Nanopatterned Monolayers of Bioinspired, Sequence-Defined Polypeptoid Brushes for Semiconductor/Bio Interfaces.

The ability to control and manipulate semiconductor/bio interfaces is essential to enable biological nanofabrication pathways and bioelectronic devices. Traditional surface functionalization methods, such as 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.

Colossal electrocaloric effect in an interface-augmented ferroelectric polymer.

The electrocaloric effect demands the maximized degree of freedom (DOF) of polar domains and the lowest energy barrier to facilitate the transition of polarization. However, optimization of the DOF and energy barrier-including domain size, crystallinity, multiconformation coexistence, polar correlation, and other factors in bulk ferroelectrics-has reached a limit. We used organic crystal dimethylhexynediol (DMHD) as a three-dimensional sacrificial master to assemble polar conformations at the heterogeneous interface in poly(vinylidene fluoride)-based terpolymer. DMHD was evaporated, and the epitaxy-like process induced an ultrafinely distributed, multiconformation-coexisting polar interface exhibiting a giant conformational entropy. Under a low electric field, the interface-augmented terpolymer had a high entropy change of 100 J/(kg·K). This interface polarization strategy is generally applicable to dielectric capacitors, supercapacitors, and other related applications.

Heterostructure particles enable omnidispersible in water and oil towards organic dye recycle.

Dispersion of colloidal particles in water or oil is extensively desired for industrial and environmental applications. However, it often strongly depends on indispensable assistance of chemical surfactants or introduction of nanoprotrusions onto the particle surface. Here we demonstrate the omnidispersity of hydrophilic-hydrophobic heterostructure particles (HL-HBPs), synthesized by a surface heterogeneous nanostructuring strategy. Photo-induced force microscopy (PiFM) and adhesion force images both indicate the heterogeneous distribution of hydrophilic domains and hydrophobic domains on the particle surface. These alternating domains allow HL-HBPs to be dispersed in various solvents with different polarity and boiling point. The HL-HBPs can efficiently adsorb organic dyes from water and release them into organic solvents within several seconds. The surface heterogeneous nanostructuring strategy provides an unconventional approach to achieve omnidispersion of colloidal particles beyond surface modification, and the omnidispersible HL-HBPs demonstrate superior capability for dye recycle merely by solvent exchange. These omnidispersible HL-HBPs show great potentials in industrial process and environmental protection.

Time-Resolved Thickness and Shape-Change Quantification using a Dual-Band Nanoplasmonic Ruler with Sub-Nanometer Resolution.

Time-resolved measurements of changes in the size and shape of nanobiological objects and layers are crucial to understand their properties and optimize their performance. Optical sensing is particularly attractive with high throughput and sensitivity, and label-free operation. However, most state-of-the-art solutions require intricate modeling or multiparameter measurements to disentangle conformational or thickness changes of biomolecular layers from complex interfacial refractive index variations. Here, we present a dual-band nanoplasmonic ruler comprising mixed arrays of plasmonic nanoparticles with spectrally separated resonance peaks. As electrodynamic simulations and model experiments show, the ruler enables real-time simultaneous measurements of thickness and refractive index variations in uniform and heterogeneous layers with sub-nanometer resolution. Additionally, nanostructure shape changes can be tracked, as demonstrated by quantifying the degree of lipid vesicle deformation at the critical coverage prior to rupture and supported lipid bilayer formation. In a broader context, the presented nanofabrication approach constitutes a generic route for multimodal nanoplasmonic optical sensing.

Quantitative analysis of biomolecule release from polystyrene-block-polyethylene oxide thin films.

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.

Protein-coated nanostructured surfaces affect the adhesion of Escherichia coli.

Developing new implant surfaces with anti-adhesion bacterial properties used for medical devices remains a challenge. Here we describe a novel study investigating nanotopography influences on bacterial adhesion on surfaces with controlled interspatial nanopillar distances. The surfaces were coated with proteins (fibrinogen, collagen, serum and saliva) prior to E. coli-WT adhesion under flow conditions. PiFM provided chemical mapping and showed that proteins adsorbed both between and onto the nanopillars with a preference for areas between the nanopillars. E. coli-WT adhered least to protein-coated areas with low surface nanopillar coverage, most to surfaces coated with saliva, while human serum led to the lowest adhesion. Protein-coated nanostructured surfaces affected the adhesion of E. coli-WT.

An Optimized Fibril Network Morphology Enables High-Efficiency and Ambient-Stable Polymer Solar Cells.

Morphological stability is crucially important for the long-term stability of polymer solar cells (PSCs). Many high-efficiency PSCs suffer from metastable morphology, resulting in severe device degradation. Here, a series of copolymers is developed by manipulating the content of chlorinated benzodithiophene-4,8-dione (T1-Cl) via a random copolymerization approach. It is found that all the copolymers can self-assemble into a fibril nanostructure in films. By altering the T1-Cl content, the polymer crystallinity and fibril width can be effectively controlled. When blended with several nonfullerene acceptors, such as TTPTT-4F, O-INIC3, EH-INIC3, and Y6, the optimized fibril interpenetrating morphology can not only favor charge transport, but also inhibit the unfavorable molecular diffusion and aggregation in active layers, leading to excellent morphological stability. The work demonstrates the importance of optimization of fibril network morphology in realizing high-efficiency and ambient-stable PSCs, and also provides new insights into the effect of chemical structure on the fibril network morphology and photovoltaic performance of PSCs.

The Role of Growth Directors in Controlling the Morphology of Hematite Nanorods.

The control of the growth of hematite nanoparticles from iron chloride solutions under hydrothermal conditions in the presence of two different structure promoters has been studied using a range of both structural and spectroscopic techniques including the first report of photo induced force microscopy (PiFM) to map the topographic distribution of the structure-directing agents on the developing nanoparticles. We show that the shape of the nanoparticles can be controlled using the concentration of phosphate ions up to a limit determined to be ~6 × 10-3 mol. Akaganéite (ß-FeOOH) is a major component of the nanoparticles formed in the absence of structure directors but only present in the very early stages (< 8 h) of particle growth when phosphate is present. The PiFM data suggest a correlation between the areas in which phosphate ions are adsorbed and areas where akaganéite persists on the surface. In contrast, goethite (α-FeOOH) is a directly observed precursor of the hematite nanorods when 1,2-diamino propane is present. The PiFM data shows goethite in the center of the developing particles consistent with a mechanism in which the iron hydroxide re-dissolves and precipitates at the nanorod ends as hematite.

Synthesis of monodisperse rod-shaped silica particles through biotemplating of surface-functionalized bacteria.

Mesoporous silica particles of controlled size and shape are potentially beneficial for many applications, but their usage may be limited by the complex procedure of fabrication. Biotemplating provides a facile approach to synthesize materials with desired shapes. Herein, a bioinspired design principle is adopted through displaying silaffin-derived 5R5 proteins on the surface of Escherichia coli by genetic manipulations. The genetically modified Escherichia coli provides a three-dimensional template to regulate the synthesis of rod-shaped silica. The silicification is initiated on the cell surface under the functionality of 5R5 proteins and subsequentially the inner space is gradually filled. Density functional theory simulation reveals the interfacial interactions between silica precursors and R5 peptides at the atomic scale. There is a large conformation change of this protein during biosilicification. Electrostatic interactions contribute to the high affinity between positively charged residues (Lys4, Arg16, Arg17) and negatively charged tetraethyl orthosilicate. Hydrogen bonds develop between Arg16 (OH), Arg17 (OH and NH), Leu19 (OH) residues and the forming silica agglomerates. In addition, the resulting rod-shaped silica copy of the bacteria can transform into mesoporous SiOx nanorods composed of carbon-coated nanoparticles after carbonization, which is shown to allow superior lithium storage performance.