Complex Three-dimensional Architectures Research Articles

Visible-Light-Promoted Tandem Skeletal Rearrangement/Dearomatization of Heteroaryl Enallenes

Access to complex three-dimensional molecular architectures via dearomatization of ubiquitous aryl rings is a powerful synthetic tool, which faces, however, an inherent challenge to overcome energetic costs due to the loss of aromatic stabilization energy. Photochemical methods that allow one to populate high-energy states can thus be an ideal strategy to accomplish otherwise prohibitive reaction pathways. We present an original dearomative rearrangement of heteroaryl acryloylallenamides that leads to complex fused tricycles. The visible-light-promoted method occurs under mild conditions and tolerates a variety of functional groups. According to DFT modeling used to rationalize the outcome of the cascade, the reaction involves a sequential [2+2] allene–alkene photocycloaddition, which is followed by a selective retro- [2+2] step that paves the way for the dearomatization of the heteroaryl partner. This scenario is original with respect to the reported photochemical reactivity of similar substrates and thus holds promise for ample future developments.

Interconversion of Highly Entangled Polyhedra into Concave Polyhedra by Nitrate-Induced Ternary Coordination.

Entangled (M3L2) n polyhedral complexes represent a unique class of supramolecular architectures that are stabilized by relatively weak metal-acetylene interactions in cooperation with conventional metal-pyridyl coordination. Counter-anion exchange of these complexes with a nitrate (NO3-) ion triggered formal metal insertion between the metal centers, and a heteroleptic ternary coordination mode with acetylenic, pyridyl, and nitrate donors was generated on the metal centers. As a result, the main frameworks of the polyhedral complexes M18L12 and M12L8 were formally extended into a new series of concave polyhedra having the compositions M21L12 and M13L8, respectively. This transformation also resulted in the local disconnection of the highly entangled trifurcate topology of the framework, providing clues toward the skeletal editing of extended and complex three-dimensional (3D) architectures.

Development of intensiometric indicators for visualizing N-cadherin interaction across cells

N-cadherin (NCad) is a classical cadherin that mediates cell–cell interactions in a Ca2+-dependent manner. NCad participates in various biological processes, from ontogenesis to higher brain functions, though the visualization of NCad interactions in living cells remains limited. Here, we present intensiometric NCad interaction indicators, named INCIDERs, that utilize dimerization-dependent fluorescent proteins. INCIDERs successfully visualize reversible NCad interactions across cells. Compared to FRET-based indicators, INCIDERs have a ~70-fold higher signal contrast, enabling clear identification of NCad interactions. In primary neuronal cells, NCad interactions are visualized between closely apposed processes. Furthermore, visualization of NCad interaction at cell adhesion sites in dense cell populations is achieved by two-photon microscopy. INCIDERs are useful tools in the spatiotemporal investigation of NCad interactions across cells; future research should evaluate the potential of INCIDERs in mapping complex three-dimensional architectures in multi-cellular systems.

Silanization of 3D-Printed Silica Fibers and Monoliths.

Surface functionalization of complex three-dimensional (3D) porous architectures has not been widely investigated despite their potential in different application domains. In this work, silanization was performed in silica 3D-printed porous structures, and the homogeneity of functional groups within the architecture was investigated by comparing the extent of the functionalization in the walls and core of the monolith. A silica ink was used for direct ink writing (DIW) to shape fibers and monoliths with different architectures and stacking designs. The surfaces of the fibers and monoliths were functionalized with 3-aminopropyl(triethoxysilane) (APTES) using different reaction conditions. The nature of the functional groups on the surface and the presence of RSiO1.5 bonds were identified by solid-state 13C-NMR, 29Si-NMR, and by ξ-potential measurements. Elemental analysis was used to quantify the concentration of bonded APTES in the core and walls of the monolith. The availability and hydrolytic stability of the introduced amine group on fibers were evaluated using the adsorption of PdCl42- ions within the pH range of 2-5. The study found that geometries with interfiber distances above 250 μm are homogeneously functionalized with amine groups. As the interfiber distance of the monolith decreases, a significantly lower density of amine groups is detected in the core of the monolith. The determination of the homogeneity of 3D-printed monoliths makes this work relevant as it provides the limits of functionalization carried out in stirred batch reactors for geometrically defined structures produced from a 3D-printing process.

Considering lithium-ion battery 3D-printing via thermoplastic material extrusion and polymer powder bed fusion

In this paper, the ability to 3D print lithium-ion batteries through Pmnbspace thermoplastic material extrusion and polymer powder bed fusion is considered. Focused on the formulation of positive electrodes composed of polypropylene, LiFePO4 as active material, and conductive additives, advantages and drawbacks of both additive manufacturing technologies, are thoroughly discussed from the electrochemical, electrical, morphological and mechanical perspectives. Based on these preliminary results, strategies to further optimize the electrochemical performances are proposed. Through a comprehensive modeling study, the enhanced electrochemical suitability at high current densities of various complex three-dimensional lithium-ion battery architectures, in comparison with classical two-dimensional planar design, is highlighted. Finally, the direct printing capability of the complete lithium-ion battery by means of multi-materials printing options processes is examined.

Bioprinting Cell- and Spheroid-Laden Protein-Engineered Hydrogels as Tissue-on-Chip Platforms.

Human tissues, both in health and disease, are exquisitely organized into complex three-dimensional architectures that inform tissue function. In biomedical research, specifically in drug discovery and personalized medicine, novel human-based three-dimensional (3D) models are needed to provide information with higher predictive value compared to state-of-the-art two-dimensional (2D) preclinical models. However, current in vitro models remain inadequate to recapitulate the complex and heterogenous architectures that underlie biology. Therefore, it would be beneficial to develop novel models that could capture both the 3D heterogeneity of tissue (e.g., through 3D bioprinting) and integrate vascularization that is necessary for tissue viability (e.g., through culture in tissue-on-chips). In this proof-of-concept study, we use elastin-like protein (ELP) engineered hydrogels as bioinks for constructing such tissue models, which can be directly dispensed onto endothelialized on-chip platforms. We show that this bioprinting process is compatible with both single cell suspensions of neural progenitor cells (NPCs) and spheroid aggregates of breast cancer cells. After bioprinting, both cell types remain viable in incubation for up to 14 days. These results demonstrate a first step toward combining ELP engineered hydrogels with 3D bioprinting technologies and on-chip platforms comprising vascular-like channels for establishing functional tissue models.

3D-printed flexible, Ag-coated PNN-PZT ceramic-polymer grid-composite for electromechanical energy conversion

Abstract Piezoelectric ceramic materials such as Pb(Zr,Ti)O3 (PZT) based ceramics have excellent electromechanical energy conversion ability, however, their rigid and undeformed characters are not suitable for flexible electronics application. Here, we report the design of flexible (0–3) connection ceramic-polymer composite made of polydimethylsiloxane (PDMS) elastomeric matrix doped with Ag-coated PNN-PZT (0.55Pb(Ni1/3Nb2/3)O3-0.135PbZrO3-0.315PbTiO3) ceramic heterojunction particles, and the 3D printing method for fabricating complex three-dimensional grid architectures. It was found that the 3D-printing, non-stereolithographic grid-composite exhibits a greater flexible character after doping ceramic particles and also excellent electromechanical coupling with a piezoelectric voltage coefficient g33 as high as 400 × 10−3 m V N−1, which is one order of magnitude higher than that of PZT based ceramics. Under drop hammer (~20 N) impact, it can instantly drive over 20 commercial red-LEDs lighting directly without using a charge storage capacitor. This work shows that 3D-printed flexible ceramic-polymer composite has potential to replace brittle piezoceramics for electromechanical energy conversion and touching force sensor applications, such as soft robotics, artificial muscles and biology signal identification.

Three-Dimensional Superconducting Nanohelices Grown by He+-Focused-Ion-Beam Direct Writing.

Novel schemes based on the design of complex three-dimensional (3D) nanoscale architectures are required for the development of the next generation of advanced electronic components. He+ focused-ion-beam (FIB) microscopy in combination with a precursor gas allows one to fabricate 3D nanostructures with an extreme resolution and a considerably higher aspect ratio than FIB-based methods, such as Ga+ FIB-induced deposition, or other additive manufacturing technologies. In this work, we report the fabrication of 3D tungsten carbide nanohelices with on-demand geometries via controlling key deposition parameters. Our results show the smallest and highest-densely packed nanohelix ever fabricated so far, with dimensions of 100 nm in diameter and aspect ratio up to 65. These nanohelices become superconducting at 7 K and show a large critical magnetic field and critical current density. In addition, given its helical 3D geometry, fingerprints of vortex and phase-slip patterns are experimentally identified and supported by numerical simulations based on the time-dependent Ginzburg–Landau equation. These results can be understood by the helical geometry that induces specific superconducting properties and paves the way for future electronic components, such as sensors, energy storage elements, and nanoantennas, based on 3D compact nanosuperconductors.

Independent Geometrical Control of Spin and Charge Resistances in Curved Spintronics.

Spintronic devices operating with pure spin currents represent a new paradigm in nanoelectronics, with a higher energy efficiency and lower dissipation as compared to charge currents. This technology, however, will be viable only if the amount of spin current diffusing in a nanochannel can be tuned on demand while guaranteeing electrical compatibility with other device elements, to which it should be integrated in high-density three-dimensional architectures. Here, we address these two crucial milestones and demonstrate that pure spin currents can effectively propagate in metallic nanochannels with a three-dimensional curved geometry. Remarkably, the geometric design of the nanochannels can be used to reach an independent tuning of spin transport and charge transport characteristics. These results laid the foundation for the design of efficient pure spin current-based electronics, which can be integrated in complex three-dimensional architectures.

Development and characterization of a low-cost 3D bioprinter

Bioprinting complex three-dimensional architectures of cell-laden hydrogels is a promising approach for creating custom living tissues. However, it is challenging to fabricate hydrogel-based constructs at both high-throughput and high-resolution; bioprinters that offer both advantages are generally not affordable for most researchers. Thus, there is an unmet need for low-cost, open-source bioprinters. Such an accessible tool will enable rapid design iterations to accelerate the ongoing research and development of biomimetic tissues and biomaterial use. Here, we develop and implement a low-cost hybrid bioprinter using both inkjet and extrusion print heads, which are capable of printing gelatin methacryloyl and alginate, respectively. We characterized the geometric accuracy of the plotter. Moreover, the printing and crosslinking parameters were optimized to maximize the cell viability.

Three-dimensional printing of piezoelectric materials with designed anisotropy and directional response.

Piezoelectric coefficients are constrained by the intrinsic crystal structure of the constituent material. Here we describe design and manufacturing routes to previously inaccessible classes of piezoelectric materials that have arbitrary piezoelectric coefficient tensors. Our scheme is based on the manipulation of electric displacement maps from families of structural cell patterns. We implement our designs by additively manufacturing free-form, perovskite-based piezoelectric nanocomposites with complex three-dimensional architectures. The resulting voltage response of the activated piezoelectric metamaterials at a given mode can be selectively suppressed, reversed or enhanced with applied stress. Additionally, these electromechanical metamaterials achieve high specific piezoelectric constants and tailorable flexibility using only a fraction of their parent materials. This strategy may be applied to create the next generation of intelligent infrastructure, able to perform a variety of structural and functional tasks, including simultaneous impact absorption and monitoring, three-dimensional pressure mapping and directionality detection.

Morphological and textural evolution of the prismatic ultrastructure in mollusc shells: A comparative study of Pinnidae species

Molluscan shells, exhibiting a variety of complex three-dimensional architectures, are an exemplar model system to study biogenic mineral formation by living organisms. Recent studies have demonstrated that the deposition process of some shell ultrastructures can be described using classical analytical models borrowed from materials physics, which were developed to predict the structural evolution of man-made and geological polycrystalline composite assemblies. In the current study, we use this newly developed capacity to quantitatively describe the morphogenesis of the prismatic ultrastructure in three shells from the bivalve family Pinnidae towards establishing a correlation between structure, texture, growth kinetics, topology and phylogeny of the species. Using data collected by electron microscopy, synchrotron-based microtomography, electron backscatter diffraction analysis (EBSD) and X-ray diffraction we demonstrate that the prismatic ultrastructures in Pinnidae are formed following either ideal or triple-junction-controlled kinetics, which are shown to be closely linked to the morphological and topological characteristics, as well as crystallographic texture of these biocomposites. The experimental and analytical framework presented in this comparative study can serve as an additional tool for classifying molluscan shell ultrastructures on the levels of structural and textural morphogenesis. Statement of SignificanceThe ability to quantitatively describe the structural evolution of the prismatic architecture in mollusc shells is used for the first time to derive and compare between analytical parameters that define the growth kinetics and morphological and topological evolution during the growth of three shells from the family Pinnidae from two different genera. Furthermore, these parameters are linked to the evolution of crystallographic texture in the studied architectures. The developed experimental and analytical framework not only enables us to quantitatively describe species-specific growth mechanisms but also suggests a direct correlation between the evolution of morphology and texture.

Viscoelastic Characteristics of Mechanically Assembled Three-Dimensional Structures Formed by Compressive Buckling

Vibrational microplatforms that exploit complex three-dimensional (3D) architectures assembled via the controlled compressive buckling technique represent promising candidates in 3D micro-electromechanical systems (MEMS), with a wide range of applications such as oscillators, actuators, energy harvesters, etc. However, the accuracy and efficiency of such 3D MEMS might be significantly reduced by the viscoelastic damping effect that arises from material viscosity. Therefore, a clear understanding and characterization of such effects are essential to progress in this area. Here, we present a study on the viscoelastic damping effect in complex 3D structures via an analytical model and finite element analysis (FEA). By adopting the Kelvin–Voigt model to characterize the material viscoelasticity, an analytical solution is derived for the vibration of a buckled ribbon. This solution then yields a scaling law for the half-band width or the quality factor of vibration that can be extended to other classes of complex 3D structures, as validated by FEA. The scaling law reveals the dependence of the half-band width on the geometries of 3D structures and the compressive strain. The results could serve as guidelines to design novel 3D vibrational microplatforms for applications in MEMS and other areas of technology.

Nonconventional applications of Mueller matrix-based scatterometry for advanced technology nodes

The semiconductor industry continues to drive patterning solutions that enable devices with higher memory storage capacity, faster computing performance, and lower cost per transistor. These developments in the field of semiconductor manufacturing along with the overall minimization of the size of transistors require continuous development of metrology tools used for characterization of these complex three-dimensional device architectures. Optical scatterometry or optical critical dimension (OCD) is one of the most prevalent inline metrology techniques in semiconductor manufacturing because it is a quick, precise, and nondestructive metrology technique. However, at present OCD is predominantly used to measure the feature dimensions such as line-width, height, side-wall angle, etc. of the patterned nanostructures. Use of optical scatterometry for characterizing patterning process errors such as pitch-walking, overlay, etc. is fairly limited. Characterization of process-induced errors is a fundamental part of process yield improvement. It provides process engineers with important information about process errors, and consequently helps optimize materials and process parameters. Scatterometry is an averaging technique and extending it to measure the position of local process-induced errors and feature-to-feature variation is extremely challenging. This report is an overview of applications and benefits of using optical scatterometry for characterizing defects such as pitch-walking, overlay, and fin bending for advanced technology nodes beyond 7 nm. Currently, the optical scatterometry is based on conventional spectroscopic ellipsometry and spectroscopic reflectometry measurements, but generalized ellipsometry or Mueller matrix (MM) spectroscopic ellipsometry data provide important, additional information about complex structures that exhibit anisotropy and depolarization effects. In addition, the symmetry–antisymmetry properties associated with MM elements provide an excellent means of measuring asymmetry present in the structure. The useful additional information as well as symmetry–antisymmetry properties of MM elements is used to characterize fin bending, overlay defects, and design improvements in the OCD test structures are used to boost OCDs’ sensitivity to pitch-walking. In addition, the validity of the OCD-based results is established by comparing the results to the top down critical dimension-scanning electron microscope and cross-sectional transmission electron microscope images.

Deterministic Design of Chemistry and Mesostructure in Li-Ion Battery Electrodes.

All battery electrodes have complex internal three-dimensional architectures that have traditionally been formed through the random packing of the electrode components. What is now emerging is a new concept in battery electrode design, where the important electronic and ionic pathways, as well as the chemical interactions between the components of the electrode, are deterministically designed. Deterministic design enables far better properties than are possible through random packing, including dramatic improvements in both power and energy. Such a design approach is particularly attractive for emerging high-energy-density materials, which require available free volume as they swell during cycling. In addition to controlled structure, another important facet of the design of such systems is the stable chemical linkages between the active material and the conductive network that survive the lithiation and delithiation processes. In this Perspective, we discuss and provide our views on deterministically designed battery electrodes.

Three-dimensional Reconstruction of the Vascular Architecture of the Passive CLARITY-cleared Mouse Ovary.

The ovary is the main organ of the female reproductive system and is essential for the production of female gametes and for controlling the endocrine system, but the complex structural relationships and three-dimensional (3D) vasculature architectures of the ovary are not well described. In order to visualize the 3D connections and architecture of blood vessels in the intact ovary, the first important step is to make the ovary optically clear. In order to avoid tissue shrinkage, we used the hydrogel fixation-based passive CLARITY (Clear Lipid-exchanged Acrylamide-hybridized Rigid Imaging/ Immunostaining/In situ-hybridization-compatible Tissue Hydrogel) protocol method to clear an intact ovary. Immunostaining, advanced multiphoton confocal microscopy, and 3D image-reconstructions were then used for the visualization of ovarian vessels and follicular capillaries. Using this approach, we showed a significant positive correlation (P <0.01) between the length of the follicular capillaries and volume of the follicular wall.

Composing RNA Nanostructures from a Syntax of RNA Structural Modules.

Natural stable RNAs fold and assemble into complex three-dimensional architectures by relying on the hierarchical formation of intricate, recurrent networks of noncovalent tertiary interactions. These sequence-dependent networks specify RNA structural modules enabling orientational and topological control of helical struts to form larger self-folding domains. Borrowing concepts from linguistics, we defined an extended structural syntax of RNA modules for programming RNA strands to assemble into complex, responsive nanostructures under both thermodynamic and kinetic control. Based on this syntax, various RNA building blocks promote the multimolecular assembly of objects with well-defined three-dimensional shapes as well as the isothermal folding of long RNAs into complex single-stranded nanostructures during transcription. This work offers a glimpse of the limitless potential of RNA as an informational medium for designing programmable and functional nanomaterials useful for synthetic biology, nanomedicine, and nanotechnology.

Construction of a photothermal Venus flytrap from conductive polymer bimorphs

A photothermally foldable soft bimorph was prepared via the dry transfer of poly(3,4-ethylenedioxythiophene) (PEDOT) doped with tosylate onto a poly(dimethylsiloxane) film. The photothermal folding was optimized via reversible actuation by controlling the thickness of each layer and the temperature increase to afford large deflection and displacement up to 150° and >20 mm, respectively, upon exposure to near-infrared (NIR) light (808 nm). A two-dimensional array of the bimorph converted into complex three-dimensional architectures, such as a Venus flytrap, under light and reversibly unfolded in the dark. Taking advantage of the photothermal nature of PEDOT, a localized heat pocket was generated inside the folding structure. Thus, a Venus flytrap with a hot pocket reaching 100 °C was realized for the first time. The Venus flytrap could trap and move an object within a few seconds of NIR exposure.

Modular, Discrete Micromixer Elements Fabricated by 3D Printing

3D printing facilitates the straightforward construction of microchannels with complex three-dimensional architectures. Here, we demonstrate 3D-printed modular mixing components that operate on the basis of splitting and recombining fluid streams to decrease interstream diffusion length. These are compared to helical mixers that operate on the principle of chaotic advection.

Amorphous and Crystalline Vanadium Oxides as High-Energy and High-Power Cathodes for Three-Dimensional Thin-Film Lithium Ion Batteries

Flexible wearable electronics and on-chip energy storage for wireless sensors drive rechargeable batteries toward thin-film lithium ion batteries. To enable more charge storage on a given surface, higher energy density materials are required, while faster energy storage and release can be obtained by going to thinner films. Vanadium oxides have been examined as cathodes in classical and thin-film lithium ion batteries for decades, but amorphous vanadium oxide thin films have been mostly discarded. Here, we investigate the use of atomic layer deposition, which enables electrode deposition on complex three-dimensional (3D) battery architectures, to obtain both amorphous and crystalline VO2 and V2O5, and we evaluate their thin-film cathode performance. Very high volumetric capacities are found, alongside excellent kinetics and good cycling stability. Better kinetics and higher volumetric capacities were observed for the amorphous vanadium oxides compared to their crystalline counterparts. The conformal deposition of these vanadium oxides on silicon micropillar structures is demonstrated. This study shows the promising potential of these atomic layer deposited vanadium oxides as cathodes for 3D all-solid-state thin-film lithium ion batteries.