Radical pair substitution in chemically induced dynamic nuclear polarization. Co-operative effects

The problem of radical pair substitution in Chemically Induced Dynamic Nuclear Polarization is reconsidered. The singlet—triplet evolution in the radical pairs is described in a continuous fashion, assuming non-disturbance of the electron spin state during the scavenging reaction. The CIDNP effect of the recombination product of the secondary pair is demonstrated to result from the “co-operative effect” of singlet—triplet evolution in both the primary and the secondary pair. The hypothetical one proton case, in which the primary pair has different g-factors and a zero hyperfine interaction, and the secondary pair equal g-factors and a non-zero hyperfine interaction is treated qualitatively. Some examples are discussed in which older models lead to a faulty interpretation of experimental results.     

Annealed Scaling for a Charged Polymer

This paper studies an undirected polymer chain living on the one-dimensional integer lattice and carrying i.i.d. random charges. Each self-intersection of the polymer chain contributes to the interaction Hamiltonian an energy that is equal to the product of the charges of the two monomers that meet. The joint probability distribution for the polymer chain and the charges is given by the Gibbs distribution associated with the interaction Hamiltonian. The focus is on the annealed free energy per monomer in the limit as the length of the polymer chain tends to infinity. We derive a spectral representation for the free energy and use this to prove that there is a critical curve in the parameter plane of charge bias versus inverse temperature separating a ballistic phase from a subballistic phase. We show that the phase transition is first order. We prove large deviation principles for the laws of the empirical speed and the empirical charge, and derive a spectral representation for the associated rate functions. Interestingly, in both phases both rate functions exhibit flat pieces, which correspond to an inhomogeneous strategy for the polymer to realise a large deviation. The large deviation principles in turn lead to laws of large numbers and central limit theorems. We identify the scaling behaviour of the critical curve for small and for large charge bias. In addition, we identify the scaling behaviour of the free energy for small charge bias and small inverse temperature. Both are linked to an associated Sturm-Liouville eigenvalue problem. A key tool in our analysis is the Ray-Knight formula for the local times of the one-dimensional simple random walk. This formula is exploited to derive a closed form expression for the generating function of the annealed partition function, and for several related quantities. This expression in turn serves as the starting point for the derivation of the spectral representation for the free energy, and for the scaling theorems. What happens for the quenched free energy per monomer remains open. We state two modest results and raise a few questions.     

Correlation structure of intermittency in the parabolic Anderson model

Consider the Cauchy problem ∂u(x, t)/∂t = ℋu(x, t) (x∈ℤ^d, t≥ 0) with initial condition u(x, 0) ≡ 1 and with ℋ the Anderson Hamiltonian ℋ = κΔ + ξ. Here Δ is the discrete Laplacian, κ∈ (0, ∞) is a diffusion constant, and ξ = {ξ(x): x∈ℤ ^d } is an i.i.d.random field taking values in ℝ. G?rtner and Molchanov (1990) have shown that if the law of ξ(0) is nondegenerate, then the solution u is asymptotically intermittent. In the present paper we study the structure of the intermittent peaks for the special case where the law of ξ(0) is (in the vicinity of) the double exponential Prob(ξ(0) > s) = exp[−e ^{s /θ}] (s∈ℝ). Here θ∈ (0, ∞) is a parameter that can be thought of as measuring the degree of disorder in the ξ-field. Our main result is that, for fixed x, y∈ℤ ^d and t→∈, the correlation coefficient of u(x, t) and u(y, t) converges to ∥w _ρ∥⁻² _ℓ2Σ_{z ∈ℤd} w _ρ(x+z)w _ρ(y+z). In this expression, ρ = θ/κ while w _ρ:ℤ^d→ℝ⁺ is given by w _ρ = (v _ρ)^{⊗ d} with v _ρ: ℤ→ℝ⁺ the unique centered ground state (i.e., the solution in ℓ²(ℤ) with minimal l ²-norm) of the 1-dimensional nonlinear equation Δv + 2ρv log v = 0. The uniqueness of the ground state is actually proved only for large ρ, but is conjectured to hold for any ρ∈ (0, ∞). empty It turns out that if the right tail of the law of ξ(0) is thicker (or thinner) than the double exponential, then the correlation coefficient of u(x, t) and u(y, t) converges to δ _{x, y} (resp.the constant function 1). Thus, the double exponential family is the critical class exhibiting a nondegenerate correlation structure. Received: 5 March 1997 / Revised version: 21 September 1998     

Long-Time tails in a random diffusion model

Letw = {w(x)xZ^d} be a positive random field with i.i.d. distribution. Given its realization, letX _t be the position at timet of a particle starting at the origin and performing a simple random walk with jump rate w^–1(X_t). The processX={X _t:t0} combined withw on a common probability space is an example of random walk in random environment. We consider the quantities _t =(d/dt) E (X _t ² –M ^–1 t and _t(w) = (d/dt)E_w(X _t ² – M^– 1t). Here E_w. is expectation overX at fixedw and E = E_w (dw) is the expectation over bothX andw. We prove the following long-time tail results: (1) lim_t t^d/2_t= V²M^d/2–3(d/2)^d/2 and (2) lim_t t^d/4 _st(w)= Z_s weakly in path space, with {Z_s:s>0} the Gaussian process with EZ_s=0 and EZ_rZ_s= V²M^d/2–4(d)^d/2 (r + s)^–d/2. HereM and V² are the mean and variance of w(0) under . The main surprise is that fixingw changes the power of the long-time tail fromd/2 tod/4. Since , with ₀ the stationary measure for the environment process, our result (1) exhibits a long-time tail in an equilibrium autocorrelation function.     

Random walk in a high density dynamic random environment

The goal of this note is to prove a law of large numbers for the empirical speed of a green particle that performs a random walk on top of a field of red particles which themselves perform independent simple random walks on Z^d${\mathbb{Z}}^d$, d≥1$d\ge 1$. The red particles jump at rate 1 and are in a Poisson equilibrium with density μ$\mu$. The green particle also jumps at rate 1, but uses different transition kernels p^′$p^{\prime }$ and p^″$p^{″}$ depending on whether it sees a red particle or not. It is shown that, in the limit as μ→∞$\mu \to \infty$, the speed of the green particle tends to the average jump under p^′$p^{\prime }$. This result is far from surprising, but it is non-trivial to prove. The proof that is given in this note is based on techniques that were developed in Kesten and Sidoravicius (2005) to deal with spread-of-infection models. The main difficulty is that, due to particle conservation, space–time correlations in the field of red particles decay slowly. This places the problem in a class of random walks in dynamic random environments for which scaling laws are hard to obtain.     

Kawasaki Dynamics with Two Types of Particles: Critical Droplets

This is the third in a series of three papers in which we study a two-dimensional lattice gas consisting of two types of particles subject to Kawasaki dynamics at low temperature in a large finite box with an open boundary. Each pair of particles occupying neighboring sites has a negative binding energy provided their types are different, while each particle has a positive activation energy that depends on its type. There is no binding energy between particles of the same type. At the boundary of the box particles are created and annihilated in a way that represents the presence of an infinite gas reservoir. We start the dynamics from the empty box and are interested in the transition time to the full box. This transition is triggered by a critical droplet appearing somewhere in the box. In the first paper we identified the parameter range for which the system is metastable, showed that the first entrance distribution on the set of critical droplets is uniform, computed the expected transition time up to and including a multiplicative factor of order one, and proved that the nucleation time divided by its expectation is exponentially distributed, all in the limit of low temperature. These results were proved under three hypotheses, and involved three model-dependent quantities: the energy, the shape and the number of critical droplets. In the second paper we proved the first and the second hypothesis and identified the energy of critical droplets. In the third paper we prove the third hypothesis and identify the shape and the number of critical droplets, thereby completing our analysis. Both the second and the third paper deal with understanding the geometric properties of subcritical, critical and supercritical droplets, which are crucial in determining the metastable behavior of the system, as explained in the first paper. The geometry turns out to be considerably more complex than for Kawasaki dynamics with one type of particle, for which an extensive literature exists. The main motivation behind our work is to understand metastability of multi-type particle systems.     

A directly labeled TR-FRET assay for monitoring phosphoinositide-3-kinase activity

Phosphoinositide 3-kinases (PI3Ks) comprise a family of kinases that transfer the terminal phosphate of adenosine triphosphate to phosphoinositides at the 3-hydroxyl of the inositol ring to form phosphoinositide (3,4,5) triphosphate (PIP3). The PI3Ks have been shown to play key roles in cell growth, motility, morphology, and survival and thus are of interest as targets in anti-inflammatory and anti-oncogenic drug development. To facilitate identification of novel and selective inhibitors of PI3Ks, we have developed a TR-FRET assay that uses directly labeled reagents. The assay makes use of the high affinity binding of phosphoinositides to a Pleckstrin homology (PH) domain in the general receptor for phosphoinositides 1 (Grp1) protein. It monitors PIP3 produced from the enzymatic reaction by measuring its competition with Bodipy-FL-labeled PIP3 for binding to Terbium chelate-labeled Grp1. By using directly labeled reagents, this assay configuration offers higher sensitivity and faster binding/dissociation kinetics than existing non-radioactive assays, which are critical for competitive assay formats. The assay is homogenous, robust (Z' = 0.88), and simple and, thus, compatible with high throughput screening (HTS) processes.     

Random walks in a random field of decaying traps

We study random walks on ^d (d 1) containing traps subject to decay. The initial trap distribution is random. In the course of time, traps decay independently according to a given lifetime distribution. We derive a necessary and sufficient condition under which the walk eventually gets trapped with probability 1. We prove bounds and asymptotic estimates for the survival probability as a function of time and for the average trapping time. These are compared with some well-known results for nondecaying traps.