Formation of DNA‐Copolymer Fibrils Through an Amyloid‐Like Nucleation Polymerization Mechanism

Conjugation of a hydrophobic poly(2‐oxazoline) bearing tertiary amide groups along its backbone with a short single stranded nucleotide sequence results in an amphiphilic comb/graft copolymer, which organizes in fibrils upon direct dissolution in water. Supported by circular dichroism, atomic force microscopy, transmission electron microscopy, and scattering data, fibrils are formed through inter‐ and intramolecular hydrogen bonding between hydrogen accepting amide groups along the polymer backbone and hydrogen donating nucleic acid grafts leading to the formation of hollow tubes.

     

Dynamic and molecular association in premicellar aqueous solutions of dicarboxylate amino acid-based surfactant as studied by 1H NMR

We examined a series of amino acid-based surfactants with two carboxylic groups separated by a spacer of one, two, or three carbon atoms with sodium and calcium counterions in the premicellar concentration region near the CMC. ¹H nuclear magnetic resonance (NMR) spectroscopy and NMR diffusometry techniques were used to study the local environment, association, and translational dynamics of the surfactant's molecules. We measured the self-diffusion coefficients of the micelles, calculated the effective hydrodynamic radii, and determined the temperature region in which the premicelles exist. With an increase in temperature from 295 to 335 K, the premicellar state of the surfactant is replaced by the monomeric state.     

Three-dimensional simulation of irregular dynamics of topological solitons in moving magnetic domain walls

A three-dimensional computer simulation of dynamic processes occurring in a domain wall moving in a soft-magnetic uniaxial film with in-plane anisotropy has been performed based on the micromagnetic approach. It has been shown that the domain wall motion is accompanied by topological transformations of the magnetization distribution, or, more specifically, by “fast” processes associated with the creation and annihilation of vortices, antivortices, and singular (Bloch) points. The method used for visualizing the topological structure of magnetization distributions is based on the numerical determination of topological charges of two types by means of the integration over the contours and surfaces with variable geometry. The obtained data indicate that the choice of the initial configuration predetermines the dynamic scenario of topological transformations.     

Spin polarized current controlled dynamics of domain walls in magnetic films with in-plane anisotropy

We study the dynamic properties of asymmetric vortex Bloch walls and classical 1D Néel walls controlled by a spin-polarized current in magnetic films with in-plane anisotropy. It is shown that fairly high velocities of domain walls (up to 100 m/s) can be obtained for the current density in the range j = 10⁶–10⁸ A/cm². The nonlinear dependence of the wall velocity on the film thickness and the linear dependence of the velocity on the current density and inverse damping parameter are found.     

Charge screening in a plasma with an external ionization source

An asymptotic theory for the screening of the electric field of a dust particle or a spherical probe in a plasma with an external steady and/or internal (proportional to the electron density) gas ionization source has been developed for the first time. It has been established that the screening of the charge of a spherical body adsorbing the charge of the incident plasma particles is described by a superposition of two exponentials with different screening constants. The two exponentials are retained even in the absence of nonequilibrium fluxes on the macroparticle and only in the special case of an isothermal plasma does the screening become Debye one. The screening length is determined by the ratio of the electron-ion, β_ei, and Langevin, β_L = 4πeμ_i (where μ_i is the ion mobility), recombination coefficients. If β_L ? β_ei, then it is much larger than the electron Debye length. The ions in an isothermal plasma have been found to give the same contribution to the screening as the electrons if the electron-ion recombination coefficient exceeds the Langevin ion recombination coefficient by a factor of 2 or more, β_ei ≥ 2β_L. The Vlasov equation is used to analyze the asymptotic behavior of the macroparticle potential in a collisionless plasma.     

Conformations of molecular brushes based on polyimide and poly(methyl methacrylate) in selective solvents: Experiment and computer simulation

The effect of solvent quality with respect to main and side chains on the conformations of molecular brushes is investigated by the methods of molecular hydrodynamics and optics as well as by computer simulation. Copolymers with a polyimide backbone and poly(methyl methacrylate) side chains are studied in solvents featuring strongly different thermodynamic qualities (chloroform, ethyl acetate, and 3-heptanone). The studied samples have close total molecular masses and backbone lengths but differ in grafting densities and lengths of side chains: a brush with densely grafted and relatively short side chains versus a brush with loosely grafted but very long side chains. For both types of brushes, similar changes in hydrodynamic behavior with improvement in the solvent quality are found experimentally. Computer simulation shows that these changes have different origins. In the former case, macromolecules are elongated, and their volumes grow simultaneously, while in the latter case, the shape of the macromolecules remains close to spherical and the changes in hydrodynamic parameters are mainly due to an increase in the volume of macromolecules.     

Synthesis and investigation of the solution behavior of graft block copolymers of polyimide and poly(methyl methacrylate)

Graft copolymers with a polyimide backbone and poly(methyl methacrylate) side chains are investigated in dilute chloroform and ethyl acetate solutions via the methods of molecular hydrodynamics and optics. Copolymer samples are prepared through the “grafting from” method via atom-transfer radical polymerization with a multicenter polyimide macroinitiator. In solutions of copolymers with low degrees of functionalization Z (40%), supermolecular structures are formed as a result of interactions between the polyimide backbones. In samples with Z → 100%, the backbone is well screened by side chains; therefore, molecular solutions are formed in both solvents. The hydrodynamic and conformational behavior of samples with high functionalization degrees changes after the transition from ethyl acetate to chloroform owing to the different thermodynamic qualities of the solvents with respect to the copolymer components. In both solvents, the backbone tends to avoid contact with a poor solvent. This effect is more pronounced in the case of ethyl acetate. Macromolecules of the studied graft copolymers are characterized by high equilibrium rigidities (>40 nm) that are 10 times higher than the corresponding characteristics of aromatic polyimides.     

Furanosyl Oxocarbenium Ion Stability and Stereoselectivity

Lewis acid mediated substitution reactions using [D]triethylsilane as a nucleophile at the anomeric center of the four pentofuranoses, ribose, arabinose, xylose, and lyxose, all proceed with good to excellent stereoselectivity to provide the 1,2‐cis adducts. To unravel the stereoelectronic effects underlying the striking stereoselectivity in these reactions we have mapped the energy landscapes of the complete conformational space of the oxocarbenium ions of the four pentofuranoses. The potential energy surface maps provide a detailed picture of the influence of the differently oriented substituents and their mutual interactions on the stability of the oxocarbenium ions and the maps can be used to account for the observed stereoselectivities of the addition reactions.     

Simulation of the range of keV-energy electrons in a dielectric target upon spatial charge accumulation

A method is proposed for calculating the relative range of electrons in the material with low conductivity, which surface is coated by a conductive film. The method takes into account the average retarding electric field of spatial charge created in the material. The calculations were carried out using the classical generalized Widdington’s law of slowing down within the model of single-collision loss. Due to the approximations used, the calculations have a qualitative character.