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At least 127 records · Page 7

Designer Nanomaterials through Programmable Assembly

Nanoparticles have long been recognized for their unique properties, leading to exciting potential applications across optics, electronics, magnetism, and catalysis. These specific functions often require a designed organization of particles, which includes the type of order as well as placement and relative orientation of particles of the same or different kinds. DNA nanotechnology offers the ability to introduce highly addressable bonds, tailor particle interactions, and control the geometry of bindings motifs. Here, we discuss how developments in structural DNA nanotechnology have enabled greater control over 1D, 2D, and 3D particle organizations through programmable assembly. This Review focuses on how the use of DNA binding between nanocomponents and DNA structural motifs has progressively allowed the rational formation of prescribed particle organizations. Here, we offer insight into how DNA-based motifs and elements can be further developed to control particle organizations and how particles and DNA can be integrated into nanoscale building blocks, so-called “material voxels”, to realize designer nanomaterials with desired functions.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Programmable 3D Hexagonal Geometry of DNA Tensegrity Triangles

Abstract Non‐canonical interactions in DNA remain under‐explored in DNA nanotechnology. Recently, many structures with non‐canonical motifs have been discovered, notably a hexagonal arrangement of typically rhombohedral DNA tensegrity triangles that forms through non‐canonical sticky end interactions. Here, we find a series of mechanisms to program a hexagonal arrangement using: the sticky end sequence; triangle edge torsional stress; and crystallization condition. We showcase cross‐talking between Watson–Crick and non‐canonical sticky ends in which the ratio between the two dictates segregation by crystal forms or combination into composite crystals. Finally, we develop a method for reconfiguring the long‐range geometry of formed crystals from rhombohedral to hexagonal and vice versa. These data demonstrate fine control over non‐canonical motifs and their topological self‐assembly. This will vastly increase the programmability, functionality, and versatility of rationally designed DNA constructs.

Lu, Brandon↗

Programmable 3D Hexagonal Geometry of DNA Tensegrity Triangles

Non-canonical interactions in DNA remain under-explored in DNA nanotechnology. Recently, many structures with non-canonical motifs have been discovered, notably a hexagonal arrangement of typically rhombohedral DNA tensegrity triangles that forms through non-canonical sticky end interactions. Here, in this study, we find a series of mechanisms to program a hexagonal arrangement using: the sticky end sequence; triangle edge torsional stress; and crystallization condition. We showcase cross-talking between Watson–Crick and non-canonical sticky ends in which the ratio between the two dictates segregation by crystal forms or combination into composite crystals. Finally, we develop a method for reconfiguring the long-range geometry of formed crystals from rhombohedral to hexagonal and vice versa. These data demonstrate fine control over non-canonical motifs and their topological self-assembly. This will vastly increase the programmability, functionality, and versatility of rationally designed DNA constructs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Programmable Gene Knockdown in Diverse Bacteria Using Mobile‐CRISPRi

Abstract Facile bacterial genome sequencing has unlocked a veritable treasure trove of novel genes awaiting functional exploration. To make the most of this opportunity requires powerful genetic tools that can target all genes in diverse bacteria. CRISPR interference (CRISPRi) is a programmable gene‐knockdown tool that uses an RNA‐protein complex comprised of a single guide RNA (sgRNA) and a catalytically inactive Cas9 nuclease (dCas9) to sterically block transcription of target genes. We previously developed a suite of modular CRISPRi systems that transfer by conjugation and integrate into the genomes of diverse bacteria, which we call Mobile‐CRISPRi. Here, we provide detailed protocols for the modification and transfer of Mobile‐CRISPRi vectors for the purpose of knocking down target genes in bacteria of interest. We further discuss strategies for optimizing Mobile‐CRISPRi knockdown, transfer, and integration. We cover the following basic protocols: sgRNA design, cloning new sgRNA spacers into Mobile‐CRISPRi vectors, Tn 7 transfer of Mobile‐CRISPRi to Gram‐negative bacteria, and ICE Bs1 transfer of Mobile‐CRISPRi to Bacillales. © 2020 The Authors. Basic Protocol 1 : sgRNA design Basic Protocol 2 : Cloning of new sgRNA spacers into Mobile‐CRISPRi vectors Basic Protocol 3 : Tn 7 transfer of Mobile‐CRISPRi to Gram‐negative bacteria Basic Protocol 4 : ICE Bs1 transfer of Mobile‐CRISPRi to Bacillales Support Protocol 1 : Quantification of CRISPRi repression using fluorescent reporters Support Protocol 2 : Testing for gene essentiality using CRISPRi spot assays on plates Support Protocol 3 : Transformation of E. coli by electroporation Support Protocol 4 : Transformation of CaCl 2 ‐competent E. coli

59 BASIC BIOLOGICAL SCIENCES↗

Programmable hydrogels by combining persistent and transient dynamic bonds

Out-of-equilibrium chemistry is currently being applied to polymer systems to mimic the autonomous behavior of biological materials. In this study, hydrogels with self-healing properties were developed that combine persistent crosslinks from dynamic metal-ligand coordination with transient crosslinks from dynamic anhydride bonds. Polymers containing terpyridine ligands and carboxylic acid groups were synthesized and crosslinked with divalent metal ions (Fe 2+ , Ni 2+ , Co 2+ , Zn 2+ , Cu 2+ ). The coordination bonds from terpyridine–metal coordination impart persistent stability, while transient anhydrides formed on treatment with 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC) temporarily increase crosslink density. Distinct behaviors are observed depending on the choice of metal, with Ni 2+ forming robust, stable networks; Zn 2+ creating moderately dynamic gels; and Cu 2+ yielding highly dynamic, soft materials. Treatment with EDC increased storage moduli significantly, with transient effects lasting up to 280 min depending on the metal ion. Self-healing experiments demonstrated independent contributions from metal coordination and transient anhydrides, enabling recovery of stress and strain under varying conditions. Additionally, complex and reversible 2D stiffness patterns were generated by spatially controlled EDC treatment of Zn 2+ and Cu 2+ hydrogel films, demonstrating programmability and reusability.

Rajawasam, Chamoni W. H. [Miami University, Oxford↗

CRISPR-Cas9 Circular Permutants as Programmable Scaffolds for Genome Modification

The ability to engineer natural proteins is pivotal to a future, pragmatic biology. CRISPR proteins have revolutionized genome modification, yet the CRISPR-Cas9 scaffold is not ideal for fusions or activation by cellular triggers. Here in this paper, we show that a topological rearrangement of Cas9 using circular permutation provides an advanced platform for RNA-guided genome modification and protection. Through systematic interrogation, we find that protein termini can be positioned adjacent to bound DNA, offering a straightforward mechanism for strategically fusing functional domains. Additionally, circular permutation enabled protease-sensing Cas9s (ProCas9s), a unique class of single-molecule effectors possessing programmable inputs and outputs. ProCas9s can sense a wide range of proteases, and we demonstrate that ProCas9 can orchestrate a cellular response to pathogen-associated protease activity. Together, these results provide a toolkit of safer and more efficient genome-modifying enzymes and molecular recorders for the advancement of precision genome engineering in research, agriculture, and biomedicine.

59 BASIC BIOLOGICAL SCIENCES↗

Three-dimensional DNA-programmable nanoparticle superlattices

In recent decades, there have been considerable efforts made in the design and synthesis of materials comprised of functional nanoscale particles. However, there is an increasing need to establish platform approaches for creating large-scale three-dimensional (3D) organizations from these particles, with the ability to control and prescribe ordered structures. The use of DNA, as a means of programming interactions between nanocomponents, provides powerful and tailorable means for the rational self-assembly of nanomaterials. Here, the assembly pathway and assembled phases are highly dependent on both particle shape and interparticle interactions, governed by particle DNA coronas, binding modes, or linking mediators capable of complex topologies. This review highlights and discusses recent significant advancements in the field, as well as offers outlook towards future paths in the assembly of the DNA programmable three-dimensional nanoparticle superlattices.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Nanocrystal programmable assembly beyond hard spheres (or shapes) and other (simple) potentials

Ligands are the key to almost any strategy in the assembly of programmable nanocrystals (or nanoparticles) and must be accurately considered in any predictive model. Hard Spheres (or Shapes) provide the simplest and yet quite successful approach to assembly, with remarkable sophisticated predictions verified in experiments. There are, however, many situations where hard spheres/shapes predictions fail. This prompts three important questions: In what situations should hard spheres/shapes models be expected to work? and when they do not work, Is there a general model that successfully corrects hard sphere/shape predictions? and given other successful models where ligands are included explicitly, and of course, numerical simulations, can we unify hard sphere/shape models, explicit ligand models and all atom simulations? . Further, the Orbifold Topological Model (OTM) provides a positive answer to these three questions. In this paper, I give a detailed review of OTM, describing the concept of ligand vortices and how it leads to spontaneous valence and nanoparticle “eigenshapes” while providing a prediction of the lattice structure, without fitting parameters, which accounts for many body effects not captured by (two-body) potentials. I present a thorough survey of experiments and simulations and show that, to this date, they are in full agreement with the OTM predictions. I conclude with a discussion on whether NC superlattices are equilibrium structures and some significant challenges in structure prediction.

36 MATERIALS SCIENCE↗

Memory forensic analysis of a programmable logic controller in industrial control systems

In industrial control systems (ICS), programmable logic controllers (PLCs) are used to automate physical processes such as nuclear plants and power grid stations, and are often subject to cyber attacks. As in conventional IT domain, the memory analysis of the PLCs can help answer important forensic questions about the attack, such as the presence of malicious firmware, injection of modified control logic (the program running on the PLC), and manipulation of I/O devices (e.g., sensors and actuators). Unlike conventional IT domain, PLCs have heterogeneous hardware architecture, proprietary firmware and control software, making it challenging to employ a unified framework for their memory forensics. For merely extracting artifacts of forensic importance, reverse-engineering the firmware is a tedious task, and the effort needs to be repeated for every PLC model. As a community, a step-wise approach to tackle this challenge is to analyze the memory of specific PLCs, and subsequently find a generic framework applicable to all PLCs. Our work is a step forward in this direction. By following a methodology that focuses on the functional layer of PLCs instead of reverse engineering the firmware, we analyze the digital forensic artifacts available in a common PLC, Allen-Bradley ControlLogix 1756-L61. Before diving into the memory dump, we analyze the PLC control software to create a list of important artifacts that are sure to exist in the PLC memory dump. The approach employs a setup where PLC control software RSLogix-5000 is connected to the PLC, and the memory dump can be obtained as and when needed. We create test cases that sequentially highlight each category of artifacts, followed by an examination of the resultant impact on memory. After attaining the listed artifacts, we employ conventional string and known data searches to extract interesting information present in this PLC's memory. The memory analysis profile, presented as a Python library and shared with the community, can help a forensic investigator to readily extract forensic artifacts from the same model's controller. The adopted approach may help researchers in creating memory profile of other PLCs, and ultimately formulating a generic PLC memory analysis framework.

Rais, Muhammad Haris↗

Towards generic memory forensic framework for programmable logic controllers

A Programmable Logic Controller (PLC) is a microprocessor-based controller that is used to automate physical processes in critical infrastructure and various other industries and manufacturing sectors. Initially, PLCs were completely isolated from the Internet, and cyber security was not incorporated at the time of development. The introduction of industry 4.0 and the evolution of ICS systems to communicate over public IP addresses from the Internet enhanced productivity and efficiency, but Internet connectivity exposed the systems and their vulnerabilities, which led to an increase in cyber attacks. When a system is sabotaged/compromised, security analysts need to get to the root cause of the attack as quickly as possible to recover the system. To do so, memory forensic analysis is critical to provide a unique insight into the run-time memory activities and extract a reliable source of evidence. In this paper, we analyze the memory structure of the Schneider Electric Modicon M221 PLC. To build a memory profile, we reverse engineer the communication protocol and conduct differential analysis to gain knowledge about the structure of the memory and the low-level representation of control logic instructions. We then identify dynamic and static memory regions by modifying different project fields and conducting differential analysis, which allows us to identify boundaries of critical memory structures and extract important forensic artifacts that can be found in the memory. The Python implementation of the memory profile can help reduce the time and effort required for manual analysis in case of cyber incident or system failure.

97 MATHEMATICS AND COMPUTING↗

Feasibility of critical infrastructure protection using network functions for programmable and decoupled ICS policy enforcement over WAN

Industrial control systems (ICS) represent a major component of our critical infrastructure. With the increasing need for more control and monitoring of such systems, ICS have seen an increase in connectivity to wide area networks (WAN) exposing aging equipment to rapidly evolving cybersecurity threats. Furthermore, the ICS data requires a reliability measure from the networks for critical functions for infrastructure monitoring and control. Especially when remote plant sites are involved such as pipelines, energy distribution networks, and transportation, WAN transport impairments most often provide a best effort delivery with no strict reliability guarantees. Network functions can provide a vendor agnostic, programmable critical infrastructure protection with a single maintenance, policy determination, and reliability assurance surface. A network function (NF) can be utilized for policy enforcement over the communication between remote entities and the main control office. This paper presents the research on transparent integration with existing ICS without disrupting communications, resulting in minimal downtime while decoupling the fast paced evolution of defensive security measures from the upgrade cycle of expensive long term hardware. We report our measurements on the resource requirements and overhead in the network for successful NF insertion under a wide variety of network impairments (network packet delay, reordering, and loss). Our paired NF implementation provides a policy enforcement platform extensible to cover myriad cybersecurity-related communication goals, including packet signing for verification, encryption for data privacy, packet filtering and data diode operation (i.e. protecting against eavesdropping, packet injection, and denial-of-service). Furthermore, bundling communication specifications into packet flows allows for tunability in applying policies as coarse- or fine-grained as the needs of the operator. We report on network function resource requirements in the form of required queue depth and network utilization overhead to inform the decision making against hardware cost constraints.

42 ENGINEERING↗

Dynamic and Programmable Cellular-Scale Granules Enable Tissue-like Materials

Living tissues are an integrated, multiscale architecture consisting of dense cellular ensembles and extracellular matrices (ECMs). The cells and ECMs cooperate to enable specialized mechanical properties and dynamic responsiveness. However, the mechanical properties of living tissues are difficult to replicate. A particular challenge is identification of a cell-like synthetic component, which is tightly integrated with its matrix and also responsive to external stimuli. Here, we demonstrate that cellular-scale hydrated starch granules, an underexplored component in materials science, can turn conventional hydrogels into tissue-like materials when composites are formed. By using several synchrotron-based X-ray techniques, we reveal the mechanically induced organization and training dynamics of the starch granules in the hydrogel matrix. These dynamic behaviors enable multiple tissue-like properties such as programmability, anisotropy, strain-stiffening, mechanochemistry, and self-healability.

36 MATERIALS SCIENCE↗

Precompensation of gain nonuniformity in a Nd:glass amplifier using a programmable beam-shaping system

A programmable liquid crystal beam-shaping system was installed for a 200-mJ optical parametric chirped-pulse amplification (OPCPA) system front end and was applied to dramatically improve the beam uniformity in the subsequent amplifier. A highly nonuniform beam profile caused by gain inhomogeneity in the amplifier was pre-compensated by the beam shaping system using significantly improved open-loop and closed-loop algorithms. The details of the improved algorithms will be described. The issues of running a liquid crystal device with a high-energy, ultrashort-pulse laser, such as damage risk and temporal contrast degradation, will be addressed.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

A fixed-target programme at the LHC: Physics case and projected performances for heavy-ion, hadron, spin and astroparticle studies

Here we review the context, the motivations and the expected performances of a comprehensive and ambitious fixed-target programme using the multi-TeV proton and ion LHC beams. We also provide a detailed account of the different possible technical implementations ranging from an internal wire target to a full dedicated beam line extracted with a bent crystal. The possibilities offered by the use of the ALICE and LHCb detectors in the fixed-target mode are also reviewed.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Stairway to discovery: A report on the CMS programme of cross section measurements from millibarns to femtobarns

The Large Hadron Collider at CERN, delivering proton-proton collisions at much higher energies and far higher luminosities than previous machines, has enabled a comprehensive programme of measurements of the standard model (SM) processes by the CMS experiment. These unprecedented capabilities facilitate precise measurements of the properties of a wide array of processes, the most fundamental being cross sections. The discovery of the Higgs boson and the measurement of its mass became the keystone of the SM. Knowledge of the mass of the Higgs boson allows precision comparisons of the predictions of the SM with the corresponding measurements. These measurements span the range from one of the most copious SM processes, the total inelastic cross section for proton-proton interactions, to the rarest ones, such as Higgs boson pair production. They cover the production of Higgs bosons, top quarks, single and multibosons, and hadronic jets. Associated parameters, such as coupling constants, are also measured. These cross section measurements can be pictured as a descending stairway, on which the lowest steps represent the rarest processes allowed by the SM, some never seen before.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Programmable Colloidal Approach to Hierarchical Structures of Methylammonium Lead Bromide Perovskite Nanocrystals with Bright Photoluminescent Properties

Here, systematic tailoring of nanocrystal architecture could provide unprecedented control over their electronic, photophysical, and charge transport properties for a variety of applications. However, at present, manipulation of the shape of perovskite nanocrystals is done mostly by trial-and-error-based experimental approaches. Here, we report systematic colloidal synthetic strategies to prepare methylammonium lead bromide quantum platelets and quantum cubes. In order to control the nucleation and growth processes of these nano crystals, we appropriately manipulate the solvent system, surface ligand chemistry, and reaction temperature causing syntheses into anisotropic shapes. We demonstrate that both the presence of chlorinated solvent and a long chain aliphatic amine in the reaction mixture are crucial for the formation of ultrathin quantum platelets (similar to 1.5 nm in thickness), which is driven by mesoscale-assisted growth of spherical seed nanocrystals (similar to 1.6 nm in diameter) through attachment of monomers onto selective crystal facets. A combined surface and structural characterization, along with small-angle X-ray scattering analysis, confirm that the long hydrocarbon of the aliphatic amine is responsible for the well ordered hierarchical stacking of the quantum platelets of 3.5 nm separation. In contrast, the formation of similar to 12 nm edge-length quantum cubes is a kinetically driven process in which a high flux of monomers is achieved by supplying thermal energy. The photoluminescence quantum yield of our quantum platelets (similar to 52%) is nearly 2-fold higher than quantum cubes. Moreover, the quantum platelets display a lower nonradiative rate constant than that found with quantum cubes, which suggests less surface trap states. Together, our research has the potential both to improve the design of synthetic methods for programmable control of shape and assembly and to provide insight into optoelectronic properties of these materials for solid-state device fabrication, e.g., light-emitting diodes, solar cells, and lasing materials.

36 MATERIALS SCIENCE↗

Field Programmable Gate Arrays for Enhancing the Speed and Energy Efficiency of Quantum Dynamics Simulations

We present the first application of field programmable gate arrays (FPGAs) as new, customizable hardware architectures for carrying out fast and energy-efficient quantum dynamics simulations of large chemical/material systems. Instead of tailoring the software to fixed hardware, which is the typical case for writing quantum chemistry code for central processing units (CPUs) and graphics processing units (GPUs), FPGAs allow us to directly customize the underlying hardware (even at the level of specific electrical signals in the circuit) to give a truly optimized computational performance for quantum dynamics calculations. By offloading the most intensive and repetitive calculations onto an FPGA, we show that the computational performance of our real-time electron dynamics calculations can even exceed that of optimized commercial mathematical libraries running on high-performance GPUs. In addition to this impressive computational speedup, we show that FPGAs are immensely energy-efficient and consume 4 times less energy than modern GPU or CPU architectures. These energy savings are a practical and important metric for supercomputing centers (many of which exceed over $1 million in power costs alone), as exascale computing capabilities become more widespread and commonplace. Taken together, the implementation techniques and performance metrics of our study demonstrate that FPGAs could play a promising role in upcoming quantum chemistry and materials science applications, particularly for the acceleration and energy-efficient execution of quantum dynamics calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DNA-Directed Non-Langmuir Deposition of Programmable Atom Equivalents

Particle assembly at interfaces via programmed DNA interactions allows for independent modification of both nanoparticle–surface interaction strength and the magnitude of interparticle repulsion. Together, these factors allow for modification of the deposited thin film morphology via alterations in DNA binding sequence. Importantly, both Langmuir and random sequential adsorption models yield insights into the thermodynamics of deposition but cannot fully explain particle coverage as a function of all relevant variables, indicating that the particle deposition mechanism for DNA-grafted colloids is more complex than prior adsorption phenomena. Here, it is shown that these deviations from standard behavior arise from the fact that each nanoparticle is attached to the surface via multiple weak DNA duplex interactions, enabling diffusion of adsorbed colloids across the substrate. Thus, surface migration of individual particles causes reorganization of the deposited monolayer, leading to the unusual behavior of coverage increasing at elevated temperatures that are just below the particle desorption temperature. The programmability of DNA-directed particle deposition therefore allows for precise control over the morphology of monolayer films, as well as the ability to generate crystalline materials with controllable surface roughness and grain size through layer-by-layer growth. As a result, the increased control over thin film morphology potentially enables tailoring of mechanical and optical properties and holds promise for use in a variety of applications.

59 BASIC BIOLOGICAL SCIENCES↗