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The first total synthesis of (±)-jujuyane, a cyclooctanoid natural product, was accomplished from a (5 + 3) dimerization product of oxidopyrylium ylide that forms the cyclooctanoid core structure along with inherited stereochemical bias. Selective functional group modifications of the highly oxygenated dimeric structure, followed by the tactical functional group manipulation around the eight-membered carbocyclic core, enabled the total synthesis of (±)-jujuyane, which will serve a guide for future applications of oxidopyrylium dimers to the natural product total synthesis.

Magnetic graphene composite comprising graphene sheets decorated with magnetite nanoparticles (NPs) is an important material with numerous successful and potential applications in electronics, chemistry, physics, and bio-medicine. The further use of this material relies on the development of an appropriate patterning method for the production of two-dimensional (2D) and three-dimensional (3D) magnetic graphene composite objects. This study presents a simple and effective strategy to fabricate 2D and 3D micropatterns of Fe3O4 functionalized graphene-polymer (FGP) nanocomposite using extrusion-based 3D printing with a highly loaded FGP nanocomposite ink. The ink consisted of Fe3O4 nanoparticles (NPs), graphene microflakes (GMFs), and hydroxypropyl cellulose (HPC), and was stable and suitable for 3D printing of FGP objects. Various FGP 3D microarchitectures, including a grid, honeycomb, pyramid, and square, were successfully printed using the layer-by-layer (LbL) printing approach. The printed objects exhibited a conductivity of ∼580 S m−1 and magnetic property of 15.8 emu g−1. Successful demonstrations of electronic devices such as a magnet-guided car, a magnetic switch, and a 3D grid for electromagnetic interference (EMI) shielding are also described herein. This 3D printing approach was effective for the 2D and 3D patterning of functional nanocomposites and shows promise for advanced printed electronic applications.

Presented here is a concise synthesis of secu'amamine A, and fluvirosaones A and B from readily available allosecurinine and viroallosecurinine. The key C2-enamine derivative of (viro)allosecurinine, the presumed biosynthetic precursors of these natural products, was accessed, for the first time, by a VO(acac)2 -mediated regioselective Polonovski reaction. Formal hydration and 1,2-amine shift of this pluripotent enamine compound afforded secu'amamine A. Formal oxidative [3+2] cycloaddition reaction between this enamine and TMS-substituted methallyl iodide reagent paved the way to the precursors of fluvirosaones A and B. The relative stereochemistry at the C2 position of these advanced intermediates governs the fate of 1,2-amine shift leading to fluvirosaones A and B. The syntheses of potential biosynthetic precursors and investigations of their chemical reactivities have provided insights regarding the biogenesis of these natural products.

Photoelectrochemical (PEC) water splitting is an alternative to fossil fuel combustion involving the generation of renewable hydrogen without environmental pollution or greenhouse gas emissions. Cuprous oxide (Cu2O) is a promising semiconducting material for the simple reduction of hydrogen from water, in which the conduction band edge is slightly negative compared to the water reduction potential. However, the solar-to-hydrogen conversion efficiency of Cu2O is lower than the theoretical value due to a short carrier-diffusion length under the effective light absorption depth. Thus, increasing light absorption in the electrode–electrolyte interfacial layer of a Cu2O photoelectrode can enhance PEC performance. In this study, a Cu2O 3D photoelectrode comprised of pyramid arrays was fabricated using a two-step method involving direct-ink-writing of graphene structures. This was followed by the electrodeposition of a Cu current-collecting layer and a p–n homojunction Cu2O photocatalyst layer onto the printed structures. The performance for PEC water splitting was enhanced by increasing the total light absorption area (Aa) of the photoelectrode via controlling the electrode topography. The 3D photoelectrode (Aa = 3.2 cm2) printed on the substrate area of 1.0 cm2 exhibited a photocurrent (Iph) of −3.01 mA at 0.02 V (vs. RHE), which is approximately three times higher than that of a planar photoelectrode with an Aa = 1.0 cm2 (Iph = −0.91 mA). Our 3D printing strategy provides a flexible approach for the design and the fabrication of highly efficient PEC photoelectrodes.

Three-dimensional (3D) printing is a next-generation free-form manufacturing technology for structural electronics. The realization of structural electronic devices necessitates the direct integration of electronic circuits into 3D objects. However, creating highly conductive, high-resolution patterns in 3D remains a major challenge. Here, we report on a metallic 3D printing method that incorporates electroless deposition (ELD) into the direct ink writing method. Our approach consists of two steps: (1) direct ink writing of catalyst microstructures with a functional catalyst ink containing Ag ions and (2) ELD of Cu onto the printed catalyst structures. High-quality, stable Cu 3D printing is achieved through the design of the Ag catalyst ink; hydroxypropyl cellulose is added as both a rheological modifier (printing) and dissolution inhibitor (ELD). As a result, various two-dimensional (2D) and 3D Cu micro circuitries with high conductivity (∼65% of bulk) can be directly integrated onto 3D plastic substrates without the need for high-temperature annealing. A hybrid strategy that combines ELD-assisted 3D printing and conventional fused deposition modeling enables full fabrication of structural electronic devices. This 3D printing strategy can be a low-cost and facile method for obtaining highly conductive metallic 2D and 3D microstructures in structural electronics.

The pixel is the minimum unit used to represent or record information in photonic devices. The size of the pixel determines the density of the integrated information, such as the resolution of displays or cameras. Most methods used to produce display pixels are based on two-dimensional patterning of light-emitting materials. However, the brightness of the pixels is limited when they are miniaturized to nanoscale dimensions owing to their limited volume. Herein, we demonstrate the production of three-dimensional (3D) pixels with nanoscale dimensions based on the 3D printing of quantum dots embedded in polymer nanowires. In particular, a femtoliter meniscus was used to guide the solidification of liquid inks to form vertically freestanding nanopillar structures. Based on the 3D layout, we show high-density integration of color pixels, with a lateral dimension of 620 nm and a pitch of 3 μm for each of the red, green, and blue colors. The 3D structure enabled a 2-fold increase in brightness without significant effects on the spatial resolution of the pixels. In addition, we demonstrate individual control of the brightness based on a simple adjustment of the height of the 3D pixels. This method can be used to achieve super-high-resolution display devices and various photonic applications across a range of disciplines.

Many emerging applications in microscale engineering rely on the fabrication of three-dimensional architectures in inorganic materials. Small-scale additive manufacturing (AM) aspires to provide flexible and facile access to these geometries. Yet, the synthesis of device-grade inorganic materials is still a key challenge towards the implementation of AM in microfabrication. Here, we present a comprehensive overview of the microstructural and mechanical properties of metals fabricated by most state-of-the-art AM methods that offer a spatial resolution $\leq$10$\mu$m. Standardized sets of samples were studied by cross-sectional electron microscopy, nanoindentation and microcompression. We show that current microscale AM techniques synthesize metals with a wide range of microstructures and elastic and plastic properties, including materials of dense and crystalline microstructure with excellent mechanical properties that compare well to those of thin-film nanocrystalline materials. The large variation in materials performance can be related to the individual microstructure, which in turn is coupled to the various physico-chemical principles exploited by the different printing methods. The study provides practical guidelines for users of small-scale additive methods and establishes a baseline for the future optimization of the properties of printed metallic objects $-$ a significant step towards the potential establishment of AM techniques in microfabrication.

An effective approach is required to improve the spatial resolution and electrical conductivity of printed graphene patterns for advanced graphene-based printed electronics. Here, we describe a simple and effective strategy to fabricate few-micrometer-wide graphene patterns by meniscus-guided printing, using a highly concentrated graphene oxide (GO, 2 wt%) ink. Our approach exploits the rapid solidification of an ink meniscus formed by horizontal pulling of a micronozzle. To achieve uniform printing with continuous flow of the highly concentrated GO ink through the nozzle, polyvinylpyrrolidone (PVP), which acts as a gelation inhibitor and rheology modifier, was added to the aqueous GO solution. GO reduction and PVP removal from the printed patterns was achieved simultaneously, by thermal treatment. Electrical conductivities and widths of the reduced GO (rGO) patterns could be easily modulated by adjusting the nozzle-pulling rate and changing the nozzle-opening size, respectively. Toward applications in electronics, successful fabrication of a field-effect transistor based on a printed rGO channel is also described. This approach can be effective for high-resolution printing of graphene patterns for electronic applications.

Although three-dimensional (3D) printing has recently emerged as a technology to potentially bring about the next industrial revolution, the limited selection of usable materials restricts its use to simple prototyping. In particular, metallic 3D printing with submicrometer spatial resolution is essential for the realization of 3D-printed electronics. Herein, a meniscus-guided 3D printing method that exploits a low-viscosity (∼7 mPa·s) silver nanoparticle (AgNP) ink meniscus with Newtonian fluid characteristics (which is compatible with conventional inkjet printers) to fabricate 3D silver microarchitectures is reported. Poly(acrylic acid)-capped AgNP ink that exhibits a continuous ink flow through a confined nozzle without aggregation is designed in this study. Guiding the ink meniscus with controlled direction and speed enables both vertical pulling and layer-by-layer processing, resulting in the creation of 3D microobjects with designed shapes other than those for simple wiring. Various highly conductive (10

Silver (Ag) nanoparticle-based inks are frequently used in printed electronics to form conductive patterns, but often require high-temperature sintering to achieve the optimum electrical conductivity, hindering their use in substrates with poor heat resistance. Herein, a three-dimensional (3D) printing strategy to produce highly conductive Ag 3D architectures that can be sintered at low temperatures is reported. This strategy is based on the additive deposition of Ag nanoparticles and microflakes via extrusion-based 3D printing with the Ag ink that involves poly(acrylic acid) (PAA)-stabilized Ag nanoparticles, Ag microflakes, and NaCl - a destabilizing agent. The designed Ag inks are stable and suitable for ink-extrusion 3D printing. In chemical sintering, Cl- can detach PAA from the Ag nanoparticle surface, enabling nanoparticle coalescence and sintering. An elevated annealing temperature induces increased NaCl density in the printed patterns and accelerates the surface and grain boundary diffusion of Ag atoms, contributing to enhance chemical sintering. On annealing at ∼110 °C for 30 min, the printed structures exhibited an electrical conductivity of ∼9.72 × 104 S cm-1, which is ∼15.6% of that of bulk Ag. Complicated Ag architectures with diverse shapes were successfully fabricated on polymeric substrates. Several structural electronic applications were demonstrated by hybrid 3D printing combining our extrusion-based 3D printing and conventional fused deposition modeling (FDM).

Moving printed electronics to three dimensions essentially requires advanced additive manufacturing techniques yielding multifunctionality materials and high spatial resolution. Here, we report the meniscus-guided 3D printing of highly conductive multiwall carbon nanotube (MWNT) microarchitectures that exploit rapid solidification of a fluid ink meniscus formed by pulling a micronozzle. To achieve high-quality printing with continuous ink flow through a confined nozzle geometry, that is, without agglomeration and nozzle clogging, we design a polyvinylpyrrolidone-wrapped MWNT ink with uniform dispersion and appropriate rheological properties. The developed technique can produce various desired 3D microstructures, with a high MWNT concentration of up to 75 wt % being obtained via post-thermal treatment. Successful demonstrations of electronic components such as sensing transducers, emitters, and radio frequency inductors are also described herein. We expect that the technique presented in this study will facilitate selection of diverse materials in 3D printing and enhance the freedom of integration for advanced conceptual devices.

Printed strain sensors have promising potential as a human–machine interface (HMI) for health-monitoring systems, human-friendly wearable interactive systems, and smart robotics. Herein, flexible strain sensors based on carbon nanotube (CNT)–polymer composites were fabricated by meniscus-guided printing using a CNT ink formulated from multiwall nanotubes (MWNTs) and polyvinylpyrrolidone (PVP); the ink was suitable for micropatterning on nonflat (or curved) substrates and even three-dimensional structures. The printed strain sensors exhibit a reproducible response to applied tensile and compressive strains, having gauge factors of 13.07 under tensile strain and 12.87 under compressive strain; they also exhibit high stability during ∼1500 bending cycles. Applied strains induce a contact rearrangement of the MWNTs and a change in the tunneling distance between them, resulting in a change in the resistance (ΔR/R0) of the sensor. Printed MWNT–PVP sensors were used in gloves for finger movement detection; these...

A. Zinger defined reduced Gromov-Witten (GW) invariants and proved a comparison theorem of standard and reduced genus one GW invariants for every symplectic manifold (with all dimension). H. -L. Chang and J. Li provided a proof of the comparison theorem for quintic Calabi-Yau 3-folds in algebraic geometry by taking a definition of reduced invariants as an Euler number of certain vector bundle. T. Coates and C. Manolache have defined reduced GW invariants in algebraic geometry following the idea by Vakil and Zinger and proved the comparison theorem for every Calabi-Yau threefold. In this paper, we prove the comparison theorem for every (not necessarily Calabi-Yau) complete intersection of dimension 2 or 3 in projective spaces by taking a definition of reduced GW invariants in the paper of Coates and Manolache., Comment: 27 pages

As competing with the established silicon technology, organic-inorganic metal halide perovskites are continually gaining ground in optoelectronics due to their excellent material properties and low-cost production. The ability to have control over their shape, as well as composition and crystallinity, is indispensable for practical materialization. Many sophisticated nanofabrication methods have been devised to shape perovskites; however, they are still limited to in-plane, low-aspect-ratio, and simple forms. This is in stark contrast with the demands of modern optoelectronics with freeform circuitry and high integration density. Here, a nanoprecision 3D printing is developed for organic-inorganic metal halide perovskites. The method is based on guiding evaporation-induced perovskite crystallization in mid-air using a femtoliter ink meniscus formed on a nanopipette, resulting in freestanding 3D perovskite nanostructures with a preferred crystal orientation. Stretching the ink meniscus with a pulling process enables on-demand control of the nanostructure's diameter and hollowness, leading to an unprecedented tubular-solid transition. With varying the pulling direction, a layer-by-layer stacking of perovskite nanostructures is successfully demonstrated with programmed shapes and positions, a primary step for additive manufacturing. It is expected that the method has the potential to create freeform perovskite nanostructures for customized optoelectronics.