Geometry-controlled kinetics

It has long been appreciated that transport properties can control reaction kinetics. This effect can be characterized by the time it takes a diffusing molecule to reach a target -- the first-passage time (FPT). Although essential to quantify the kinetics of reactions on all time scales, determining the FPT distribution was deemed so far intractable. Here, we calculate analytically this FPT distribution and show that transport processes as various as regular diffusion, anomalous diffusion, diffusion in disordered media and in fractals fall into the same universality classes. Beyond this theoretical aspect, this result changes the views on standard reaction kinetics. More precisely, we argue that geometry can become a key parameter so far ignored in this context, and introduce the concept of "geometry-controlled kinetics". These findings could help understand the crucial role of spatial organization of genes in transcription kinetics, and more generally the impact of geometry on diffusion-limited reactions.Comment: Submitted versio

Mean first-passage time of surface-mediated diffusion in spherical domains

We present an exact calculation of the mean first-passage time to a target on the surface of a 2D or 3D spherical domain, for a molecule alternating phases of surface diffusion on the domain boundary and phases of bulk diffusion. The presented approach is based on an integral equation which can be solved analytically. Numerically validated approximation schemes, which provide more tractable expressions of the mean first-passage time are also proposed. In the framework of this minimal model of surface-mediated reactions, we show analytically that the mean reaction time can be minimized as a function of the desorption rate from the surface.Comment: to appear in J. Stat. Phy

Scaling of mean first-passage time as efficiency measure of nodes sending information on scale-free Koch networks

A lot of previous work showed that the sectional mean first-passage time (SMFPT), i.e., the average of mean first-passage time (MFPT) for random walks to a given hub node (node with maximum degree) averaged over all starting points in scale-free small-world networks exhibits a sublinear or linear dependence on network order $N$ (number of nodes), which indicates that hub nodes are very efficient in receiving information if one looks upon the random walker as an information messenger. Thus far, the efficiency of a hub node sending information on scale-free small-world networks has not been addressed yet. In this paper, we study random walks on the class of Koch networks with scale-free behavior and small-world effect. We derive some basic properties for random walks on the Koch network family, based on which we calculate analytically the partial mean first-passage time (PMFPT) defined as the average of MFPTs from a hub node to all other nodes, excluding the hub itself. The obtained closed-form expression displays that in large networks the PMFPT grows with network order as $N \ln N$, which is larger than the linear scaling of SMFPT to the hub from other nodes. On the other hand, we also address the case with the information sender distributed uniformly among the Koch networks, and derive analytically the entire mean first-passage time (EMFPT), namely, the average of MFPTs between all couples of nodes, the leading scaling of which is identical to that of PMFPT. From the obtained results, we present that although hub nodes are more efficient for receiving information than other nodes, they display a qualitatively similar speed for sending information as non-hub nodes. Moreover, we show that the location of information sender has little effect on the transmission efficiency. The present findings are helpful for better understanding random walks performed on scale-free small-world networks.Comment: Definitive version published in European Physical Journal

Geometrical organization of solutions to random linear Boolean equations

The random XORSAT problem deals with large random linear systems of Boolean variables. The difficulty of such problems is controlled by the ratio of number of equations to number of variables. It is known that in some range of values of this parameter, the space of solutions breaks into many disconnected clusters. Here we study precisely the corresponding geometrical organization. In particular, the distribution of distances between these clusters is computed by the cavity method. This allows to study the `x-satisfiability' threshold, the critical density of equations where there exist two solutions at a given distance.Comment: 20 page

Non-Markovian polymer reaction kinetics

Describing the kinetics of polymer reactions, such as the formation of loops and hairpins in nucleic acids or polypeptides, is complicated by the structural dynamics of their chains. Although both intramolecular reactions, such as cyclization, and intermolecular reactions have been studied extensively, both experimentally and theoretically, there is to date no exact explicit analytical treatment of transport-limited polymer reaction kinetics, even in the case of the simplest (Rouse) model of monomers connected by linear springs. We introduce a new analytical approach to calculate the mean reaction time of polymer reactions that encompasses the non-Markovian dynamics of monomer motion. This requires that the conformational statistics of the polymer at the very instant of reaction be determined, which provides, as a by-product, new information on the reaction path. We show that the typical reactive conformation of the polymer is more extended than the equilibrium conformation, which leads to reaction times significantly shorter than predicted by the existing classical Markovian theory.Comment: Main text (7 pages, 5 figures) + Supplemantary Information (13 pages, 2 figures

Mean first-passage times of non-Markovian random walkers in confinement

The first-passage time (FPT), defined as the time a random walker takes to reach a target point in a confining domain, is a key quantity in the theory of stochastic processes. Its importance comes from its crucial role to quantify the efficiency of processes as varied as diffusion-limited reactions, target search processes or spreading of diseases. Most methods to determine the FPT properties in confined domains have been limited to Markovian (memoryless) processes. However, as soon as the random walker interacts with its environment, memory effects can not be neglected. Examples of non Markovian dynamics include single-file diffusion in narrow channels or the motion of a tracer particle either attached to a polymeric chain or diffusing in simple or complex fluids such as nematics \cite{turiv2013effect}, dense soft colloids or viscoelastic solution. Here, we introduce an analytical approach to calculate, in the limit of a large confining volume, the mean FPT of a Gaussian non-Markovian random walker to a target point. The non-Markovian features of the dynamics are encompassed by determining the statistical properties of the trajectory of the random walker in the future of the first-passage event, which are shown to govern the FPT kinetics.This analysis is applicable to a broad range of stochastic processes, possibly correlated at long-times. Our theoretical predictions are confirmed by numerical simulations for several examples of non-Markovian processes including the emblematic case of the Fractional Brownian Motion in one or higher dimensions. These results show, on the basis of Gaussian processes, the importance of memory effects in first-passage statistics of non-Markovian random walkers in confinement.Comment: Submitted version. Supplementary Information can be found on the Nature website : http://www.nature.com/nature/journal/v534/n7607/full/nature18272.htm

Enhanced reaction kinetics in biological cells

The cell cytoskeleton is a striking example of "active" medium driven out-of-equilibrium by ATP hydrolysis. Such activity has been shown recently to have a spectacular impact on the mechanical and rheological properties of the cellular medium, as well as on its transport properties : a generic tracer particle freely diffuses as in a standard equilibrium medium, but also intermittently binds with random interaction times to motor proteins, which perform active ballistic excursions along cytoskeletal filaments. Here, we propose for the first time an analytical model of transport limited reactions in active media, and show quantitatively how active transport can enhance reactivity for large enough tracers like vesicles. We derive analytically the average interaction time with motor proteins which optimizes the reaction rate, and reveal remarkable universal features of the optimal configuration. We discuss why active transport may be beneficial in various biological examples: cell cytoskeleton, membranes and lamellipodia, and tubular structures like axons.Comment: 10 pages, 2 figure

Kinetics of active surface-mediated diffusion in spherically symmetric domains

We present an exact calculation of the mean first-passage time to a target on the surface of a 2D or 3D spherical domain, for a molecule alternating phases of surface diffusion on the domain boundary and phases of bulk diffusion. We generalize the results of [J. Stat. Phys. {\bf 142}, 657 (2011)] and consider a biased diffusion in a general annulus with an arbitrary number of regularly spaced targets on a partially reflecting surface. The presented approach is based on an integral equation which can be solved analytically. Numerically validated approximation schemes, which provide more tractable expressions of the mean first-passage time are also proposed. In the framework of this minimal model of surface-mediated reactions, we show analytically that the mean reaction time can be minimized as a function of the desorption rate from the surface.Comment: Published online in J. Stat. Phy

Role of fractal dimension in random walks on scale-free networks

Fractal dimension is central to understanding dynamical processes occurring on networks; however, the relation between fractal dimension and random walks on fractal scale-free networks has been rarely addressed, despite the fact that such networks are ubiquitous in real-life world. In this paper, we study the trapping problem on two families of networks. The first is deterministic, often called $(x,y)$-flowers; the other is random, which is a combination of $(1,3)$-flower and $(2,4)$-flower and thus called hybrid networks. The two network families display rich behavior as observed in various real systems, as well as some unique topological properties not shared by other networks. We derive analytically the average trapping time for random walks on both the $(x,y)$-flowers and the hybrid networks with an immobile trap positioned at an initial node, i.e., a hub node with the highest degree in the networks. Based on these analytical formulae, we show how the average trapping time scales with the network size. Comparing the obtained results, we further uncover that fractal dimension plays a decisive role in the behavior of average trapping time on fractal scale-free networks, i.e., the average trapping time decreases with an increasing fractal dimension.Comment: Definitive version published in European Physical Journal

Organic residues in archaeology - the highs and lows of recent research

YesThe analysis of organic residues from archaeological materials has become increasingly important to our understanding of ancient diet, trade and technology. Residues from diverse contexts have been retrieved and analysed from the remains of food, medicine and cosmetics to hafting material on stone arrowheads, pitch and tar from shipwrecks, and ancient manure from soils. Research has brought many advances in our understanding of archaeological, organic residues over the past two decades. Some have enabled very specific and detailed interpretations of materials preserved in the archaeological record. However there are still areas where we know very little, like the mechanisms at work during the formation and preservation of residues, and areas where each advance produces more questions rather than answers, as in the identification of degraded fats. This chapter will discuss some of the significant achievements in the field over the past decade and the ongoing challenges for research in this area.Full text was made available in the Repository on 15th Oct 2015, at the end of the publisher's embargo period