Equilibrium phase behavior of gyroid-forming diblock polymer thin films.

Thin-film confinement of self-assembling block polymers results in materials with myriad potential applications-including membranes and optical devices-and provides design parameters for altering phase behavior that are not available in the bulk, namely, film thickness and preferential wetting. However, most research has been limited to lamella- and cylinder-forming polymers; three-dimensional phases, such as double gyroid (DG), have been observed in thin films, but their phase behavior under confinement is not yet well understood. We use self-consistent field theory to predict the equilibrium morphology of bulk-gyroid-forming AB diblock polymers under thin-film confinement.

Boundary Frustration in Double-Gyroid Thin Films.

Self-consistent field theory for thin films of AB diblock polymers in the double-gyroid phase reveals that in the absence of preferential wetting of monomer species at the film boundaries, films with the (211) plane oriented parallel to the boundaries are more stable than other orientations, consistent with experimental results. This preferred orientation is explained in the context of boundary frustration. Specifically, the angle of intersection between the A/B interface and the film boundary, the wetting angle, is thermodynamically restricted to a narrow range of values.

Thermodynamics and morphology of linear multiblock copolymers at homopolymer interfaces.

Block copolymers at homopolymer interfaces are poised to play a critical role in the compatibilization of mixed plastic waste, an area of growing importance as the rate of plastic accumulation rapidly increases. Using molecular dynamics simulations of Kremer-Grest polymer chains, we have investigated how the number of blocks and block degree of polymerization in a linear multiblock copolymer impacts the interface thermodynamics of strongly segregated homopolymer blends, which is key to effective compatibilization. The second virial coefficient reveals that interface thermodynamics are more sensitive to block degree of polymerization than to the number of blocks.

Probing physical properties of single amyloid fibrils using nanofluidic channels.

Amyloid fibril formation is central to the pathology of many diseases, including neurodegenerative disorders such as Alzheimer's and Parkinson's disease. Amyloid fibrils can also have functional and scaffolding roles, for example in bacterial biofilms, and have also been exploited as useful biomaterials. Despite being linear protein homopolymers, amyloid fibrils can exhibit significant structural and morphological polymorphism, making it relevant to study them on the single fibril level.

Gaming self-consistent field theory: Generative block polymer phase discovery.

Block polymers are an attractive platform for uncovering the factors that give rise to self-assembly in soft matter owing to their relatively simple thermodynamic description, as captured in self-consistent field theory (SCFT). SCFT historically has found great success explaining experimental data, allowing one to construct phase diagrams from a set of candidate phases, and there is now strong interest in deploying SCFT as a screening tool to guide experimental design. However, using SCFT for phase discovery leads to a conundrum: How does one discover a new morphology if the set of candidate phases needs to be specified in advance? This long-standing challenge was surmounted by training a deep convolutional generative adversarial network (GAN) with trajectories from converged SCFT solutions, and then deploying the GAN to generate input fields for subsequent SCFT calculations.

Liquid-Like States in Micelle-Forming Diblock Copolymer Melts.

Large cell self-consistent field theory (SCFT) solutions for a neat, micelle-forming diblock copolymer melt, initialized using the structure of a Lennard-Jones fluid, reveal the existence of a vast number of liquid-like states, with free energies of order 10 per chain higher than the body-centered cubic (bcc) state near the order-disorder transition (ODT). Computation of the structure factor for these liquids at temperatures below the ODT indicates that their intermicellar distance is slightly swollen compared to bcc. In addition to providing a mean-field picture of the disordered micellar state, the number of liquid-like states and their near-degeneracy with the equilibrium bcc morphology suggest that self-assembly of micelle-forming diblock copolymers navigates a rugged free energy landscape with many local minima.

Diffusion of knots in nanochannel-confined DNA molecules.

We used Langevin dynamics simulations without hydrodynamic interactions to probe knot diffusion mechanisms and the time scales governing the evolution and the spontaneous untying of trefoil knots in nanochannel-confined DNA molecules in the extended de Gennes regime. The knot untying follows an "opening up process," wherein the initially tight knot continues growing and fluctuating in size as it moves toward the end of the DNA molecule before its annihilation at the chain end. The mean knot size increases significantly and sub-linearly with increasing chain contour length.

Dynamics and Equilibration Mechanisms in Block Copolymer Particles.

Self-assembly of block copolymers into interesting and useful nanostructures, in both solution and bulk, is a vibrant research arena. While much attention has been paid to characterization and prediction of equilibrium phases, the associated dynamic processes are far from fully understood. Here, we explore what is known and not known about the equilibration of particle phases in the bulk, and spherical micelles in solution.

Tuning conformational asymmetry in particle-forming diblock copolymer alloys.

Self-consistent field theory is employed to compute the phase behavior of binary blends of conformationally asymmetric, micelle-forming diblock copolymers with miscible corona blocks and immiscible core blocks (a diblock copolymer "alloy"). The calculations focus on establishing conditions that promote the formation of Laves phases by tuning the relative softness of the cores of the two different Laves phase particles independent control of their conformational asymmetries. Increasing the conformational asymmetry of the more spherical particles of the Laves structure has a stabilizing effect, consistent with the expectations of increased imprinting of the Wigner-Seitz cells on the core/corona interface as conformational asymmetry increases.

DNA fragmentation in a steady shear flow.

We have determined the susceptibility of T4 DNA (166 kilobase pairs, kbp) to fragmentation under steady shear in a cone-and-plate rheometer. After shearing for at least 30 min at a shear rate of , corresponding to a Reynolds number of and a Weissenberg number of , % of the sample is broken into a polydisperse mixture with a number-averaged molecular weight of  kbp and a polydispersity index of , as measured by pulsed-field gel electrophoresis (with a 95% confidence interval). The molecular weight distributions observed here from a shear flow are similar to those produced by a (dominantly extensional) sink flow of DNA and are qualitatively different than the midpoint scission observed in simple extensional flow.

DNA in nanochannels: theory and applications.

Nanofluidic structures have over the last two decades emerged as a powerful platform for detailed analysis of DNA on the kilobase pair length scale. When DNA is confined to a nanochannel, the combination of excluded volume and DNA stiffness leads to the DNA being stretched to near its full contour length. Importantly, this stretching takes place at equilibrium, without any chemical modifications to the DNA.

Stabilizing a Double Gyroid Network Phase with 2 nm Feature Size by Blending of Lamellar and Cylindrical Forming Block Oligomers.

Molecular dynamics simulations are used to study binary blends of an AB-type diblock and an AB-type miktoarm triblock amphiphiles (also known as high-χ block oligomers) consisting of sugar-based (A) and hydrocarbon (B) blocks. In their pure form, the AB diblock and AB triblock amphiphiles self-assemble into ordered lamellar (LAM) and cylindrical (CYL) structures, respectively. At intermediate compositions, however, the AB-rich blend (0.

Alternating Gyroid in Block Polymer Blends.

Alternating gyroid is a lower symmetry variant of the double gyroid morphology, where the left-handed and right-handed chiral networks are physically distinct. This structure is of particular interest for photonic applications owing to predictions of a complete photonic band gap subject to the requirement of a large dielectric contrast between the individual networks and sufficient optical matching between one of the networks and the matrix. We provide evidence, via self-consistent field theory (SCFT), that stoichiometric blends of double-gyroid-forming AB and BC diblock copolymers with relatively immiscible A and C blocks should form an alternating gyroid morphology with complementary three-dimensional A and C networks that have a free energy that is nearly degenerate with two phase-separated double gyroid states.

Free Energy Trajectory for Escape of a Single Chain from a Diblock Copolymer Micelle.

We use umbrella sampling to compute the free energy trajectory of a single chain undergoing expulsion from an isolated diblock copolymer micelle. This approach elucidates the experimentally unobservable transition state, identifies the spatial position of the maximum free energy, and reveals the chain conformation of a single chain as it undergoes expulsion. Combining umbrella sampling with dissipative particle dynamics simulations of AB micelles reveals that the core block (A) of the expelled chain remains partially stretched at the transition state, in contrast with the collapsed state assumed in some previous models.

Interactions between two knots in nanochannel-confined DNA molecules.

Experimental data on the interaction between two knots in deoxyribonucleic acid (DNA) confined in nanochannels produced two particular behaviors of knot pairs along the DNA molecules: (i) widely separated knots experience an attractive interaction but only remain in close proximity for several seconds and (ii) knots tend to remain separated until one of the knots unravels at the chain end. The associated free energy profile of the knot-knot separation distance for an ensemble of DNA knots exhibits a global minimum when knots are separated, indicating that the separated knot state is more stable than the intertwined knot state, with dynamics in the separated knot state that are consistent with independent diffusion. The experimental observations of knot-knot interactions under nanochannel confinement are inconsistent with previous simulation-based and experimental results for stretched polymers under tension wherein the knots attract and then stay close to each other.

The C36 Laves phase in diblock polymer melts.

The C14 and C15 Laves phases form as micelle packing structures in many types of soft matter, but the related C36 phase, which consists of alternating C14-type and C15-type layers, has not been observed in any such system. To understand this absence in the context of diblock polymers, we used self-consistent field theory to relate the morphology and energetics of C36 to other known mesophases. Two case studies were conducted: blends of AB diblock polymers with A homopolymers (where A forms the micelle core), in which C14 and C15 have stability windows, and neat AB diblock melts, in which Laves phases are metastable.

Open-source platform for block polymer formulation design using particle swarm optimization.

Facile exploration of large design spaces is critical to the development of new functional soft materials, including self-assembling block polymers, and computational inverse design methodologies are a promising route to initialize this task. We present here an open-source software package coupling particle swarm optimization (PSO) with an existing open-source self-consistent field theory (SCFT) software for the inverse design of self-assembling block polymers to target bulk morphologies. To lower the barrier to use of the software and facilitate exploration of novel design spaces, the underlying SCFT calculations are seeded with algorithmically generated initial fields for four typical morphologies: lamellae, network phases, cylindrical phases, and spherical phases.

Modeling of Quasi-Static Floating-Gate Transistor Biosensors.

Floating-gate transistors (FGTs) are a promising class of electronic sensing architectures that separate the transduction elements from molecular sensing components, but the factors leading to optimum device design are unknown. We developed a model, generalizable to many different semiconductor/dielectric materials and channel dimensions, to predict the sensor response to changes in capacitance and/or charge at the sensing surface upon target binding or other changes in surface chemistry. The model predictions were compared to experimental data obtained using a floating-gate (extended gate) electrochemical transistor, a variant of the generic FGT architecture that facilitates low-voltage operation and rapid, simple fabrication using printing.

Order and Disorder in ABCA' Tetrablock Terpolymers.

Self-assembly of poly(styrene)--poly(isoprene)--poly(lactide)--poly(styrene) (PS-PI-PLA-PS' or SILS') tetrablock terpolymers, where the volume fractions of the first three blocks are nearly equivalent, was studied both experimentally and using the self-consistent field theory (SCFT). SCFT indicates that addition of the terminal PS' chain to a low-molecular-mass, hexagonally packed cylinders forming, SIL precursor can produce a disordered state due to preferential mixing of the polystyrene end-blocks with the PI and PLA midblocks in the SILS' tetrablock, alleviating the unfavorable contact between the highly incompatible PI and PLA segments. In contrast, SCFT predicts that higher-molar-mass triblock precursors will maintain an ordered morphology upon addition of the terminal PS' block due to stronger overall segregation strengths.

3D Printing-Enabled DNA Extraction for Long-Read Genomics.

Long-read genomics technologies such as nanopore sequencing and genome mapping in nanochannels extract genomic information in the kilobase to megabase pair range from single DNA molecules, thereby overcoming read-length limitations in next-generation DNA sequencing. Long-read technologies start with long DNA molecules as the input and thus benefit from universal sample preparation methods that are fast and shear-free and present a scope of automation and direct upstream integration. We describe a 3D printing-assisted poly(dimethylysiloxane)-based DNA sample preparation device, where diffusive chemical lysis followed by electrophoresis produces circa 100 ng of long DNA directly from cells with less than 5 min of labor.

Symmetry breaking in particle-forming diblock polymer/homopolymer blends.

Compositionally asymmetric diblock copolymers provide an attractive platform for understanding the emergence of tetragonally close-packed, Frank-Kasper phases in soft matter. Block-polymer phase behavior is governed by a straightforward competition between chain stretching and interfacial tension under the constraint of filling space at uniform density. Experiments have revealed that diblock copolymers with insufficient conformational asymmetry to form Frank-Kasper phases in the neat-melt state undergo an interconversion from body-centered cubic (bcc) close-packed micelles to a succession of Frank-Kasper phases (σ to C14 to C15) upon the addition of minority-block homopolymer in the dry-brush regime, accompanied by the expected transition from bcc to hexagonally packed cylinders in the wet-brush regime.

Glomerular filtration and podocyte tensional homeostasis: importance of the minor type IV collagen network.

The minor type IV collagen chain, which is a significant component of the glomerular basement membrane in healthy individuals, is known to assemble into large structures (supercoils) that may contribute to the mechanical stability of the collagen network and the glomerular basement membrane as a whole. The absence of the minor chain, as in Alport syndrome, leads to glomerular capillary demise and eventually to kidney failure. An important consideration in this problem is that the glomerular capillary wall must be strong enough to withstand the filtration pressure and porous enough to permit filtration at reasonable pressures.

Open-source code for self-consistent field theory calculations of block polymer phase behavior on graphics processing units.

Self-consistent field theory (SCFT) is a powerful approach for computing the phase behavior of block polymers. We describe a fast version of the open-source Polymer Self-Consistent Field (PSCF) code that takes advantage of the massive parallelization provided by a graphical processing unit (GPU). Benchmarking double-precision calculations indicate up to 30× reduction in time to converge SCFT calculations of various diblock copolymer phases when compared to the Fortran CPU version of PSCF using the same algorithms, with the speed-up increasing with increasing unit cell size for the diblock polymer problems examined here.