Toward Single Cell Tattoos: Biotransfer Printing of Lithographic Gold Nanopatterns on Live Cells.

Lithographic nanopatterning techniques such as photolithography, electron-beam lithography, and nanoimprint lithography (NIL) have revolutionized modern-day electronics and optics. Yet, their application for creating nanobio interfaces is limited by the cytotoxic and two-dimensional nature of conventional fabrication methods. Here, we present a biocompatible and cost-effective transfer process that leverages (a) NIL to define sub-300 nm gold (Au) nanopattern arrays, (b) amine functionalization of Au to transfer the NIL-arrays from a rigid substrate to a soft transfer layer, (c) alginate hydrogel as a flexible, degradable transfer layer, and (d) gelatin conjugation of the Au NIL-arrays to achieve conformal contact with live cells. We demonstrate biotransfer printing of the Au NIL-arrays on rat brains and live cells with high pattern fidelity and cell viability and observed differences in cell migration on the Au NIL-dot and NIL-wire printed hydrogels. We anticipate that this nanolithography-compatible biotransfer printing method could advance bionics, biosensing, and biohybrid tissue interfaces.

Toward single cell tattoos: Biotransfer printing of lithographic gold nanopatterns on live cells.

Lithographic nanopatterning techniques like photolithography, electron-beam lithography, and nanoimprint lithography (NIL) have revolutionized modern-day electronics and optics. Yet, their application for creating nano-bio interfaces is limited by the cytotoxic and two-dimensional nature of conventional fabrication methods. Here, we present a biocompatible and cost-effective transfer process that leverages (a) NIL to define sub-300 nm gold (Au) nanopattern arrays, (b) amine functionalization of Au to transfer the NIL-arrays from a rigid substrate to a soft transfer layer, (c) alginate hydrogel as a flexible, degradable transfer layer, and (d) gelatin conjugation of the Au NIL-arrays to achieve conformal contact with live cells. We demonstrate biotransfer printing of the Au NIL-arrays on rat brains and live cells with high pattern fidelity and cell viability and observed differences in cell migration on the Au NIL-dot and NIL-wire printed hydrogels. We anticipate that this nanolithography-compatible biotransfer printing method could advance bionics, biosensing, and biohybrid tissue interfaces.

Label-Free Spectroscopic SARS-CoV-2 Detection on Versatile Nanoimprinted Substrates.

Widespread testing and isolation of infected patients is a cornerstone of viral outbreak management, as underscored during the ongoing COVID-19 pandemic. Here, we report a large-area and label-free testing platform that combines surface-enhanced Raman spectroscopy and machine learning for the rapid and accurate detection of SARS-CoV-2. Spectroscopic signatures acquired from virus samples on metal-insulator-metal nanostructures, fabricated using nanoimprint lithography and transfer printing, can provide test results within 25 min. Not only can our technique accurately distinguish between different respiratory and nonrespiratory viruses, but it can also detect virus signatures in physiologically relevant matrices such as human saliva without any additional sample preparation. Furthermore, our large area nanopatterning approach allows sensors to be fabricated on flexible surfaces allowing them to be mounted on any surface or used as wearables. We envision that our versatile and portable label-free spectroscopic platform will offer an important tool for virus detection and future outbreak preparedness.

Nano-folded Gold Catalysts for Electroreduction of Carbon Dioxide.

The local structure and geometry of catalytic interfaces can influence the selectivity of chemical reactions. Selectivity is often critical for the practical realization of reactions such as the electroreduction of carbon dioxide (CO2). Previously developed strategies to manipulate the structure and geometry of catalysts for electroreduction of CO2 involve complex processes or fail to efficiently alter the selectivity. Here, using a prestrained polymer, we uniaxially and biaxially compress a 60 nm gold film to form a nano-folded electrocatalyst for CO2 reduction. We observe two kinds of folds and can tune the ratio of loose to tight folds by varying the extent of prestrain in the polymer. We characterize the nano-folded catalysts using X-ray diffraction, scanning, and transmission electron microscopy. We observe grain reorientation and coarsening in the nano-folded gold catalysts. We measure an enhancement of Faradaic efficiency for carbon monoxide formation with the biaxially compressed nano-folded catalyst by a factor of about nine as compared to the flat catalyst (up to 87.4%). We rationalize this observation by noting that an increase of the local pH in the tight folds of the catalyst outweighs the effects of alterations in grain characteristics. Together, our studies demonstrate that nano-folded geometries can significantly alter grain characteristics, mass transport, and catalytic performance.

Ultrathin Shape Change Smart Materials.

With the discovery of graphene, significant research has focused on the synthesis, characterization, and applications of ultrathin materials. Graphene has also brought into focus other ultrathin materials composed of organics, polymers, inorganics, and their hybrids. Together, these ultrathin materials have unique properties of broad significance. For example, ultrathin materials have a large surface area and high flexibility which can enhance conformal contact in wearables and sensors leading to improved sensitivity. When porous, the short transverse diffusion length in these materials allows rapid mass transport. Alternatively, when impermeable, these materials behave as an ultrathin barrier. Such controlled permeability is critical in the design of encapsulation and drug delivery systems. Finally, ultrathin materials often feature defect-free and single-crystal-like two-dimensional atomic structures resulting in superior mechanical, optical, and electrical properties. A unique property of ultrathin materials is their low bending rigidity, which suggests that they could easily be bent, curved, or folded into 3D shapes. In this Account, we review the emerging field of 2D to 3D shape transformations of ultrathin materials. We broadly define ultrathin to include materials with a thickness below 100 nm and composed of a range of organic, inorganic, and hybrid compositions. This topic is important for both fundamental and applied reasons. Fundamentally, bending and curving of ultrathin films can cause atomistic and molecular strain which can alter their physical and chemical properties and lead to new 3D forms of matter which behave very differently from their planar precursors. Shape change can also lead to new 3D architectures with significantly smaller form factors. For example, 3D ultrathin materials would occupy a smaller space in on-chip devices or could permeate through tortuous media which is important for miniaturized robots and smart dust applications. Our Account highlights several differences between ultrathin and traditional shape change materials. The latter is typically associated with hydrogels, liquid crystals, or shape memory elastomers. As compared to bulk materials, ultrathin materials can much more easily bend and fold due to the significantly reduced bending modulus. Consequently, it takes much less energy to alter the shape of ultrathin materials, and even small environmental stimuli can trigger a large response. Further, the energy barriers between different configurations are small which allow a variety of conformations and enhances programmability. Finally, due to their ultrathin nature, the shape changes are typically not slowed down by sluggish mass or thermal transport, and thus, responses can be much faster than those of bulk materials. The latter point is important in the design of high-speed actuators. Consequently, ultrathin materials could enable low-power, rapid, programmable, and complex shape transformations in response to a broad range of stimuli such as pH, temperature, electromagnetic fields, or chemical environments. The Account also includes a discussion of applications, important challenges, and future directions.

Functionalized ultrathin palladium nanosheets as patches for HepG2 cancer cells.

Flexible, charged Pd nanosheets were prepared by using short chain thiolated carboxylic acids and amines. They could wrap around amine or hydroxyl functionalized micron-sized spheres driven by electrostatic interactions. Upon incubation with HepG2 cells, the positively charged cysteamine (CA) functionalized Pd nanosheets exhibited a much higher cytotoxicity, showing more than 80% cell death at 100 ppm than the negatively charged 3-mercaptopropionic acid (MPA) functionalized ones which caused 30% cell death. The results show through surface functionalization Pd nanosheets can be modified to interact differently with HepG2 cancerous cells, resulting in varied cytotoxicity.

Higher-order nanostructures of two-dimensional palladium nanosheets for fast hydrogen sensing.

Two-dimensional (2D) materials often show a range of intriguing electronic, catalytic, and optical properties that differ greatly from conventional nanoparticles. While planar configuration is often desirable, a range of applications such as catalysis and sensing benefit greatly from the accessibility to large surface areas. The 2D materials generally tend to form stacks in order to reduce the overall surface energy. Such densely packed structures however are detrimental when access to high surface area is required. Herewith we demonstrate a chemical strategy to generate Pd three-dimensional (3D) structures from its flexible 2D nanosheets. Solvent polarity is shown to play an important role to control the final morphology of these nanosheets. Our data indicate when these Pd 3D materials were integrated into hydrogen sensing devices, response time was found to be an order of magnitude faster than their 2D-constrained counterparts. The easy accessibility to the surfaces by hydrogen gas is considered to be an important factor for the observed fast response time based on the sensing model.