Reaction‐Diffusion‐Mediated Photolithography for Designing Pseudo‐3D Microstructures

Microstructures with 3D features provide advanced functionalities in many applications. Reaction‐diffusion process has been employed in photolithography to produce pseudo‐3D microstructures in a reproducible manner. In this work, the influences of various parameters on growth behavior of polymeric structures are investigated and the use of the reaction‐diffusion‐mediated photolithography (RDP) is expanded to a wide range of structural dimensions. In addition, how a lens effect alters the growth behavior of microstructures in conjunction with reaction‐diffusion process is studied. For small separation between reaction sites in the array, ultraviolet (UV) exposure time is optimized along with the separation to avoid film or plateau formation. It is further proved that the RDP process is highly reproducible and applicable to various photocurable resins. In a demonstrative purpose, the use of microdomes created by the RDP process as microlens arrays is shown. The RDP process enables the production of pseudo‐3D microstructures even with collimated UV light in the absence of complex optical setups, thereby potentially serving as a useful means to create micropatterns and particles with unique structural features.     

Biochips for Cell Biology by Combined Dip‐Pen Nanolithography and DNA‐Directed Protein Immobilization

A general methodology for patterning of multiple protein ligands with lateral dimensions below those of single cells is described. It employs dip pen nanolithography (DPN) patterning of DNA oligonucleotides which are then used as capture strands for DNA‐directed immobilization (DDI) of oligonucleotide‐tagged proteins. This study reports the development and optimization of PEG‐based liquid ink, used as carrier for the immobilization of alkylamino‐labeled DNA oligomers on chemically activated glass surfaces. The resulting DNA arrays have typical spot sizes of 4–5 μm with a pitch of 12 μm micrometer. It is demonstrated that the arrays can be further functionalized with covalent DNA‐streptavidin (DNA‐STV) conjugates bearing ligands recognized by cells. To this end, biotinylated epidermal growth factor (EGF) is coupled to the DNA‐STV conjugates, the resulting constructs are hybridized with the DNA arrays and the resulting surfaces used for the culturing of MCF‐7 (human breast adenocarcinoma) cells. Owing to the lateral diffusion of transmembrane proteins in the cell's plasma membrane, specific recruitment and concentration of EGF receptor can be induced specifically at the sites where the ligands are bound on the solid substrate. This is a clear demonstration that this method is suitable for precise functional manipulations of subcellular areas within living cells.     

DNA‐Modification of Eukaryotic Cells

A novel bioorthogonal method for the modification of cells with single‐stranded DNA oligomers is compared to five alternative methods with respect to labeling efficacy, specificity, and effects on cell viability. The new method is based on oxime ligation of aminooxybiotin to aldehyde groups installed by periodate cleavage of cell‐surface glycans, followed by the coupling of preformed DNA–streptavidin conjugates. As compared with two literature‐reported methods based on direct coupling of N‐hydroxysuccinimidyl (NHS)–DNA or NHS–biotinylation as well as with techniques based on strain‐promoted alkyne‐azide cycloaddition, this method shows the highest labeling densities and is sufficiently mild to avoid cell damage. Functionality of the DNA tags is demonstrated by DNA‐directed immobilization on solid substrates and assembly of small cell aggregates.     

Polymer Microstructures through Two‐Photon Crosslinking

Two‐photon crosslinking of polymers (2PC) is proposed as a novel method for the fabrication of freestanding microstructures via two‐photon lithography. During this process in the confocal volume, two‐photon absorption leads to (formal) C,H‐insertion reactions, and consequently to a strictly localized crosslinking of the polymer. To achieve this, the polymer is coated as a solvent‐free (glassy) film onto an appropriate substrate, and the desired microstructure is written by 2PC into this glass. In all regions outside of the focal volume where no two‐photon process occurs, the polymer remains uncrosslinked and can be washed away during a developing process. Using a self‐assembled monolayer containing the same photoreactive group allows covalent attachment of the forming freestanding structures to the substrate, and thus guarantees an improved stability of these structures against shear‐induced detachment. As the two photon process is carried out in the glassy state, in a simple way, multilayer structures can be used to write structures having a varying chemical composition perpendicular to the surface. As an example, the 2PC process is used to build a structure from both protein‐repellent and protein‐adsorbing polymers so that the resulting 3D structure exhibits spatially controlled protein adsorption.     

Capillary Force‐Driven,Hierarchical Co‐Assembly of Dandelion‐Like Peptide Microstructures

The wetting and drying of drops on flexible fibers occurs ubiquitously in nature, and the capillary force underlying this phenomenon has motivated our great interest in learning how to direct supramolecular self‐assembly. Here, the hierarchical co‐assembly of two aromatic peptides, diphenylalanine (FF) and ferrocene‐diphenylalanine (Fc‐FF), is reported via sequential, combinatorial assembly. The resulting dandelion‐like microstructures have highly complex architectures, where FF microtube arrays serve as the scapes and the Fc‐FF nanofibers serve as the flower heads. Homogeneous FF microtubes with diameters tailored between 1 and 9 μm and wall thickness ranging from 70 to 950 nm are initially formed by controlling the degree of supersaturation of the FF and the water content. Once the FF microtubes are formed, the growth of the dandelion‐like microstructures is then driven by the capillary force, derived from the wetting and drying of the Fc‐FF solution on the FF microtubes. This simple and ingenious strategy offers many opportunities to develop new and creative methods for controlling the hierarchical self‐assembly of peptides and thus building highly complex nano and microstructures.     

Droplet Transport on a Nano‐ and Microstructured Surface with a Wettability Gradient in Low‐Temperature or High‐Humidity Environments

Directional driving of a droplet can be achieved on a gradient‐exhibiting, nanostructured microhump (GNMH) surface at low temperature and high humidity. The GNMH surface is fabricated using a commercial carbon fiber plate with an array of microscale hump structures; nanotechniques are used to form varying nanostructures on the microhump array, producing the micro‐ and nanostructured surface. The different nanostructures result in a wettability gradient along the surface, enabling droplet transport with the help of vibration—even at low temperature or high humidity. In contrast, simply nanostructured surfaces or microstructured surfaces that also have a wettable gradient do not enable droplet transport at low temperature or high humidty. In a range of subzero temperatures or in a range of high‐humidity conditions, the GNMH surface retains its superhydrophobicity and ability for directional droplet transport along its wettability gradient. These results may assist in the design of surfaces required for cold environments, such as microreactors, chemical analytic devices, and sensors.     

Low‐cycle fatigue behavior of rolled WE43‐T5 magnesium alloy

This paper describes the main results from an investigation into the strength and low‐cycle fatigue (LCF) behavior of a rolled plate of WE43 Mg alloy in its T5 condition at room temperature. The alloy was found to exhibit small tension/compression yield asymmetry and small anisotropy being stronger in transverse direction (TD) than in rolling direction (RD) along with some anisotropy in strain hardening. The LCF tests were conducted under strain‐controlled conditions with the strain amplitudes ranging from 0.6% to 1.4% without the mean strain component. While the stress amplitudes during the LCF were higher for tests along TD than RD, the LCF life was similar for both directions. As revealed by electron microscopy, the fractured surfaces under tension consisted mainly of microvoid coalescence with some transgranular facets, while those fractured in LCF showed a combination of intergranular fracture and transgranular facets with minor content of microvoid coalescence.     

Unraveling the Solution‐State Supramolecular Structures of Donor–Acceptor Polymers and their Influence on Solid‐State Morphology and Charge‐Transport Properties

Polymer self‐assembly in solution prior to film fabrication makes solution‐state structures critical for their solid‐state packing and optoelectronic properties. However, unraveling the solution‐state supramolecular structures is challenging, not to mention establishing a clear relationship between the solution‐state structure and the charge‐transport properties in field‐effect transistors. Here, for the first time, it is revealed that the thin‐film morphology of a conjugated polymer inherits the features of its solution‐state supramolecular structures. A “solution‐state supramolecular structure control” strategy is proposed to increase the electron mobility of a benzodifurandione‐based oligo(p‐ phenylene vinylene) (BDOPV)‐based polymer. It is shown that the solution‐state structures of the BDOPV‐based conjugated polymer can be tuned such that it forms a 1D rod‐like structure in good solvent and a 2D lamellar structure in poor solvent. By tuning the solution‐state structure, films with high crystallinity and good interdomain connectivity are obtained. The electron mobility significantly increases from the original value of 1.8 to 3.2 cm² V^?1 s^?1. This work demonstrates that “solution‐state supramolecular structure” control is critical for understanding and optimization of the thin‐film morphology and charge‐transport properties of conjugated polymers.