Nonaffinity of Liquid Networks and Bicontinuous Mesophases.

Amphiphiles self-assemble into a variety of bicontinuous mesophases whose equilibrium structures take the form of high-symmetry cubic networks. Here, we show that the symmetry-breaking distortions in these systems give rise to anomalously large, nonaffine collective deformations, which we argue to be a generic consequence of "mass equilibration" within deformed networks. We propose and study a minimal "liquid network" model of bicontinuous networks, in which acubic distortions are modeled by the relaxation of residually stressed mechanical networks with constant-tension bonds. We show that nonaffinity is strongly dependent on the valency of the network as well as the degree of strain-softening or strain-stiffening tension in the bonds. Taking diblock copolymer melts as a model system, liquid network theory captures quantitative features of two bicontinuous phases based on comparison with self-consistent field theory predictions and direct experimental characterization of acubic distortions, which are likely to be pronounced in soft amphiphilic systems more generally.

Gradient Transformation of the Double Gyroid to the Double Diamond in Soft Matter.

Transitions between gyroid and diamond intercatenated double network phases occur in many types of soft matter, but to date, the structural pathway and the crystallographic relationships remain unclear. Slice and view scanning electron microscopy tomography of a diblock copolymer affords monitoring of the evolving shape of the intermaterial dividing surface, allowing structural characterization of both the majority and minority domains. Two trihedral malleable mesoatoms combine to form a single tetrahedral mesoatom in a volume additive manner while preserving network topology, as the types of loops, the number of mesoatoms in a loop, minority domain strut lengths, and directions that connect a given mesoatom to its neighbors evolve across a 150 nm wide transition zone (TZ). The [111]DD direction is coincident with the [110]DG direction so that the (111)DD and (110)DG planes define the boundaries of the TZ. Selection of the particular crystal orientations and direction and width of the transition zone is to minimize the cost of morphing the mesoatoms from one structure to the other, by maximizing like-block continuity and minimizing the variation of the surface curvature and thickness of the domains across the TZ. Such coherent continuity of the independent, intercatenated networks across the transition zone is critical for applications such as graded mechanical trusses where the pair of different networks are joined to provide different mechanical properties for adjacent grains or could serve as a nanoscale anode/cathode allowing super charging and discharging provided the networks are continuous and rigorously separate.

Flexible Block Copolymer Metamaterials Featuring Hollow Ordered Nanonetworks with Ultra-High Porosity and Surface-To-Volume Ratio.

By utilizing bicontinuous and nanoporous ordered nanonetworks, such as double gyroid (DG) and double diamond (DD), metamaterials with exceptional optical and mechanical properties can be fabricated through the templating synthesis of functional materials. However, the volume fraction range of DG in block copolymers is significantly narrow, making it unable to vary its porosity and surface-to-volume ratio. Here, the theoretically limited structural volume of the DG phase in coil-coil copolymers is overcome by enlarging the conformational asymmetry through the association of mesogens, providing fast access to achieving flexible structured materials of ultra-high porosities. The new materials design, dual-extractable nanocomposite, is created by incorporating a photodegradable block with a solvent-extractable mesogen (m) into an accepting block, resulting in a new hollow gyroid (HG) with the largely increased surface-to-volume ratio and porosity of 77 vol%. The lightweight HG exhibits a low refractive index of 1.11 and a very high specific reduced modulus, almost two times that of the typical negative gyroid (porosity≈53%) and three times that of the positive gyroid (porosity≈24%). This novel concept can significantly extend the DG phase window of block copolymers and the corresponding surface-to-volume ratio, being applicable for nanotemplate-synthesized nanomaterials with a great gain of mechanical, catalytic, and optoelectronic properties.

Soft, malleable double diamond twin.

A twin boundary (TB) is a common low energy planar defect in crystals including those with the atomic diamond structure (C, Si, Ge, etc.). We study twins in a self-assembled soft matter block copolymer (BCP) supramolecular crystal having the double diamond (DD) structure, consisting of two translationally shifted, interpenetrating diamond networks of the minority polydimethyl siloxane block embedded in a polystyrene block matrix. The coherent, low energy, mirror-symmetric double tubular network twin has one minority block network with its nodes offset from the (222) TB plane, while nodes of the second network lie in the plane of the boundary. The offset network, although at a scale about a factor of 103 larger, has precisely the same geometry and symmetry as a (111) twin in atomic single diamond where the tetrahedral units spanning the TB retain nearly the same strut (bond) lengths and strut (bond) angles as in the normal unit cell. In DD, the second network undergoes a dramatic restructuring-the tetrahedral nodes transform into two new types of mirror-symmetric nodes (pentahedral and trihedral) which alternate and link to form a hexagonal mesh in the plane of the TB. The collective reorganization of the supramolecular packing highlights the hierarchical structure of ordered BCP phases and emphasizes the remarkable malleability of soft matter.

Visualization of nonsingular defect enabling rapid control of structural color.

Stimuli-interactive structural color (SC) of a block copolymer (BCP) photonic crystal (PC) uses reversible alteration of the PC using external fluids and applied forces. The origin of the diffusional pathways of a stimulating fluid into a BCP PC has not been examined. Here, we directly visualize the vertically oriented screw dislocations in a one-dimensional lamellar BCP PC that facilitate the rapid response of visible SC. To reveal the diffusional pathway of the solvent via the dislocations, BCP lamellae are swollen with an interpenetrated hydrogel network, allowing fixation of the swollen state and subsequent microscopic examination. The visualized defects are low-energy helicoidal screw dislocations having unique, nonsingular cores. Location and areal density of these dislocations are determined by periodic concentric topographic nanopatterns of the upper surface-reconstructed layer. The nonsingular nature of the interlayer connectivity in the core region demonstrates the beneficial nature of these defects on sensing dynamics.

High-Strength, Microporous, Two-Dimensional Polymer Thin Films with Rigid Benzoxazole Linkage.

Two-dimensional (2D) rigid polymers provide an opportunity to translate the high-strength, high-modulus mechanical performance of classic rigid-rod 1D polymers across a plane by extending covalent bonding into two dimensions while simultaneously reducing density due to microporosity by structural design. Thus far, this potential has remained elusive because of the challenge of producing high-quality 2D polymer thin films, particularly those with irreversible, rigid benzazole linkages. Here, we present a facile two-step process that allows the deposition of a uniform intermediate film network via reversible, non-covalent interactions, followed by a subsequent solid-state annealing step that facilitates the irreversible conversion to a 2D covalently bonded polymer product with benzoxazole linkages. We demonstrate the versatility of this synthesis method by producing films with four different aromatic core units. The resulting films show microporosity and anisotropy with a 2D layered structure that can be exfoliated into few-layer nanosheets using a freeze-thaw method. These films have promising mechanical properties with an in-plane ultimate tensile strength of nearly 40 MPa and axial tensile and transverse compressive elastic moduli on the scale of several GPa, rivaling the performance of solution-cast films of 1D polybenzoxazole, as well as several other 1D high-strength polymer films.

Nanonetwork Thermosets from Templated Polymerization for Enhanced Energy Dissipation.

Herein, we aim to develop a facile method for the fabrication of mechanical metamaterials from templated polymerization of thermosets including phenolic and epoxy resins using self-assembled block copolymer, polystyrene-polydimethylsiloxane with tripod network (gyroid), and tetrapod network (diamond) structures, as templates. Nanoindentation studies on the nanonetwork thermosets fabricated reveal enhanced energy dissipation from intrinsic brittle thermosets due to the deliberate structuring; the calculated energy dissipation for gyroid phenolic resins is 0.23 nJ whereas the one with diamond structure gives a value of 0.33 nJ. Consistently, the gyroid-structured epoxy gives a high energy dissipation value of 0.57 nJ, and the one with diamond structure could reach 0.78 nJ. These enhanced properties are attributed to the isotropic periodicity of the nanonetwork texture with plastic deformation, and the higher number of struts in the tetrapod diamond network in contrast to tripod gyroid, as confirmed by the finite element analysis.

Extreme Energy Dissipation via Material Evolution in Carbon Nanotube Mats.

Thin layered mats comprised of an interconnected meandering network of multiwall carbon nanotubes (MWCNT) are subjected to a hypersonic micro-projectile impact test. The mat morphology is highly compliant and while this leads to rather modest quasi-static mechanical properties, at the extreme strain rates and large strains resulting from ballistic impact, the MWCNT structure has the ability to reconfigure resulting in extraordinary kinetic energy (KE) absorption. The KE of the projectile is dissipated via frictional interactions, adiabatic heating, tube stretching, and ultimately fracture of taut tubes and the newly formed fibrils. The energy absorbed per unit mass of the film can range from 7-12 MJ kg-1, much greater than any other material.

Visualizing the double-gyroid twin.

Periodic gyroid network materials have many interesting properties (band gaps, topologically protected modes, superior charge and mass transport, and outstanding mechanical properties) due to the space-group symmetries and their multichannel triply continuous morphology. The three-dimensional structure of a twin boundary in a self-assembled polystyrene-b-polydimethylsiloxane (PS-PDMS) double-gyroid (DG) forming diblock copolymer is directly visualized using dual-beam scanning microscopy. The reconstruction clearly shows that the intermaterial dividing surface (IMDS) is smooth and continuous across the boundary plane as the pairs of chiral PDMS networks suddenly change their handedness. The boundary plane therefore acts as a topological mirror. The morphology of the normally chiral nodes and strut loops within the networks is altered in the twin-boundary plane with the formation of three new types of achiral nodes and the appearance of two new classes of achiral loops. The boundary region shares a very similar surface/volume ratio and distribution of the mean and Gaussian curvatures of the IMDS as the adjacent ordered DG grain regions, suggesting the twin is a low-energy boundary.

Projectile Impact Shock-Induced Deformation of One-Component Polymer Nanocomposite Thin Films.

Matrix-free assemblies of polymer-grafted nanoparticles (PGNs) enable mechanically robust materials for a variety of structural, electronic, and optical applications. Recent quasi-static mechanical studies have identified the key parameters that enhance canopy entanglement and promote plasticity of the PGNs below Tg. Here we experimentally explore the high-strain-rate shock impact behavior of polystyrene grafted NPs and compare their energy absorption capabilities to that of homopolystyrene for film thicknesses ranging from 75 to 550 nm and for impact velocities from 350 to 800 m/s. Modeling reveals that the initial shock compression results in a rapid temperature increase at the impact site. The uniformity of this heating is consistent with observations of greater kinetic energy absorption per mass (Ep*) of thinner films due to extensive visco-plastic deformation of molten film around the penetration site. Adiabatic heating is insufficient to raise the temperature at the exit surface of the thickest films resulting in increased strain localization at the impact periphery with less melt elongation. The extent and distribution of entanglements also influence Ep*. Structurally, each NP acts as a giant cross-link node, coupling surrounding nodes via the number of canopy chains per NP and the nature and number of entanglements between canopies anchored to different NPs. Load sharing via this dual network, along with geometrical factors such as film thickness, lead to extreme Ep* arising from the sequence of instantaneous adiabatic shock heating followed by visco-plastic drawing of the film by the projectile. These observations elucidate the critical factors necessary to create robust polymer-nanocomposite multifunctional films.

Dendrons and Dendritic Terpolymers: Synthesis, Characterization and Self-Assembly Comparison.

To the best of our knowledge, this is the very first time that a thorough study of the synthetic procedures, molecular and thermal characterization, followed by structure/properties relationship for symmetric and non-symmetric second generation (2-G) dendritic terpolymers is reported. Actually, the synthesis of the non-symmetric materials is reported for the first time in the literature. Anionic polymerization enables the synthesis of well-defined polymers that, despite the architecture complexity, absolute control over the average molecular weight, as well as block composition, is achieved. The dendritic type macromolecular architecture affects the microphase separation, because different morphologies are obtained, which do not exhibit long range order, and various defects or dislocations are evident attributed to the increased number of junction points of the final material despite the satisfactory thermal annealing at temperatures above the highest glass transition temperature of all blocks. For comparison reasons, the initial dendrons (miktoarm star terpolymer precursors) which are connected to each other in order to synthesize the final dendritic terpolymers are characterized in solution and in bulk and their self-assembly is also studied. A major conclusion is that specific structures are adopted which depend on the type of the core connection between the ligand and the active sites of the dendrons.

Networks with controlled chirality via self-assembly of chiral triblock terpolymers.

Nanonetwork-structured materials can be found in nature and synthetic materials. A double gyroid (DG) with a pair of chiral networks but opposite chirality can be formed from the self-assembly of diblock copolymers. For triblock terpolymers, an alternating gyroid (GA) with two chiral networks from distinct end blocks can be formed; however, the network chirality could be positive or negative arbitrarily, giving an achiral phase. Here, by taking advantage of chirality transfer at different length scales, GA with controlled chirality can be achieved through the self-assembly of a chiral triblock terpolymer. With the homochiral evolution from monomer to multichain domain morphology through self-assembly, the triblock terpolymer composed of a chiral end block with a single-handed helical polymer chain gives the chiral network from the chiral end block having a particular handed network. Our real-space analyses reveal the preferred chiral sense of the network in the GA, leading to a chiral phase.

Alternating Gyroid Network Structure in an ABC Miktoarm Terpolymer Comprised of Polystyrene and Two Polydienes.

The synthesis, molecular and morphological characterization of a 3-miktoarm star terpolymer of polystyrene (PS, M¯n = 61.0 kg/mol), polybutadiene (PB, M¯n = 38.2 kg/mol) and polyisoprene (PI, M¯n = 29.2 kg/mol), corresponding to volume fractions (φ) of 0.46, 0.31 and 0.23 respectively, was studied. The major difference of the present material from previous ABC miktoarm stars (which is a star architecture bearing three different segments, all connected to a single junction point) with the same block components is the high 3,4-microstructure (55%) of the PI chains. The interaction parameter and the degree of polymerization of the two polydienes is sufficiently positive to create a three-phase microdomain structure as evidenced by differential scanning calorimetry and transmission electron microscopy (TEM). These results in combination with small-angle X-ray scattering (SAXS) and birefringence experiments suggest a cubic tricontinuous network structure, based on the I4132 space group never reported previously for such an architecture.

3D touchless multiorder reflection structural color sensing display.

The development of a lightweight, low-power, user-interactive three-dimensional (3D) touchless display in which a human stimulus can be detected and simultaneously visualized in noncontact mode is of great interest. Here, we present a user-interactive 3D touchless sensing display based on multiorder reflection structural colors (SCs) of a thin, solid-state block copolymer (BCP) photonic crystal (PC). Full-visible-range SCs are developed in a BCP PC consisting of alternating lamellae, one of which contains a chemically cross-linked, interpenetrated hydrogel network. The absorption of a nonvolatile ionic liquid into the domains of the interpenetrated network allows for further manipulation of SC by using multiple-order photonic reflections, giving rise to unprecedented visible SCs arising from reflective color mixing. Furthermore, by using a hygroscopic ionic liquid ink, a printable 3D touchless interactive display is created where 3D position of a human finger is efficiently visualized in different SCs as a function of finger-to-display distance.

Determination of the Complete Elasticity of Nephila pilipes Spider Silk.

Spider silks are remarkable materials designed by nature to have extraordinary elasticity. Their elasticity, however, remains poorly understood, as typical stress-strain experiments only allow access to the axial Young's modulus. In this work, micro-Brillouin light spectroscopy (micro-BLS), a noncontact, nondestructive technique, is utilized to probe the direction-dependent phonon propagation in the Nephila pilipes spider silk and hence solve its full elasticity. To the best of our knowledge, this is the first demonstration on the determination of the anisotropic Young's moduli, shear moduli, and Poisson's ratios of a single spider fiber. The axial and lateral Young's moduli are found to be 20.9 ± 0.8 and 9.2 ± 0.3 GPa, respectively, and the anisotropy of the Young's moduli further increases upon stretching. In contrast, the shear moduli and Poisson's ratios exhibit very weak anisotropy and are robust to stretching.

Non-viral reprogramming and induced pluripotent stem cells for cardiovascular therapy.

Despite significant effort devoted to developing new treatments and procedures, cardiac disease is still one of the leading causes of death in the world. The loss of myocytes due to ischemic injury remains a major therapeutic challenge. However, cell-based therapy to repair the injured heart has shown significant promise in basic and translation research and in clinical trials. Embryonic stem cells have been successfully used to improve cardiac outcomes. Unfortunately, treatment with these cells is complicated by ethical and legal issues. Recent progress in developing induced pluripotent stem cells (iPSCs) using non-viral vectors has made it possible to derive cardiomyocytes for therapy. This review will focus on these non-integration-based approaches for reprogramming and their therapeutic advantages for cardiovascular medicine.

Role of Human Mesenchymal Stem Cells in Regenerative Therapy.

Mesenchymal stem cells (MSCs) are multipotent cells which can proliferate and replace dead cells in the body. MSCs also secrete immunomodulatory molecules, creating a regenerative microenvironment that has an excellent potential for tissue regeneration. MSCs can be easily isolated and grown in vitro for various applications. For the past two decades, MSCs have been used in research, and many assays and tests have been developed proving that MSCs are an excellent cell source for therapy. This review focusses on quality control parameters required for applications of MSCs including colony formation, surface markers, differentiation potentials, and telomere length. Further, the specific mechanisms of action of MSCs under various conditions such as trans-differentiation, cell fusion, mitochondrial transfer, and secretion of extracellular vesicles are discussed. This review aims to underline the applications and benefits of MSCs in regenerative medicine and tissue engineering.

Seeing mesoatomic distortions in soft-matter crystals of a double-gyroid block copolymer.

Supramolecular soft crystals are periodic structures that are formed by the hierarchical assembly of complex constituents, and occur in a broad variety of 'soft-matter' systems1. Such soft crystals exhibit many of the basic features (such as three-dimensional lattices and space groups) and properties (such as band structure and wave propagation) of their 'hard-matter' atomic solid counterparts, owing to the generic symmetry-based principles that underlie both2,3. 'Mesoatomic' building blocks of soft-matter crystals consist of groups of molecules, whose sub-unit-cell configurations couple strongly to supra-unit-scale symmetry. As yet, high-fidelity experimental techniques for characterizing the detailed local structure of soft matter and, in particular, for quantifying the effects of multiscale reconfigurability are quite limited. Here, by applying slice-and-view microscopy to reconstruct the micrometre-scale domain morphology of a solution-cast block copolymer double gyroid over large specimen volumes, we unambiguously characterize its supra-unit and sub-unit cell morphology. Our multiscale analysis reveals a qualitative and underappreciated distinction between this double-gyroid soft crystal and hard crystals in terms of their structural relaxations in response to forces-namely a non-affine mode of sub-unit-cell symmetry breaking that is coherently maintained over large multicell dimensions. Subject to inevitable stresses during crystal growth, the relatively soft strut lengths and diameters of the double-gyroid network can easily accommodate deformation, while the angular geometry is stiff, maintaining local correlations even under strong symmetry-breaking distortions. These features contrast sharply with the rigid lengths and bendable angles of hard crystals.

Asymmetric acoustic energy transport in non-Hermitian metamaterials.

The ability to control and direct acoustic energy is essential for many engineering applications such as vibration and noise control, invisibility cloaking, acoustic sensing, energy harvesting, and phononic switching and rectification. The realization of acoustic regulators requires overcoming fundamental challenges inherent to the time-reversal nature of wave equations. Typically, this is achieved by utilizing either a parameter that is odd-symmetric under time-reversal or by introducing passive nonlinearities. The former approach is power consuming while the latter has two major deficiencies: it has high insertion losses and the outgoing signal is harvested in a different frequency than that of the incident wave due to harmonic generation. Here, a unique approach is adopted that exploits spatially distributed linear and nonlinear losses in a fork-shaped resonant metamaterials. This compact metamaterial design demonstrates asymmetric acoustic reflectance and transmittance, and acoustic switching. In contrast to previous studies, the non-Hermitian metamaterials exhibit asymmetric transport with high frequency purity of the outgoing signal.