Molecular Vista (United States)

Abstract Silk fibroin is a fiber-forming protein derived from the thread of Bombyx mori silkworm cocoons. This biocompatible protein, under the kosmotropic influence of potassium phosphate, can undergo supramolecular self-assembly driven by a random coil to β-sheet secondary structure transition. By leveraging concurrent non-specific adsorption and self-assembly of silk fibroin, we demonstrate an interfacial phenomenon that yields adherent, defect-free nano-thin protein coatings that grow continuously in time, without observable saturation in mass deposition. This non-covalent growth of silk fibroin coatings is a departure from traditionally studied protein adsorption phenomena, which generally yield adsorbed layers that saturate in mass with time and often do not completely cover the surface. Here, we explore the fundamental mechanisms of coating growth by examining the effects of coating solution parameters that promote or inhibit silk fibroin self-assembly. Results show a strong dependence of coating kinetics and structure on solution pH, salt species, and salt concentration. Moreover, coating growth was observed to occur in two stages: an early stage driven by protein-surface interactions and a late stage driven by protein-protein interactions. To describe this phenomenon, we developed a kinetic adsorption model with Langmuir-like behavior at early times and a constant steady-state growth rate at later times. Structural analysis by FTIR and photo-induced force microscopy show that small β-sheet-rich structures serve as anchoring sites for absorbing protein nanoaggregates, which is critical for coating formation. Additionally, β-sheets are preferentially located at the interface between protein nanoaggregates in the coating, suggesting their role in forming stable, robust coatings.

The ability to control and manipulate semiconductor/bio interfaces is essential to enable biological nanofabrication pathways and new bioelectronic devices. Traditional surface functionalization methods, like self-assembled monolayers (SAMs), provide limited customization for these interfaces. Polymer brushes offer a wider range of chemistries, but choices that maintain compatibility with both lithographic patterning and biological systems are scarce. Here we developed a class of bioinspired, sequence-defined polymers, i.e., polypeptoids, as tailored polymer brushes for surface modification of semiconductor substrates. Polypeptoids featuring a terminal hydroxyl (–OH) group are designed and synthesized for efficient melt grafting onto the native oxide layer of Si substrates, forming ultrathin (~1 nm) monolayers. By programming monomer chemistry, our polypeptoid brush platform offers versatile surface modification, including adjustments to surface energy, passivation, preferential biomolecule attachment, and specific biomolecule binding. Importantly, the polypeptoid brush monolayers remain compatible with electron-beam lithographic patterning and retain their chemical characteristics even under harsh lithographic conditions. Electron-beam lithography is used over polypeptoid brushes to generate highly precise, binary nanoscale patterns with localized functionality for the selective immobilization (or passivation) of biomacromolecules such as DNA origami or streptavidin onto addressable arrays. This surface modification strategy with bioinspired, sequence-defined polypeptoid brushes enables monomer-level control over surface properties with a large parameter space of monomer chemistry and sequence, and therefore is a highly versatile platform to precisely engineer semiconductor/bio interfaces for bioelectronics applications.

The ability to control and manipulate semiconductor/bio interfaces is key to enable biological nanofabrication pathways and new bioelectronic devices. Conventional surface functionalization strategies like self-assembled monolayers (SAMs) provide a limited level of customization for such interfaces. Polymer brushes offer a wider range of chemistries, but choices that maintain compatibility with both lithographic patterning and biological systems are limited. Here we developed a class of bioinspired, sequence-defined polymers, polypeptoids, as tailored polymer brushes for surface modification of semiconductor substrates. Polypeptoids with a terminal hydroxyl (–OH) group are designed and synthesized to enable efficient melt grafting onto the native oxide layer of Si substrates, forming ~1 nm thick monolayers. By programming monomer chemistry, the polypeptoid brush platform enables efficient and versatile surface modification in surface energy, passivation to preferential attachment of biomolecules, and specific binding of biomolecules. The polypeptoid brush monolayers are compatible with electron-beam lithographic patterning and maintain their chemical characteristics after exposure to the harsh conditions of the lithographic patterning workflow. Highly precise, well-defined chemical contrast nanopatterns consisting of two polymer brushes are designed and generated with a passivation background and active binding regions to achieve selective immobilization of biomacromolecules including DNA origami and streptavidin at length scales defined by electron-beam lithography. This surface modification strategy with bioinspired, sequence-defined polypeptoid brushes enables monomer- level control over surface properties with a large parameter space of monomer chemistry and sequence, and therefore is a highly versatile platform to precisely engineer semiconductor/bio interfaces for bioelectronics applications.

Block copolymers have garnered recent attention due to their ability to contain molecular cargo within nanoscale domains and release said cargo in aqueous environments. However, the release kinetics of cargo from these thin-films has not yet been reported. Knowledge of the release quantities and release profiles of these systems is paramount for applications of these systems. Here, Polystyrene-block-poly(ethylene oxide) (PS-b-PEO) was co-assembled with fluorescein isothiocyanate isomer I-lysozyme (FITC-LZ) and fluorescein isothiocyanate isomer I-TAT (FITC-TAT), such that these molecular cargos arrange within the PEO domains of the thin films. We show that high loading ratios of cargo/PS-b-PEO do not significantly impact the nanostructure of the films; however, a loading limit appears to be present with aggregates of protein forming at the microscale with higher loading ratios. The presence of lysozyme (LZ) within the films was confirmed qualitatively after aqueous exposure through photo-induced force microscopy (PiFM) imaging at the Amide I characteristic peak (∼1650 cm-1). Furthermore, we demonstrate that LZ maintains activity and structure after exposure to the polymer solvent (benzene/methanol/water mix). Finally, we demonstrate quantitatively 20-80 ng cm-2 of cargo is released from these films, depending on the cargo incorporated. We show that the larger molecule lysozyme is released over a longer time than the smaller TAT peptide. Finally, we demonstrate the ability to tune the quantity of cargo released by altering the thickness of the PS-b-PEO thin-films during fabrication.

Abstract Nanoscale microscopy is an important technique in analyzing current semiconductor processes and devices. Many of the current microscopy techniques can render high resolution images of morphology and, in some cases, elemental information. However, techniques are still needed to give definitive nanoscale mapping of compound materials utilized in semiconductor processes such as Si3N4, SiO2, SiGe, and low-k materials. Photo-induced force microscopy (PiFM) combines IR spectroscopy with atomic force microscopy (AFM) to provide concurrent information on topography and chemical mapping. PiFM measures the attractive dipole-dipole photo-response between the tip and the sample and does not rely on repulsive force arising from absorption-based sample expansion. As such, PiFM works well with many of the inorganic semiconductor compounds (with low thermal expansion coefficients) as well as organic materials (with high thermal expansion coefficients) [1]. In this study, various examples of nanoscale chemical mapping of semiconductor samples (surfaces processed via directed self-assembly (DSA), strain in SiGe/SiO2 structure, photoresist, etc.) will be presented, all demonstrating ~ 10 nm spatial resolution

Abstract All‐polymer solar cells (all‐PSCs) offer unique morphology stability for the application as flexible devices, but the lack of high‐performance polymer acceptors limits their power conversion efficiency (PCE) to a value lower than those of the PSCs based on fullerene derivative or organic small molecule acceptors. We herein demonstrate a strategy to synthesize a high‐performance polymer acceptor PZ1 by embedding an acceptor–donor–acceptor building block into the polymer main chain. PZ1 possesses broad absorption with a low band gap of 1.55 eV and high absorption coefficient (1.3×105 cm−1). The all‐PSCs with the wide‐band‐gap polymer PBDB‐T as donor and PZ1 as acceptor showed a record‐high PCE of 9.19 % for the all‐PSCs. The success of our polymerization strategy can provide a new way to develop efficient polymer acceptors for all‐PSCs.

We perform time-resolved pump-probe microscopy measurements by recording the local force between a sharp tip and the photo-excited sample as a readout mechanism for the material's nonlinear polarization. We show that the photo-induced force is sensitive to the same excited state dynamics as measured in an optical pump-probe experiment. Ultrafast pump-probe force microscopy constitutes a non-optical detection technique with nanoscale resolution that pushes pump-probe sensitivities close to the realm of single molecule studies.