Decatungstate-Catalyzed C(sp³)–H Alkylation of a Val Residue Proximal to the N‑Terminus Controlled by an Electrostatic Interaction

The decatungstate photocatalyst [W10O32]4– efficiently promoted the C­(sp3)–H alkylation of the trifluoroacetic acid salt of valine methyl ester (H-Val-OMe·TFA) with electron-deficient alkenes under UV irradiation. The electrostatic interaction between the cationic ammonium group (+NH3) of the main chain and anionic [W10O32]4– played an important role in this reaction. The influence of various protected amino acids in the C­(sp3)–H alkylation was investigated as the model reaction for the alkylation of Val-containing peptides. The introduction of an alkyne moiety into Val through this alkylation was successful, and successive copper-catalyzed azide–alkyne cycloaddition (CuAAC) was demonstrated. The C­(sp3)–H bond of a Val residue located at the second from the N-terminus was also successfully converted. C­(sp3)–H alkylation of oligopeptides containing two Val residues selectively proceeded proximally to the N-terminus

Switchable Adhesive Based on Shape Memory Polymer with Micropillars of Different Heights for Laser-Driven Noncontact Transfer Printing

Switchable adhesive is essential to develop transfer printing, which is an advanced heterogeneous material integration technique for developing electronic systems. Designing a switchable adhesive with strong adhesion strength that can also be easily eliminated to enable noncontact transfer printing still remains a challenge. Here, we report a simple yet robust design of switchable adhesive based on a thermally responsive shape memory polymer with micropillars of different heights. The adhesive takes advantage of the shape-fixing property of shape memory polymer to provide strong adhesion for a reliable pick-up and the various levels of shape recovery of micropillars under laser heating to eliminate the adhesion for robust printing in a noncontact way. Systematic experimental and numerical studies reveal the adhesion switch mechanism and provide insights into the design of switchable adhesives. This switchable adhesive design provides a good solution to develop laser-driven noncontact transfer printing with the capability of eliminating the influence of receivers on the performance of transfer printing. Demonstrations of transfer printing of silicon wafers, microscale Si platelets, and micro light emitting diode (μ-LED) chips onto various challenging nonadhesive receivers (e.g., sandpaper, stainless steel bead, leaf, or glass) to form desired two-dimensional or three-dimensional layouts illustrate its great potential in deterministic assembly

Switchable Adhesive Based on Shape Memory Polymer with Micropillars of Different Heights for Laser-Driven Noncontact Transfer Printing

Switchable adhesive is essential to develop transfer printing, which is an advanced heterogeneous material integration technique for developing electronic systems. Designing a switchable adhesive with strong adhesion strength that can also be easily eliminated to enable noncontact transfer printing still remains a challenge. Here, we report a simple yet robust design of switchable adhesive based on a thermally responsive shape memory polymer with micropillars of different heights. The adhesive takes advantage of the shape-fixing property of shape memory polymer to provide strong adhesion for a reliable pick-up and the various levels of shape recovery of micropillars under laser heating to eliminate the adhesion for robust printing in a noncontact way. Systematic experimental and numerical studies reveal the adhesion switch mechanism and provide insights into the design of switchable adhesives. This switchable adhesive design provides a good solution to develop laser-driven noncontact transfer printing with the capability of eliminating the influence of receivers on the performance of transfer printing. Demonstrations of transfer printing of silicon wafers, microscale Si platelets, and micro light emitting diode (μ-LED) chips onto various challenging nonadhesive receivers (e.g., sandpaper, stainless steel bead, leaf, or glass) to form desired two-dimensional or three-dimensional layouts illustrate its great potential in deterministic assembly

Switchable Adhesive Based on Shape Memory Polymer with Micropillars of Different Heights for Laser-Driven Noncontact Transfer Printing

Switchable adhesive is essential to develop transfer printing, which is an advanced heterogeneous material integration technique for developing electronic systems. Designing a switchable adhesive with strong adhesion strength that can also be easily eliminated to enable noncontact transfer printing still remains a challenge. Here, we report a simple yet robust design of switchable adhesive based on a thermally responsive shape memory polymer with micropillars of different heights. The adhesive takes advantage of the shape-fixing property of shape memory polymer to provide strong adhesion for a reliable pick-up and the various levels of shape recovery of micropillars under laser heating to eliminate the adhesion for robust printing in a noncontact way. Systematic experimental and numerical studies reveal the adhesion switch mechanism and provide insights into the design of switchable adhesives. This switchable adhesive design provides a good solution to develop laser-driven noncontact transfer printing with the capability of eliminating the influence of receivers on the performance of transfer printing. Demonstrations of transfer printing of silicon wafers, microscale Si platelets, and micro light emitting diode (μ-LED) chips onto various challenging nonadhesive receivers (e.g., sandpaper, stainless steel bead, leaf, or glass) to form desired two-dimensional or three-dimensional layouts illustrate its great potential in deterministic assembly

Biaxially Stretchable “Wavy” Silicon Nanomembranes

This Letter introduces a biaxially stretchable form of single crystalline silicon that consists of two dimensionally buckled, or “wavy”, silicon nanomembranes on elastomeric supports. Fabrication procedures for these structures are described, and various aspects of their geometries and responses to uniaxial and biaxial strains along various directions are presented. Analytical models of the mechanics of these systems provide a framework for quantitatively understanding their behavior. These classes of materials might be interesting as a route to high-performance electronics with full, two-dimensional stretchability

Copper-Catalyzed Tertiary Alkylative Cyanation for the Synthesis of Cyanated Peptide Building Blocks

In this paper, we report efficient cyanation of various peptides containing the α-bromocarbonyl moiety using a Cu-catalyzed radical-based methodology employing zinc cyanide as the cyanide source. Mechanistic studies revealed that in situ formed CuCN was a key intermediate during the catalytic cycle. Our method could be useful for the synthesis of modified peptides containing quaternary carbons

Fast Digital Patterning of Surface Topography toward Three-Dimensional Shape-Changing Structures

Exiting strategies for 3D shape-changing structures are constrained by either the complicated fabrication process or the harsh demands of active materials. Facile preparation of 3D shape-changing structures with an extremely simple approach based on the elastomeric polymer still remains a challenging topic. Here, we report a fast digital patterning of surface topography of a single-layer elastomeric polymer toward 3D shape-changing structures. The surface topography features digitally engraved grooves by a laser engraver on a poly­(dimethylsiloxane) (PDMS) sheet, which is surface oxidized by the UV-ozone treatment. The resulting engraved PDMS sheets exhibit programmable shape-changing behaviors to form various 3D structures under the action of organic solvent. Experimental and numerical studies reveal the fundamental aspects of surface topography-guided 3D shape-changing structures. Demonstrations of this concept in developing various complex 3D shape-changing structures illustrate the simplicity and effectiveness of our approach, thereby creating engineering opportunities in a wide range of applications such as actuators and soft robots

Fast Digital Patterning of Surface Topography toward Three-Dimensional Shape-Changing Structures

Exiting strategies for 3D shape-changing structures are constrained by either the complicated fabrication process or the harsh demands of active materials. Facile preparation of 3D shape-changing structures with an extremely simple approach based on the elastomeric polymer still remains a challenging topic. Here, we report a fast digital patterning of surface topography of a single-layer elastomeric polymer toward 3D shape-changing structures. The surface topography features digitally engraved grooves by a laser engraver on a poly­(dimethylsiloxane) (PDMS) sheet, which is surface oxidized by the UV-ozone treatment. The resulting engraved PDMS sheets exhibit programmable shape-changing behaviors to form various 3D structures under the action of organic solvent. Experimental and numerical studies reveal the fundamental aspects of surface topography-guided 3D shape-changing structures. Demonstrations of this concept in developing various complex 3D shape-changing structures illustrate the simplicity and effectiveness of our approach, thereby creating engineering opportunities in a wide range of applications such as actuators and soft robots