Role of Defects in Ion Transport in Block Copolymer Electrolytes.

Ion conducting block copolymers can overcome traditional limitations of homopolymer electrolytes by phase separating into nanoarchitectures that can be simultaneously optimized for two or more orthogonal material properties such as high ionic conductivity and mechanical stability. A key challenge in understanding the ion transport properties of these materials is the difficulty of extracting structure-function relationships without having complete knowledge of all nanoscale transport pathways in bulk samples. Here we demonstrate a method for deriving structure-transport relationships for ion conducting block copolymers using thin films and interdigitated electrodes. Well-defined and directly imaged structure in films of poly(styrene)-block-poly(2-vinylpyridine) is controlled using techniques of directed self-assembly then the poly(2-vinylpyridine) is selectively converted into an ion conductor. The ion conductivity is found to be directly proportional to the total number of connected paths between electrodes and the path length. A single defect such as a dislocation anywhere in the path of an ion conducting route disconnects and precludes that pathway from contributing to the conductivity and results in an increase in the dielectric parameter of the film. When all the ion conduction pathways are blocked between electrodes, the conductivity is negligible, 4 orders of magnitude lower compared to a completely connected morphology and the dielectric parameter increases by a factor of 50. These results have profound implications for the interpretation, design, and processing of block copolymer electrolytes for applications as ion conducting membranes.

Modification of Lipase with Poly(4-acryloylmorpholine) Enhances Solubility and Transesterification Activity in Anhydrous Ionic Liquids.

Tuning the molecular interaction between enzymes and their solvent environment through polymer modification can greatly improve activity and thus utility in biocatalytic reactions. In this work, this approach was exploited to enhance the activity of lipase A (LipA) from Bacillus subtilis in anhydrous ionic liquids (ILs), which are highly attractive solvents for biocatalysis. Specifically, we showed that the transesterification activity of LipA in anhydrous 1-butyl-3-methyl imidazolium hexafluorophosphate ([BMIM][PF6]) was improved up to 19-fold via covalently conjugating the enzyme with the IL-soluble polymer poly(4-acryloylmorpholine) (PAcMO). The increase in transesterification activity correlated with an increase in LipA solubility in [BMIM][PF6] as well as, notably, the number of conjugated PAcMO repeat units. Light scattering results further showed that the attachment of PAcMO disrupted the aggregation of LipA in aqueous buffer, which was used as a proxy to understand the mechanism of activation of LipA in the IL, where aggregation was more pronounced. Additionally, using static light scattering, the Flory-Huggins interaction parameter (χ) for the polymer-IL interactions was determined (0.457). The favorable PAcMO-IL interactions presumably compensated for the unfavorable interactions between the enzyme and IL, which resulted in the improvement in dissolution and, in turn, activity due to reduced diffusional limitations. Through rationally considering χ, a similar approach may be used to tune the molecular interaction between other enzymes and ILs with other polymers, which has widespread implications for the enhancement of biocatalysis in ILs.

Amine Induced Retardation of the Radical-Mediated Thiol-Ene Reaction via the Formation of Metastable Disulfide Radical Anions.

The effect of amines on the kinetics and efficacy of radical-mediated thiol-ene coupling (TEC) reactions was investigated. By varying the thiol reactant and amine additive, it was shown that amines retard thiyl radical-mediated reactions when the amine is adequately basic enough to deprotonate the thiol affording the thiolate anion, e.g., when the weakly basic amine tetramethylethylenediamine was incorporated in the TEC reaction between butyl 2-mercaptoacetate and an allyl ether at 5 mol %, the final conversion was reduced from quantitative to <40%. Alternatively, no effect is observed when the less acidic thiol butyl 3-mercaptopropionate is employed. The thiolate anion was established as the retarding species through the introduction of ammonium and thiolate salt additives into TEC formulations. The formation of a two-sulfur three-electron bonded disulfide radical anion (DRA) species by the reaction of a thiyl radical with a thiolate anion was determined as the cause for the reduction in catalytic radicals and the TEC rate. Thermodynamic and kinetic trends in DRA formations were computed using density functional theory and by modeling the reaction as an associative electron transfer process. These trends correlate well with the experimental retardation trends of various thiolate anions in TEC reactions.

Optically diffracting hydrogels for screening kinase activity in vitro and in cell lysate: impact of material and solution properties.

Optically diffracting films based on hydrogel-encapsulated crystalline colloidal arrays have considerable utility as sensors for detecting enzymaticphosphorylation and, thus, in screening small molecule modulators of kinases. In this work, we have investigated the impact of hydrogel properties, as well as the role of the ionic character of the surrounding environment, on the optical sensitivity of kinase responsive crystalline colloidal array-containing hydrogels. In agreement with a model of hydrogel swelling, the optical sensitivity of such materials increased as the shear modulus and the Flory-Huggins interaction parameter between polymer and solvent decreased. Additionally, elimination of extraneous charges in the polymer backbone by exploiting azide-alkyne click chemistry to functionalize the hydrogels with a peptide substrate for protein kinase A further enhanced the sensitivity of the optically diffracting films. Increasing peptide concentration and, in turn, immobilized charge within the hydrogel network was shown to increase the optical response over a range of ionic strength conditions. Ultimately, we showed that, by tuning the hydrogel and solution properties, as little as 0.1 U/µL protein kinase A could be detected in short reaction times (i.e., 2 h), which is comparable to conventional biochemical kinase assays. We further showed that this approach can be used to detect protein kinase A activity in lysate from HEK293 cells. The sensitivity of the resulting films, coupled with the advantages of photonic crystal based sensors (e.g., label free detection), makes this approach highly attractive for screening enzymatic phosphorylation.

Photopatterning of cross-linkable epoxide-functionalized block copolymers and dual-tone nanostructure development for fabrication across the nano- and microscales.

The self-assembly of block copolymers in thin films provides an attractive approach to patterning 5-100 nm structures. Cross-linking and photopatterning of the self-assembled block copolymer morphologies provide further opportunities to structure such materials for lithographic applications, and to also enhance the thermal, chemical, or mechanical stability of such nanostructures to achieve robust templates for subsequent fabrication processes. Here, model lamellar-forming diblock copolymers of polystyrene and poly(methyl methacrylate) with an epoxide functionality are synthesized by atom transfer radical polymerization. We demonstrate that self-assembly and cross-linking of the reactive block copolymer materials in thin films can be decoupled into distinct, controlled process steps using solvent annealing and thermal treatment/ultraviolet exposure, respectively. Conventional optical lithography approaches can also be applied to the cross-linkable block copolymer materials in thin films and enable simultaneous structure formation across scales-micrometer scale patterns achieved by photolithography and nanostructures via self-assembly of the block copolymer. Such materials and processes are thus shown to be capable of self-assembling distinct block copolymers (e.g., lamellae of significantly different periodicity) in adjacent regions of a continuous thin film.

Charge-tunable polymers as reversible and recyclable flocculants for the dewatering of microalgae.

Microalgae-derived biofuels have potential advantages over other renewable, crop-based resources; however, large-scale production is not currently economical due, in part, to challenges in the harvesting step. In this article, we present a novel approach for the dewatering and harvesting of microalgae using flocculants that can be recovered and recycled. Polyampholytes with molecular charges dependent upon pH (ranging from net positively- to net negatively-charged) are used as a model flocculant system and provide reversible electrostatic interactions with the negatively-charged algal cells. These pH-dependent properties allow the polyampholytic flocculants to efficiently desorb from concentrated biomass and, unlike most commercial flocculants that have permanently charged functionalities, be recovered and recycled for further dewatering processes. The behavior of the model polyampholytic flocculants is characterized for the dewatering of Chlorella vulgaris (UTEX 395). The reversible and recyclable flocculants achieve >99% flocculation efficiencies, are recovered at more than 98 wt% yields after biomass dewatering, and can be recycled over five times for flocculation.

Label-free detection of missense mutations and methylation differences in the p53 gene using optically diffracting hydrogels.

We have developed a novel approach for DNA detection as well as genetic screening of mutations by uniquely combining DNA-responsive and optically diffracting materials. This approach entails the polymerization of a photonic crystal within a hydrogel network that alters the diffraction of light in response to a target DNA strand. The utility of this approach, which permits label-free sensing, was demonstrated via the detection of a target sequence from the DNA binding domain of the major tumor suppressor protein p53. Using a complementary capture probe strand, we were able to detect down to picomole concentrations of the target p53 sequence. Moreover, we demonstrated that this approach could readily detect a single base pair mutation in the target strand, which corresponds to the hotspot cancer mutation R175H in p53. The sensitivity of detection was increased by lowering the rate of annealing of the target strand and adjusting the solution ionic strength during optical characterization. Changes in ionic strength during characterization impact the melting temperature of the bound target DNA and the Donnan potential between the hydrogel and solution, which influence detection. We further showed that this approach is sensitive to epigenetic changes via the detection of a fully methylated form of the target p53 sequence. Ultimately, this approach represents a new paradigm for DNA detection and specifically genetic screening of p53 as well as other disease markers and nucleotide modifications that alter the properties of DNA (e.g., epigenetic alterations and adducts with chemical carcinogens).

Photonic crystal kinase biosensor.

We have developed a novel biosensor for kinases that is based on a kinase-responsive polymer hydrogel, which enables label-free screening of kinase activity via changes in optical properties. The hydrogel is specifically designed to swell reversibly upon phosphorylation of a target peptide, triggering a change in optical diffraction from a crystalline colloidal array of particles impregnated into the hydrogel. Diffraction measurements, and charge staining, confirmed the responsive nature of the hydrogel. Moreover, the change in diffraction of the hydrogel upon treatment with kinase exhibited a time- and dose-dependent response. A theoretical model for ionic polymer networks describes the observed optical response well and can be used to quantify the extent of phosphorylation.

A hemispherical electronic eye camera based on compressible silicon optoelectronics.

The human eye is a remarkable imaging device, with many attractive design features. Prominent among these is a hemispherical detector geometry, similar to that found in many other biological systems, that enables a wide field of view and low aberrations with simple, few-component imaging optics. This type of configuration is extremely difficult to achieve using established optoelectronics technologies, owing to the intrinsically planar nature of the patterning, deposition, etching, materials growth and doping methods that exist for fabricating such systems. Here we report strategies that avoid these limitations, and implement them to yield high-performance, hemispherical electronic eye cameras based on single-crystalline silicon. The approach uses wafer-scale optoelectronics formed in unusual, two-dimensionally compressible configurations and elastomeric transfer elements capable of transforming the planar layouts in which the systems are initially fabricated into hemispherical geometries for their final implementation. In a general sense, these methods, taken together with our theoretical analyses of their associated mechanics, provide practical routes for integrating well-developed planar device technologies onto the surfaces of complex curvilinear objects, suitable for diverse applications that cannot be addressed by conventional means.

Seed-mediated growth of shape-controlled wurtzite CdSe nanocrystals: platelets, cubes, and rods.

Prior investigations into the synthesis of colloidal CdSe nanocrystals with a wurtzite crystal structure (wz-CdSe) have given rise to well-developed methods for producing particles with anisotropic shapes such as rods, tetrapods, and wires; however, the synthesis of other shapes has proved challenging. Here we present a seed-mediated approach for the growth of colloidal, shape-controlled wz-CdSe nanoparticles with previously unobserved morphologies. The synthesis, which makes use of small (2-3 nm) wz-CdSe nanocrystals as nucleation sites for subsequent growth, can be tuned to selectively yield colloidal wz-CdSe nanocubes and hexagonal nanoplatelets in addition to nanorod and bullet-shaped particles. We thoroughly characterize the morphology and crystal structures of these new shapes, as well as discuss possible growth mechanisms in the context of control over surface chemistry and the nucleation stage.

Quantification of Metabolic Products from Microbial Hosts in Complex Media Using Optically Diffracting Hydrogels.

We herein describe a highly versatile platform approach for the in situ and real-time screening of microbial biocatalysts for enhanced production of bioproducts using photonic crystal hydrogels. This approach was demonstrated by preparing optically diffracting films based on polymerized N-isopropylacrylamide that contracted in the presence of alcohols and organic acids. The hydrogel films were prepared in a microwell plate format, which allows for high-throughput screening, and characterized optically using a microwell plate reader. While demonstrating the ability to detect a broad range of relevant alcohols and organic acids, we showed that the response of the films correlated strongly with the octanol-water partition coefficient (log P) of the analyte. Differences in the secretion of ethanol and succinic acid from strains of Zymomonas mobilis and Actinobacillus succinogenes, respectively, were further detected via optical characterization of the films. These differences, which in some cases were as low as ∼3 g/L, were confirmed by high-performance liquid chromatography, thereby demonstrating the sensitivity of this approach. Our findings highlight the potential utility of this multiplexed approach for the detection of small organic analytes in complex biological media, which overcomes a major challenge in conventional optical sensing methods.

Epitaxial self-assembly of block copolymers on lithographically defined nanopatterned substrates.

Parallel processes for patterning densely packed nanometre-scale structures are critical for many diverse areas of nanotechnology. Thin films of diblock copolymers can self-assemble into ordered periodic structures at the molecular scale (approximately 5 to 50 nm), and have been used as templates to fabricate quantum dots, nanowires, magnetic storage media, nanopores and silicon capacitors. Unfortunately, perfect periodic domain ordering can only be achieved over micrometre-scale areas at best and defects exist at the edges of grain boundaries. These limitations preclude the use of block-copolymer lithography for many advanced applications. Graphoepitaxy, in-plane electric fields, temperature gradients, and directional solidification have also been demonstrated to induce orientation or long-range order with varying degrees of success. Here we demonstrate the integration of thin films of block copolymer with advanced lithographic techniques to induce epitaxial self-assembly of domains. The resulting patterns are defect-free, are oriented and registered with the underlying substrate and can be created over arbitrarily large areas. These structures are determined by the size and quality of the lithographically defined surface pattern rather than by the inherent limitations of the self-assembly process. Our results illustrate how hybrid strategies to nanofabrication allow for molecular level control in existing manufacturing processes.

Flocculation behavior and mechanisms of block copolymer architectures on silica microparticle and Chlorella vulgaris systems.

HYPOTHESIS: Flocculation performance using polyelectrolytes is influenced by critical design parameters including molecular weight, amount and sign of the ionic charge, and polymer architecture. It is expected that systematic variation of these characteristics will impact not only flocculation efficiency (FE) achieved but that charge density and architecture, specifically, can alter the flocculation mechanism. Therefore, it should be possible to tune these design parameters for a desired flocculation application. EXPERIMENTS: Cationic-neutral and polyampholytic copolymers, exhibiting a range of molecular weights (103-106 g/mol), varying charge levels (0-100% cationic, neutral and anionic), and random or block copolymer architecture, were applied to dilute suspensions of silica microparticles (control) and Chlorella vulgaris. FE and zeta potential values were determined over a range of flocculant doses to evaluate effectiveness and mechanism achieved. FINDINGS: These different classes of copolymers provide specific benefits for flocculation, with many achieving >95% flocculation. Block copolymer flocculants exhibit a proposed, dominant bridging mechanism, therefore reducing flocculant dosage required for effective flocculation when compared to analogous random copolymer flocculants. Polyampholytic copolymers applied to C. vulgaris generally exhibited a bridging mechanism and increased FE compared to equivalent cationic-neutral copolymers, indicating a benefit of the anionic component on a more, complex, diversely charged suspension.

Curvilinear electronics formed using silicon membrane circuits and elastomeric transfer elements.

Materials and methods to achieve electronics intimately integrated on the surfaces of substrates with complex, curvilinear shapes are described. The approach exploits silicon membranes in circuit mesh structures that can be deformed in controlled ways using thin, elastomeric films. Experimental and theoretical studies of the micromechanics of such curvilinear electronics demonstrate the underlying concepts. Electrical measurements illustrate the high yields that can be obtained. The results represent significant experimental and theoretical advances over recently reported concepts for creating hemispherical photodetectors in electronic eye cameras and for using printable silicon nanoribbons/membranes in flexible electronics. The results might provide practical routes to the integration of high performance electronics with biological tissues and other systems of interest for new applications.

High-Performance pH-Switchable Supramolecular Thermosets via Cation-π Interactions.

Supramolecular chemistry has provided versatile and affordable solutions for the design of intelligent soft materials, but it cannot be applied in stiff materials. This paper describes a new concept for the design of high-performance supramolecular thermosets by using the noncovalent cation-π interaction as cross-linking. These supramolecular thermosets are a class of infusible and insoluble stiff polymers having excellent mechanical properties even at temperatures exceeding 300 °C. The cation-π interaction can be locally and reversibly installed and removed by aqueous treatments at high or low pH, respectively. Local manipulation of cross-linking confers these thermosets with multiple stimuli-responsive functions, such as recyclability, healability, adhesion, and nondestructive detection of cross-linking and mechanical properties.

Ionic Liquids as Additives to Polystyrene- Block-Poly(Methyl Methacrylate) Enabling Directed Self-Assembly of Patterns with Sub-10 nm Features.

Polystyrene- block-poly(methyl methacrylate) (PS- b-PMMA) is one of the prototypical block copolymers in directed self-assembly (DSA) research and development, with standardized protocols in place for processing on industrially relevant 300 mm wafers. Scaling of DSA patterns to pitches below 20 nm using PS- b-PMMA, however, is hindered by the relatively low Flory-Huggins interaction parameter, χ. Here, we investigate the approach of adding small amounts of ionic liquids (ILs) into PS- b-PMMA, which selectively segregates into the PMMA domain and effectively increases the χ parameter and thus the pattern resolution. The amount of IL additive is small enough to result in limited changes in PS- b-PMMA's surface and interfacial properties, thus maintaining industry-friendly processing by thermal annealing with a free surface. Three different ILs are studied comparatively regarding their compositional process window, capability of increasing χ, and thermal stability. By adding ∼3.1 vol % of the champion IL into a low-molecular-weight PS- b-PMMA ( Mn = 10.3k- b-9.5k), we demonstrated DSA on chemically patterned substrates of lamellar structures with feature sizes <8.5 nm. Compatibility of the PS- b-PMMMA/IL blends with the standardized processes that have been previously developed suggests that such blend materials could provide a drop-in solution for sub-10 nm lithography with the processing advantages of PS- b-PMMA.

Enhanced Optical Sensitivity in Thermoresponsive Photonic Crystal Hydrogels by Operating Near the Phase Transition.

Photonic crystal hydrogels composed of analyte-responsive hydrogels and crystalline colloidal arrays have immense potential as reagentless chemical and biological sensors. In this work, we investigated a general mechanism to rationally tune the sensitivity of photonic crystal hydrogels consisting of stimuli-responsive polymers to small molecule analytes. This mechanism was based on modulating the demixing temperature of such hydrogels relative to the characterization temperature to in effect maximize the extent of phase separation behavior; thus, the volume changes in response to the target analytes. Using ethanol as a model analyte, we demonstrated that this mechanism led to a dramatic increase in the sensitivity of optically diffracting poly(N-isopropylacrylamide) (pNIPAM) hydrogel films that exhibit a lower critical solution temperature (LCST) behavior. The demixing temperature of the pNIPAM films was modulated by copolymerization of the films with relatively hydrophobic and hydrophilic comonomers, as well as by varying the ionic strength of the characterization solution. Our results showed that copolymerization of the films with 2.5 mol % of N-tert-butylacrylamide, which is hydrophobic relative to pNIPAM, enabled the detection limit of the pNIPAM films to ethanol to be lowered ∼2-fold at 30 °C. Additionally, increasing the ionic strength of the characterization solution above 200 mM resulted in a dramatic increase in the extent of contraction of the films in the presence of ethanol. Ultimately, it was demonstrated that as little as 16 g/L or 2 vol % of ethanol in water could reliably be detected, and that the sensitivity of the films to ethanol was predictably greatest when operating near the phase transition, such that even small additions of the analyte induced the start of demixing and the collapse of the hydrogel. Such a mechanism may be extended to photonic crystal hydrogel sensors prepared from other stimuli-responsive polymers and more broadly exploited to enhance the utility of these sensors for a broad range of analytes.

Beam broadening in transmission and conventional EBSD.

Transmission electron backscatter diffraction (t-EBSD) has become a routine technique for crystal orientation mapping when ultrahigh resolution is needed and has demonstrated advantages in the characterization of nanoscale and micron-sized samples (Babinsky et al., 2015). In this work, we use experimental measurements and simulations to compare the resolution of the transmission and conventional reflection EBSD techniques across a range of sample volumes and characterization conditions. Monte Carlo simulations of electron trajectories provide the opportunity to estimate beam size and effective resolution, as well as electron flux, as a function of sample thickness or incident beam energy in t-EBSD. Increasing incident beam energy is shown to negatively impact beam diameter in some cases, and the effect of thinning a sample for conventional EBSD is shown to improve characterization resolution but dramatically decrease the number of high-loss electrons backscattered to the detector. In addition to considering spatial resolution when implementing EBSD techniques, it is found that maintaining a high yield of diffracted electrons to the detector is also of critical importance, which is supported by experimental results. Consequently, this work provides key insights into the nature of electron scattering and probe volume for the practical implementation of both transmission and reflection EBSD techniques.

Structural Modeling of Mechanosensitivity in Non-Muscle Cells: Multiscale Approach to Understand Cell Sensing.

The contraction and spreading of nonmuscle cells are important phenomena in a number of cellular processes such as differentiation, morphogenesis, and tissue growth. Recent experimental work has shown that the topology and the mechanical properties of the underlying substrate play a significant role in directing the cell's response. In this work, we introduce a multiscale model to understand the sensing, activation, and contraction of the actin cytoskeleton of nonmuscle cells based on the idea that acto-myosin cross-bridges display a catch-bond response. After investigating the respective roles of bond catchiness and acto-myosin assembly on the mechano-sensitivity of stress fibers, we present full simulations of cells laying on arrays of micropillars. Model predictions show good qualitative agreements with experimental observation, suggesting that acto-myosin catch bonds are a major mechano-sensing element in nonmuscle cells.

Remotely Triggered Locomotion of Hydrogel Mag-bots in Confined Spaces.

In this study, soft hydrogel crawlers with remote magnetic-responsive motility in confined spaces have been developed. Inspired by the motion of maggots, the hydrogel crawlers can reversibly contract and elongate their body controlled by repeatedly switching on/off an alternating magnetic field. Based on the cyclic deformation, the hydrogel crawlers can move peristaltically in a confined space that is coated with asymmetric micro-patterns. The dependence of the hydrogel motility on the pattern structures and lubrication is characterized using experimental measurements. Such a hydrogel system pioneers the study of active motile systems in porous media and has the potential to impact the fields of targeted drug delivery and active actuators.