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At least 973 records · Page 54

Design and implementation of a shearing apparatus for the experimental study of shear displacement in rocks

Fluid flow in the subsurface is not well understood in the context of “impermeable” geologic media. This is especially true of formations that have undergone significant stress fluctuations due to injection or withdrawal of fluids that alters the localized pressure regime. When the pressure regime is altered, these formations, which are often already fractured, move via shear to reduce the imbalance in the stress state. While this process is known to happen, the evolution of these fractures and their effects on fluid transport are still relatively unknown. Numerous simulation and several experimental studies have been performed that characterize the relationship between shearing and permeability in fractures; while many of these studies utilize measurements of fluid flow or the starting and ending geometries of the fracture to characterize shear, they do not characterize the intermediate stages during shear. We present an experimental apparatus based on slight modifications to a commonly available Hassler core holder that allows for shearing of rocks, while measuring the hydraulic and mechanical changes to geomaterials during intermediate steps. The core holder modification employs the use of semi-circular end caps and structural supports for the confining membrane that allow for free movement of the sheared material while preventing membrane collapse. By integrating this modified core holder with a computed tomography scanner, we show a new methodology for understanding the interdependent behavior between fracture structure and flow properties during intermediate steps in shearing. Here, we include a case study of this device function which is shown here through shearing of a fractured shale core and simultaneous observation of the mechanical changes and evolution of the hydraulic properties during shearing.

58 GEOSCIENCES↗

Structural and dynamical description of the enzymatic reaction of a phosphohexomutase

Enzymes are known to adopt various conformations at different points along their catalytic cycles. Here, we present a comprehensive analysis of 15 isomorphous, high resolution crystal structures of the enzyme phosphoglucomutase from the bacterium Xanthomonas citri. The protein was captured in distinct states critical to function, including enzyme-substrate, enzyme-product, and enzyme-intermediate complexes. Key residues in ligand recognition and regions undergoing conformational change are identified and correlated with the various steps of the catalytic reaction. In addition, we use principal component analysis to examine various subsets of these structures with two goals: (1) identifying sites of conformational heterogeneity through a comparison of room temperature and cryogenic structures of the apo-enzyme and (2) a priori clustering of the enzyme-ligand complexes into functionally related groups, showing sensitivity of this method to structural features difficult to detect by traditional methods. This study captures, in a single system, the structural basis of diverse substrate recognition, the subtle impact of covalent modification, and the role of ligand-induced conformational change in this representative enzyme of the α-D-phosphohexomutase superfamily.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Resonant-Plasmon-Assisted Subwavelength Ablation by a Femtosecond Oscillator

Here, we experimentally demonstrate the use of subwavelength optical nanoantennas to assist a direct nanoscale ablation using the ultralow fluence of a Ti:sapphire oscillator through the excitation of surface plasmon waves. The mechanism is attributed to nonthermal transient unbonding and electrostatic ablation, which is triggered by the surface plasmon-enhanced field electron emission and acceleration in vacuum. We show that the electron-driven ablation appears for both nanoscale metallic as well as dielectric materials. While the observed surface plasmon-enhanced local ablation may limit the applications of nanostructured surfaces in extreme nonlinear nanophotonics, it, nevertheless, also provides a method for nanomachining, manipulation, and modification of nanoscale materials. Lastly, collateral thermal damage to the antenna structure can be suitably avoided, and nonlinear conversion processes can be stabilized by a dielectric overcoating of the antenna.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Effect of atomic-scale defects and dopants on phosphorene electronic structure and quantum transport properties

By means of a multi-scale first-principles approach, a description of the local electronic structure of 2D and narrow phosphorene sheets with various types of modifications is presented. Firtly, a rational argument based on the geometry of the pristine and modified P network, and supported by the Wannier functions formalism is introduced to describe a hybridization model of the P atomic orbitals. Ab initio calculations show that non-isoelectronic foreign atoms form quasi-bound states at varying energy levels and create different polarization states depending on the number of valence electrons between P and the doping atom. The quantum transport properties of modified phosphorene ribbons are further described with great accuracy. The distortions on the electronic bands induced by the external species lead to strong backscattering effects on the propagating charge carriers. Depending on the energy of the charge carrier and the type of doping, the conduction may range from the diffusive to the localized regime. Interstitial defects at vacant sites lead to homogeneous transport fingerprints across different types of doping atoms. We suggest that the relatively low values of charge mobility reported in experimental measurements may have its origin in the presence of defects.

36 MATERIALS SCIENCE↗

Designing and defining dynamic protein cage nanoassemblies in solution

Central challenges in the design of large and dynamic macromolecular assemblies for synthetic biology lie in developing effective methods for testing design strategies and their outcomes, including comprehensive assessments of solution behavior. Here, we created and validated an advanced design of a 600-kDa protein homododecamer that self-assembles into a symmetric tetrahedral cage. The monomeric unit is composed of a trimerizing apex-forming domain genetically linked to an edge-forming dimerizing domain. Enhancing the crystallographic results, high-throughput small-angle x-ray scattering (SAXS) comprehensively contrasted our modifications under diverse solution conditions. To generate a phase diagram associating structure and assembly, we developed force plots that measure dissimilarity among multiple SAXS data sets. These new tools, which provided effective feedback on experimental constructs relative to design, have general applicability in analyzing the solution behavior of heterogeneous nanosystems and have been made available as a web-based application. Specifically, our results probed the influence of solution conditions and symmetry on stability and structural adaptability, identifying the dimeric interface as the weak point in the assembly. Force plots comparing SAXS data sets further reveal more complex and controllable behavior in solution than captured by our crystal structures. Lastly, these methods for objectively and comprehensively comparing SAXS profiles for systems critically affected by solvent conditions and structural heterogeneity provide an enabling technology for advancing the design and bioengineering of nanoscale biological materials.

59 BASIC BIOLOGICAL SCIENCES↗

Photocatalysis of Modified Transition Metal Oxide Surfaces

The goal of this project has been to establish a cause-effect relationship for photocatalytic activity variations of different structures of the same material; and furthermore gain fundamental understanding on modification of photocatalysts by compositional or surface modifications. The reasoning is that gaining atomic scale understanding of how surface and bulk modifications alter the photo reactivity will lead to design principles for next generation photocatalysts. As a prototypical photocatalyst the research focused on TiO 2 synthesized in well-defined single crystalline form to enable fundamental characterizations.We have obtained results in the following areas: (a) Preparation of epitaxial anatase TiO 2 samples by pulsed laser deposition. (b) Comparison of hydrogen diffusion on different crystallographic surface. (c) Determining the stability of the TiO 2 (011)-2x1 reconstruction upon interactions with adsorbates. (d) Characterization of adsorption and (thermal and photo) reaction of molecules with nitro-endgroups, (e) Exploring the possibility of modifying planar model photocatalyst surfaces with graphene to enable fundamental studies on reported enhanced photocatalytic activities of graphene modified transition metal oxides, (f) gained fundamental understanding on the role of crystallographic polymorphs of the same material for their photocatalytic activities.

36 MATERIALS SCIENCE↗

Enhanced Light Outcoupling from OLEDs Fabricated on Novel Low-Cost Patterned Plastic Substrates of Varying Periodicity

OLEDs continue to make strides in display applications, but their commercial utilization in solid-state lighting (SSL) is lagging. An ongoing challenge, in particular for manufacturing, is the need for enhanced efficiency and hence the necessity to increase in an inexpensive approach the extraction of the light generated inside the OLED into the forward (viewing) hemisphere. In conventional OLEDs fabricated on a transparent flat anode coated on glass, the external quantum efficiency (EQE) is only ~20%. About 50% of the light is lost to internal waveguiding in the high refractive index (RI) organic + ITO anode layers and to surface plasmon polaritons (SPPs) at the organic/metal cathode interface. Another ~30% of the light is externally waveguided in the substrate to its edges. While extraction of the externally waveguided light is commonly addressed by adding a microlens array (MLA) or a scattering layer at the substrate’s air-side, light outcoupling increases by only ~1.6-1.7x (vs up to 2.5x in improving from ~20% to ~50%). The use of a hemispherical lens or an index matching fluid (IMF) at the substrate/photodetector (PD) interface increases the outcoupling by at least 2x; these approaches however, are not viable industrially, and even a MLA is sometimes undesirable due to its non-planar, scattering structure. In multi-stack tandem OLEDs, where the metal cathode is far from the emitting zone(s), the impact of photons loss to SPPs decreases. Our project addressed the ~50% loss to the internally waveguided light and SPPs. We evaluated OLEDs fabricated on patterned or planarized plastic substrates manufactured in a cost-effective approach compatible with a roll-to-roll (R2R) process. The OLEDs were either (i) patterned to various degrees depending on the pitch a and height or depth h of the pattern features or (ii) planar, with a pattern buried under a flat high RI planarization layer. We demonstrated that the outcoupling from green patterned OLEDs reaches ~50% by mitigating plasmon–related loss and internal waveguiding, even without the addition of a MLA, a hemispherical lens, or IMF. Simulations conducted in parallel with the experimental effort demonstrated how diffraction by conformally corrugated OLEDs increases the outcoupling to >60%. Structures with varying pitch values were also simulated indicating that combining domains of varying pitch could increase outcoupling to 55-60%. Experimentally, we additionally assessed the role a and h in determining not only the OLED efficiencies, but also their structural properties, i.e., the uniformity and conformality throughout the OLED stack. As planar OLEDs are preferred over corrugated devices, we studied different patterns in plastic substrates that were planarized by a high RI formulation. Planar green OLEDs on such structures showed enhanced efficiencies with EQEs larger than 60% with the addition of an IMF (to extract the substrate mode) at the substrate/Si PD interface. White OLEDs showed EQEs of 45.5%. Plastic substrates are currently less attractive than glass substrates due to drawbacks such as permeability to water vapor and oxygen, and in some cases thermal instability. Plastic substrates however, are flexible and easy to handle unlike thin flexible glass, and once transparent thin barrier films are available, they will become more attractive; they are already of interest in medical applications. Importantly, as it is easy to generate various patterns in different plastic materials, they provide excellent means for assessing and optimizing enhancing extracting structures. Such structures can also be transferred to glass substrates with some process modifications. The technical effectiveness and economic feasibility of the project lie in the patterning of the extracting plastic substrates in an approach that is scalable to R2R manufacturing. R2R processes are of drastically lower-cost than batch or single-unit fabrication. The patterned plastic can be a part of an integrated substrate either plastic or glass, which includes also a MLA or a planar layer with embedded scattering particles, as well as a conductive metal mesh/electrode design. SSL is environmentally-friendly and as OLED SSL becomes more efficient it will reduce electricity consumption, and hence lighting cost, as well as produce less expensive attractive lighting fixtures. Our university-industry collaboration is hence of major benefit to the public as it demonstrates the feasibility of manufacturing optimized extracting substrates for highly efficient OLEDs for SSL in a future R2R process, which would drastically reduce the manufacturing cost and increase production in the USA. Moreover, newly developed methods by our team allow low-cost roll manufactured substrates to be transferred to flexible or rigid glass substrates, which solves the plastic substrate barrier issues, and when combined with device encapsulation will increase the OLEDs’ environmental stability.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Modeling the Interaction of Laser-Produced Proton Beams with Matter

A major goal of this project is to significantly increase our understanding of isochoric heating of matter using laser produced proton beams, and the associated high energy density (HED) and warm dense matter (WDM) regimes generated. This will benefit research fields such as planetary science, fusion energy, plasma physics, and material science. For example, it will enhance our understanding of WDM properties of iron and silica under conditions encountered in planetary interiors and diagnostic components in fusion devices exposed to high fluxes of energetic plasma ions. The project is motivated by recent experiments that irradiated Si targets with proton beams generated by the 20 TW-laser at the SLAC MEC end-station. The HED/WDM states are probed using the 50 fs hard X-rays available in the 3rd harmonic of the LCLS. As part of this project, results from the phase contrast X-ray imaging, which shows the generation of compression waves that produces rear surface spallation, are compared with results from the 3D multi-physics multi- material code, PISALE, that combines Arbitrary Lagrangian-Eulerian (ALE) hydrodynamics with Adaptive Mesh Refinement (AMR). This comparison required modifications to several physics models in the PISALE (Pacific Island Structured-AMR with ALE) code. An important aspect of this project is the continued training of graduate students in HED physics and in conducting complex multiphysics simulations.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Use of Novel Diglycolamide Extractants in Liquid-liquid Separations of Light Rare Earths

Creation of a novel extractant that can improve rare earth separations both economically and environmentally will be pivotal for industry progression. Diglycolamide (DGA) extractants provide chemistries that support this goal by serving as an extractant with high affinity for lanthanides and improved separation factors for light rare earths as compared to current extractants like PC88A. Initial organic phase loading capacity and phase dispersion tests performed with various modified DGAs generated results that were unfavorable for industrial processing, but further modification of the DGA alkyl chain substituents have resulted in new structures with promising results. Dispersion time measurements taken in small scale batch contacts of the extractant with a simulated leach liquor containing La, Ce, Nd, and Pr support implementation in both mixer-settlers and centrifugal contactors for larger scale separations. Furthermore, this confirmation allowed for preliminary flowsheet design using extraction equilibria at various organic to aqueous flow ratios (O/A) for extraction, scrubbing, and stripping stages. These values along with expected product/effluent compositions for each section aid in the testing for specific distribution ratios and final flowsheet design. Implementation of the DGA extractant into solvent extraction equipment will provide essential information for the next steps of this project and how this extractant may be optimized for future applications.

42 ENGINEERING↗

Structural Basis of Duplex Thermodynamic Stability and Enhanced Nuclease Resistance of 5'- C -Methyl Pyrimidine-Modified Oligonucleotides

Although judicious use of chemical modifications has contributed to the success of nucleic acid therapeutics, poor systemic stability remains a major hurdle. The introduction of functional groups around the phosphate backbone can enhance the nuclease resistance of oligonucleotides (ONs). In this paper, we report the synthesis of enantiomerically pure ( R )- and ( S )-5'- C -methyl (C5'-Me) substituted nucleosides and their incorporation into ONs. These modifications generally resulted in a decrease in thermal stability of oligonucleotide (ON) duplexes in a manner dependent on the stereoconfiguration at C5' with greater destabilization characteristic of ( R )-epimers. Enhanced stability against snake venom phosphodiesterase resulted from modification of the 3'-end of an ON with either ( R )- or ( S )-C5'-Me nucleotides. The ( S )-isomers with different 2'-substituents provided greater resistance against 3'-exonucleases than the corresponding ( R )-isomers. Crystal structure analyses of RNA octamers with ( R )- or ( S )-5'- C -methyl-2'-deoxy-2'-fluorouridine [( R )- or ( S )-C5'-Me-2'-FU, respectively] revealed that the stereochemical orientation of the C5'-Me and the steric effects that emanate from the alkyl substitution are the dominant determinants of thermal stability and are likely molecular origins of resistance against nucleases. X-ray and NMR structural analyses showed that the ( S )-C5'-Me epimers are spatially and structurally more similar to their natural 5' nonmethylated counterparts than the corresponding ( R )-epimers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

O-GlcNAc forces an α-synuclein amyloid strain with notably diminished seeding and pathology

Amyloid-forming proteins such α-synuclein and tau, which are implicated in Alzheimer’s and Parkinson’s disease, can form different fibril structures or strains with distinct toxic properties, seeding activities and pathology. Understanding the determinants contributing to the formation of different amyloid features could open new avenues for developing disease-specific diagnostics and therapies. Here we report that O-GlcNAc modification of α-synuclein monomers results in the formation of amyloid fibril with distinct core structure, as revealed by cryogenic electron microscopy, and diminished seeding activity in seeding-based neuronal and rodent models of Parkinson’s disease. Although the mechanisms underpinning the seeding neutralization activity of the O-GlcNAc-modified fibrils remain unclear, our in vitro mechanistic studies indicate that heat shock proteins interactions with O-GlcNAc fibril inhibit their seeding activity, suggesting that the O-GlcNAc modification may alter the interactome of the α-synuclein fibrils in ways that lead to reduce seeding activity in vivo. Our results show that posttranslational modifications, such as O-GlcNAc modification, of α-synuclein are key determinants of α-synuclein amyloid strains and pathogenicity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Across the Scales of the Nucleus: Understanding Short Range Correlations from Medium Modification to Probe Independence

The atomic nucleus presents an intricate system due to the non-linear forces described by Quantum Chromodynamics (QCD) that govern its structure. The range of scales involved is remarkable; the most massive nuclei weigh approximately five orders of magnitude more than the quarks that compose them. The nucleus can be analyzed at various levels, from quarks to hadrons to the nucleus as a whole. Short-Range Correlations (SRCs) within the nucleus play a significant role that spans these diverse scales. At the most fundamental level, SRCs influence the interaction between nucleons. The nucleon-nucleon (NN) interaction, arising from QCD, is crucial in determining nuclear properties. SRCs serve as valuable probes for measuring this NN interaction, as the nucleons within SRCs become effectively decoupled from the rest of the nucleus. Multiple experimental techniques, including electron scattering, have been employed to investigate the NN interaction through SRCs. However, our first project demonstrates that inclusive measurements alone are inadequate to constrain this interaction fully. Moving to the scale of the nucleus, SRCs contribute to the high-momentum tail of the nuclear spectral function. While the low-momentum region is characterized by nucleons exhibiting bulk properties, nucleons begin to pair into SRCs at higher momenta. Our research aims to bridge the understanding between the mean-field portion of the nucleus and its high-momentum SRC components. Additionally, SRCs affect the quark structure of protons, as evidenced by the EMC effect, which indicates that quarks behave differently when protons are embedded within a nucleus—an effect referred to as medium modification. This thesis explores the correlation between SRCs and medium modification across various experimental setups. Finally, we seek to establish an interpretation of the nuclear ground state. Accomplishing this requires demonstrating that our SRC observables are independent of the probe’s scale and scheme. The concluding project of this thesis illustrates how we utilize triple coincidence quasi-elastic scattering across a range of (Q2) values to develop a model-dependent framework for understanding SRC distributions within the nucleus’s ground-state wavefunction.

Denniston, A. W. Denniston [University of Tel Aviv↗

Systematic mapping of the conformational landscape and dynamism of soluble fibrinogen

Background: Fibrinogen is a soluble, multisubunit, and multidomain dimeric protein, which, upon its proteolytic cleavage by thrombin, is converted to insoluble fibrin, initiating polymerization that substantially contributes to clot growth. Fibrinogen contains numerous, transiently accessible “cryptic” epitopes for hemostatic and immunologic proteins, suggesting that fibrinogen exhibits conformational flexibility, which may play functional roles in its temporal and spatial interactions. Hitherto, there have been limited integrative approaches characterizing the solution structure and internal flexibility of fibrinogen. Methods: Here, utilizing a multipronged, biophysical approach involving 2 solution-based techniques, temperature-dependent hydrogen-deuterium exchange mass spectrometry and small angle X-ray scattering, corroborated by negative stain electron microscopy, we present a holistic, conformationally dynamic model of human fibrinogen in solution. Results: Our data reveal 4 major and distinct conformations of fibrinogen accommodated by a high degree of internal protein flexibility along its central scaffold. We propose that the fibrinogen structure in the solution consists of a complex, conformational landscape with multiple local minima. This is further supported by the location of numerous point mutations that are linked to dysfibrinogenemia and posttranslational modifications, residing near the identified fibrinogen flexions. Conclusion: Further, this work provides a molecular basis for the structural “dynamism” of fibrinogen that is expected to influence the broad swath of its functionally diverse macromolecular interactions and fine-tune the structural and mechanical properties of blood clots.

59 BASIC BIOLOGICAL SCIENCES↗

Effect of Monomer Structure on Crystallization and Glass Transition of Flexible Copolyesters

Amorphous flexible (co)polyesters with low glass transition temperature (T{sub g}) are very desirable in impact modification of biodegradable brittle polymers and synthesis of biodegradable elastomers. However, most flexible polyesters and binary copolyesters made from linear diacid(s) and diol(s) are crystalline polymers. In order to investigate the effect of monomer structure on the crystallization and T{sub g} of such copolyesters, novel ternary or multiple flexible copolyesters containing various structural units were designed and synthesized in this study, and characterized with {sup 1}HNMR, GPC, DSC, WAXD, TGA and tensile testing. Introducing aromatic diacid (especially asymmetric one) or short-chain branched diol is favorable to depress copolyester crystallization, and leads to higher T{sub g} at the same time. From easily crystallized to fully amorphous copolyesters with low T{sub g} were successfully synthesized by adopting different combination of structural units. In addition, the existence of aromatic structural unit in copolyesters is helpful to improve their tensile properties. Graphical Abstract: Flexible copolyesters containing various structural units were designed and synthesized. Introducing asymmetric, rigid aromatic or short-chain branched unit is favorable to depress copolyester crystallization, and leads to higher T{sub g} at the same time. Crystalline to fully amorphous copolyesters with low enough T{sub g} have been successfully synthesized by adjusting the structural units. .

36 MATERIALS SCIENCE↗

Leveraging Structured Biological Knowledge for Counterfactual Inference: A Case Study of Viral Pathogenesis

Counterfactual inference is a useful tool for comparing outcomes of interventions on complex systems. It requires us to represent the system in form of a structural causal model, complete with a causal diagram, probabilistic assumptions on exogenous variables, and functional assignments. Specifying such models can be extremely difficult in practice. The process requires substantial domain expertise, and does not scale easily to large systems, multiple systems, or novel system modifications. At the same time, many application domains, such as molecular biology, are rich in structured causal knowledge that is qualitative in nature. This manuscript proposes a general approach for querying a causal knowledge graph with a causal question and converting the qualitative result into a quantitative structural causal model that can learn from data to answer the question. Here, we demonstrate the feasibility, accuracy and versatility of this approach using two case studies in systems biology. The first demonstrates the appropriateness of the underlying assumptions and the accuracy of the results. The second demonstrates the versatility of the approach by querying a knowledge base for the molecular determinants of a severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2)-induced cytokine storm and performing counterfactual inference to predict the causal effect of medical countermeasures for severely ill COVID-19 patients.

60 APPLIED LIFE SCIENCES↗

High-Sensitivity Low-Energy Ion Spectroscopy with Sub-Nanometer Depth Resolution Reveals Oxidation Resistance of MoS 2 Increases with Film Density and Shear-Induced Nanostructural Modifications of the Surface

For decades, density has been attributed as a critical aspect of the structure of sputter-deposited nanocrystalline molybdenum disulfide (MoS 2 ) coatings impacting oxidation resistance and wear resistance. Despite its importance, there are few examples in the literature that explicitly investigate the relationship between the density and oxidation behaviors of MoS 2 coatings. Aging and oxidation are primary considerations for the use of MoS 2 coatings in aerospace applications as they inevitably experience prolonged storage in water and oxygen-rich environments prior to use. Oxidation that is either limited to the first few nanometers or through the bulk of the coating can result in seizure due to high initial coefficients of friction or component failure from excessive wear. High-sensitivity low-energy ion spectroscopy (HS-LEIS) and Rutherford backscattering spectrometry (RBS) are both used to understand the extent of oxidation throughout the first ~10 nanometers of the surface of pure sputtered nanocrystalline MoS 2 coatings after high-temperature aging and how it is impacted by the density of coatings as measured by RBS. Results show that low-density coatings (ρ = 3.55 g/cm 3 ) exhibit a more columnar microstructure and voiding, which act as pathways for oxidative species to penetrate and interact with edge sites, causing severe surface and subsurface oxidation. Furthermore, HS-LEIS of surfaces sheared prior to oxidation reveals that the oxidation resistance of low-density MoS 2 coatings can be significantly improved by shear-induced reorientation of the surface microstructure to a basal orientation and elimination of pathways for oxygen into the bulk through compaction of surface and subsurface voids.

36 MATERIALS SCIENCE↗

Recruiting physisorbed water in surface polymerization for bio-inspired materials of tunable hydrophobicity

Here, chemical grafting has been widely used to modify the surface properties of materials, especially surface energy for controlled wetting, because of the resilience of such coatings/modifications. Reagents with multiple reactive sites have been used with the expectation that a monolayer will form. The step-growth polymerization mechanism, however, suggests the possibility of gel formation for hydrolyzable moieties in the presence of physisorbed water. In this report, we demonstrated that using alkyltrichlorosilanes (trivalent [i.e., 3 reactive sites]) in the surface modification of a cellulosic material (paper) does not yield a monolayer but rather gives surface-bound particles. We infer that the presence of physisorbed (surface-bound) water allows for polymerization (or oligomerization) of the silane prior to its attachment on the surface. Surface energy mismatch between the hydrophobic tails of the growing polymer and any unreacted bound water leads to the assembly of the polymerizing material into spherical particles to minimize surface tension. By varying paper grammage (16.2–201.4 g m –2 ), we varied the accessible surface area and thus the amount of surface-adsorbed water, allowing us to control the ratio of the silane to the bound water. Using this approach, polymeric particles were formed on the surface of cellulose fibers ranging from ~70 nm to a film. The hydrophobicity of the surface, as determined by water contact angles, correlates with particle sizes (p < 0.001, Student's t-test), and, hence, the hydrophobicity can be tuned (contact angle between 94° and 149°). Using a model structure of a house, we demonstrated that as a result of this modification, paper-based houses can be rendered self-cleaning or tolerant to surface running water. In another application, we demonstrated that the felicitous choice of architectural design allows for the hydrophobic paper to be used for water harvesting.

36 MATERIALS SCIENCE↗

Metal-Mediated DNA Nanotechnology in 3D: Structural Library by Templated Diffraction

DNA double helices containing metal-mediated DNA (mmDNA) base pairs are constructed from Ag + and Hg 2+ ions between pyrimidine:pyrimidine pairs with the promise of nanoelectronics. Rational design of mmDNA nanomaterials is impractical without a complete lexical and structural description. Here, in this study, the programmability of structural DNA nanotechnology toward its founding mission of self-assembling a diffraction platform for biomolecular structure determination is explored. The tensegrity triangle is employed to build a comprehensive structural library of mmDNA pairs via X-ray diffraction and generalized design rules for mmDNA construction are elucidated. Two binding modes are uncovered: N3-dominant, centrosymmetric pairs and major groove binders driven by 5-position ring modifications. Energy gap calculations show additional levels in the lowest unoccupied molecular orbitals (LUMO) of mmDNA structures, rendering them attractive molecular electronic candidates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗