Browsing by Subject "Electrostatic interactions"

Now showing 1 - 8 of 8

Open Access
Controlled optical transition rates in nanodroplets
(IEEE, 2000) Özçelik, Serdar
The time-resolved fluorescence measurements of 3,3′-diethyl-5,5′-dichloro-9-phenylthiacarbocyanine (DDPT) in bulk solvents and methanol-in-oil reverse micellar systems is presented which include nano-sized methanol droplets stabilized with anionic surfactant aerosol-OT (AOT) in n-heptane, at room temperature. Relative fluorescence intensities of DDPT increase with a factor of 16 in m/o reverse micelles in comparison to those in bulk methanol. The radiative and nonradiative rate constants decreases in methanol dispersions, indicating that internal motions of DDPT in the droplets is reduced due to strong electrostatic interactions between the positively charged DDPT and the negatively charged sulfonate head-groups of AOT.
Open Access
Dependence of triboelectric charging behavior on material microstructure
(American Physical Society, 2017-08-23) Wang, A. E.; Gill, P. S.; Holonga, M.; Yavuz, Z.; Baytekin, H. T.; Sankaran, R. M.; Lacks, D. J.
We demonstrate that differences in the microstructure of chemically identical materials can lead to distinct triboelectric charging behavior. Contact charging experiments are carried out between strained and unstrained polytetrafluoroethylene samples. Whereas charge transfer is random between samples of identical strain, when one of the samples is strained, systematic charge transfer occurs. No significant changes in the molecular-level structure of the polymer are observed by XRD and micro-Raman spectroscopy after deformation. However, the strained surfaces are found to exhibit void and craze formation spanning the nano- to micrometer length scales by molecular dynamics simulations, SEM, UV-vis spectroscopy, and naked-eye observations. This suggests that material microstructure (voids and crazes) can govern the triboelectric charging behavior of materials.
Open Access
Dielectric trapping of biopolymers translocating through insulating membranes
(MDPI AG, 2018) Büyükdağlı, Şahin; Sarabadani, J.; Ala-Nissila, T.
Sensitive sequencing of biopolymers by nanopore-based translocation techniques requires an extension of the time spent by the molecule in the pore. We develop an electrostatic theory of polymer translocation to show that the translocation time can be extended via the dielectric trapping of the polymer. In dilute salt conditions, the dielectric contrast between the low permittivity membrane and large permittivity solvent gives rise to attractive interactions between the cis and trans portions of the polymer. This self-attraction acts as a dielectric trap that can enhance the translocation time by orders of magnitude. We also find that electrostatic interactions result in the piecewise scaling of the translocation time t with the polymer length L. In the short polymer regime L ≲ 10 nm where the external drift force dominates electrostatic polymer interactions, the translocation is characterized by the drift behavior τ ~ L2. In the intermediate length regime 10 nm. ≲ L ≲ kb -1 where kb is the Debye-Hückel screening parameter, the dielectric trap takes over the drift force. As a result, increasing polymer length leads to quasi-exponential growth of the translocation time. Finally, in the regime of long polymers L ≳ kb -1 where salt screening leads to the saturation of the dielectric trap, the translocation time grows linearly as τ ~ L. This strong departure from the drift behavior highlights the essential role played by electrostatic interactions in polymer translocation.
Open Access
Electrostatic effects on nanofiber formation of self-assembling peptide amphiphiles
(Elsevier, 2011) Toksoz, S.; Mammadov R.; Tekinay, A. B.; Güler, Mustafa O.
Self-assembling peptide amphiphile molecules have been of interest to various tissue engineering studies. These molecules self-assemble into nanofibers which organize into three-dimensional networks to form hydrocolloid systems mimicking the extracellular matrix. The formation of nanofibers is affected by the electrostatic interactions among the peptides. In this work, we studied the effect of charged groups on the peptides on nanofiber formation. The self-assembly process was studied by pH and zeta potential measurements, FT-IR, circular dichroism, rheology, atomic force microscopy, scanning electron microscopy and transmission electron microscopy. The aggregation of the peptides was triggered upon neutralization of the charged residues by pH change or addition of electrolyte or biomacromolecules. Understanding the controlled formation of the hydrocolloid gels composed of peptide amphiphile nanofibers can lead us to develop in situ gel forming bioactive collagen mimetic nanofibers for various tissue engineering studies including bioactive surface coatings. © 2010 Elsevier Inc.
Open Access
Interactions between zwitterionic membranes in complex electrolytes
(American Physical Society, 2020) Büyükdağlı, Şahin; Podgornik, R.
We investigate the electrostatic interactions of zwitterionic membranes immersed in mixed electrolytes composed of mono- and multivalent ions. We show that the presence of monovalent salt is a necessary condition for the existence of a finite electrostatic force on the membrane. As a result, the mean-field membrane pressure originating from the surface dipoles exhibits a nonuniform salt dependence, characterized by an enhancement for dilute salt conditions and a decrease at intermediate salt concentrations. On addition of multivalent cations to the submolar salt solution, the separate interactions of these cations with the opposite charges of the surface dipoles makes the intermembrane pressure more repulsive at low membrane separation distances and strongly attractive at intermediate distances, resulting in a discontinuous like-charge binding transition followed by the membrane binding transition. By extending our formalism to account for correlation corrections associated with large salt concentrations, we show that membranes of high surface dipole density immersed in molar salt solutions may undergo a membrane binding transition even without the multivalent cations. Hence, the tuning of the surface polarization forces by membrane engineering can be an efficient way to adjust the equilibrium configuration of dipolar membranes in concentrated salt solutions.
Open Access
Orientational transition and complexation of DNA with anionic membranes: weak and intermediate electrostatic coupling
(American Physical Society, 2019) Büyükdağlı, Şahin; Podgornik, R.
We characterize the role of charge correlations in the adsorption of a short, rodlike anionic polyelectrolyte onto a similarly charged membrane. Our theory reveals two different mechanisms driving the like-charge polyelectrolyte-membrane complexation: In weakly charged membranes, repulsive polyelectrolyte-membrane interactions lead to the interfacial depletion and a parallel orientation of the polyelectrolyte with respect to the membrane; while in the intermediate membrane charge regime, the interfacial counterion excess gives rise to an attractive “salt-induced” image force. This furthermore results in an orientational transition from a parallel to a perpendicular configuration and a subsequent short-ranged like-charge adsorption of the polyelectrolyte to the substrate. A further increase of the membrane charge engenders a charge inversion, originating from surface-induced ionic correlations, that act as a separate mechanism capable of triggering the like-charge polyelectrolyte-membrane complexation over an extended distance interval from the membrane surface. The emerging picture of this complexation phenomenon identifies the interfacial “salt-induced” image forces as a powerful control mechanism in polyelectrolyte-membrane complexation.
Open Access
Peptide-mediated constructs of quantum dot nanocomposites for enzymatic control of nonradiative energy transfer
(American Chemical Society, 2011) Seker U.O.S.; Ozel, T.; Demir, Hilmi Volkan
A bottom-up approach for constructing colloidal semiconductor quantum dot (QDot) nanocomposites that facilitate nonradiative Förster-type resonance energy transfer (FRET) using polyelectrolyte peptides was proposed and realized. The electrostatic interaction of these polypeptides with altering chain lengths was probed for thermodynamic, structural, and morphological aspects. The resulting nanocomposite film was successfully cut with the protease by digesting the biomimetic peptide layer upon which the QDot assembly was constructed. The ability to control photoluminescence decay lifetime was demonstrated by proteolytic enzyme activity, opening up new possibilities for biosensor applications.
Open Access
Theoretical modeling of polymer translocation: from the electrohydrodynamics of short polymers to the fluctuating long polymers
(MDPI AG, 2019) Büyükdağlı, Şahin; Sarabadani, J.; Ala-Nissila, T.
The theoretical formulation of driven polymer translocation through nanopores is complicated by the combination of the pore electrohydrodynamics and the nonequilibrium polymer dynamics originating from the conformational polymer fluctuations. In this review, we discuss the modeling of polymer translocation in the distinct regimes of short and long polymers where these two effects decouple. For the case of short polymers where polymer fluctuations are negligible, we present a stiff polymer model including the details of the electrohydrodynamic forces on the translocating molecule. We first show that the electrohydrodynamic theory can accurately characterize the hydrostatic pressure dependence of the polymer translocation velocity and time in pressure-voltage-driven polymer trapping experiments. Then, we discuss the electrostatic correlation mechanisms responsible for the experimentally observed DNA mobility inversion by added multivalent cations in solid-state pores, and the rapid growth of polymer capture rates by added monovalent salt in α-Hemolysin pores. In the opposite regime of long polymers where polymer fluctuations prevail, we review the iso-flux tension propagation (IFTP) theory, which can characterize the translocation dynamics at the level of single segments. The IFTP theory is valid for a variety of polymer translocation and pulling scenarios. We discuss the predictions of the theory for fully flexible and rodlike pore-driven and end-pulled translocation scenarios, where exact analytic results can be derived for the scaling of the translocation time with chain length and driving force.