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Efficient lithium recovery from geothermal brines is crucial for the battery industry. Current electrochemical separation methods struggle with the simultaneous presence of Na + , K + , Mg 2+ , and Ca 2+ because these cations are similar to Li + , making it challenging to separate effectively. We address these challenges with a three-chamber reactor featuring a polymer porous solid electrolyte in the middle layer. This design improves the transference number of Li + (t Li + ) by 2.1 times compared to the two-chamber reactor and also reduces the chlorine evolution reaction, a common side reaction in electrochemical lithium extraction, to only 6.4% in Faradaic Efficiency. Employing a lithium-ion conductive glass ceramic (LICGC) membrane, the reactor achieved high t Li + of 97.5% in LiOH production from simulated brine, while the concentrations of Na + K + , Mg 2+ , and Ca 2+ are below the detection limit. Electrochemical experiments and surface analysis elucidated the cation transport mechanism, highlighting the impact of Na + on Li + migration at the LICGC interface., Competing Interests: Competing interests statement:Y.F., Z.F., H.W., and S.L.B. are inventors on a provisional United States patent application titled “Electrochemical Manufacturing of Lithium Hydroxide from Geothermal Brines in a Three-chamber Solid Electrolyte Reactor using a LICGC membrane” for the technology related to this work.

Precise control at the colloidal scale is one of the most promising bottom-up approaches to fabricating new materials and devices with tunable and precisely engineered properties. Magnetically driven colloidal assembly offers great versatility because of the ability to externally tune particle-particle interactions and to construct a host of particle arrangements. However, despite previous efforts to probe the parameter space, global orientational control in conjunction with two-dimensional microstructural control has remained out of reach. Furthermore, the magnetic relaxation time of superparamagnetic beads has been largely overlooked despite being a key feature of the magnetic response. Here, we take advantage of the magnetic relaxation time of superparamagnetic beads in an alternating rotating magnetic field and show how harnessing this feature facilitates the formation of oriented clusters. The orientation of these clusters can be controlled by field parameters. Using experiments, simulations, and theory, we probe a two-particle system (dimer) under this alternating rotating magnetic field and use its dynamics to provide insights into the collective response that forms clusters. We find that the type of field has significant implications for the dipolar interactions between the colloids because of the nonnegligible magnetic relaxation. Moreover, we find that the competing time scales of the magnetic relaxation and the alternating field generate an anisotropic interaction potential that drives cluster alignment. By exploiting the magnetic relaxation time of magnetic systems, we can tailor new types of interparticle interactions, thereby expanding the capabilities of colloidal assembly in engineering unique materials and devices., Competing Interests: Competing interests statement:The authors declare no competing interest.

Current methods for detecting pipeline oil leaks depend primarily on optical detection, which can be slow and have deployment limitations. An alternative non-optical approach for earlier and faster detection of oil leaks would enable a rapid response and reduce the environmental impact of oil leaks. Here, we demonstrate that organic electrochemical transistors (OECTs) can be used as non-optical sensors for crude oil detection in subsea environments. OECTs are thin film electronic devices that can be used for sensing in a variety of environments, but they have not yet been tested for crude oil detection in subsea environments. We fabricated OECTs with poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) as the channel and showed that coating the channel with a polystyrene film results in an OECT with a large and measurable response to oil. Oil that comes in contact with the device will adsorb onto the polystyrene film and increases the impedance at the electrolyte interface. We performed electrochemical impedance spectroscopy measurements to quantify the impedance across the device and found an optimal thickness for the polystyrene coating for the detection of oil. Under optimal device characteristics, as little as 10 μg of oil adsorbed on the channel surface produced a statistically significant change in the source-drain current. The OECTs were operable in seawater for the detection of oil, and we demonstrated that the devices can be transferred to flexible substrates which can be easily implemented in vehicles, pipelines, or other surfaces. This work demonstrates a low-cost device for oil detection in subsea environments and provides a new application of OECT sensors for sensing.

Evaluating the heterogeneity of extracellular vesicles (EVs) is crucial for unraveling their complex actions and biodistribution. Here, we identify consistent architectural heterogeneity of EVs using cryogenic transmission electron microscopy (cryo-TEM), which has an inherent ability to image biological samples without harsh labeling methods while preserving their native conformation. Imaging EVs isolated using different methodologies from distinct sources, such as cancer cells, normal cells, immortalized cells, and body fluids, we identify a structural atlas of their dominantly consistent shapes. We identify EV architectural attributes by utilizing a segmentation neural network model. In total, 7,576 individual EVs were imaged and quantified by our computational pipeline. Across all 7,576 independent EVs, the average eccentricity was 0.5366 ± 0.2, and the average equivalent diameter was 132.43 ± 67 nm. The architectural heterogeneity was consistent across all sources of EVs, independent of purification techniques, and compromised of single spherical, rod-like or tubular, and double shapes. This study will serve as a reference foundation for high-resolution images of EVs and offer insights into their potential biological impact.

The effects of velocity and gas type on foam flow through porous media have yet to be completely elucidated. Pressure drop and capillary pressure measurements were made at ambient conditions during a series of foam quality scan experiments in a homogenous sandpack while foam texture was simultaneously visualized. New insights into foam-flow behavior in porous media were discovered. Previously accepted "limiting" capillary pressure theory is challenged by the findings in this work, and the "limiting" terminology is replaced with the word "plateau" to reflect these novel observations. Plateau capillary pressure [Formula: see text] and transition foam quality were found to increase with velocity. Transition foam quality was found to depend mostly on liquid velocity rather than gas velocity and is physically linked to foam type (continuous vs. discontinuous) and texture (fine vs. coarse). Distinct rheological behaviors also arose in the low- and high-quality foam regimes as a function of velocity. Foam flow was found to be strongly shear thinning in the low-quality regime where foam texture was fine and discontinuous. In the high-quality regime, the rheology was weakly shear thinning to Newtonian for coarsely textured foam and continuous-gas flow respectively. When all other variables were held constant, at ambient conditions, CO 2 foam was found to be weaker with also lower capillary pressures than N 2 foam and the differences in gas solubility is a likely explanation., (© 2023. The Author(s).)

Active colloids use energy input at the particle level to propel persistent motion and direct dynamic assemblies. We consider three types of colloids animated by chemical reactions, time-varying magnetic fields, and electric currents. For each type, we review the basic propulsion mechanisms at the particle level and discuss their consequences for collective behaviors in particle ensembles. These microscopic systems provide useful experimental models of nonequilibrium many-body physics in which dissipative currents break time-reversal symmetry. Freed from the constraints of thermodynamic equilibrium, active colloids assemble to form materials that move, reconfigure, heal, and adapt. Colloidal machines based on engineered particles and their assemblies provide a basis for mobile robots with increasing levels of autonomy. This review provides a conceptual framework for understanding and applying active colloids to create material systems that mimic the functions of living matter. We highlight opportunities for chemical engineers to contribute to this growing field.

Semiflexible filaments deform into a variety of configurations that dictate different phenomena manifesting at low Reynolds number. Harnessing the elasticity of these filaments to perform transport-related processes at the microfluidic scale requires structures that can be directly manipulated to attain controllable geometric features during their deformation. The configuration of semiflexible chains assembled from paramagnetic colloids can be readily controlled upon the application of external time-varying magnetic fields. In circularly rotating magnetic fields, these chains undergo coiling dynamics in which their ends close into loops that wrap inward, analogous to the curling of long nylon filaments under shear. The coiling is promising for the precise loading and targeted transport of small materials, however effective implementation requires an understanding of the role that field parameters and chain properties play on the coiling features. Here, we investigate the formation of coils in semiflexible paramagnetic chains using numerical simulations. We demonstrate that the size and shape of the initial coils are governed by the Mason and elastoviscous numbers, related to the field parameters and the chain bending stiffness. The size of the initial coil follows a nonmonotonic behavior with Mason number from which two regions are identified: (1) an elasticity-dependent nonlinear regime in which the coil size decreases with increasing field strength and for which loop shape tends to be circular, and (2) an elasticity-independent linear regime where the size increases with field strength and the shape become more elliptical. From the time scales associated to these regimes, we identify distinct coiling mechanisms for each case that relate the coiling dynamics to two other configurational dynamics of paramagnetic chains: wagging and folding behaviors.

Transitioning our society to a sustainable future, with low or net-zero carbon emissions to the atmosphere, will require a wide-spread transformation of energy and environmental technologies. In this perspective article, we describe how lab-on-a-chip (LoC) systems can help address this challenge by providing insight into the fundamental physical and geochemical processes underlying new technologies critical to this transition, and developing the new processes and materials required. We focus on six areas: (I) subsurface carbon sequestration, (II) subsurface hydrogen storage, (III) geothermal energy extraction, (IV) bioenergy, (V) recovering critical materials, and (VI) water filtration and remediation. We hope to engage the LoC community in the many opportunities within the transition ahead, and highlight the potential of LoC approaches to the broader community of researchers, industry experts, and policy makers working toward a low-carbon future.

The complexity of shear-induced grain boundary dynamics has been historically difficult to view at the atomic scale. Meanwhile, two-dimensional (2D) colloidal crystals have gained prominence as model systems to easily explore grain boundary dynamics at single-particle resolution but have fallen short at exploring these dynamics under shear. Here, we demonstrate how an inherent interfacial shear in 2D colloidal crystals drives microstructural evolution. By assembling paramagnetic particles into polycrystalline sheets using a rotating magnetic field, we generate a particle circulation at the interface of particle-free voids. This circulation shears the crystalline bulk, operating as both a source and sink for grain boundaries. Furthermore, we show that the Read-Shockley theory for hard-condensed matter predicts the misorientation angle and energy of shear-induced low-angle grain boundaries based on their regular defect spacing. Model systems containing shear provide an ideal platform to elucidate shear-induced grain boundary dynamics for use in engineering improved/advanced materials.

Crude oils are complex mixtures of organic molecules, of which asphaltenes are the heaviest component. Asphaltene precipitation and deposition have been recognized to be a significant problem in oil production, transmission, and processing facilities. These macromolecular aromatics are challenging to characterize due to their heterogeneity and complex molecular structure. Microfluidic devices are able to capture key characteristics of reservoir rocks and provide new insights into the transport, reactions, and chemical interactions governing fluids used in the oil and gas industry. Understanding the microscale phenomena has led to better design of macroscale processes used by the industry. One area that has seen significant growth is in the area of chemical analysis under flowing conditions. Microfluidics and microscale analysis have advanced the understanding of complex mixtures by providing in situ imaging that can be combined with other chemical characterization methods to give details of how oil, water, and added chemicals interface with pore-scale detail. This review article aims to showcase how microfluidic devices offer new physical, chemical, and dynamic information on the behavior of asphaltenes. Specifically, asphaltene deposition and related flow assurance problems, interfacial properties and rheology, and evaluation of remediation strategies studied in microchannels and microfluidic porous media are presented. Examples of successful applications that address key asphaltene-related problems highlight the advances of microscale systems as a tool for advancing the physicochemical characterization of complex fluids for the oil and gas industry.

Vapor pressure refers to the pressure exerted by the vapor phase in thermodynamic equilibrium with either its liquid or solid phase. An important class of active matter is field-driven colloids. A suspension of dipolar colloids placed in a high-frequency rotating magnetic field undergoes a nonequilibrium phase transition into a dilute and dense phase, akin to liquid–vapor coexistence in a simple fluid. Here, we compute the vapor pressure of this colloidal fluid. The number of particles that exist as the dilute bulk phase versus condensed cluster phases can be directly visualized. An exponential relationship between vapor pressure and effective temperature is determined as a function of applied field strength, analogous to the thermodynamic expression between vapor pressure and temperature found for pure liquids. Additionally, we demonstrate the applicability of Kelvin’s equation to this field-driven system. In principle, this appears to be in conflict with macroscopic thermodynamic assumptions due to the nonequilibrium and discrete nature of this colloidal system. However, the curvature of the vapor–liquid interface provides a mechanical equilibrium characterized by interfacial tension that connects the condensed clusters observed with these active fluids to classical colligative fluid properties.

Elastic filaments driven out of equilibrium display complex phenomena that involve periodic changes in their shape. Here, the periodic deformation dynamics of semiflexible colloidal chains in an eccentric magnetic field are presented. This field changes both its magnitude and direction with time, leading to novel nonequilibrium chain structures. Deformation into S-, Z-, and 4-mode shapes arises via the propagation and growth of bending waves. Transitions between these morphologies are governed by an interplay among magnetic, viscous, and elastic forces. Furthermore, the periodic behavior leading to these structures is described by four distinct stages of motion that include rotation, arrest, bending, and stretching of the chain. These stages correspond to specific intervals of the eccentric field's period. A scaling analysis that considers the relative ratio of viscous to magnetic torques via a critical frequency illustrates how to maximize the bending energy. These results provide new insights into controlling colloidal assemblies by applying complex magnetic fields., (Creative Commons Attribution license.)

High energy capacity silicon (Si) anodes in Li-ion batteries incorporate polymeric binders to improve cycle life, which is otherwise limited by large volume and stress fluctuations during charging/discharging cycles. Several properties of the polymeric binder play a role in achieving optimal battery performance, including interfacial adhesion strength, mechanical elasticity, and lithium-ion conduction rate. In this work, we utilize atomistic simulations with the ReaxFF force field and complementary experiments to investigate how these properties dictate the performance of Si/binder anodes. We study three C/N/H-based polymer binders with varying structures (pyrolyzed polyacrylonitrile (PPAN), polyacrylonitrile (PAN), and polyaniline (PANI)) to determine how the structure-property characteristics of the binder affect performance. The Si/binder adhesion analysis reveals some counter-intuitive results: although an individual PANI chain has a stronger affinity to Si compared to PPAN, the PANI bulk binds weaker to the Si surface. Interfacial structural analyses from simulations of the bulk phase show that PANI chains have poor stacking at the interface, while PPAN chains exhibit dense and highly ordered stacking behavior, leading to stronger adhesion. PPAN also has a lower Young's modulus compared to PANI and PAN owing to its ordered and less entangled bulk structure. This added elasticity better accommodates volume changes associated with cycling, making it a more suitable candidate for Si anodes. Finally, both simulations and experimental measurements of Li-ion diffusion rates show higher Li mobility through PPAN than PAN and PANI because the ordered stacking of PPAN chains creates channels that are favorable for Li diffusion to the Si surface. Galvanostatic charge-discharge cycling experiments show that PPAN is indeed a highly promising binder for Si anodes in Li-ion batteries, retaining a capacity of ∼1400 mAh g -1 for 150 cycles. This work demonstrates that the orientation and structure of the polymer at and near the interface are essential for optimizing binder performance as well as showcases the initial steps for binder evaluation, selection, and application for electrodes in Li-ion batteries.

Magnetically-guided colloidal assembly has proven to be a versatile method for building hierarchical particle assemblies. This review describes the dipolar interactions that govern superparamagnetic colloids in time-varying magnetic fields, and how such interactions have guided colloidal assembly into materials with increasing complexity that display novel dynamics. The assembly process is driven by magnetic dipole-dipole interactions, whose strength can be tuned to be attractive or repulsive. Generally, these interactions are directional in static external magnetic fields. More recently, time-varying magnetic fields have been utilized to generate dipolar interactions that vary in both time and space, allowing particle interactions to be tuned from anisotropic to isotropic. These interactions guide the dynamics of hierarchical assemblies of 1-D chains, 2-D networks, and 2-D clusters in both static and time-varying fields. Specifically, unlinked and chemically-linked colloidal chains exhibit complex dynamics, such as fragmentation, buckling, coiling, and wagging phenomena. 2-D networks exhibit controlled porosity and interesting coarsening dynamics. Finally, 2-D clusters have shown to be an ideal model system for exploring phenomena related to statistical thermodynamics. This review provides recent advances in this fast-growing field with a focus on its scientific potential.

This study examines the compatibility of multielectrolyte additives for NMC-silicon lithium-ion batteries. Research studies with Si-based anodes have shown stable reversible cycling using electrolytes containing fluoroethylene carbonate (FEC). At the same time, the electrolyte additive, tris(trimethylsilyl) phosphite (TTMSP), has shown to improve the electrochemical performance of nickel-rich layered cathodes, such as LiNi 0.5 Mn 0.3 Co 0.2 O 2 (NMC). However, the combination of these electrolyte additives for the realization of a full-cell NMC-Si lithium-ion battery has not been previously explored. Changes in the electrochemical performance (capacity retention, internal cell resistance, and electrochemical impedance) in half-cells are studied as the ratio of TTMSP and FEC is tuned. At the optimal TTMSP/FEC ratio of 0.33 (T1F3), the NMC-Si full-cells achieve a 2× longer cycle life when compared to the FEC-rich (T0F4) electrolyte. Moreover, T1F3 full-cells demonstrate 1.5 mAh/cm 2 areal capacities and high-capacity retention (25% more than T0F4). A detailed investigation of the electrode-electrolyte interfaces is conducted by using time-of-flight secondary ion mass spectroscopy (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS). The chemical species depth profiles and elemental analysis illustrate adequate hydrogen fluoride (HF) scavenging. These results demonstrate the synergistic effects of electrolyte additives in minimizing the capacity degradation in NMC-Si full-cells by effectively stabilizing the electrode-electrolyte interfaces.

Phase separation processes are widely utilized to assemble complex fluids into novel materials. These separation processes can be thermodynamically driven due to changes in concentration, pressure, or temperature. Phase separation can also be induced with external stimuli, such as magnetic fields, resulting in novel nonequilibrium systems. However, how external stimuli influence the transition pathways between phases has not been explored in detail. Here, we describe the phase separation dynamics of superparamagnetic colloids in time-varying magnetic fields. An initially homogeneous colloidal suspension can transition from a continuous colloidal phase with voids to discrete colloidal clusters, through a bicontinuous phase formed via spinodal decomposition. The type of transition depends on the particle concentration and magnitude of the applied magnetic field. The spatiotemporal evolution of the microstructure during the nucleation and growth period is quantified by analyzing the morphology using Minkowski functionals. The characteristic length of the colloidal systems was determined to correlate with system variables such as magnetic field strength, particle concentration, and time in a power-law scaling relationship. Understanding the interplay between particle concentration and applied magnetic field allows for better control of the phases observed in these magnetically tunable colloidal systems.

We investigate the dynamic adsorption of anionic surfactant C 14 - 16 alpha olefin sulfonate on Berea sandstone cores with different surface wettability and redox states under high temperature that represents reservoir conditions. Surfactant adsorption levels are determined by analyzing the effluent history data with a dynamic adsorption model assuming Langmuir isotherm. A variety of analyses, including surface chemistry, ionic composition, and chromatography, is performed. It is found that the surfactant breakthrough in the neutral-wet core is delayed more compared to that in the water-wet core because the deposited crude oil components on the rock surface increase the surfactant adsorption via hydrophobic interactions. As the surfactant adsorption is satisfied, the crude oil components are solubilized by surfactant micelles and some of the adsorbed surfactants are released from the rock surface. The released surfactant dissolves in the flowing surfactant solution, thereby resulting in an overshoot of the produced surfactant concentration with respect to the injection value. Furthermore, under water-wet conditions, changing the surface redox potential from an oxidized to a reduced state decreases the surfactant adsorption level by 40%. We find that the decrease in surfactant adsorption is caused not only by removing the iron oxide but also by changing the calcium concentration after the core restoration process (calcite dissolution and ion exchange as a result of using EDTA). Findings from this study suggest that laboratory surfactant adsorption tests need to be conducted by considering the wettability and redox state of the rock surface while recognizing how core restoration methods could significantly alter the ionic composition during surfactant flooding.

The apparent viscosity of viscous heavy oil emulsions in water can be less than that of the bulk oil. Microfluidic flooding experiments were conducted to evaluate how alkali-surfactant-foam enhanced oil recovery (ASF EOR) of heavy oil is affected by emulsion formation. A novel phase-behavior viscosity map-a plot of added salinity vs. soap fraction combining phase behavior and bulk apparent viscosity information-is proposed as a rapid and convenient method for identifying suitable injection compositions. The characteristic soap fraction, [Formula: see text], is shown to be an effective benchmark for relating information from the phase-viscosity map to expected ASF flood test performance in micromodels. Characteristically more hydrophilic cases were found to be favorable for recovering oil, despite greater interfacial tensions, due to wettability alteration towards water-wet conditions and the formation of low apparent-viscosity oil-in-water (O/W) macroemulsions. Wettability alteration and bubble-oil pinch-off were identified as contributing mechanisms to the formation of these macroemulsions. Conversely, characteristically less hydrophilic cases were accompanied by a large increase in apparent viscosity due to the formation of water-in-oil (W/O) macroemulsions.

Asphaltenes are a significant contributor to flow assurance problems related to crude oil production. Because of their polydispersity, model molecules such as coronene and violanthrone-79 (VO-79) have been used as mimics to represent the physiochemical properties of asphaltenes. This work aims to evaluate the emulsion-stabilization characteristics of fractionated asphaltenes and these two model molecules. Such evaluation is expected to better characterize the stabilizing mechanisms of asphaltenes on water-in-oil emulsions. The coalescence process of water-in-oil emulsion droplets is visualized using a microfluidic flow-focusing geometry. The rate of coalescence events is used as the parameter to assess emulsion stability. Interfacial tension (IFT) and oil/brine zeta potential are measured to help explain the differences in the rates of coalescence. VO-79 is found to be better at stabilizing emulsions as compared to coronene. Although VO-79 and asphaltenes have similar interfacial tension and oil/brine zeta potential values, the rate of coalescence differs significantly. This highlights the difficulty in using model molecules to mimic the transport dynamics of asphaltenes.

Hypothesis: We present a systematic study of the "smart water" induced wettability alteration. This process is believed to be greatly affected by the brine salinity and the presence of Mg 2+ and SO 4 2- in the brine., Experiments and Modelling: To characterize the wettability alteration, we perform spontaneous imbibition measurement using Indiana limestone cores and a model oil with added naphthenic acid. Both single-electrolyte-based and seawater-based "smart water" are tested to investigate the effect of Mg 2+ , SO 4 2- and salinity on wettability alteration. Rock/brine and oil/brine zeta potentials are measured, and the electrostatic component of disjoining pressure is calculated to understand the role of electrostatics in the wettability alteration. The surface concentration of charged species on the limestone surface is analyzed based on a natural carbonate surface complexation model (SCM)., Findings: Both the reduction of Na + and addition of SO 4 2- are found to contribute to wettability alteration. Mg 2+ is found to be unfavorable for wettability alteration. Ca 2+ is believed to facilitate SO 4 2- with wettability alteration based on the comparison between the single-electrolyte-based and seawater-based brines. The reduction of the Na + surface complexation (>CaOH⋯Na +0.25 ) in low salinity brines is believed to be a critical mechanism responsible for wettability alteration based on the SCM calculations., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Cancer cells release extracellular vesicles known as extracellular vesicles (EVs), containing tumor-derived DNA, RNA and proteins within their cargo, into the circulation. Circulating tumor-derived extracellular vesicles (TEV) can be used in the context of serial "liquid biopsies" for early detection of cancer, for monitoring disease burden in patients, and for assessing recurrence in the post-resection setting. Nonetheless, isolating sufficient TEV by ultracentrifugation-based approaches, in order to enable molecular assessment of EVs cargo, can be an arduous, time-consuming process and is inconsistent in the context of yield and purity among institutions. Herein, we describe a microfluidic platform, which we have named MITEV (Microfluidic Isolation of Tumor-derived Extracellular Vesicles) for the rapid isolation of TEV from the plasma of pancreatic cancer patients. The device, which has ~100,000 pillars placed in a zigzag pattern and is coated with antibodies against generic EV surface proteins (anti-CD63, -CD9, and -CD81 antibodies) or the TEV specific anti-Epithelial Cell Adhesion Molecule (EpCAM) antibody, is capable of high-throughput EVs isolation and yields sufficient DNA (total of ~2-14 ng from 2-ml plasma) for downstream genomic analysis. Using two independent quantitative platforms, droplet digital polymerase chain reaction (ddPCR) and molecular barcoding using nanoString nCounter® technology, we can reliably identify KRAS mutations within isolated TEV of treatment-naïve metastatic pancreatic cancer patients. Our study suggests that the MITEV device can be used for point-of-care applications, such as in the context of monitoring residual or recurrent tumor presence in pancreatic cancer patients undergoing therapy.

The injection of low-salinity brine enhances oil recovery by altering the mineral wettability in carbonate reservoirs. However, the reported effectiveness of low-salinity water varies significantly in the literature, and the underlying mechanism of wettability alteration is controversial. In this work, we investigate the relationships between characteristics of crude oils and the oils' response to low-salinity water in a spontaneous imbibition test, aiming (1) to identify suitable indicators of the effectiveness of low-salinity water and (2) to evaluate possible mechanisms of low-salinity-induced wettability alteration, including rock/oil charge repulsion and microdispersion formation. Seven oils are tested by spontaneous imbibition and fully characterized in terms of their acidity, zeta potential, interfacial tension, microdispersion propensity, water-soluble organics content and saturate-aromatic-resin-asphaltene fractionation. For the first time, the effectiveness of low-salinity water is found to positively correlate with the oil interfacial tension in low-salinity water. Oils with higher interfacial activity are found to respond more positively to low-salinity water. Moreover, cryogenic transmission electron microscopy images suggest that microdispersion is essentially macroemulsion, and its formation is an effective indicator - but not the root cause - of wettability alteration. The repulsive zeta potential for the rock and the oil in low-salinity water is found to be an insufficient condition for wettability alteration in carbonate minerals.

Densely packed wet foam was subjected to gradual expansion and contraction in a wide (1400-1800 μm) microfluidic channel to study localized plastic deformation events within the monodisperse bubble matrix. Dislocation glide, reflection, nucleation, and dipole transformations from extensional and compressive stresses were observed across a range of fluid flow rates and bubble packing densities. Disparate, cyclic reflections occur in two independent regions of the flowing foam, and the mechanisms of dislocation reflection under tension are expanded. The use of an asymmetric channel created a dichotomy in the model crystalline system between straighter, aligned bubble rows and curved, misaligned rows due to the corresponding streamlines within the channel. The resulting gradient in crystalline alignment had numerous effects on dislocation mobility and plastic deformation. 7/7 dipoles were found to rearrange to a more stable configuration aligned with the foam flow before dissociating. Dislocations comprising 5/5 dipoles (resembling the inverse-Stone-Wales defect in carbon nanostructures) were discovered to pass through one another via intermediate ring structures, which most commonly consisted of three dislocation pairs around a triangular-shaped central bubble.

The adsorption of a switchable cationic surfactant, N, N, N'-trimethyl- N'-tallow-1,3-diaminopropane (DTTM, Duomeen TTM), at the silica/aqueous solution interface is characterized using a quartz crystal microbalance with dissipation (QCM-D). The adsorption isotherms reveal that changes in the solution pH or salinity affect surfactant adsorption in competing ways. In particular, the combination of the degree of protonation of the surfactant and electrostatic interactions is responsible for surfactant adsorption. The kinetics of adsorption is carefully measured using the real-time measurement of a QCM-D, allowing us to fit the experimental data with analytical models. At pH values of 3 and 5, where the DTTM is protonated, DTTM exhibits two-step adsorption. This is representative of a fast step in which the surfactant molecules are adsorbed with head-groups orientated toward the surface, followed by a slower second step corresponding to formation of interfacial surfactant aggregates on the silica surface.

By incorporating the techniques of geometrically mediated splitting and bubble-bubble breakup, the present work offers a novel microfluidic foam generation system via production of segregated, mono- or bidisperse bubbles at capacities exceeding 10 000 bubbles per second. Bubble-bubble pinch-off is precise at high capillary numbers (Ca > 0.065), generating monodisperse or bidisperse daughter bubbles for a symmetric or an asymmetric expansion respectively. Bi- or tridisperse foam is produced as pinch-off perfectly alternates such that the system contains twice the number of fragmented bubbles as intact bubbles. A relationship between the upstream bubble extension and the capillary number demarcates the different regimes of pinch-off defined with respect to frequency and precision: non-splitting, irregular, polydisperse, and monodisperse (or bidisperse for an asymmetric expansion). For tridisperse foam generation via a fixed asymmetric expansion geometry, the wall bubble confinement can be tuned to adjust the pinch-off accuracy in order to access a spectrum of fragmented bubble size ratios. The simplicity in operating and characterizing our system will enable studies on dynamic bubble interactions and ordered, wet foam applications.

Hypothesis: The viscosity and stability of CO 2 /water foams at elevated temperature can be increased significantly with highly viscoelastic aqueous lamellae. The slow thinning of these viscoelastic lamellae leads to greater foam stability upon slowing down Ostwald ripening and coalescence. In the aqueous phase, the viscoelasticity may be increased by increasing the surfactant tail length to form more entangled micelles even at high temperatures and salinity., Experiments: Systematic measurements of the steady state shear viscosity of aqueous solutions of the diamine surfactant (C 16-18 N(CH 3 )C 3 N(CH 3 ) 2 ) were conducted at varying surfactant concentrations and salinity to determine the parameters for formation of entangled wormlike micelles. The apparent viscosity and stability of CO 2 /water foams were compared for systems with viscoelastic entangled micellar aqueous phases relative to those with much less viscous spherical micelles., Findings: We demonstrated for the first time stable CO 2 /water foams at temperatures up to 120 °C and CO 2 volumetric fractions up to 0.98 with a single diamine surfactant, C 16-18 N(CH 3 )C 3 N(CH 3 ) 2 . The foam stability was increased by increasing the packing parameter of the surfactant with a long tail and methyl substitution on the amine to form entangled viscoelastic wormlike micelles in the aqueous phase. The foam was more viscous and stable compared to foams with spherical micelles in the aqueous lamellae as seen with C 12-14 N(EO) 2 and C 16-18 N(EO)C 3 N(EO) 2 ., (Copyright © 2018. Published by Elsevier Inc.)

We present the contractile buckling dynamics of superparamagnetic filaments using experimental, theoretical, and simulation approaches. Under the influence of an orthogonal magnetic field, flexible magnetic filaments exhibit higher-order buckling dynamics that can be identified as occurring in three stages: initiation, development, and decay. Unlike initiation and decay stages where the balance between magnetic interactions and elastic forces is dominant, in the development stage, the influence of hydrodynamic drag results in transient buckling dynamics that is nonlinear along the filament contour. The inhomogeneous temporal evolution of the buckling wavelength is analyzed and the contractions under various conditions are compared.

Swimming at low Reynolds number is typically dominated by a large viscous drag, therefore microscale swimmers require non-reciprocal body deformation to generate locomotion. Purcell described a simple mechanical swimmer at the microscale consisting of three rigid components connected together with two hinges. Here we present a simple microswimmer consisting of two rigid paramagnetic particles with different sizes. When placed in an eccentric magnetic field, this simple microswimmer exhibits non-reciprocal body motion and its swimming locomotion can be directed in a controllable manner. Additional components can be added to create a multibody microswimmer, whereby the particles act cooperatively and translate in a given direction. For some multibody swimmers, the stochastic thermal forces fragment the arm, which therefore modifies the swimming strokes and changes the locomotive speed. This work offers insight into directing the motion of active systems with novel time-varying magnetic fields. It also reveals that Brownian motion not only affects the locomotion of reciprocal swimmers that are subject to the Scallop theorem, but also affects that of non-reciprocal swimmers.

Hypothesis: The adsorption of anionic surfactants onto positively charged carbonate minerals is typically high due to electrostatic interactions. By blending anionic surfactants with cationic or zwitterionic surfactants, which naturally form surfactant complexes, surfactant adsorption is expected to be influenced by a competition between surfactant complexes and surfactant-surface interactions., Experiments: The adsorption behavior of surfactant blends known to form complexes was investigated. The surfactants probed include an anionic C 15-18 internal olefin sulfonate (IOS), a zwitterionic lauryl betaine (LB), and an anionic C 13 -alcohol polyethylene glycol ether carboxylic acid (L38). An analytical method based on high-performance liquid chromatography evaporative light scattering detector (HPLC-ELSD) was developed to measure three individual surfactant concentrations from a blended surfactant solution. The adsorption of the individual surfactants and surfactant blends were systematically investigated on different mineral surfaces using varying brine solutions., Findings: LB adsorption on calcite surfaces was found to be significantly increased when blended with IOS or L38 since it forms surfactant complexes that partition to the surface. However, the total adsorption of the LB-IOS-L38 solution on dolomite decreased from 3.09 mg/m 2 to 1.97 mg/m 2 when blended together compared to summing the adsorption values of individual surfactants, which highlights the importance of mixed surfactant association., (Copyright © 2017 Elsevier Inc. All rights reserved.)

Foam flooding in porous media is of increasing interest due to its numerous applications such as enhanced oil recovery, aquifer remediation, and hydraulic fracturing. However, the mechanisms of oil-foam interactions have yet to be fully understood at the pore level. Here, we present three characteristic zones identified in experiments involving the displacement of crude oil from model porous media via surfactant-stabilized foam, and we describe a series of pore-level dynamics in these zones which were not observed in experiments involving paraffin oil. In the displacement front zone, foam coalesces upon initial contact with crude oil, which is known to destabilize the liquid lamellae of the foam. Directly upstream, a transition zone occurs where surface wettability is altered from oil-wet to water-wet. After this transition takes place, a strong foam bank zone exists where foam is generated within the porous media. We visualized each zone using a microfluidic platform, and we discuss the unique physicochemical phenomena that define each zone. In our analysis, we also provide an updated mechanistic understanding of the "smart rheology" of foam which builds upon simple "phase separation" observations in the literature.

Microfluidic devices are versatile tools for studying transport processes at a microscopic scale. A demand exists for microfluidic devices that are resistant to low molecular-weight oil components, unlike traditional polydimethylsiloxane (PDMS) devices. Here, we demonstrate a facile method for making a device with this property, and we use the product of this protocol for examining the pore-scale mechanisms by which foam recovers crude oil. A pattern is first designed using computer-aided design (CAD) software and printed on a transparency with a high-resolution printer. This pattern is then transferred to a photoresist via a lithography procedure. PDMS is cast on the pattern, cured in an oven, and removed to obtain a mold. A thiol-ene crosslinking polymer, commonly used as an optical adhesive (OA), is then poured onto the mold and cured under UV light. The PDMS mold is peeled away from the optical adhesive cast. A glass substrate is then prepared, and the two halves of the device are bonded together. Optical adhesive-based devices are more robust than traditional PDMS microfluidic devices. The epoxy structure is resistant to swelling by many organic solvents, which opens new possibilities for experiments involving light organic liquids. Additionally, the surface wettability behavior of these devices is more stable than that of PDMS. The construction of optical adhesive microfluidic devices is simple, yet requires incrementally more effort than the making of PDMS-based devices. Also, though optical adhesive devices are stable in organic liquids, they may exhibit reduced bond-strength after a long time. Optical adhesive microfluidic devices can be made in geometries that act as 2-D micromodels for porous media. These devices are applied in the study of oil displacement to improve our understanding of the pore-scale mechanisms involved in enhanced oil recovery and aquifer remediation.

This study presents experiment and surface complexation modeling (SCM) of synthetic calcite zeta potential in brine with mixed potential determining ions (PDI) under various CO 2 partial pressures. Such SCM, based on systematic zeta potential measurement in mixed brines (Mg 2+ , SO 4 2- , Ca 2+ and CO 3 2- ), is currently not available in the literature and is expected to facilitate understanding of the role of electrostatic forces in calcite wettability alteration. We first use a double layer SCM to model experimental zeta potential measurements and then systematically analyze the contribution of charged surface species. Calcite surface charge is investigated as a function of four PDIs and CO 2 partial pressure. We show that our model can accurately predict calcite zeta potential in brine containing a combination of four PDIs and apply it to predict zeta potential in ultra-low and pressurized CO 2 environments for potential application in enhanced oil recovery in carbonate reservoirs. Model prediction reveals that calcite surface will be positively charged in all considered brines in pressurized CO 2 environment (>1atm). The calcite zeta potential is sensitive to CO 2 partial pressure in the various brine in the order of Na 2 CO 3 >Na 2 SO 4 >NaCl>MgCl 2 >CaCl 2 (Ionic strength=0.1M)., (Copyright © 2017 Elsevier Inc. All rights reserved.)

The solid-liquid melting transition in a two-dimensional (2-D) attractive colloidal system is visualized using superparamagnetic colloids that interact through a long-range isotropic attractive interaction potential, which is induced using a high-frequency rotating magnetic field. Various experiments, supported by Monte Carlo simulations, are carried out over a range of interaction potentials and densities to determine structure factors, Lindermann parameters, and translational and orientational order parameters. The system shows a first-order solid-liquid melting transition. Simulations and experiments suggest that dislocations and disclinations simultaneously unbind during melting. This is in direct contrast with reports of 2-D melting of paramagnetic particles that interact with a repulsive interaction potential.

The static adsorption of C 12-14 E 22 , which is a highly ethoxylated nonionic surfactant, was studied on different minerals using high-performance liquid chromatography (HPLC) combined with an evaporative light scattering detector (ELSD). Of particular interest is the surfactant adsorption in the presence of CO 2 because it can be used for foam flooding in enhanced oil recovery applications. The effects of the mineral type, impurities, salinity, and temperature were investigated. The adsorption of C 12-14 E 22 on pure calcite was as low as 0.01 mg/m 2 but higher on dolomite depending on the silica and clay content in the mineral. The adsorption remained unchanged when the experiments were performed using a brine solution or 0.101 MPa (1 atm) CO 2 , which indicates that electrostatic force is not the governing factor that drives the adsorption. The adsorption of C 12-14 E 22 on silica may be due to hydrogen bonding between the oxygen in the ethoxy groups of the surfactant and the hydroxyl groups on the mineral surface. Additionally, thermal decomposition of the surfactant was severe at 80 °C but can be inhibited by operating in a reducing environment. Under reducing conditions, adsorption of C 12-14 E 22 increased at higher temperatures.

Asphaltenes are known to cause severe flow assurance problems in the near-wellbore region of oil reservoirs. Understanding the mechanism of asphaltene deposition in porous media is of great significance for the development of accurate numerical simulators and effective chemical remediation treatments. Here, we present a study of the dynamics of asphaltene deposition in porous media using microfluidic devices. A model oil containing 5 wt % dissolved asphaltenes was mixed with n-heptane, a known asphaltene precipitant, and flowed through a representative porous media microfluidic chip. Asphaltene deposition was recorded and analyzed as a function of solubility, which was directly correlated to particle size and Péclet number. In particular, pore-scale visualization and velocity profiles, as well as three stages of deposition, were identified and examined to determine the important convection-diffusion effects on deposition.

We present the results of an experimental investigation of the effect of gas type and composition on foam transport in porous media. Steady-state foam strengths with respect to three cases of distinct gases and two cases containing binary mixtures of these gases were compared. The effects of gas solubility, the stability of lamellae, and the gas diffusion rate across the lamellae were examined. Our experimental results showed that the steady-state foam strength is inversely correlated with the gas permeability across a liquid lamella, a parameter that characterizes the rate of mass transport. The results are also in good agreement with existing observations that the foam strength for a mixture of gases is correlated with the less soluble component. Three hypotheses with different predictions of the underlying mechanism that explain the role of gas type and composition in foam strength are discussed in detail.

The dynamics of magnetorheological fluids have typically been described by the Mason number, a governing parameter defined as the ratio between viscous and magnetic forces in the fluid. For most experimental suspensions of magnetic particles, surface forces, such as steric and electrostatic interactions, can significantly influence the dynamics. Here we propose a theory of a modified Mason number that accounts for surface forces and show that this modified Mason number is a function of interparticle distance. We demonstrate that this modified Mason number is accurate in describing the dynamics of a rotating pair of paramagnetic colloids of identical or mismatched sizes in either high or low salt solutions. The modified Mason number is confirmed to be pseudoconstant for particle pairs and particle chains undergoing a stable-metastable transition during rotation. The interparticle distance term can be calculated using theory or can be measured experimentally. This modified Mason number is more applicable to magnetorheological systems where surface forces are not negligible.

The interfacial properties for surfactants at the supercritical CO2-water (C-W) interface at temperatures above 80°C have very rarely been reported given limitations in surfactant solubility and chemical stability. These limitations, along with the weak solvent strength of CO2, make it challenging to design surfactants that adsorb at the C-W interface, despite the interest in CO2-in-water (C/W) foams (also referred to as macroemulsions). Herein, we examine the thermodynamic, interfacial and rheological properties of the surfactant C12-14N(EO)2 in systems containing brine and/or supercritical CO2 at elevated temperatures and pressures. Because the surfactant is switchable from the nonionic state to the protonated cationic state as the pH is lowered over a wide range in temperature, it is readily soluble in brine in the cationic state below pH 5.5, even up to 120°C, and also in supercritical CO2 in the nonionic state. As a consequence of the affinity for both phases, the surfactant adsorption at the CO2-water interface was high, with an area of 207Å(2)/molecule. Remarkably, the surfactant lowered the interfacial tension (IFT) down to ∼5mN/m at 120°C and 3400 psia (23MPa), despite the low CO2 density of 0.48g/ml, indicating sufficient solvation of the surfactant tails. The phase behavior and interfacial properties of the surfactant in the cationic form were favorable for the formation and stabilization of bulk C/W foam at high temperature and high salinity. Additionally, in a 1.2 Darcy glass bead pack at 120°C, a very high foam apparent viscosity of 146 cP was observed at low interstitial velocities given the low degree of shear thinning. For a calcium carbonate pack, C/W foam was formed upon addition of Ca(2+) and Mg(2+) in the feed brine to keep the pH below 4, by the common ion effect, in order to sufficiently protonate the surfactant. The ability to form C/W foams at high temperatures is of interest for a variety of applications in chemical synthesis, separations, materials science, and subsurface energy production., (Copyright © 2016 Elsevier Inc. All rights reserved.)

Injuries that result in the loss of limb functionality may be caused by the severing of the peripheral nerves within the affected limb. Several bioengineered peripheral nerve scaffolds have been developed in order to provide the physical support and topographical guidance necessary for the naturally disorganized axon outgrowth to reattach to distal nerve stumps as an alternative to other procedures, like nerve grafting. PDMS has been chosen for the base material of the scaffolds due to its biocompatibility, flexibility, transparency, and well-developed fabrication techniques. The process of observing the axon outgrowth across the nerve gaps with PDMS scaffolds has been challenging due to the limited number and fineness of longitudinal sections that can be extracted from harvested nerve tissue samples after implantation. To address this, multilayer microchannel scaffolds were developed with the object of providing more refined longitudinal observation of axon outgrowth by longitudinally 'sectioning' the device during fabrication, removing the need for much of the sample preparation process. This device was then implanted into the sciatic nerves of Lewis rats, and then harvested after two and four weeks to analyze the difference in nerve regeneration between two different time periods. The present layer by layer structure, which is separable after nerve regeneration and is treated as an individual layer during the histology process, provides the details of biological events during axonal regeneration. Confocal microscopic imaging showed the details of peripheral nerve regeneration including nerve branches and growth cones observable from within the microchannels of the multilayer PDMS microchannel scaffolds.

The methylene blue (MB) two-phase titration method is a rapid and efficient method for determining the concentrations of anionic surfactants. The point at which the aqueous and chloroform phases appear equally blue is called Epton's end point. However, many inorganic anions, e.g., Cl(-), NO3(-), Br(-), and I(-), can form ion pairs with MB(+) and interfere with Epton's end point, resulting in the failure of the MB two-phase titration in high-salinity brine. Here we present a method to extend the MB two-phase titration method for determining the concentration of various cationic surfactants in both deionized water and high-salinity brine (22% total dissolved solid). A colorless end point, at which the blue color is completely transferred from the aqueous phase to the chloroform phase, is proposed as titration end point. Light absorbance at the characteristic wavelength of MB is measured using a spectrophotometer. When the absorbance falls below a threshold value of 0.04, the aqueous phase is considered colorless, indicating that the end point has been reached. By using this improved method, the overall error for the titration of a permanent cationic surfactant, e.g., dodecyltrimethylammonium bromide, in deionized (DI) water and high-salinity brine is 1.274% and 1.322% with limits of detection (LOD) of 0.149 and 0.215 mM, respectively. Compared to the traditional acid-base titration method, the error of this improved method for a switchable cationic surfactant, e.g., tertiary amine surfactant (Ethomeen C12), is 2.22% in DI water and 0.106% with LOD of 0.369 and 0.439 mM, respectively.

Foam mobility control and novel oil displacement mechanisms were observed in a microfluidic device representing a porous media system with layered permeability. Foam was pre-generated using a flow-focusing microfluidic device and injected into an oil-wet, oil-saturated 2-D PDMS microfluidic device. The device is designed with a central fracture flanked by high-permeability and low-permeability zones stratified in the direction of injection. A 1 : 1, 1% blend of alpha olefin sulfonate 14-16 (AOS) and lauryl betaine (LB) surfactants produced stable foam in the presence of paraffin oil. The oil saturation and pressure drop across the microfluidic device were measured as a function of time and the injected pore volume, indicating an increase in apparent viscosity for foam with an accompanying decrease in oil saturation. In contrast to the control experiments, foam was shown to more effectively mobilize trapped oil by increasing the flow resistance in the fracture and high-permeability zones and by diverting the surfactant solution into adjacent low-permeability zones. The foam was observed to separate into gas-rich and aqueous-rich phases depending on matrix permeability, suggesting that it is not appropriate to treat foam as a homogeneous dispersion of gas and liquid.

We report the use of lipid membrane-coated microcantilevers to probe the interactions between phospholipid membranes and membrane-active peptides. This sensing method integrates two well-developed techniques: solid-supported lipid bilayers (SLBs) and microcantilever sensors. SLBs are prepared on the silicon dioxide surface of the microcantilevers using a vesicle fusion method. As molecules adsorb onto the surface of the microcantilever, the microcantilever bends due to the induced compressive or tensile stresses, which result from the surface free energy change. Real-time surface stress changes in the SLB due to interactions with small molecules can be detected by monitoring the deflection of the microcantilever. We investigate the mechanism for the interaction between SLBs and PEP1, a synthetic amphipathic peptide resembling a segment of the nonstructural protein (NS5A) of the hepatitis C virus. Initially, the PEP1 peptides adsorb onto the lipid membranes, and then at a critical concentration, the peptides begin to aggregate and form pores; finally, the peptides destabilize and induce solubilization of the supported membranes. The membrane-coated microcantilever sensor is capable of characterizing the kinetics and dynamics of this process with great sensitivity.

Pluronics are a class of amphiphilic triblock copolymers that are known to interact with cellular membranes in interesting ways. The solubility of these triblock copolymers in free lipid membranes can be altered with temperature, allowing the possibility of tuning their membrane insertion. However, for supported lipid membranes, the asymmetric local environment and the strong influence of the solid support can alter the solubility of these triblock copolymers in lipid membranes. Here, we probe the interactions of these copolymers with supported lipid membranes using microcantilevers and fluorescence recovery after photobleaching (FRAP) measurements. We measure the solubility and interactions of triblock copolymers (F68 and F98) in supported lipid bilayers as a function of temperature and the length of the copolymer lipophilic block. A Langmuir isotherm model and a free mean area theory are applied to describe the polymer-lipid interactions at the microcantilever surface, determine association constants, and analyze the effect of triblock copolymers on lateral lipid diffusion.

Typically, the force between paramagnetic particles in a uniform magnetic field is calculated using either dipole-based models or the Maxwell stress tensor combined with Laplace's equation for magnetostatics. Dipole-based models are fast but involve many assumptions, leading to inaccuracies in determining forces for clusters of particles. The Maxwell stress tensor yields an exact force calculation, but solving Laplace's equation is very time consuming. Here, we present a more elaborate dipole-based model: the micro-mutual-dipolar model. Our model has a time complexity that is similar to that of other dipole-based models but is much more accurate especially when used to calculate the force of small aggregates. Using this model, we calculate the force between two paramagnetic spheres in a uniform magnetic field and a circular rotational magnetic field and compare our results with those of other models. The forces for three-particle and ten-particle systems dispersed in two-dimensional (2D) space are examined using the same model. We also apply this model to calculate the force between two paramagnetic disks dispersed in 2D space. The micro-mutual-dipolar model is demonstrated to be useful for force calculations in dynamic simulations of small clusters of particles for which both accuracy and efficiency are desirable.

We report the formation of colloidal macromolecules consisting of chains of micron-sized paramagnetic particles assembled using a magnetic field and linked with DNA. The interparticle spacing and chain flexibility were controlled by varying the magnetic field strength and the linker spring constant. Variations in the DNA lengths allowed for the generation of chains with an improved range of flexibility as compared to previous studies. These chains adopted the rigid-rod, semiflexible, and flexible conformations that are characteristic of linear polymer systems. These assembly techniques were investigated to determine the effects of the nanoscale DNA linker properties on the properties of the microscale colloidal chains. With stiff DNA linkers (564 base pairs) the chains were only stable at moderate to high field strengths and produced rigid chains. For flexible DNA linkers (8000 base pairs), high magnetic field strengths caused the linkers to be excluded from the gap between the particles, leading to a transition from very flexible chains at low field strengths to semiflexible chains at high field strengths. In the intermediate range of linker sizes, the chains exhibited predictable behavior, demonstrating increased flexibility with longer DNA linker length or smaller linking field strengths. This study provides insight into the process of directed assembly using magnetic fields and DNA by precisely tuning the components to generate colloidal analogues of linear macromolecular chains.

Controlling the morphology of conjugated polymers has recently attracted considerable attention because of their applications in photovoltaic (PV) devices and organic light-emitting diodes (OLEDs). Here, we describe the self-assembly of a common conjugated polymer, poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV), into ringlike structures via solvent evaporation on an air/water interface. The films are monitored using Brewster angle microscopy (BAM) and transferred onto a solid substrate by either the Langmuir-Blodgett (LB) or the Langmuir-Schaefer (LS) method and further characterized by atomic force microscopy (AFM). The morphology of the MEH-PPV thin film at the air/water interface can be controlled by the spreading solvent. By mixing solvents of varying spreading coefficients and evaporation rates, such as chloroform and chlorobenzene, MEH-PPV can be assembled into micrometer-sized ring structures. The optical properties of these MEH-PPV ring structures are also characterized. Lastly, MEH-PPV can be used as a soft template to organize microscale structures of nanoparticles.

Typically the force between paramagnetic particles in a uniform magnetic field is described using the dipolar model, which is inaccurate when particles are in close proximity to each other. Instead, the exact force between paramagnetic particles can be determined by solving a three-dimensional Laplace's equation for magnetostatics under specified boundary conditions and calculating the Maxwell stress tensor. The analytical solution to this multi-boundary-condition Laplace's equation can be obtained by using a solid harmonics expansion in conjunction with the Hobson formula. However, for a multibody system, finite truncation of the Hobson formula does not lead to convergence of the expansion at all points, which makes the approximation physically unrealistic. Here we present a numerical method for solving this Laplace's equation for magnetostatics. This method uses a smoothed representation to replace all the boundary conditions. A two-step propagation is used to dramatically accelerate the calculation without losing accuracy. Using this method, we calculate the force between two paramagnetic particles in a uniform and a rotational external field and compare our results with other models. Furthermore, the many-body effects for three-particle, ten-particle, and 24-particle systems are examined using the same method. We also calculate the interaction between particles with different magnetic susceptibilities and particle diameters. The Laplace's equation solver method described in this article that is used to determine the force between paramagnetic particles is shown to be very useful for dynamic simulations for both two-particle systems and a large cluster of particles.

We report the use of an array of microcantilevers to measure the specific binding of Salmonella to peptides derived from phage display libraries. Selectivity of these phage-derived peptides for Salmonella spp. and other pathogens ( Listeria monocytogenes and Escherichia coli ) are compared with a commercially available anti- Salmonella antibody and the antimicrobial peptide alamethicin. A Langmuir isotherm model was applied to determine the binding affinity constants of the peptides to the pathogens. One particular peptide, MSal 020417, demonstrated a higher binding affinity to Salmonella spp. than the commercially available antibody and is able to distinguish among eight Salmonella serovars on a microcantilever. A multiplexed screening system to quickly determine the binding affinities of various peptides to a particular pathogen highly improves the efficiency of the peptide screening process. Combined with phage-derived peptides, this microcantilever-based technique provides a novel biosensor to rapidly and accurately detect pathogens and holds potential to be further developed as a screening method to identify pathogen-specific recognition elements.

We report the use of microcantilevers to measure the phase transition temperature (T(m)) of supported lipid bilayers or lipid monolayers. During the solid-liquid phase transition, a supported lipid bilayer or monolayer undergoes a conformational change in which the lipid acyl chains transition from an ordered state to a disordered state. This process is accompanied by a free energy change, which is coupled to changes in the surface stress in the underlying solid support layer. These surface stress changes can be readily detected using microcantilevers. The surface stress of the solid-like phase of 1-myristoyl-2-palmitoyl-sn-glycero-3-phosphocholine (MPPC) decreases linearly as the temperature increases and abruptly jumps at the main phase transition temperature. This phase transition temperature corresponds well with that found for free membranes. For an MPPC monolayer, this phase transition temperature is shifted, indicating that the existence of the solid support affects the monolayer structure. The addition of cholesterol into the bilayer decreases the phase transition temperature by ~0.38 °C per mol % of cholesterol. Differences in MPPC stability when it is either a bilayer or a monolayer can be detected through these sensitive surface stress measurements.