The ''capacitive mixing'' (CAPMIX) technique is aimed at the extraction of energy from the salinity difference between the sea and rivers. It is based on the voltage rise that takes place at the electrodes when changing the salt concentration of the solution in which the two electrodes are dipped. In this paper, we focus on activated carbon electrodes, produced with various methods and treatments, and we measure their behaviour in CAPMIX experiments. We find that they behave as polarizable electrodes only on time scales of the order of minutes, while on longer time scales they tend to move to a specific ''spontaneous'' potential, likely due to chemical redox reactions. This analysis sheds light on the charge leakage, i.e. the loss of the stored charge due to undesired chemical reactions, which is one of the main hurdles of the CAPMIX technique when performed with activated carbon electrodes. We show that the leakage finds its origin in the tendency of the electrode to move to its spontaneous potential. Our investigation allows us to completely get rid of the leakage and demonstrates the striking result that CAPMIX cycles can be performed without an external power supply.

An enormous dissipation of the order of 2 kJ/L takes place during the natural mixing process of fresh river water entering the salty sea. "Capacitive mixing" is a promising technique to efficiently harvest this energy in an environmentally clean and sustainable fashion. This method has its roots in the ability to store a very large amount of electric charge inside supercapacitor or battery electrodes dipped in a saline solution. Three different schemes have been studied so far, namely, Capacitive Double Layer Expansion (CDLE), Capacitive Donnan Potential (CDP) and Mixing Entropy Battery (MEB), respectively based on the variation upon salinity change of the electric double layer capacity, on the Donnan membrane potential, and on the electrochemical energy of intercalated ions.

Electrochemical cells containing two electrodes dipped in an ionic solution are widely used as charge accumulators, either with polarizable (supercapacitor) or nonpolarizable (battery) electrodes. Recent applications include desalination ("capacitive deionization") and energy extraction from salinity differences ("capacitive mixing"). In this Letter, we analyze a general relation between the variation of the electric potential as a function of the concentration and the salt adsorption. This relation comes from the evaluation of the electrical and mechanical energy exchange along a reversible cycle, which involves salt adsorption and release by the electrodes. The obtained relation thus describes a connection between capacitive deionization and capacitive mixing. We check this relation with experimental data already reported in the literature, and moreover by some classical physical models for electrodes, including polarizable and nonpolarizable electrodes. The generality of the relation makes it very useful in the study of the properties of the electric double layer.

A model of the electro-diffusion of ions in porous electrodes is applied to analyze the dynamics of capacitive-mixing extraction of energy from salinity gradients with carbon porous electrodes. The complex time-evolution of the cell voltage observed in experiments is satisfactorily described. The asymmetry on the duration of the solution-change steps performed in open circuit is found to be due to the nonlinear voltage–concentration relationship of the electric double layers and to a current that redistributes the counterions along the depth of the electrode leading to nonuniform charge and salt adsorption. The validated model is an essential tool for the design and optimization of renewable energy extraction by this technique.

The opening of DNA double strands is extremely relevant to several biological functions, such as replication and transcription or binding of specific proteins. Such opening phenomenon is particularly sensitive to the aqueous solvent conditions in which the DNA molecule is dispersed, as it can be observed by considering the classical dependence of DNA melting temperature on pH and salt concentration. In the present work, we report a single-molecule study of the stability of DNA against denaturation when subjected to changes in solvent. We investigated the appearance of DNA instability under specific external applied force and imposed twist values, which was revealed by an increase in the temporal fluctuations in the DNA extension. These fluctuations occur in the presence of a continuous interval of equilibrium states, ranging from a plectonemic state to a state characterized by denaturation bubbles. In particular, we observe the fluctuations only around a characteristic force value. Moreover, this characteristic force is demonstrated to be notably sensitive to variations in the pH and ionic strength. Finally, an extension of a theoretical model of plectoneme formation is used to estimate the average denaturation energy, which is found to be linearly correlated to the melting temperature of the DNA double strands.

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The "capacitive mixing" (CAPMIX) technique is an emerging technology aimed at the extraction of energy from salinity differences, e.g. between sea and river waters. CAPMIX benefits from the voltage rise that takes place between two electrodes dipped in a saline solution when its salt concentration is changed. Several kinds of electrodes have been proposed so far: activated carbon materials (Brogioli, 2009), membrane-based ion-selective electrodes (Sales et al., 2010), and battery electrodes (Biesheuvel and van der Wal, 2010). The power production mainly depends on two properties of each single electrode: the amplitude of the potential rise upon salinity change, and the potential in the high-salinity solution. The various electrode materials that have been used returned different values of the two parameters, and hence to different power productions. In this paper, we apply electrokinetic and electrochemical models to qualitatively explain the experimentally observed behaviors of various materials under different experimental conditions. The analysis allows to devise techniques for tailoring new materials, particularly suited for the CAPMIX technique.

We use the "magnetic tweezers" technique to reveal the structural transitions that DNA undergoes in the force-torsion space. In particular, we focus on regions corresponding to negative supercoiling. These regions are characterized by the formation of so-called denaturation bubbles, which have an essential role in the replication and transcription of DNA. We experimentally map the region of the force-torsion space where the denaturation takes place. We observe that large fluctuations in DNA extension occur at one of the boundaries of this region, i.e., when the formation of denaturation bubbles and of plectonemes are competing. To describe the experiments, we introduce a suitable extension of the classical model. The model correctly describes the position of the denaturation regions, the transition boundaries, and the measured values of the DNA extension fluctuations.PACS numbers: 82.37. Rs, 87.14.gk, 87.15.La The nanomechanics of DNA play an important role at the biological and biochemical levels [1]. Thus, understanding the transcription and duplication phenomena is a relevant open topic to which a quantitative comprehension of DNA mechanical characteristics is fundamental. In particular, because any transcription or duplication process implies the local and temporary separation of the two DNA strands (i.e., DNA breathing [2,3] or denaturation bubbles [4-6]), understanding denaturation represents the first building block towards the theoretical comprehension of DNA metabolism. A well-known and promising technique for studying nanomechanical properties is the magnetic tweezers (MT), which allows one to impose a stretching force and a torsion to a single DNA molecule while also monitoring the simultaneous extension of the same molecule [7,8]. The versatility of the MT technique has been exploited to investigate DNA nanomechanics in the presence of proteins, enzymes, ligands, and drugs [9][10][11][12][13], and phenomenologically analyzed [14]. The initial pioneering MT studies focused on the topology of DNA molecules and showed that torsion can produce a so-called "plectoneme", which reduces DNA extension [15,16]. For modeling plectoneme formation, the DNA can be simply described as an elastic rod [17]. The experiments showed that the plectonemes disappear when the force becomes sufficiently high and the direction of the torsion is toward the unwinding of the DNA double helix [8]. This chiral effect, which goes beyond the elastic rod model, has been explained in terms of denaturation of the double helix [18].In this work we use the asymmetry between the DNA extension under positive and negative torsion as a hallmark of denaturation. For the first time, we systematically evaluate the occurrence of mechanical denaturation in the force-torsion space. We find that large temporal fluctuations of extension arise at one of the boundaries of the denaturation region. Finally, we interpret the experimental data with a simple mechanical model obtained by considering a denaturation term to the classical energy [17] used t...