Flowmicro in-Line Analysis-Driven Design of Reactions Mediated by Unstable Intermediates: Flash Monitoring Approach.

Invited for the cover of this issue is the group of Aiichiro Nagaki, Yosuke Ashikari and co-workers at Hokkaido University. The image depicts flash monitoring of reactive intermediate in a flow microreactor. Read the full text of the article at 10.1002/chem.202303774.

Flowmicro In-Line Analysis-Driven Design of Reactions Mediated by Unstable Intermediates: Flash Monitoring Approach.

The direct observation of reactive intermediates is an important issue for organic synthesis. However, intermediates with an extreme instability are hard to be monitored by common spectroscopic methods such as FTIR. We have developed synthetic method utilizing flow microreactors, which enables a generation and reactions of unstable intermediates. Herein we report that, based on our flowmicro techniques, we developed an in-line analysis method for reactive intermediates in increments of milliseconds. We demonstrated the direct observation of the living and dead species of the anionic polymerization of alkyl methacrylates. The direct information of the living species enabled the anionic polymerization and copolymerization of oligo(ethylene glycol) methyl ether methacrylates, which is the important but difficult reaction in the conventional method.

Cointegration of single-transistor neurons and synapses by nanoscale CMOS fabrication for highly scalable neuromorphic hardware.

Cointegration of multistate single-transistor neurons and synapses was demonstrated for highly scalable neuromorphic hardware, using nanoscale complementary metal-oxide semiconductor (CMOS) fabrication. The neurons and synapses were integrated on the same plane with the same process because they have the same structure of a metal-oxide semiconductor field-effect transistor with different functions such as homotype. By virtue of 100% CMOS compatibility, it was also realized to cointegrate the neurons and synapses with additional CMOS circuits. Such cointegration can enhance packing density, reduce chip cost, and simplify fabrication procedures. The multistate single-transistor neuron that can control neuronal inhibition and the firing threshold voltage was achieved for an energy-efficient and reliable neural network. Spatiotemporal neuronal functionalities are demonstrated with fabricated single-transistor neurons and synapses. Image processing for letter pattern recognition and face image recognition is performed using experimental-based neuromorphic simulation.

Total Syntheses of Allelopathic 4-Oxyprotoilludanes, Melleolides, and Echinocidins.

Stereocontrolled total syntheses of allelopathic 4-oxyprotoilludane sesquiterpenes, melleolide, melleolide F, and echinocidins B and D were achieved. The curved 5/6/4 tricyclic system with an angular hydroxy group was built via three key transformations: (1) Me3Al-catalyzed [2 + 2] cycloaddition of a ketene silyl acetal with a propiolate, (2) reductive ring-opening of a cyclic hemiketal, and (3) the intramolecular Morita-Baylis-Hillman reaction. This synthetic route represents a new and reliable strategy to obtain protoilludanes with several oxy-functional groups.

Toward the Synthesis of Yuzurimine-Type Alkaloids: Stereoselective Construction of the Heterocyclic Portions of Deoxyyuzurimine and Macrodaphnine.

The heterocyclic portions of yuzurimine-type alkaloids, such as deoxyyuzurimine and macrodaphnine, were synthesized by using a stereoselective hydroboration-oxidation reaction to install the C20 methyl group, the intramolecular Mitsunobu reaction to construct the E-ring portion, and the intramolecular SN2 reaction to construct the F-ring portion as key steps.

Thermo-optic control of the longitudinal radiation angle in a silicon-based optical phased array.

We demonstrate longitudinal beam-steering with a 1×16 silicon optical phased array (OPA) using a monochromatic light source and thermo-optic control of the refractive index in the grating radiator region. The refractive index is controlled by forming a series of n-i-n heaters, placing i-regions in each radiator of the OPA. When the biased voltage in the heaters is increased, the refractive index of the radiator region is increased by the thermo-optic effect, and the longitudinal radiation angle is changed according to the Bragg condition. The transversal beam-steering is accomplished by phase control with the phase shifters, which are devised with a p-i-n diode using the electro-optic effect. With these electro-optic p-i-n phase shifters and n-i-n thermo-optic radiators, we achieve a relatively wide 2D beam-steering in a range of 10.0°/45.4° in the longitudinal/transversal directions with a 1.55 µm light source. The tuning efficiency is 0.016°/mW in the longitudinal beam-steering.

Moth-Eye TiO2 Layer for Improving Light Harvesting Efficiency in Perovskite Solar Cells.

A moth-eye nanostructured mp-TiO2 film using conventional lithography, nano-imprinting and polydimethyl-siloxane (PDMS) stamping methods is demonstrated for the first time. Power conversion efficiency of the moth-eye patterned perovskite solar cell is improved by ≈11%, which mainly results from increasing light harvesting efficiency by structural optical property.