We report the discovery and in-depth investigation of interfacial crystallization (IFC), the assembly and formation of membrane-like crystalline sheets from both chiral amino acid and achiral -substituted glycine "peptoid" amide monomers selectively at vapor-liquid and liquid-liquid interfaces. This is the first assembly process known to be shared by two peptidomimic families of molecules with crucial backbone differences. A series of AFM, SEM, TOF-SIMS, FTIR, X-ray crystallography, counterion screening experiments, QM calculations, and MD simulation studies identified that IFC is based on the assembly of single monomer layers with alternating molecular orientations, which results in bilayers of unit thickness 1.
View Article and Find Full Text PDFShort peptides are versatile molecules for the construction of supramolecular materials. Most reported peptide materials are hydrophobic, stiff, and show limited response to environmental conditions in the solid-state. Herein, we describe a design strategy for minimalistic supramolecular metallo-peptide nanofibers that, depending on their sequence, change stiffness, or reversibly assemble in the solid-state, in response to changes in relative humidity (RH).
View Article and Find Full Text PDFAll-solid-state lithium-sulfur batteries (ASSLSBs) are promising next-generation battery technologies with a high energy density and excellent safety. Because of the insulating nature of sulfur/LiS, conventional cathode designs focus on developing porous hosts with high electronic conductivities such as porous carbon. However, carbon hosts boost the decomposition of sulfide electrolytes and suffer from sulfur detachment due to their weak bonding with sulfur/LiS, resulting in capacity decays.
View Article and Find Full Text PDFTwo-dimensional antiferromagnets have garnered considerable interest for the next generation of functional spintronics. However, many bulk materials from which two-dimensional antiferromagnets are isolated are limited by their air sensitivity, low ordering temperatures, and insulating transport properties. TaFeTe aims to address these challenges with increased air stability, metallic transport, and robust antiferromagnetism.
View Article and Find Full Text PDFControlling crystallization and grain growth is crucial for realizing highly efficient hybrid perovskite solar cells (PSCs). In this work, enhanced PSC photovoltaic performance and stability by accelerating perovskite crystallization and grain growth via 2D hexagonal boron nitride (hBN) nanosheet additives incorporated into the active perovskite layer are demonstrated. In situ X-ray scattering and infrared thermal imaging during the perovskite annealing process revealed the highly thermally conductive hBN nanosheets promoted the phase conversion and grain growth in the perovskite layer by facilitating a more rapid and spatially uniform temperature rise within the perovskite film.
View Article and Find Full Text PDFSupramolecular self-assembly of fibrous components and liquid-liquid phase separation are at the extremes of the order-to-disorder spectrum. They collectively play key roles in cellular organization. It is still a major challenge to design systems where both highly ordered nanostructures and liquid-liquid phase-separated domains can coexist.
View Article and Find Full Text PDFBranched actin networks are self-assembling molecular motors that move biological membranes and drive many important cellular processes, including phagocytosis, endocytosis, and pseudopod protrusion. When confronted with opposing forces, the growth rate of these networks slows and their density increases, but the stoichiometry of key components does not change. The molecular mechanisms governing this force response are not well understood, so we used single-molecule imaging and AFM cantilever deflection to measure how applied forces affect each step in branched actin network assembly.
View Article and Find Full Text PDFDevelopment of low cost biosensing using convenient and environmentally benign materials is important for wide adoption and ultimately improved healthcare and sustainable development. Immobilized antibodies are often incorporated as an essential biorecognition element in point-of-care biosensors but these proteins are costly. We present a strategy of combining convenient and low-cost surface functionalization approaches for increasing the overall binding activity of antibody functionalized natural and synthetic fibers.
View Article and Find Full Text PDFThere is concern about the buildup of plastic waste in soil, their degradation into microplastics, and their potential to interfere with the natural processing of soil organic carbon and other nutrient cycling processes. Here we used scanning electron microscopy (SEM) and C isotope ratio mass spectrometry to determine if precut consumer plastics comprised of either high density polyethylene (HDPE), a blend of linear low density polyethylene and low density polyethylene (L/LDPE), or polyethylene terephthalate (PETE) would degrade or transform during a short-term, 32 day, exposure to soil or sludge in laboratory microcosms. SEM confirmed morphological changes occurred to all plastics, but the attachment of biofilm and presence of microorganisms mostly favored PETE and HDPE surfaces.
View Article and Find Full Text PDFBombyx (B.) mori silk's water-responsive actuation correlates to its high β-sheet crystallinity. In this research, we demonstrated that stiff silica nanoparticles can mimic the role of dispersed β-sheet nanocrystals and dramatically increase amorphous silk's water-responsive actuation energy density to ∼700 kJ m.
View Article and Find Full Text PDFIn perovskite solar cells, doped organic semiconductors are often used as charge-extraction interlayers situated between the photoactive layer and the electrodes. The π-conjugated small molecule 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9-spirobifluorene (spiro-OMeTAD) is the most frequently used semiconductor in the hole-conducting layer, and its electrical properties considerably affect the charge collection efficiencies of the solar cell. To enhance the electrical conductivity of spiro-OMeTAD, lithium bis(trifluoromethane)sulfonimide (LiTFSI) is typically used in a doping process, which is conventionally initiated by exposing spiro-OMeTAD:LiTFSI blend films to air and light for several hours.
View Article and Find Full Text PDFProc Natl Acad Sci U S A
February 2021
The small structures that decorate biological surfaces can significantly affect behavior, yet the diversity of animal-environment interactions essential for survival makes ascribing functions to structures challenging. Microscopic skin textures may be particularly important for snakes and other limbless locomotors, where substrate interactions are mediated solely through body contact. While previous studies have characterized ventral surface features of some snake species, the functional consequences of these textures are not fully understood.
View Article and Find Full Text PDFUnderstanding the atomistic origin of defects in two-dimensional transition metal dichalcogenides, their impact on the electronic properties, and how to control them is critical for future electronics and optoelectronics. Here, we demonstrate the integration of thermochemical scanning probe lithography (tc-SPL) with a flow-through reactive gas cell to achieve nanoscale control of defects in monolayer MoS. The tc-SPL produced defects can present either p- or n-type doping on demand, depending on the used gasses, allowing the realization of field effect transistors, and p-n junctions with precise sub-μm spatial control, and a rectification ratio of over 10.
View Article and Find Full Text PDFMacromol Rapid Commun
April 2020
Water-responsive (WR) materials that strongly swell and shrink in response to changes in relative humidity (RH) have shown a great potential to serve as high-energy actuators for soft robotics and new energy-harvesting systems. However, the design criteria governing the scalable and high-efficiency WR actuation remain unclear, and thus inhibit further development of WR materials for practical applications. Nature has provided excellent examples of WR materials that contain stiff nanocrystalline structures that can be crucial to understand the fundamentals of WR behavior.
View Article and Find Full Text PDFThere is strong demand for achieving morphological control of conducting polymers in its many potential applications, from energy harvesting to spintronics. Here, the static magnetic-field-induced alignment of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) particles is demonstrated. PEDOT:PSS thin films cast under modest mT-level magnetic fields exhibit a fourfold increase in the Seebeck coefficient and doubled electrical conductivity.
View Article and Find Full Text PDFACS Appl Mater Interfaces
November 2018
Proteins represent complex biomolecules capable of wide-ranging but also highly specific functionalities. Their immobilization on material supports can enable broad applications from sensing and industrial biocatalysis to biomedical interfaces and materials. We demonstrate the advantages of using aqueous-processed cross-linked polyphenol coatings for immobilizing proteins, including IgG, avidin, and various single and multidomain enzymes on diverse materials, to enable active biofunctional structures (e.
View Article and Find Full Text PDFA large effort is underway to investigate the properties of two-dimensional (2D) materials for their potential to become building blocks in a variety of integrated nanodevices. In particular, the ability to understand the relationship between friction, adhesion, electric charges and defects in 2D materials is of key importance for their assembly and use in nano-electro-mechanical and energy harvesting systems. Here, we report on a new oscillatory behavior of nanoscopic friction in continuous polycrystalline MoS2 films for an odd and even number of atomic layers, where odd layers show higher friction and lower work function.
View Article and Find Full Text PDFWASP-family proteins are known to promote assembly of branched actin networks by stimulating the filament-nucleating activity of the Arp2/3 complex. Here, we show that WASP-family proteins also function as polymerases that accelerate elongation of uncapped actin filaments. When clustered on a surface, WASP-family proteins can drive branched actin networks to grow much faster than they could by direct incorporation of soluble monomers.
View Article and Find Full Text PDFMelanins are a family of heterogeneous polymeric pigments that provide ultraviolet (UV) light protection, structural support, coloration, and free radical scavenging. Formed by oxidative oligomerization of catecholic small molecules, the physical properties of melanins are influenced by covalent and noncovalent disorder. We report the use of tyrosine-containing tripeptides as tunable precursors for polymeric pigments.
View Article and Find Full Text PDFProtein-coated microbeads provide a consistent approach for activating and expanding populations of T cells for immunotherapy but do not fully capture the properties of antigen presenting cells. In this report, we enhance T cell expansion by replacing the conventional, rigid bead with a mechanically soft elastomer. Polydimethylsiloxane (PDMS) was prepared in a microbead format and modified with activating antibodies to CD3 and CD28.
View Article and Find Full Text PDFMonolayer MoS can effectively screen the vdW interaction of underlying substrates with external systems by >90% because of the substantial increase in the separation between the substrate and external systems due to the presence of the monolayer. This substantial screening of vdW interactions by MoS monolayer is different from what reported at graphene.
View Article and Find Full Text PDFWe present an Atomic Force Microscopy (AFM) based method to investigate the rheological properties of liquids confined within a nanosize gap formed by an AFM tip apex and a solid substrate. In this method, a conventional AFM cantilever is sheared parallel to a substrate surface by means of a lock-in amplifier while it is approaching and retracting from the substrate in liquid. The normal solvation forces and lateral viscoelastic shear forces experienced by the AFM tip in liquid can be simultaneously measured as a function of the tip-substrate distance with sub-nanometer vertical resolution.
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