@article{WagnerLazarSchnakenbergetal.2016, author = {Wagner, Tom and Lazar, Jaroslav and Schnakenberg, Uwe and B{\"o}ker, Alexander}, title = {In situ Electrothemical Impedance Spectroscopy of Electrostatically Driven Selective Gold Nanoparticle Adsorption on Block Copolymer Lamellae}, series = {Trials}, volume = {8}, journal = {Trials}, publisher = {American Chemical Society}, address = {Washington}, issn = {1944-8244}, doi = {10.1021/acsami.6b07708}, pages = {27282 -- 27290}, year = {2016}, abstract = {Electrostatic attraction between charged nano particles and oppositely charged nanopatterned polymeric films enables tailored structuring of functional nanoscopic surfaces. The bottom-up fabrication of organic/inorganic composites for example bears promising potential toward cheap fabrication of catalysts, optical sensors, and the manufacture of miniaturized electric circuitry. However, only little is known about the time-dependent adsorption behavior and the electronic or ionic charge transfer in the film bulk and at interfaces during nanoparticle assembly via electrostatic interactions. In situ electrochemical impedance spectroscopy (EIS) in combination with a microfluidic system for fast and reproducible liquid delivery was thus applied to monitor the selective deposition of negatively charged gold nanoparticles on top of positively charged poly(2-vinylpyridinium) (qP2VP) domains of phase separated lamellar poly(styrene)-block-poly(2-vinylpyridinium) (PS-b-qP2VP) diblock copolymer thin films. The acquired impedance data delivered information with respect to interfacial charge alteration, ionic diffusion, and the charge dependent nanoparticle adsorption kinetics, considering this yet unexplored system. We demonstrate that the selective adsorption of negatively charged gold nanoparticles (AuNPs) on positively charged qP2VP domains of lamellar PS-b-qP2VP thin films can indeed be tracked by EIS. Moreover, we show that the nanoparticle adsorption kinetics and the nanoparticle packing density are functions of the charge density in the qP2VP domains.}, language = {en} } @article{CherstvyTeif2014, author = {Cherstvy, Andrey G. and Teif, Vladimir B.}, title = {Electrostatic effect of H1-histone protein binding on nucleosome repeat length}, series = {Physical biology : a journal for the fundamental understanding of biological systems}, volume = {11}, journal = {Physical biology : a journal for the fundamental understanding of biological systems}, number = {4}, publisher = {IOP Publ. Ltd.}, address = {Bristol}, issn = {1478-3967}, doi = {10.1088/1478-3975/11/4/044001}, pages = {6}, year = {2014}, abstract = {Within a simple biophysical model we describe the effect of electrostatic binding of H1 histone proteins on the nucleosome repeat length in chromatin. The length of wrapped DNA optimizes its binding energy to the histone core and the elastic energy penalty of DNA wrapping. The magnitude of the effect predicted from our model is in agreement with the systematic experimental data on the linear variation of nucleosome repeat lengths with H1/nucleosome ratio (Woodcock C L et al 2006 Chromos. Res. 14 17-25). We compare our model to the data for different cell types and organisms, with a widely varying ratio of bound H1 histones per nucleosome. We underline the importance of this non-specific histone-DNA charge-balance mechanism in regulating the positioning of nucleosomes and the degree of compaction of chromatin fibers in eukaryotic cells.}, language = {en} } @article{Cherstvy2012, author = {Cherstvy, Andrey G.}, title = {Critical polyelectrolyte adsorption under confinement Planar slit, cylindrical pore, and spherical cavity}, series = {Biopolymers}, volume = {97}, journal = {Biopolymers}, number = {5}, publisher = {Wiley-Blackwell}, address = {Hoboken}, issn = {0006-3525}, doi = {10.1002/bip.22023}, pages = {311 -- 317}, year = {2012}, abstract = {We explore the properties of adsorption of flexible polyelectrolyte chains in confined spaces between the oppositely charged surfaces in three basic geometries. A method of approximate uniformly valid solutions for the Green function equation for the eigenfunctions of polymer density distributions is developed to rationalize the critical adsorption conditions. The same approach was implemented in our recent study for the inverse problem of polyelectrolyte adsorption onto a planar surface, and on the outer surface of rod-like and spherical obstacles. For the three adsorption geometries investigated, the theory yields simple scaling relations for the minimal surface charge density that triggers the chain adsorption, as a function of the Debye screening length and surface curvature. The encapsulation of polyelectrolytes is governed by interplay of the electrostatic attraction energy toward the adsorbing surface and entropic repulsion of the chain squeezed into a thin slit or small cavities. Under the conditions of surface-mediated confinement, substantially larger polymer linear charge densities are required to adsorb a polyelectrolyte inside a charged spherical cavity, relative to a cylindrical pore and to a planar slit (at the same interfacial surface charge density). Possible biological implications are discussed briefly in the end.}, language = {en} } @article{CaetanoCarvalhoMetzleretal.2020, author = {Caetano, Daniel L. Z. and Carvalho, Sidney Jurado de and Metzler, Ralf and Cherstvy, Andrey G.}, title = {Critical adsorption of multiple polyelectrolytes onto a nanosphere}, series = {Interface : journal of the Royal Society}, volume = {17}, journal = {Interface : journal of the Royal Society}, number = {167}, publisher = {Royal Society}, address = {London}, issn = {1742-5689}, doi = {10.1098/rsif.2020.0199}, pages = {10}, year = {2020}, abstract = {Employing extensive Monte Carlo computer simulations, we investigate in detail the properties of multichain adsorption of charged flexible polyelectrolytes (PEs) onto oppositely charged spherical nanoparticles (SNPs). We quantify the conditions of critical adsorption-the phase-separation curve between the adsorbed and desorbed states of the PEs-as a function of the SNP surface-charge density and the concentration of added salt. We study the degree of fluctuations of the PE-SNP electrostatic binding energy, which we use to quantify the emergence of the phase subtransitions, including a series of partially adsorbed PE configurations. We demonstrate how the phase-separation adsorption-desorption boundary shifts and splits into multiple subtransitions at low-salt conditions, thereby generalizing and extending the results for critical adsorption of a single PE onto the SNP. The current findings are relevant for finite concentrations of PEs around the attracting SNP, such as the conditions for PE adsorption onto globular proteins carrying opposite electric charges.}, language = {en} }