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At least 307 records · Page 17

ReaxFF Simulations of Laser-Induced Graphene (LIG) Formation for Multifunctional Polymer Nanocomposites

Irradiation of polymer films by a CO 2 infrared laser under ambient conditions converts the polymer into porous graphene or laser-induced graphene (LIG). In this work, we simulate the formation of LIG from five different commercially available polymers using reactive molecular dynamics. We determined that the molecular structure of the parent polymer has a significant effect on the final graphitic structure. CO is liberated during the initial part of the LIG formation process when the polymer is converted into an amorphous structure, while H 2 is evolved steadily as the amorphous structure is converted to an ordered graphitic structure. The LIG structure has out-of-plane undulations and bends due to a significant number of 5- and 7-member carbon rings present throughout the structure. We find that the simulated molecular structure compares well with recent experimental observations from the literature. We also demonstrate that the yield of LIG is higher in inert conditions, compared to environments with oxygen. Polybenzimidazole-derived LIG has the highest surface area and yield among the five polymers examined. These findings provide knowledge of LIG formation mechanisms that can be leveraged for bulk LIG applications such as sensors, electrocatalysts, microfluidics, and targeted heating for welding polymers.

36 MATERIALS SCIENCE↗

Adhesion of Self-Complementary, Sinusoidal Surfaces Fabricated Using Two-Photon Polymerization

Microscale, pick-and-place assembly is a non-lithographic assembly method poised to impact diverse fields including flexible electronics, microfluidics and robotics. However, a major technological challenge is the need to deterministically control adhesion between parts. Here, switchable adhesion involving 3D-printed, self-complementary surfaces is demonstrated. Mechanical properties of metasurfaces pressed against flat, rigid substrates are modeled using finite element methods. A series of flat slabs and metastructured slabs with 2D sinusoidal surfaces are printed using two-photon polymerization (2PP) of a shape-memory resin. The surface frequency of featured slabs was varied between $3.\bar3$ mm −1 and $26.\bar6$ mm −1 with similar amplitudes. Adhesion between printed metasurfaces and glass and between printed, self-complementary metasurfaces is studied above and below the cured resin’s glass transition temperature (∼45 °C). Simple heating of adhering surfaces to above 60 °C lowers adhesion, and compression of surfaces while above the glass transition temperature followed by cooling to room temperature elevates adhesion. The nominal adhesive strength between printed, self-complementary surfaces, as determined by the maximum observable pull-off stress, exceeds 3 MPa. Further tailoring complementary surfaces for adhesion control may facilitate microscale disassembly for recovery of components or precious metals.

amorphous materials↗

Biomimetic Rebuilding of Multifunctional Red Blood Cells: Modular Design Using Functional Components

The design and synthesis of artificial materials that mimic the structures, mechanical properties, and ultimately functionalities of biological cells remains a current holy grail of materials science. Here based on a silica cell bio-replication approach, we report the design and construction of synthetic rebuilt red blood cells (RRBCs) that fully mimic the broad properties of native RBCs: size, biconcave shape, deformability, oxygen carrying capacity, long circulation time. Four successive nano-scale processing steps: RBC bioreplication, layer-by-layer polymer deposition, and precision silica etching, followed by RBC ghost membrane vesicles fusion are employed for RRBC construction. A panel of physicochemical analyses including zeta potential measurement, fluorescence microscopy, and antibody-mediated agglutination assay proved the recapitulation of RBC shape, size, and membrane structure. Flow-based deformation studies carried out in a microfluidic blood capillary model confirrned the ability of RRBCs to deform and pass through small slits and reconstitute themselves in a manner comparable to native RBCs. Circulation studies of RRBCs conducted ex-ovo in a chick embryo and in vivo in a mouse model demonstrated the requirement of both deformability and native cell membrane surface to achieve long-term circulation. To confer additional non-native functionalities to RRBCs, we developed modular procedures in which to load functional cargos such as hemoglobin, drugs, magnetic nanoparticles, and ATP biosensors within the RRBC interior to enable various functions, including oxygen delivery, therapeutic drug delivery, magnetic manipulation, and toxin biosensing and detection. Taken together, RRBCs represent a class of long circulating RBC-inspired artificial hybrid materials with a broad range of potential applications.

59 BASIC BIOLOGICAL SCIENCES↗

Ultra-Low Viscosity and High Magnetic Susceptibility Magnetic Ionic Liquids Featuring Functionalized Diglycolic Acid Ester Rare-Earth and Transition Metal Chelates

Magnetic ionic liquids (MILs) comprise a subcategory of ionic liquids (ILs) and contain a paramagnetic metal center allowing them to be readily manipulated by an external magnetic field. While MILs are popularly employed as solvents in catalysis, separations, and organic synthesis, most low viscosity combinations possess a hydrophilic character that limits their use in aqueous matrices. To date, no study has reported the synthesis and characterization of hydrophobic MILs with viscosities similar to those of hydrophilic MILs and organic solvents while simultaneously exhibiting enhanced magnetic and thermal properties. In this study, diglycolic acid esters are employed as ligands to chelate with paramagnetic metals to produce cations that are paired with metal chelates composed of hexafluoroacetylacetonate ligands to form MILs incorporating multiple metal centers in the cation and anion. Viscosity values below 31.6 cP were obtained for these solvents, the lowest ever reported for hydrophobic MILs. Solubilities in nonpolar solvents such as benzene were observed to be as high as 50% (w/v) MIL-to-solvent ratio while being insoluble in water at concentrations as low as 0.01% (w/v). Effective paramagnetic moment values for these solvents ranged from 5.33 to 15.56 Bohr magnetons (μB), with mixed metal MILs containing multiple lanthanides in the anion generally offering higher magnetic susceptibilities. MILs composed of ligands containing octyl substituents were found to possess thermal stabilities up to 190 °C. The synthetic strategies explored in this study exploit the highly tunable nature of the employed cation and anion pairs to design versatile ultra-low viscosity magnetoactive solvents that possess tremendous potential and applicability in liquid–liquid separation systems, catalysis, and microfluidics where the mechanical movement of the solvent can be easily facilitated using electromagnets.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis and Characterization of Carbon Microbeads

We report a microfluidic-based droplet generation platform for synthesizing micron-sized porous carbon microspheres. The setup employs carbon materials such as graphite, carbon nanotubes, graphene, fullerenes, and carbon black as starting materials. Custom composition, structure, and function are achieved through combinations of carbon materials, cross-linkers, and additives along with variations in process parameters. Carbon materials can be assembled into spheres with a mean diameter of units to hundreds of μm with relatively tight size distribution (<25% RSD). Pore structure and size (tens to hundreds of angstrom) can be modulated by incorporating porogen/coporogen dilutants during synthesis. The microbeads have excellent mechanical stability with an elastic modulus of hundreds of MPa. They can sustain high dynamic fluid flow pressures of up to 9000 psi. This work lays the foundation for synthesizing novel tailorable and customizable carbon microbeads. It opens avenues for applying these novel materials for composite and additive manufacturing, energy, life science, and biomedical applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Developing Fluorescence-Based Sensors to Support Rare Earth Element Separation

Rare earth elements (REEs) are essential to most renewable energy technologies. Unfortunately, as we transition to sustainable energy production, the demand for REEs is rapidly growing well beyond current rates of production. As a result, novel means of efficient, scalable, and easily adaptable methods for processing primary and recycle feedstocks are needed. Development and integration of sensors for highly selective in-line monitoring can support more efficient design and testing of such novel separation processes, as well as more cost-effective deployment of those separation flowsheets. Work here will explore the application of fluorescence spectroscopy, a highly sensitive and selective technique, to quantify multiple lanthanides in complex mixtures including known interferents or quenching agents. Results include identification of the optimal excitation wavelength and the limit of detection of various rare earth elements as well as the performance of data-science-based quantification approaches in streams where “unknowns” are present. Overall, the data science tools in conjunction with optical sensor data were able to quantify analytes in the presence of other lanthanides which can be anticipated in the actual industrial stream. Here we include characterization of lanthanides in a microfluidic device similar to those used in new process development. This study demonstrates the capability of utilizing fluorescence spectroscopy to quantify analytes in a complicated solution matrix, suggesting this is a successful approach for in-line monitoring to optimize the separation efficiency in an industrial stream.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Photoresponsive Structured Liquids Enabled by Molecular Recognition at Liquid–Liquid Interfaces

Using host-guest molecular recognition at the oil-water interface, a new type of photoresponsive nanoparticle surfactant (NPS) was designed and prepared to structure liquids. With the help of a polymeric surfactant, the interfacial host-guest interactions can be significantly enhanced, leading to the rapid formation and assembly of a NP monolayer and offering sufficient binding energy to hold the NPs in a jammed state. The assembly of the NPSs can be reversibly manipulated via a photoswitchable jamming-to-unjamming transition, endowing the interface as well as the macroscopic assemblies with responsiveness to the external trigger (photons). Finally, this study for the first time opens a pathway for the construction of multiresponsive, structured all-liquid systems by introducing host-guest chemistry, showing promising potential applications in encapsulation, delivery systems, and unique microfluidic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Dynamic Pore Network Model for Imbibition Simulation Considering Corner Film Flow

Wetting films can develop in the corners of angular pores under strong wetting conditions. Modeling the dynamics of corner film remains elusive using direct numerical simulations because of the significant scale difference between main meniscus and corner film flow. In this paper, the modified interacting capillary bundle model (ICB), developed in our previous work to describe accurately corner film dynamics in a single square tube, is incorporated into a single-pressure dynamic pore network model (DPNM) to simulate imbibition in strongly wetting porous media with corner film flow. The traditional pore network is decomposed into several layers of interacting subpore networks where the 0th layer of subpore network simulates the main meniscus flow and higher layers the corner film flow. The fluid flow between different layers is captured by interlayer throats. In addition, the snap-off mechanism caused by the thickening of wetting corner film is considered. The accuracy of the developed model is validated for four cases: spontaneous imbibition in a single square tube, wetting fluid redistribution through corner films under a capillary pressure difference, snap off in a narrow throat connecting two large pores, and imbibition dynamics in a real microfluidic porous geometry. The validated model is then used to simulate both spontaneous and controlled imbibition in a pore network with random pore size distribution. Finally, the interaction between corner film and main meniscus flow in porous media is analyzed from a pore-scale perspective.

58 GEOSCIENCES↗

Quantifying the Effect of Pore‐Size Dependent Wettability on Relative Permeability Using Capillary Bundle Model

Abstract Relative permeability is a key parameter for characterizing the multiphase flow dynamics in porous media at macroscopic scale while it can be significantly impacted by wettability. Recently, it has been reported in microfluidic experiments that wettability is dependent on the pore size (Van Rooijen et al., 2022). To investigate the effect of pore‐size‐dependent wettability on relative permeability, we propose a theoretical framework informed by digital core samples to quantify the deviation of relative permeability curves due to wettability change. We find that the significance of impact is highly dependent on two factors: (i) the function between contact angle and pore size (ii) overall pore size distribution. Under linear function, this impact can be significant for tight porous media with a maximum deviation of 1,000%.

Yu, Siqin↗

A wearable patch for continuous analysis of thermoregulatory sweat at rest

The body naturally and continuously secretes sweat for thermoregulation during sedentary and routine activities at rates that can reflect underlying health conditions, including nerve damage, autonomic and metabolic disorders, and chronic stress. However, low secretion rates and evaporation pose challenges for collecting resting thermoregulatory sweat for non-invasive analysis of body physiology. Here we present wearable patches for continuous sweat monitoring at rest, using microfluidics to combat evaporation and enable selective monitoring of secretion rate. We integrate hydrophilic fillers for rapid sweat uptake into the sensing channel, reducing required sweat accumulation time towards real-time measurement. Along with sweat rate sensors, we integrate electrochemical sensors for pH, Cl - , and levodopa monitoring. We demonstrate patch functionality for dynamic sweat analysis related to routine activities, stress events, hypoglycemia-induced sweating, and Parkinson’s disease. By enabling sweat analysis compatible with sedentary, routine, and daily activities, these patches enable continuous, autonomous monitoring of body physiology at rest.

47 OTHER INSTRUMENTATION↗

Multi-scale computer-aided design and photo-controlled macromolecular synthesis boosting uranium harvesting from seawater

By integrating multi-scale computational simulation with photo-regulated macromolecular synthesis, this study presents a new paradigm for smart design while customizing polymeric adsorbents for uranium harvesting from seawater. A dissipative particle dynamics (DPD) approach, combined with a molecular dynamics (MD) study, is performed to simulate the conformational dynamics and adsorption process of a model uranium grabber, i.e., PAO m -b-PPEGMA n , suggesting that the maximum adsorption capacity with atomic economy can be achieved with a preferred block ratio of 0.18. The designed polymers are synthesized using the PET-RAFT polymerization in a microfluidic platform, exhibiting a record high adsorption capacity of uranium (11.4 ± 1.2 mg/g) in real seawater within 28 days. This study offers an integrated perspective to quantitatively assess adsorption phenomena of polymers, bridging metal-ligand interactions at the molecular level with their spatial conformations at the mesoscopic level. The established protocol is generally adaptable for target-oriented development of more advanced polymers for broadened applications.

97 MATHEMATICS AND COMPUTING↗

Self-mixing in microtubule-kinesin active fluid from nonuniform to uniform distribution of activity

Active fluids have applications in micromixing, but little is known about the mixing kinematics of systems with spatiotemporally-varying activity. To investigate, UV-activated caged ATP is used to activate controlled regions of microtubule-kinesin active fluid and the mixing process is observed with fluorescent tracers and molecular dyes. At low Péclet numbers (diffusive transport), the active-inactive interface progresses toward the inactive area in a diffusion-like manner that is described by a simple model combining diffusion with Michaelis-Menten kinetics. At high Péclet numbers (convective transport), the active-inactive interface progresses in a superdiffusion-like manner that is qualitatively captured by an active-fluid hydrodynamic model coupled to ATP transport. Results show that active fluid mixing involves complex coupling between distribution of active stress and active transport of ATP and reduces mixing time for suspended components with decreased impact of initial component distribution. This work will inform application of active fluids to promote micromixing in microfluidic devices.

59 BASIC BIOLOGICAL SCIENCES↗

Cooperative microbial interactions drive spatial segregation in porous environments

The role of microbial interactions and the underlying mechanisms that shape complex biofilm communities are poorly understood. Here we employ a microfluidic chip to represent porous subsurface environments and show that cooperative microbial interactions between free-living and biofilm-forming bacteria trigger active spatial segregation to promote their respective dominance in segregated microhabitats. During initial colonization, free-living and biofilm-forming microbes are segregated from the mixed planktonic inoculum to occupy the ambient fluid and grain surface. Contrary to spatial exclusion through competition, the active spatial segregation is induced by cooperative interactions which improves the fitness of both biofilm and planktonic populations. We further show that free-living Arthrobacter induces the surface colonization by scavenging the biofilm inhibitor, D-amino acids and receives benefits from the public goods secreted by the biofilm-forming strains. Collectively, our results reveal how cooperative microbial interactions may contribute to microbial coexistence in segregated microhabitats and drive subsurface biofilm community succession.

59 BASIC BIOLOGICAL SCIENCES↗

Exploring single-cell biosynthetic noise and dynamics for enhanced betaxanthin production in Escherichia coli

Cell-to-cell variability often limits the efficiency of microbial bioproduction, yet how individual cells fluctuate over time and how these fluctuations shape population-level output remain unclear. To address this issue, we tracked a heterologous betaxanthin pathway in Escherichia coli using microfluidics-assisted time-lapse microscopy, allowing simultaneous measurement of fluctuations in betaxanthin, its biosynthetic enzyme DOD and growth across generations. Here we show that over 50% of high betaxanthin producers become medium or low producers after two divisions. Betaxanthin variation primarily originates from DOD noise, with a smaller contribution from growth rate fluctuations. We further develop a stochastic model to explore various control circuits and find that pathway enzyme or metabolite-based growth selection strategies are most effective in enhancing production. We experimentally validate the model by coupling enzyme expression to nutrient availability, which enriches high producers and boosts titer by 4.4-fold. Our results highlight key sources of metabolic heterogeneity and provide a framework for designing robust microbial processes.

Bacterial systems biology↗

Spatiotemporal control of liquid crystal structure and dynamics through activity patterning

Active materials are capable of converting free energy into mechanical work to produce autonomous motion, and exhibit striking collective dynamics that biology relies on for essential functions. Controlling those dynamics and transport in synthetic systems has been particularly challenging. Here, we introduce the concept of spatially structured activity as a means of controlling and manipulating transport in active nematic liquid crystals consisting of actin filaments and light-sensitive myosin motors. In this work, simulations and experiments are used to demonstrate that topological defects can be generated at will and then constrained to move along specified trajectories by inducing local stresses in an otherwise passive material. These results provide a foundation for the design of autonomous and reconfigurable microfluidic systems where transport is controlled by modulating activity with light.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cellular fluidics

The natural world provides many examples of multiphase transport and reaction processes that have been optimized by evolution. These phenomena take place at multiple length and time scales and typically include gas–liquid–solid interfaces and capillary phenomena in porous media. Many biological and living systems have evolved to optimize fluidic transport. However, living things are exceptionally complex and very difficult to replicate, and human-made microfluidic devices (which are typically planar and enclosed) are highly limited for multiphase process engineering. In this paper, we introduce the concept of cellular fluidics: a platform of unit-cell-based, three-dimensional structures—enabled by emerging 3D printing methods—for the deterministic control of multiphase flow, transport and reaction processes. We show that flow in these structures can be ‘programmed’ through architected design of cell type, size and relative density. We demonstrate gas–liquid transport processes such as transpiration and absorption, using evaporative cooling and CO 2 capture as examples. We design and demonstrate preferential liquid and gas transport pathways in three-dimensional cellular fluidic devices with capillary-driven and actively pumped liquid flow, and present examples of selective metallization of pre-programmed patterns. Our results show that the design and fabrication of architected cellular materials, coupled with analytical and numerical predictions of steady-state and dynamic behaviour of multiphase interfaces, provide deterministic control of fluidic transport in three dimensions. Cellular fluidics may transform the design space for spatial and temporal control of multiphase transport and reaction processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Single-cell quantification of ribosome occupancy in early mouse development

Translation regulation is critical for early mammalian embryonic development. However, previous studies had been restricted to bulk measurements, precluding precise determination of translation regulation including allele-specific analyses. Here, to address this challenge, we developed a novel microfluidic isotachophoresis (ITP) approach, named RIBOsome profiling via ITP (Ribo-ITP), and characterized translation in single oocytes and embryos during early mouse development. We identified differential translation efficiency as a key mechanism regulating genes involved in centrosome organization and N 6 -methyladenosine modification of RNAs. Our high-coverage measurements enabled, to our knowledge, the first analysis of allele-specific ribosome engagement in early development. These led to the discovery of stage-specific differential engagement of zygotic RNAs with ribosomes and reduced translation efficiency of transcripts exhibiting allele-biased expression. By integrating our measurements with proteomics data, we discovered that ribosome occupancy in germinal vesicle-stage oocytes is the predominant determinant of protein abundance in the zygote. The Ribo-ITP approach will enable numerous applications by providing high-coverage and high-resolution ribosome occupancy measurements from ultra-low input samples including single cells.

59 BASIC BIOLOGICAL SCIENCES↗

Systematic Comparison of High-throughput Single-Cell and Single-Nucleus Transcriptomes during Cardiomyocyte Differentiation

A comprehensive reference map of all cell types in the human body is necessary for improving our understanding of fundamental biological processes and in diagnosing and treating disease. High-throughput single-cell RNA sequencing techniques have emerged as powerful tools to identify and characterize cell types in complex and heterogeneous tissues. However, extracting intact cells from tissues and organs is often technically challenging or impossible, for example in heart or brain tissue. Single-nucleus RNA sequencing provides an alternative way to obtain transcriptome profiles of such tissues. To systematically assess the differences between high-throughput single-cell and single-nuclei RNA-seq approaches, we compared Drop-seq and DroNc-seq, two microfluidic-based 3' RNA capture technologies that profile total cellular and nuclear RNA, respectively, during a time course experiment of human induced pluripotent stem cells (iPSCs) differentiating into cardiomyocytes. Clustering of timeseries transcriptomes from Drop-seq and DroNc-seq revealed six distinct cell types, five of which were found in both techniques. Furthermore, single-cell trajectories reconstructed from both techniques reproduced expected differentiation dynamics. We then applied DroNc-seq to postmortem heart tissue to test its performance on heterogeneous human tissue samples. Our data confirm that DroNcseq yields similar results to Drop-seq on matched samples and can be successfully used to generate reference maps for the human cell atlas.

59 BASIC BIOLOGICAL SCIENCES↗