Browsing by Subject "Electrolyte solutions"

Now showing 1 - 4 of 4

Open Access
Dielectric anisotropy in polar solvents under external fields
(Institute of Physics Publishing, 2015) Buyukdagli, S.
We investigate dielectric saturation and increment in polar liquids under external fields. We couple a previously introduced dipolar solvent model to a uniform electric field and derive the electrostatic kernel of interacting dipoles. This procedure allows an unambiguous definition of the liquid dielectric permittivity embodying non-linear dielectric response and correlation effects. We find that the presence of the external field results in a dielectric anisotropy characterized by a two-component dielectric permittivity tensor. The increase of the electric field amplifies the permittivity component parallel to the field direction, i.e. dielectric increment is observed along the field. However, the perpendicular component is lowered below the physiological permittivity εu ≈ 77, indicating dielectric saturation perpendicular to the field. By comparison with Molecular Dynamics simulations from the literature, we show that the mean-field level dielectric response theory underestimates dielectric saturation. The inclusion of dipolar correlations at the weak-coupling level intensify the mean-field level dielectric saturation and improves the agreement with simulation data at weak electric fields. The correlation-corrected theory predicts as well the presence of a metastable configuration corresponding to the antiparallel alignment of dipoles with the field. This prediction can be verified by solvent-explicit simulations where solvent molecules are expected to be trapped transiently in this metastable state.
Open Access
Electrostatics of Polymer Translocation Events in Electrolyte Solutions
(American Institute of Physics Inc., 2016) Buyukdagli, S.; Ala-Nissila, T.
We develop an analytical theory that accounts for the image and surface charge interactions between a charged dielectric membrane and a DNA molecule translocating through the membrane. Translocation events through neutral carbon-based membranes are driven by a competition between the repulsive DNA-image-charge interactions and the attractive coupling between the DNA segments on the trans and the cis sides of the membrane. The latter effect is induced by the reduction of the coupling by the dielectric membrane. In strong salt solutions where the repulsive image-charge effects dominate the attractive trans-cis coupling, the DNA molecule encounters a translocation barrier of ∼10 kBT. In dilute electrolytes, the trans-cis coupling takes over image-charge forces and the membrane becomes a metastable attraction point that can trap translocating polymers over long time intervals. This mechanism can be used in translocation experiments in order to control DNA motion by tuning the salt concentration of the solution.
Open Access
Like-Charge Attraction And Opposite-Charge Decomplexation Between Polymers and DNA Molecules
(American Physical Society, 2017) Buyukdagli, S.
We scrutinize the effect of polyvalent ions on polymer-DNA interactions. We extend a recently developed test-charge theory [S. Buyukdagli, Phys. Rev. E 94, 042502 (2016)1539-375510.1103/PhysRevE.94.042502] to the case of a stiff polymer interacting with a DNA molecule in an electrolyte mixture. The theory accounts for one-loop level electrostatic correlation effects such as the ionic cloud deformation around the strongly charged DNA molecule as well as image-charge forces induced by the low DNA permittivity. Our model can reproduce and explain various characteristics of the experimental phase diagrams for polymer solutions. First, the addition of polyvalent cations to the electrolyte solution results in the attraction of the negatively charged polymer by the DNA molecule. The glue of the like-charge attraction is the enhanced shielding of the polymer charges by the dense counterion layer at the DNA surface. Second, through the shielding of the DNA-induced electrostatic potential, mono- and polyvalent cations of large concentration both suppress the like-charge attraction. Within the same formalism, we also predict a new opposite-charge repulsion effect between the DNA molecule and a positively charged polymer. In the presence of polyvalent anions such as sulfate or phosphate, their repulsion by the DNA charges leads to the charge screening deficiency of the region around the DNA molecule. This translates into a repulsive force that results in the decomplexation of the polymer from DNA. This opposite-charge repulsion phenomenon can be verified by current experiments and the underlying mechanism can be beneficial to gene therapeutic applications where the control over polymer-DNA interactions is the key factor.
Open Access
Role of water in the lyotropic liquid crystalline lithium Iodide–Iodine–water–C12E10 mesophase as a gel electrolyte in a dye-sensitized solar cell
(American Chemical Society, 2021-07-13) Yılmaz Topuzlu, Ezgi; Ülgüt, Burak; Dağ, Ömer
By replacing volatile and flammable organic-based electrolytes with gel electrolytes, dye-sensitized solar cells (DSSCs) may be a viable and more practical alternative to other clean energy sources. Although they present a promising alternative, gel electrolytes still have some drawbacks for practical applications, such as low ionic conductivity and infusion difficulties into the pores of the working electrode. Here, we introduce a new one-step fabrication method that uses a lyotropic liquid crystalline (LLC) gel electrolyte (LiI:I2:H2O:C12H25(OCH2CH2)10OH) and a dye (N719) to construct a DSSC that performs (7.32%) 2.2 times better compared with a traditional two-step production. Water plays a key role in the gel electrolyte, where the H2O/LiI mole ratio is around 2.57 under ambient laboratory conditions (ALCs); however, this ratio linearly increases to 4.00 and then to 5.85 at 40 and 75% humidities, respectively, without affecting the two-dimensional (2D) hexagonal structure of the mesophase. The ionic conductivity of the gel electrolyte linearly increases accordingly, by 2.2 (4.8 × 10–5 to 10.6 × 10–5) and 13.1 times (63.0 × 10–5 S/cm) from ALC to 40 and ALC to 75% humidity, respectively. Increasing water in the gel phase improves the conductivity of the LLC mesophase and the short-circuit current (Isc) of the DSSC, but negatively influences the open-circuit voltage (Voc) of the cell, equilibrium reaction between the LiI and I2, and the anchoring of the dye molecules over the titania surface.