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Graphene has unique mechanical, electronic, and optical properties that make it of interest for an array of applications. These properties can be modulated by controlling the architecture of graphene and its interactions with surfaces. Self-assembled monolayers (SAMs) can tailor graphene-surface interactions; however, spatially controlling these interactions remains a challenge. Here, we blend colloidal lithography with varying SAM chemistries to create patterned architectures that modify the properties of graphene based on its chemical interactions with the substrate and to study how these interactions are spatially arrayed. The patterned systems and their resulting structural, nanomechanical, and optical properties have been characterized using atomic force microscopy, Raman and infrared spectroscopies, scattering-type scanning near-field optical microscopy, and X-ray photoelectron spectroscopy.

Realizing the efficiency benefits of low viscosity lubricants requires novel strategies to avoid failures resulting from increased boundary contact. Zirconium dioxide (ZrO2) nanoparticles (NPs) form protective tribofilms through tribosintering at lubricated contacts in pure hydrocarbon base oils, suggesting they hold promise for reducing boundary contact-induced failures. However, their tribological behavior alongside co-additives found in fully formulated oils has not been examined in depth. Here, the macroscopic tribological performance of dispersed ZrO2 NPs (1 wt% loading; 5 nm diameter nearly spherical ZrO2 tetragonal phase NPs with organic capping ligands for oil solubility) with and without the presence of co-additives found in fully formulated commercial gear oils was studied using a mini-traction machine (MTM). The results show that ZrO2 NPs reproducibly develop surface-bound ~ 100 nm thick tribofilms on both contacting surfaces under a wide range of rolling-sliding contact conditions, from 0 to 100% slide-to-roll ratio. Steady-state traction coefficient values of ZrO2 tribofilms formed alongside co-additives (0.10–0.11) do not substantially differ from ZrO2 tribofilms formed in neat polyalphaolefin base oils (0.10–0.13). However, there is improvement in the tribological performance of the contact, with at least a twofold reduction of wear of the steel. This behavior is proposed to be a result of cooperating mechanisms, where the extreme pressure additives adsorbed on the steel surfaces protect them against early adhesive wear, during the time that a protective ZrO2 tribofilm incorporating the co-additives forms on the steel surfaces, preventing further wear.

The genomic DNA of eukaryotic cells exists in the form of chromatin, the structure of which controls the biochemical accessibility of the underlying DNA to effector proteins. In order to gain an in depth molecular understanding of how chromatin structure regulates DNA repair, detailed in vitro biochemical and biophysical studies are required. However, because of challenges associated with reconstituting nucleosome arrays containing site-specifically positioned DNA modifications, such studies have been limited to the use of mono- and dinucleosomes as model in vitro substrates, which are incapable of folding into native chromatin structures. To address this issue, we developed a straightforward and general approach for assembling chemically defined oligonucleosome arrays (i.e., designer chromatin) containing site-specifically modified DNA. Our method takes advantage of nicking endonucleases to excise short fragments of unmodified DNA, which are subsequently replaced with synthetic oligonucleotides containing the desired modification. Using this approach, we prepared several oligonucleosome substrates containing precisely positioned 2'-deoxyuridine (dU) residues and examined the efficiency of base excision repair (BER) within several distinct chromatin architectures. We show that, depending on the translational position of the lesion, the combined catalytic activities of uracil DNA glycosylase (UDG) and apurinic/apyrimidinic endonuclease 1 (APE1) can be either inhibited by as much as 20-fold or accelerated by more than 5-fold within compact chromatin (i.e., the 30 nm fiber) relative to naked DNA. Moreover, we demonstrate that digestion of dU by UDG/APE1 proceeds much more rapidly in mononucleosomes than in compacted nucleosome arrays, thereby providing the first direct evidence that internucleosome interactions play an important role in regulating BER within higher-order chromatin structures. Overall, this work highlights the value of performing detailed biochemical studies on precisely modified chromatin substrates in vitro and provides a robust platform for investigating DNA modifications in chromatin biology.

Driving and measuring chemical reactions at the nanoscale is crucial for developing safer, more efficient, and environment-friendly reactors and for surface engineering. Quantitative understanding of surface chemical reactions in real operating environments is challenging due to resolution and environmental limitations of existing techniques. Here we report an atomic force microscope technique that can measure reaction kinetics driven at the nanoscale by multiphysical stimuli in an ambient environment. We demonstrate the technique by measuring local reduction of graphene oxide as a function of both temperature and force at the sliding contact. Kinetic parameters measured with this technique reveal alternative reaction pathways of graphene oxide reduction previously unexplored with bulk processing techniques. This technique can be extended to understand and precisely tailor the nanoscale surface chemistry of any two-dimensional material in response to a wide range of external, multiphysical stimuli.

The functional implementation of graphene as a solid boundary lubricant requires the ability to control its frictional response across a variety of interfaces. This is challenging, as being a single atomic layer thick, the nanotribological properties of graphene depend highly on the competing interaction strengths with the converse sides of the top and bottom contacts of the interfaces it is placed in between. One method to modulate these interactions is to tune the surface chemistry (of one or both counter-faces) with self-assembled monolayers (SAMs). To fully understand the effects on the graphene/SAM (G-SAM) composite interfaces formed, however, first necessitates a basic understanding of graphene–SAM interactions. To explore graphene–SAM adhesive and frictional interactions over a range of chemical functionalities, SAMs were used to functionalize atomic force microscopy (AFM) tips with varying terminal end-groups (−NH2, −CH3, and –phenyl, compared to unfunctionalized −OH terminated reference tips). AF...

Metal–organic coordinated multilayers are self-assembled thin films fabricated by alternating solution–phase deposition of bifunctional organic molecules and metal ions. The multilayer film composed of α,ω-mercaptoalkanoic acid and Cu (II) has been the focus of fundamental and applied research with its robust reproducibility and seemingly simple hierarchical architecture. However, internal structure and composition have not been unambiguously established. The composition of films up to thirty layers thick was investigated using Rutherford backscattering spectrometry and particle induced X-ray emission. Findings show these films are copper enriched, elucidating a 2:1 ratio for the ion to molecule complexation at the metal–organic interface. Results also reveal that these films have an average layer density similar to literature values established for a self-assembled monolayer, indicating a robust and stable structure. The surface structures of multilayer films have been characterized by contact angle goniometry, ellipsometry, and scanning probe microscopy. A morphological transition is observed as film thickness increases from the first few foundational layers to films containing five or more layers. Surface roughness analysis quantifies this evolution as the film initially increases in roughness before obtaining a lower roughness comparable to the underlying gold substrate. Quantitative analysis of topographical structure and internal composition for metal–organic coordinated multilayers as a function of number of deposited layers has implications for their incorporation in the fields of photonics and nanolithography.

Aramid nanofibers (ANFs), or nanoscale Kevlar fibers, are of interest for their high mechanical performance and functional nanostructure. The dispersible nature of ANFs opens up processing opportunities for creating mechanically robust and flexible nanocomposites, particularly for energy and power applications. The challenge is to manipulate ANFs into an electrode structure that balances mechanical and electrochemical performance to yield a robust and flexible electrode. Here, ANFs and graphene oxide (GO) sheets are blended using layer-by-layer (LbL) assembly to achieve mechanically flexible supercapacitor electrodes. After reduction, the resulting electrodes exhibit an ANF-rich structure where ANFs act as a polymer matrix that interfacially interacts with reduced graphene oxide sheets. It is shown that ANF/GO deposition proceeds by hydrogen bonding and π-π interactions, leading to linear growth (1.2 nm/layer pairs) and a composition of 75 wt % ANFs and 25 wt % GO sheets. Chemical reduction leads to a high areal capacitance of 221 μF/cm