Search NASASearch

SEARCH · Search NASA

Results for “Complex”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 73 records · Page 4

Chloride, Alkoxide, or Silicon: The Bridging Ligand Dictates the Spin State in Dicobalt Expanded Pincer Complexes

We report the synthesis and characterization of a series of high- and low-spin dicobalt complexes of the tBu PNNP expanded pincer ligand. Reacting this dinucleating ligand in its neutral form with two equiv of CoCl 2 (tetrahydrofuran) 1.5 yields a high-spin dicobalt complex featuring one Co inside and one Co outside of the dinucleating pocket. Performing the same reaction in the presence of two equivalents of KOtBu provides access to a high-spin dicobalt complex wherein both Co centers are bound within the PNNP pocket, and this complex also features a bridging OtBu ligand. Reacting either of the high-spin complexes with excess diethyl silane affords a low-spin dicobalt complex containing two unusual bridging Si-based ligands. These complexes were investigated using NMR spectroscopy, XAS, single crystal X-ray structure determination, and computational methods, showing that the Si-based ligands are best described as base-stabilized silylenes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

pH-Dependent Vibrational Dynamics Drives Excited-State Quenching in the Phycobiliprotein Complex PC645

Phycocyanin 645 (PC645) is a closed-form lightharvesting complex found in the lumen of the photosynthetic membrane of cryptophyte algae. These peripheral antenna complexes contain bilin chromophores that absorb sunlight and transfer excitation energy to the core antenna complexes embedded in the thylakoid membrane. The location of cryptophyte antenna complex on the luminal side of the membrane is unusual. During photosynthetic activity, the pH of the lumen drops, by up to two pH units. There is little known about how this pH-change affects the light-harvesting complexes. In this study, we report multiscale simulations using a computationally efficient density functional tight-binding framework to investigate the spectroscopy and excitation energy transfer in the PC645 complex. Complementary experiments were conducted using both steady-state and time-resolved spectroscopic measurements at low, neutral, and high pH values. Our study shows that (de)protonation of specific bilin pigments, namely, the mesobiliverdins (MBVs), modulates the excitation energies, excitonic couplings, and spectral densities. These changes cause excitation transfer rates to increase by up to a factor of two to three, leading to pH-dependent energy transfer pathways in the complex. Using this model, we calculated the pH-dependent fluorescence quantum yield of the system, obtaining quantitative agreement with the experimental results. These computational simulations, supported by experiments, identify MBVs as a more prominent excitation sink than previously realized, and that this role is tuned by pH.

Maity, Sayan [Constructor Univ., Bremen (Germany);

Structural and compositional complexities of hierarchical self-assembly: A hypergraph approach

Programmable self-assembly enables the construction of complex molecular, supramolecular, and crystalline architectures from well-designed building blocks. In this work, we introduce a hypergraph-based formalism, Blocks & Bonds (B&B), which generalizes classical chemical graph theory by incorporating directed and multicolored interactions, internal symmetries, and hierarchical organization. Within this framework, we develop the Structure Code (SC), a compact and versatile language for describing self-assembled architectures. We define a Kolmogorov-style structural complexity as the total information content of SC, obtained through its tokenization and Shannon information assignment. Complementing this encoding-based measure, we introduce a much simpler quantity, the compositional complexity, which depends only on the number and cumulative usage of block and bond types in the construction set. A central result of this work is a strong empirical correlation between the token-based structural complexity and the compositional complexity across all examined systems. Owing to this agreement, the compositional complexity emerges as the most practical and broadly applicable measure: it is easy to compute, requires no explicit encoding, and yet closely tracks the actual information content of structurally diverse architectures. Applications to molecular systems (ethylene glycol and glucose), DNA-origami lattices, and crystalline assemblies show that B&B hypergraphs provide a unified, scalable, and information-efficient representation of structural organization, naturally capturing symmetry, modularity, and stereochemistry. This framework establishes a quantitative foundation for complexity-aware classification and inverse design of programmable matter.

36 MATERIALS SCIENCE

A nut-and-bolt assembly of the bimodular large progenitor botulinum neurotoxin complex

Botulinum neurotoxin serotype A (BoNT/A) is naturally produced by bacteria along with four nontoxic neurotoxin-associated proteins (NTNH, HA70, HA33, and HA17), forming a bimodular large progenitor toxin complex (L-PTC). The BoNT/A–NTNH complex protects the toxin from adverse environment, while the complex consisting of HA proteins facilitates toxin absorption during oral intoxication. How these two independent modules assemble into the L-PTC remains unclear. Here, we report the crystal structure of the BoNT/A–NTNH–HA70 complex at ~2.9-Å resolution. The structure reveals that the BoNT/A–NTNH complex is anchored into a concentric double β-barrel channel of trimeric HA70 through a short β-hairpin of NTNH (termed nLoop), resembling a nut-and-bolt attachment. We find that the nLoop of NTNH is strictly conserved across HA-containing BoNT complexes and that NTNH–HA70 binding is interchangeable among them. Furthermore, we demonstrate that the nLoop functions as a minimal motif enabling attachment of a protein-of-interest to the HA complex, with potential applications in oral biologics delivery.

Science & Technology - Other Topics

AEOLUS: Advances in Experimental Design, Optimal Control, and Learning for Uncertain Complex Systems

Sustained advances in the mathematics of modeling and simulation have resulted in the capability today for routine simulation of a number of large scale complex DOE-relevant systems. As remarkable as this capability for solving the so-called forward problem is, it is typically only the first step-an inner loop within an outer loop that explores the simulation model's parameter space and decision space to characterize uncertainty in the model's predictions, learn unknown model parameters from data, design the most informative experiments, determine optimal control strategies, and create optimal designs. Broadly, what unifies all of these outer loop problems is that they are, in one form or another, optimization problems over parameter/control/design space that are constrained by complex uncertain models. To fully realize the power of scientific simulation as a basis for scientific discovery, technological innovation, and rational decision-making, it is imperative to move beyond simulation to tackle the outer loop of optimization for learning from data, experimental design, and control with complex uncertain models. When the models under consideration are large-scale and complex, and when the optimization variable and uncertain parameter spaces are high (or infinite) dimensional, this constitutes a grand challenge of the highest order, and is intractable with conventional methods. To overcome these challenges, the AEOLUS Center was established to develop a unified mathematical, computational, and statistical framework for (1) Learning predictive models from complex data via Bayesian inference and optimization, and (2) Optimizing experiments, processes, and designs using the resulting uncertain models. These problems are intractable with conventional methods, for several reasons: (1) The simulation problems that govern the inner loops of the optimization problems are expensive to execute (due to severe nonlinearity, heterogeneity, multiphysics/multiscale coupling); (2) The optimization variable and uncertain parameter spaces are high dimensional, often stemming from discretizations of infinite dimensional fields such as initial conditions, sources, or material properties. We argue that the key to overcoming these challenges is to develop new mathematical, computational, and statistical methods that exploit the structure of the Bayesian inference and optimization problems mediated by their underlying complex uncertain models. This structure includes the regularity, sparsity, geometry, low intrinsic dimensionality, and multifidelity nature of the maps from uncertain parameter/optimization variable spaces to the specific objectives targeted: Bayesian inference, optimal experimental design, and optimal control design. Black box methods developed as generic tools are incapable of exploiting this structure. To be successful, we must create, integrate, and cross-fertilize ideas across multiple areas of applied math--including approximation theory, Bayesian inference, data science, experimental design, information theory, machine learning, model reduction, optimal control theory, parallel algorithms, PDE-constrained optimization, randomized algorithms, stochastic optimization, and uncertainty quantification--all while exploiting the structure of the problems at hand. With this goal in mind, we have marshaled a team of leading authorities in these areas. While the methods we develop will be broadly applicable across a wide spectrum of DOE problems in which experiments inform models and the systems those models describe must be optimized under uncertainty, we have chosen a specific area, advanced manufacturing and materials, to drive our work. AMM is characterized by complex models across multiple scales, and is a rich source of challenging problems in inference, experimental design, and optimal control, requiring multifaceted and integrated advances in applied mathematics. As such, AMM serves as an excellent vehicle to motivate and demonstrate the advances in applied mathematics developed by our center.

97 MATHEMATICS AND COMPUTING

A system of three-dimensional complex variables

Some results of a new theory of multidimensional complex variables are reported, including analytic functions of a three-dimensional (3-D) complex variable. Three-dimensional complex numbers are defined, including vector properties and rules of multiplication. The necessary conditions for a function of a 3-D variable to be analytic are given and shown to be analogous to the 2-D Cauchy-Riemann equations. A simple example also demonstrates the analogy between the newly defined 3-D complex velocity and 3-D complex potential and the corresponding ordinary complex velocity and complex potential in two dimensions.

Martin, E. Dale

Conjugate gradient type methods for linear systems with complex symmetric coefficient matrices

We consider conjugate gradient type methods for the solution of large sparse linear system Ax equals b with complex symmetric coefficient matrices A equals A(T). Such linear systems arise in important applications, such as the numerical solution of the complex Helmholtz equation. Furthermore, most complex non-Hermitian linear systems which occur in practice are actually complex symmetric. We investigate conjugate gradient type iterations which are based on a variant of the nonsymmetric Lanczos algorithm for complex symmetric matrices. We propose a new approach with iterates defined by a quasi-minimal residual property. The resulting algorithm presents several advantages over the standard biconjugate gradient method. We also include some remarks on the obvious approach to general complex linear systems by solving equivalent real linear systems for the real and imaginary parts of x. Finally, numerical experiments for linear systems arising from the complex Helmholtz equation are reported.

Freund, Roland

Lanthanide Complexes as a Test for Evidence of Life

The objective of this research is to advance the understanding of the interaction of lanthanide metals with biological organic molecules and to develop a technique to detect these compounds in the solid state and in situ in Mars and other planetary bodies. The detection of these complexes should provide evidence of life past or present. In addition, detection of the metals alone will provide important information about the geological history of a planetary body. Lanthanides were chosen as our focus of interest because they form very stable complexes with organic molecules in solution and they produce intense luminescence in the ultraviolet and visible spectra. The rare earth complexes available are mostly synthetic for diverse applications in medicine. There is not much work done on the complexes that form in nature. Lanthanides have many applications and they are mined aR over the world, however, since the interest has been only in the elements, the analytical techniques employed destroy any organic ligands that may be present. In order to determine if and which lanthanide complexes form in nature and their concentration, soil samples have been collected from areas rich in soluble lanthanide compounds like phosphates and also rich in vegetation. The soil samples will be analyzed and the lanthanide complexes if present will be isolated and characterized. A spectrometer to detect the lanthanide complexes in situ and in the solid state will be designed. In this workshop, the research approach and its implications will be discussed.

Benavides, Jeannette

ROSAT HRI and ASCA Observations of the Spiral Galaxy NGC 6946 and its Northeast Complex of Luminous Supernova Remnants

Analysis of 80 ks ASCA (Advanced Satellite for Cosmology and Astrophysics) and 60 ks ROSAT HRI (High Resolution Image) observations of the face-on spiral galaxy NGC 6946 are presented. The ASCA image is the first observation of this galaxy above approximately 2 keV. Diffuse emission may be present in the inner approximately 4' extending to energies above approximately 2-3 keV. In the HRI data, 14 pointlike sources are detected, the brightest two being a source very close to the nucleus and a source to the northeast that corresponds to a luminous complex of interacting supernova remnants (SNRs). We detect a point source that lies approximately 30" west of the SNR complex but with a luminosity -1115 of the SNR complex. None of the point sources show evidence of strong variability; weak variability would escape our detection. The ASCA spectrum of the SNR complex shows evidence for an emission line at approximately 0.9 keV that could be either Ne IX at approximately 0.915 keV or a blend of ion stages of Fe L-shell emission if the continuum is fitted with a power law. However, a two-component, Raymond-Smith thermal spectrum with no lines gives an equally valid continuum fit and may be more physically plausible given the observed spectrum below 3 keV. Adopting this latter model, we derive a density for the SNR complex of 10-35 cm(exp -3), consistent with estimates inferred from optical emission-line ratios. The complex's extraordinary X-ray luminosity may be related more to the high density of the surrounding medium than to a small but intense interaction region where two of the complex's SNRs are apparently colliding.

Schlegel, E.

Studying the Iron Line Complex in the Bright Seyfert Galaxy NGC 5506

This grant was to support the reduction and analysis of our approved XMM observation of the nearby Seyfert 2 galaxy NGC 5506. The observation has been carried out simultaneously with a BeppoSAX observation of the same source. The proposal was aimed to study in detail the Compton reflection component and the complex Iron K line of this source, combining the still unique capability of BeppoSAX in hard X-rays (to strongly constrain the reflection component, and then the intrinsic nuclear continuum), and the sensitivity of XMM at the energy of the Iron Line complex. NGC 5506 is one of the brightest AGN in hard X-rays and has been intensively studied in the past. GINGA detected the complex iron line as well as the reflection component. Both ASCA (spectroscopically) and Rossi-XTE (through variability analysis) suggested that the FeK line is complex, possibly made up of several distinct components. The centroid of the FeK complex in a subsequent BeppoSAX observation was bluer than the 6.4 keV energy of the relatively low-ionization iron Kalpha transition. NGC 5506 has been observed simultaneously by NewtonXMM and BeppoSAX on February 2-3 2001. we have reduced and analyzed both the NewtonXMM and the BeppoSAX data, and have written and published a paper on our results (appeared in Volume 377 (page 31) of A&A-Letters). Our main results can be summarized as follows: (a) we confirm that the FeK line is complex, and for the first time disentangle its components: we find that at least two components made up the FeK complex, one neutral and narrow, at 6.4 keV (rest energy), and another one either broader and highly ionized, at about 6.7 keV (rest frame), or, in turn, made up of two narrow and unresolved components from the He-like and the H-like ions of Fe; (b) the two possible solution for the high-ionization Fe-K component, are statistically indistinguishable. However, physically, a blend of two narrow lines from photoionized matter seems to be preferable to emission of a relativistically broadened line from an ionized accretion disk; (c) The bulk of the Compton reflection continuum originates in neutral matter, and is therefore associated with the narrow FeK line at 6.4 keV: they are most likely emitted by distant matter.

Nicastro, Fabrizio

Theoretical Investigation of OCN(-) Charge Transfer Complexes in Condensed Phase Media: Spectroscopic Properties in Amorphous Ice

Density functional theory (DFT) calculations of cyanate (OCN(-)) charge-transfer complexes were performed to model the "XCN" feature observed in interstellar icy grain mantles. OCN(-) charge-transfer complexes were formed from precursor combinations of HNCO or HOCN with either NH3 or H2O. Three different solvation strategies for realistically modeling the ice matrix environment were explored, including (1) continuum solvation, (2) pure DFT cluster calculations, and (3) an ONIOM DFT/PM3 cluster calculation. The model complexes were evaluated by their ability to reproduce seven spectroscopic measurements associated with XCN: the band origin of the OCN(-) asymmetric stretching mode, shifts in that frequency due to isotopic substitutions of C, N, O, and H, plus two weak features. The continuum solvent field method produced results consistent with some of the experimental data but failed to account for other behavior due to its limited capacity to describe molecular interactions with solvent. DFT cluster calculations successfully reproduced the available spectroscopic measurements very well. In particular, the deuterium shift showed excellent agreement in complexes where OCN(-) was fully solvated. Detailed studies of representative complexes including from two to twelve water molecules allowed the exploration of various possible solvation structures and provided insights into solvation trends. Moreover, complexes arising from cyanic or isocyanic acid in pure water suggested an alternative mechanism for the formation of OCN(-) charge-transfer complexes without the need for a strong base such as NH3 to be present. An extended ONIOM (B3LYP/PM3) cluster calculation was also performed to assess the impact of a more realistic environment on HNCO dissociation in pure water.

Park, Jin-Young

Cosmic Complexity

What explains the extraordinary complexity of the observed universe, on all scales from quarks to the accelerating universe? My favorite explanation (which I certainty did not invent) ls that the fundamental laws of physics produce natural instability, energy flows, and chaos. Some call the result the Life Force, some note that the Earth is a living system itself (Gaia, a "tough bitch" according to Margulis), and some conclude that the observed complexity requires a supernatural explanation (of which we have many). But my dad was a statistician (of dairy cows) and he told me about cells and genes and evolution and chance when I was very small. So a scientist must look for me explanation of how nature's laws and statistics brought us into conscious existence. And how is that seemll"!gly Improbable events are actually happening a!1 the time? Well, the physicists have countless examples of natural instability, in which energy is released to power change from simplicity to complexity. One of the most common to see is that cooling water vapor below the freezing point produces snowflakes, no two alike, and all complex and beautiful. We see it often so we are not amazed. But physlc!sts have observed so many kinds of these changes from one structure to another (we call them phase transitions) that the Nobel Prize in 1992 could be awarded for understanding the mathematics of their common features. Now for a few examples of how the laws of nature produce the instabilities that lead to our own existence. First, the Big Bang (what an insufficient name!) apparently came from an instability, in which the "false vacuum" eventually decayed into the ordinary vacuum we have today, plus the most fundamental particles we know, the quarks and leptons. So the universe as a whole started with an instability. Then, a great expansion and cooling happened, and the loose quarks, finding themselves unstable too, bound themselves together into today's less elementary particles like protons and neutrons, liberating a little energy and creating complexity. Then, the expanding universe cooled some more, and neutrons and protons, no longer kept apart by immense temperatures, found themselves unstable and formed helium nuclei. Then, a little more cooling, and atomic nuclei and electrons were no longer kept apart, and the universe became transparent. Then a little more cooling, and the next instability began: gravitation pulled matter together across cosmic distances to form stars and galaxies. This instability is described as a "negative heat capadty" in which extracting energy from a gravitating system makes it hotter -- clearly the 2nd law of thermodynamics does not apply here! (This is the physicist's part of the answer to e e cummings' question: what is the wonder that's keeping the stars apart?) Then, the next instability is that hydrogen and helium nuclei can fuse together to release energy and make stars burn for billions of years. And then at the end of the fuel source, stars become unstable and explode and liberate the chemical elements back into space. And because of that, on planets like Earth, sustained energy flows support the development of additional instabilities and all kinds of complex patterns. Gravitational instability pulls the densest materials into the core of the Earth, leaving a thin skin of water and air, and makes the interior churn incessantly as heat flows outwards. And the heat from the sun, received mostly near the equator and flowing towards the poles, supports the complex atmospheric and oceanic circulations. And because or that, the physical Earth is full of natural chemical laboratories, concentrating elements here, mixing them there, raising and lowering temperatures, ceaselessly experimenting with uncountable events where new instabilities can arise. At least one of them was the new experiment called life. Now that we know that there are at least as many planets as there are stars, it is hard to imagine that nature's ceasess experimentation would not be able to produce life elsewhere -- but we don't know for sure. And life went on to cause new Instabilities, constantly evolving, with living things in an extraordinary range of environments, changing the global environment, with boom-and-bust cycles. with predators for every kInd of prey, with criminals for every possible crime, with governments to prevent them, and instabilities of the governments themselves. One of the instabilities Is that humans demand new weapons and new products of all sort, leading to serious investments in science and technology. So the natural/human world of competition and combat is structured to lead to advanced weaponry and cell phones. So here we are In 2012, with people writing essays and wondering whether their descendents will be artificial life forms travelling back into space. And, pondering what are the origins of those forces of nature that give rise to everything. Verllnde has argued that gravitation, the one force that has so far resisted our efforts at a Quantum description, is not even a fundamental force, but is itself it a statistical force, like osmosis. What an amazing turn of events! But after all I've just said, I should not be surprised a bit.

Mather, John C.

Understanding Crew Decision-Making in the Presence of Complexity: A Flight Simulation Experiment

Crew decision making and response have long been leading causal and contributing factors associated with aircraft accidents. Further, it is anticipated that future aircraft and operational environments will increase exposure to risks related to these factors if proactive steps are not taken to account for ever-increasing complexity. A flight simulation study was designed to collect data to help in understanding how complexity can, or may, be manifest. More specifically, an experimental apparatus was constructed that allowed for manipulation of information complexity and uncertainty, while also manipulating operational complexity and uncertainty. Through these manipulations, and the aid of experienced airline pilots, several issues have been discovered, related most prominently to the influence of information content, quality, and management. Flight crews were immersed in an environment that included new operational complexities suggested for the future air transportation system as well as new technological complexities (e.g. electronic flight bags, expanded data link services, synthetic and enhanced vision systems, and interval management automation). In addition, a set of off-nominal situations were emulated. These included, for example, adverse weather conditions, traffic deviations, equipment failures, poor data quality, communication errors, and unexpected clearances, or changes to flight plans. Each situation was based on one or more reference events from past accidents or incidents, or on a similar case that had been used in previous developmental tests or studies. Over the course of the study, 10 twopilot airline crews participated, completing over 230 flights. Each flight consisted of an approach beginning at 10,000 ft. Based on the recorded data and pilot and research observations, preliminary results are presented regarding decision-making issues in the presence of the operational and technological complexities encountered during the flights.

Young, Steven D.

Using the System Complexity Metric (SCM) to Compare CO2 Removal Systems

A fundamental cause of difficulty in large engineering projects is their inherent complexity. An impression of complexity occurs if a system is simply difficult to understand, where there is no obvious mental model that correctly predicts its behavior. Higher system complexity is usually associated with higher cost and higher failure rate. Complexity is perceived if a system has many diverse components, multiple interactions and feedback loops, transients and dynamic behavior, and unanticipated failure modes. Identifying and removing these signs of complexity should improve performance and reduce the cost and failure rate. Complexity can be directly measured by the number of components and their interactions. The System Complexity Metric (SCM) is defined as the sum of the number of parts in a system, N, plus the number of the one-way interconnections between them, I. SCM = N + I. The SCM is easily determined by direct inspection of the system block diagram. SCM can be used to compare systems and to guide their redesign to reduce cost and failure rate. Carbon dioxide removal systems are analyzed using SCM, cost, and failure rate. As in previous work, cost is directly proportional to SCM and that failure rate increases as a power of SCM for large differences in SCM. The SCM ranking of carbon dioxide removal systems is the same as their ranking in detailed analysis and practice.

Harry W. Jones

Using the System Complexity Metric (SCM) to Compare CO2 Reduction Systems

A fundamental cause of difficulty in large engineering projects is their inherent complexity. An impression of complexity occurs if a system is simply difficult to understand, where there is no obvious mental model that correctly predicts its behavior. Higher system complexity is usually associated with higher cost and higher failure rate. Complexity is perceived if a system has many diverse components, multiple interactions and feedback loops, transients and dynamic behavior, and unanticipated failure modes. Identifying and removing these signs of complexity should improve performance and reduce the cost and failure rate. Complexity can be directly measured by the number of components and their interactions. The System Complexity Metric (SCM) is defined as the sum of the number of parts in a system, N, plus the number of the one-way interconnections between them, I. SCM = N + I. The SCM is easily determined by direct inspection of the system block diagram. SCM can be used to compare systems and to guide their redesign to reduce cost and failure rate. Carbon dioxide reduction systems are analyzed using SCM, cost, and failure rate. As in previous work, cost is directly proportional to SCM and that failure rate increases as a power of SCM for large differences in SCM. The SCM ranking of carbon dioxide reduction systems is the same as their ranking in detailed analysis and practice.

Harry W. Jones

Compositionally-driven surface nanostructuring on refractory compositionally complex alloys under low energy helium bombardment

Additive manufacturing enables user-defined control of the compositional complexity, opening new design spaces for complex concentrated alloys (CCAs). Refractory CCAs may offer enhanced performance in the divertor region of a fusion reactor environment where plasma-facing materials will be subject to high temperatures, low energy He and D particles, and 14 MeV neutrons. In this work, specimens with the nominal composition of NbTaMoTi, NbTaMo, NbTaTi, and NbTa were fabricated via directed energy deposition (DED) then bombarded with 40 eV He ions to a fluence of 2x10 26 m −2 at ∼ 1000 K. Post irradiation, the surface morphology and composition were examined with electron microscopy and x-ray photoelectron spectroscopy to offer information on the spatial distribution of surface nano-structuring. Sub-surface He bubbles driving the nano-structuring were examined with electron microscopy techniques. Analysis indicates the local composition directly influences the He bubble and tendril size, while the region with the highest complexity showed the shortest nano-structuring. Molecular Dynamics simulations complement the experimental results, showing comparable helium bubble growth and migration as a function of compositional complexity. This work demonstrates the compositional dependence of surface nanostructure formation of compositionally complex alloys, important for future design of complex plasma facing materials in fusion reactors.

Complex concentrated alloys

The Complexation Properties of Self-Defensive Microgel-Modified Antimicrobial Surfaces

The complexation of cationic antimicrobials with polyanionic microgels on a biomaterial surface can render that surface self-defensive against bacteria by killing those bacteria which physically contact the antimicrobial-loaded microgels. This killing has been attributed to the contact-driven transfer of antimicrobial from a microgel to a challenging bacterium, though much remains unknown about this process. Here, in this study, we use a combination of experiments and computational modeling to identify key aspects of the complexation phenomena which influence the self-defensive properties. We synthesize poly(acrylic acid) (PAA) microgels (∼2–5 μm diameter) via membrane emulsification and electrostatically deposit them onto polycaprolactone (PCL) coupons or onto glass to form a discontinuous submonolayer. Subsequent microgel loading with colistin or with Sub5 antimicrobial peptide (AMP) causes microgel deswelling. Under physiological conditions Sub5 remains stably sequestered whereas colistin is quickly released. Coarse-grained molecular dynamics (CGMD) simulations confirm stronger Sub5/PAA complexation. CGMD calculations also indicate that Sub5 forms dimers and higher-order structures, a prediction confirmed experimentally by Small-Angle X-ray Scattering (SAXS). Supramolecular structure entropically enhances the complexation strength because of enhanced counterion release per complexation event, and this finding can help identify other antimicrobials well suited for such a nonelutive yet self-defensive strategy. CGMD simulations also show that Sub5 has a higher complexation strength with the Staphylococcus aureus membrane than it does with PAA, confirming that there is a thermodynamic driving force for antimicrobial transfer. Such self-defensive surfaces significantly reduce S. aureus colonization (over 90% reduction relative to unmodified controls) in an in vitro hematogenous contamination model and remain cyto-compatible as evidenced by mesenchymal stem cell spreading and proliferation.

36 MATERIALS SCIENCE

Epitaxial Thin Film Growth on Recycled SrTiO 3 Substrates Toward Sustainable Processing of Complex Oxides

Complex oxide thin films cover a range of physical properties and multifunctionalities that are critical for logic, memory, and optical devices. Typically, the high‐quality epitaxial growth of these complex oxide thin films requires single crystalline oxide substrates such as SrTiO 3 (STO), MgO, LaAlO 3 , a‐Al 2 O 3, and many others. Recent successes in transferring these complex oxides as free‐standing films not only offer great opportunities in integrating complex oxides on other devices, but also present enormous opportunities in recycling the deposited substrates after transfer for cost‐effective and sustainable processing of complex oxide thin films. In this work, the surface modification effects introduced on the recycled STO are investigated, and their impacts on the microstructure and properties of subsequently grown epitaxial oxide thin films are assessed and compared with those grown on the pristine substrates. Detailed analyses using high‐resolution scanning transmission electron microscopy and geometric phase analysis demonstrate distinct strain states on the surfaces of the recycled STO versus the pristine substrates, suggesting a pre‐strain state in the recycled STO substrates due to the previous deposition layer. These findings offer opportunities in growing highly mismatched oxide films on the recycled STO substrates with enhanced physical properties. Specifically, yttrium iron garnet (Y 3 Fe 5 O 12 ) films grown on recycled STO present different ferromagnetic responses compared to that on the pristine substrates, underscoring the effects of surface modification. The study demonstrates the feasibility of reuse and redeposition using recycled substrates. Via careful handling and preparation, high‐quality epitaxial thin films can be grown on recycled substrates with comparable or even better structural and physical properties toward sustainable process of complex oxide devices.

pre-strained STO surfaces