Chain Backfolding Research Articles

PH response of sequence-controlled polyampholyte brushes.

We use molecular simulation to investigate the pH response of sequence-controlled polyampholyte brushes (PABs) with polymer chains consisting of alternating blocks of weakly acidic and basic monomers. Changes in the ionization state, height, lateral structure, and chain conformations of PABs with pH are found to differ qualitatively from those observed for polyelectrolyte brushes. Grafting density has a relatively modest effect on PAB properties. By contrast, monomer sequence strongly affects the pH response, with the extent of the response increasing with the block size. This trend is attributed to strong electrostatic attractions between oppositely charged blocks, which lead to an increase in chain backfolding as block size increases. This behavior is consistent with that observed for polyampholytes with similar monomer sequences in solution in previous studies. Our study shows that monomer sequence can be used to tune the pH response of weak PABs to generate stimuli-responsive surfaces.

Block and Gradient Copoly(2-oxazoline) Micelles: Strikingly Different on the Inside

Herein, we provide a direct proof for differences in the micellar structure of amphiphilic diblock and gradient copolymers, thereby unambiguously demonstrating the influence of monomer distribution along the polymer chains on the micellization behavior. The internal structure of amphiphilic block and gradient co poly(2-oxazolines) based on the hydrophilic poly(2-methyl-2-oxazoline) (PMeOx) and the hydrophobic poly(2-phenyl-2-oxazoline) (PPhOx) was studied in water and water-ethanol mixtures by small-angle X-ray scattering (SAXS), small-angle neutron scattering (SANS), static and dynamic light scattering (SLS/DLS), and 1H NMR spectroscopy. Contrast matching SANS experiments revealed that block copolymers form micelles with a uniform density profile of the core. In contrast to popular assumption, the outer part of the core of the gradient copolymer micelles has a distinctly higher density than the middle of the core. We attribute the latter finding to back-folding of chains resulting from hydrophilic-hydrophobic interactions, leading to a new type of micelles that we refer to as micelles with a "bitterball-core" structure.

Body-centred cubic packing of spheres - the ultimate thermotropic assembly mode for highly divergent dendrons.

We have synthesized sodium tris(alkoxy)benzoates in which one of the three alkyl chains branches further into three C18H37 chains. These AB5 hyperbranched minidendrons melt directly into a body-centred cubic (BCC) mesophase formed by spherical "micelles". In contrast, their non-branched counterparts display various mesophases before they turn into BCC upon heating. This agrees with the predictions from a numerical geometric model that relates the shape of the molecular wedge to the type of mesophase they adopt. The spheres were found to shrink in volume upon heating and expand upon cooling, as molecules, in some cases nearly half of them, are ejected and reintegrated in the spheres. The ejection of dendrons is caused by their lateral thermal expansion. The BCC appears to be the ultimate mesophase for the extremely divergent wedges such as the hyperbranched minidendrons. In dendrons with chains of unequal length, the sphere size is fixed by the shorter chains, the longer ones back-folding or interdigitating to effectively widen the wedge. This new understanding of their assembly will help in designing new dendrons, e.g. for better encapsulation of guest molecules.

Generalized conservation law for main-chain polymer nematics.

We explore the implications of the conservation law(s) and the corresponding so-called continuity equation(s), resulting from the coupling between the positional and the orientational order in main-chain polymer nematics, by showing that the vectorial and tensorial forms of these equations are in general not equivalent and cannot be reduced to one another, but neither are they disjoint alternatives. We analyze the relation between them and elucidate the fundamental role that the chain backfolding plays in the determination of their relative strength and importance. Finally, we show that the correct penalty potential in the effective free energy, implementing these conservation laws, should actually connect both the tensorial and the vectorial constraints. We show that the consequences of the polymer chains' connectivity for their consistent mesoscopic description are thus not only highly nontrivial but that its proper implementation is absolutely crucial for a consistent coarse-grained description of the main-chain polymer nematics.

Correlation functions of main-chain polymer nematics constrained by tensorial and vectorial conservation laws.

We present and analyze correlation functions of a main-chain polymer nematic in a continuum worm-like chain description for two types of constraints formalized by the tensorial and vectorial conservation laws, both originating in the microscopic chain integrity, i.e., the connectivity of the polymer chains. In particular, our aim is to identify the features of the correlation functions that are most susceptible to the differences between the two constraints. Besides the density and director autocorrelations in both the tensorial and vectorial cases, we calculate also the density-director correlation functions, the latter being a direct signature of the presence of a specific constraint. Its amplitude is connected to the strength of the constraint and is zero if none of the constraints are present, i.e., for a standard non-polymeric nematic. Generally, the correlation functions with the constraints differ substantially from the correlation functions in the non-polymeric case, if the constraints are strong which in practice requires long chains. Moreover, for the tensorial conservation law to be well distinguishable from the vectorial one, the chain persistence length should be much smaller than the total length of the chain, so that hairpins (chain backfolding) are numerous and the polar order is small.

Detection of chain backfolding in simulation of DNA in nanofluidic channels

The DNA extension in cylindrical nanochannels under moderately strong confinements in the “transition” region, where experiments are conducted, is examined by Monte Carlo simulations. The focal point is estimation of the amount of backfolding structures such as hairpins and loops in extended (linearized) DNA molecules. At the chain-ends of DNA an extensive folding (mainly as the J-type hairpins) is detected under all confinements, covering the Odijk and de Gennes regimes and the transition region between them. In contrast, in the DNA chain interior, the backfolding into Z-type hairpins is abundant in the de Gennes regime, significantly reduced in the transition region, and practically absent in the Odijk regime. The linear relationship between the DNA extension and its contour length is validated also in the transition region where explicit theories are absent.