means of neutron scattering and muon spin rotation spectroscopy in order to determine the microscopic distribution of the magnetic and lattice dimerised regions as a function of doping. The analysis of the zero-field muon spectra has confirmed the spatial inhomogeneity of the staggered magnetisation that characterises the antiferromagnetic superlattice peaks observed with neutrons. In addition, the variation of the macroscopic order parameter with doping can be understood by considering the evolution of the local magnetic moment as well as of the various regions contributing to the muon signal. Received 6 September 2000 and Received in final form 29 January 2001     

The lifetime of the soliton in the improved Davydov model at the biological temperature 300 K for protein molecules

We study the effects of quantum fluctuations and thermal perturbations on the lifetime of the soliton in the improved Davydov model proposed by us with two-quanta and with an added interaction. By using quantum perturbation theory, we compute the soliton lifetime for a wide ranges of parameter values relevant for protein molecules. The lifetime of the new soliton at the biological temperature 300 K is of the order of 10^-10 second or τ/τ≥ 500 for parameters appropriate to α-helical protein molecules. This shows clearly that the new soliton in the improved model is a viable mechanism for the bio-energy transport in the α-helix region of proteins. Received 7 January 1999 and Received in final form 16 August 2000     

Weak violation of universality for polyelectrolyte chains: Variational theory and simulations

A variational approach is considered to calculate the free energy and the conformational properties of a polyelectrolyte chain in d dimensions. We consider in detail the case of pure Coulombic interactions between the monomers, when screening is not present, in order to compute the end-to-end distance and the asymptotic properties of the chain as a function of the polymer chain length N. We find R≃N ^ν(log N)^γ, where ν = and λ is the exponent which characterizes the long-range interaction U∝ 1/r ^λ. The exponent γ is shown to be non-universal, depending on the strength of the Coulomb interaction. We check our findings by a direct numerical minimization of the variational energy for chains of increasing size 2⁴ < N < 2¹⁵. The electrostatic blob picture, expected for small enough values of the interaction strength, is quantitatively described by the variational approach. We perform a Monte Carlo simulation for chains of length 2⁴ < N < 2¹⁰. The non-universal behavior of the exponent γ previously derived within the variational method is also confirmed by the simulation results. Non-universal behavior is found for a polyelectrolyte chain in d = 3 dimension. Particular attention is devoted to the homopolymer chain problem, when short-range contact interactions are present. Received 8 August 2000 and Received in final form 19 December 2000     

Magnetic, electronic, dielectric and optical properties of Pr(Ca:Sr)MnO 3

The charge-ordered perovskite Pr_0.65Ca_0.28Sr_0.07MnO₃ was investigated by means of magnetic susceptibility, specific heat, dielectric and optical spectroscopy and electron-spin resonance techniques. Under moderate magnetic fields, the charge order melts yielding colossal magnetoresistance effects with changes of the resistivity over eleven orders of magnitude. The optical conductivity is studied from audio frequencies far into the visible spectral regime. Below the phonon modes hopping conductivity is detected. Beyond the phonon modes the optical conductivity is explained by polaronic excitations out of a bound state. ESR techniques yield detailed informations on the (H,T ) phase diagram and reveal a broadening of the linewidth which can be modeled in terms of activated polaron hopping. Received 9 August 2000     

The new isotope 270110 and its decay products 266Hs and 262Sg

The even-even nucleus ²⁷⁰110 was synthesized using the reaction ⁶⁴Ni + ²⁰⁷Pb. A total of eight α-decay chains was measured during an irradiation time of seven days. Decay data were obtained for the ground-state and a high-spin K isomer. The new nuclei ²⁶⁶Hs and ²⁶²Sg were identified as daughter products after α-decay. Spontaneous fission of ²⁶²Sg terminates the decay chain. The measured data are in agreement with calculations using the macroscopic-microscopic model and with self-consistent HFB calculations with Skyrme-Sly4 interaction. Received: 27 November 2000 / Accepted: 16 January 2001     

The normal state scattering rate in high- cuprates

A detailed phenomenological model is developed for the normal state transport properties of optimal and overdoped high-T_c cuprates. In particular, an explicit form of scattering rate is identified that may account, qualitatively and quantitatively, for the normal state (magneto)-transport properties of Tl₂Ba₂CuO _{6 + δ} and Bi₂Sr₂CaCu₂O _{8 + δ} across the overdoped side of the phase diagram. The proscribed form of the scattering rate is consistent also with features seen in the photoemission spectroscopy of Bi₂Sr₂CaCu₂O _{8 + δ} and offers a new and intuitive way to understand the evolution of the temperature dependence of the inverse Hall angle in Bi-based cuprates with carrier concentration. Received 5 June 2002 / Received in final form 17 December 2002 Published online 6 March 2003 RID="a" ID="a"e-mail: n.e.hussey@bristol.ac.uk