Multistimuli-Responsive Foams Using an Anionic Surfactant.

In this work, we report a novel class of a commercially available surfactant which shows a multistimuli-responsive behavior toward foam stability. It comprises three components-a hydrophobe (tristyrylphenol), a temperature-sensitive block (polypropylene oxide, PO), and a pH-sensitive moiety (carboxyl group). The hydrophobicity-hydrophilicity balance of the surfactant can be tuned by changing either the pH or temperature of the system. At or below pH 4, the carboxyl functional group is dominantly protonated, resulting in zero foamability. At higher pH, the surfactant exhibits good foamability and foam stability marked with a fine bubble texture (∼200 µm). Foam destabilization could be achieved rapidly by either lowering the pH or bubbling CO2 gas. At a fixed pH in the presence of salt, increasing the temperature to 65 °C resulted in rapid defoaming because of the increased hydrophobicity of the PO chain. This stimuli-induced stabilization and destabilization of foam were found to be reversible. We envisage the use of such a multi-responsive foaming system in diverse applications such as foam-enhanced oil recovery and environmental remediation where spatial and temporal control over foam stability is desirable. The low-cost commercial availability of the surfactant further makes it lucrative.

Microencapsulation and Stimuli-Responsive Controlled Release of Particles Using Water-in-Air Powders.

In this work, we report a facile, one-step method to encapsulate hydrophilic particles (HP) (micro- or nanosize) using water-in-air powders. Hydrophobic silica nanoparticles were mixed with an aqueous phase containing HP in the presence of air under high shear, resulting in the self-assembly of silica nanoparticles on water droplets to make water-in-air powders with HP encapsulated in the aqueous phase within the silica shell. The encapsulated HP can be released on the basis of an external stimulus such as adding an external aqueous phase of a certain pH or a surfactant solution that alters the wettability of the encapsulating silica nanoparticles. A contact angle study was performed using surface-hydrophobized glass slides, which acted as a proxy for hydrophobic silica nanoparticles, to investigate the effect of these stimuli on surface hydrophobicity. Such encapsulation and a stimuli-responsive controlled release system has promising potential in subsurface petroleum engineering such as the delayed swelling of particles for conformance control and delayed acid stimulation.

Development of surfactant formulation for high-temperature off-shore carbonate reservoirs.

The residual oil left behind after water flooding in petroleum reservoirs can be mobilized by surfactant formulations that yield ultralow interfacial tension (IFT) with oil. However, finding ultralow IFT surfactant formulations is difficult for high-temperature, off-shore, carbonate reservoirs. These reservoirs are often water-flooded with seawater (with a lot of divalent ions), which is often incompatible with many surfactants at high temperatures. The goal of this research is to develop a surfactant formulation for an off-shore carbonate reservoir at 100°C previously flooded by seawater. Surfactant-oil-brine phase behavior was studied for formulations, starting from a single surfactant to mixtures of surfactants and a co-solvent. Mixtures of three surfactants and one co-solvent were needed to produce ultralow IFT formulations for the oil of interest. The surfactant system with polymer mobility control was tested in crushed reservoir rock packs. The cumulative oil recovery was >99% for the surfactant-polymer (SP) flood with an optimal salinity gradient. The constant salinity SP floods with seawater increased oil recovery significantly beyond the water flood (cumulative oil recovery >91%), even though the recovery was lower than that of the optimal salinity gradient SP flood. Our experimental work demonstrates the effectiveness of the surfactant formulation for a high-temperature carbonate reservoir at seawater salinity.

Evaluation of asymmetric immunoliposomal nanoparticles for cellular uptake.

Effective and targeted in vivo delivery of polynucleotide therapeutics is the key for the treatment of many diseases. Asymmetric immunoliposomes can be used as vehicles to deliver polynucleotides effectively because the two leaflets of the bilayer can have different compositions, which enhance the delivery capacity. The formation and in vitro cellular uptake of asymmetric immunoliposomes containing polynucleotide cargoes were studied here. Maleimide-functionalised DSPE-PEG (2000) were incorporated into the outer leaflet to produce asymmetric liposomes capable of covalently attaching antibodies. Thiolated antibodies from both human and rabbit origin were conjugated to produce asymmetric pendant-type immunoliposomes that retain their specificity towards detection antibodies through the formation process. Human IgG-conjugated asymmetric immunoliposomes were readily internalised (>20 per cell) by macrophage, HEPG2, and CV-1 monkey kidney cells. The cells internalised the liposomal nanoparticles by the endocytic pathway. The immunoliposome-encapsulated endosomes were intact for at least 5 days and sequestered the plasmid from expression by the cell.

Static and dynamic adsorption of a gemini surfactant on a carbonate rock in the presence of low salinity water.

In chemical enhanced oil recovery (cEOR) techniques, surfactants are extensively used for enhancing oil recovery by reducing interfacial tension and/or modifying wettability. However, the effectiveness and economic feasibility of the cEOR process are compromised due to the adsorption of surfactants on rock surfaces. Therefore, surfactant adsorption must be reduced to make the cEOR process efficient and economical. Herein, the synergic application of low salinity water and a cationic gemini surfactant was investigated in a carbonate rock. Firstly, the interfacial tension (IFT) of the oil-brine interface with surfactant at various temperatures was measured. Subsequently, the rock wettability was determined under high-pressure and high-temperature conditions. Finally, the study examined the impact of low salinity water on the adsorption of the cationic gemini surfactant, both statically and dynamically. The results showed that the low salinity water condition does not cause a significant impact on the IFT reduction and wettability alteration as compared to the high salinity water conditions. However, the low salinity water condition reduced the surfactant's static adsorption on the carbonate core by four folds as compared to seawater. The core flood results showed a significantly lower amount of dynamic adsorption (0.11 mg/g-rock) using low salinity water conditions. Employing such a method aids industrialists and researchers in developing a cost-effective and efficient cEOR process.

Oil-Tolerant Nonionic Worm-like Micellar Solution.

The goal of this work is to study the effect of crude oil on worm-like micelles and identify any oil-tolerant systems. A new class of nonionic surfactants was synthesized that forms viscous worm-like micelles under a wide range of temperature and salinity conditions. Aqueous stability, rheology, cryogenic transmission electron microscopy imaging, and dynamic-light-scattering measurements were performed to understand properties, shape, and size of the micelles formed using these surfactants under different temperatures and salinity conditions and in the presence of hydrocarbons. These micellar solutions maintained high viscosity in the presence of small amounts (up to 8 vol %) of crude oils and pure hydrocarbons. Similar experiments were performed with conventional surfactant systems that were known to form worm-like micelles; they did not show oil tolerance. Larger alkanes and viscous crude oils affect the viscosity and transformation of cylindrical micelles less. These new surfactants are useful for oil and gas operations such as hydraulic fracturing, conformance control, and mobility control as they form viscous worm-like micelles in the presence of small amounts of crude oils.

Recent Advances Incorporating Superparamagnetic Nanoparticles into Immunoassays.

Superparamagnetic nanoparticles (SPMNPs) have attracted interest for various biomedical applications due to their unique magnetic behavior, excellent biocompatibility, easy surface modification, and low cost. Their unique magnetic properties, superparamagnetism, and magnetophoretic mobility have led to their inclusion in immunoassays to enhance biosensor sensitivity and allow for rapid detection of various analytes. In this review, we describe SPMNP characteristics valuable for incorporation into biosensors, including the use of SPMNPs to increase detection capabilities of surface plasmon resonance and giant magneto-resistive biosensors. The current status of SPMNP-based immunoassays to improve the sensitivity of rapid diagnostic tests is reviewed, and suggested strategies for the successful adoption of SPMNPs for immunoassays are presented.

Evolutionary adaptations of biofilms infecting cystic fibrosis lungs promote mechanical toughness by adjusting polysaccharide production.

Biofilms are communities of microbes embedded in a matrix of extracellular polymeric substances, largely polysaccharides. Multiple types of extracellular polymeric substances can be produced by a single bacterial strain. The distinct polymer components of biofilms are known to provide chemical protection, but little is known about how distinct extracellular polysaccharides may also protect biofilms against mechanical stresses such as shear or phagocytic engulfment. Decades-long infections of Pseudomonas. aeruginosa biofilms in the lungs of cystic fibrosis patients are natural models for studies of biofilm fitness under pressure from antibiotics and the immune system. In cystic fibrosis infections, production of the extracellular polysaccharide alginate has long been known to increase with time and to chemically protect biofilms. More recently, it is being recognized that chronic cystic fibrosis infections also evolve to increase production of another extracellular polysaccharide, Psl; much less is known about Psl's protective benefits to biofilms. We use oscillatory bulk rheology, on biofilms grown from longitudinal clinical isolates and from genetically-manipulated lab strains, to show that increased Psl stiffens biofilms and increases biofilm toughness, which is the energy cost to cause the biofilm to yield mechanically. Further, atomic force microscopy measurements reveal greater intercellular cohesion for higher Psl expression. Of the three types of extracellular polysaccharides produced by P. aeruginosa, only Psl increases the stiffness. Stiffening by Psl requires CdrA, a protein that binds to mannose groups on Psl and is a likely cross-linker for the Psl components of the biofilm matrix. We compare the elastic moduli of biofilms to the estimated stresses exerted by neutrophils during phagocytosis, and infer that increased Psl could confer a mechanical protection against phagocytic clearance.

Mass transfer of volatile organic carbons through aqueous foams.

A model is developed to study diffusive mass transfer of hydrocarbon vapor through a flexible foam blanket. The model accounts for the diffusion of hydrocarbon vapor through gas-phase and liquid lamellae, the combined gravity and capillary drainage from the plateau border, the thinning of foam lamellae caused by the forces of capillary suction, London-van der Waals attraction, and electrostatic double-layer repulsion, and foam collapse. Uniform bubble size is assumed, and hence, interbubble gas diffusion arising out of variation in bubble sizes alone is not incorporated into the model. A high-stability aqueous foam formulation that remains stable in the presence of oil (hexane) at foam-oil contact was developed using surfactants, stabilizers, and viscosifiers. Emission of hexane vapor through the foam was measured. The model predicts that the initially taller foam columns collapse faster. Their mass-transfer resistance is higher before the onset of collapse but not very different from that of the shorter foam columns at long times. If the solubility and diffusivity of the hexane gas in the foam liquid are unaffected, the foams with higher viscosities persist longer and provide greater diffusive mass-transfer resistance. Foam bubble size does not significantly impact the mass-transfer resistance of the foam column before the onset of foam collapse. However, the foams with smaller bubbles collapse earlier, and their ability to act as a mass-transfer barrier to the diffusing hydrocarbon vapor diminishes rapidly. The experimental results compared reasonably with the model for varying initial foam heights and bubble sizes.

Extension of the dielectric breakdown model for simulation of viscous fingering at finite viscosity ratios.

Immiscible displacement of viscous oil by water in a petroleum reservoir is often hydrodynamically unstable. Due to similarities between the physics of dielectric breakdown and immiscible flow in porous media, we extend the existing dielectric breakdown model to simulate viscous fingering patterns for a wide range of viscosity ratios (µ(r)). At low values of power-law index η, the system behaves like a stable Eden growth model and as the value of η is increased to unity, diffusion limited aggregation-like fractals appear. This model is compared with our two-dimensional (2D) experiments to develop a correlation between the viscosity ratio and the power index, i.e., η = 10(-5)µ(r)(0.8775). The 2D and three-dimensional (3D) simulation data appear scalable. The fingering pattern in 3D simulations at finite viscosity ratios appear qualitatively similar to the few experimental results published in the literature.

Evaluation of asymmetric liposomal nanoparticles for encapsulation of polynucleotides.

Conventional lipid bilayer liposomes have similar inner and outer leaflet compositions; asymmetric liposomes have different lipid leaflet compositions. The goal of this work is to place cationic lipids in the inner leaflet to encapsulate negatively charged polynucleotides and to place neutral/anionic lipids on the outer leaflet to decrease nonspecific cellular uptake/toxicity. Inverse emulsion particles have been developed with a single lipid leaflet of cationic and neutral lipids surrounding an aqueous core containing a negatively charged 21-mer DNA oligo. The particles are accelerated through an oil-water interface, entrapping a second neutral lipid to form oligo encapsulated unilamellar liposome nanoparticles. Inverse emulsion particles can be consistently produced to encapsulate an aqueous environment containing negatively charged oligo. The efficiency of encapsulated liposome formation is low and depends on the hydrocarbon used as the oil phase. Dodecane, mineral oil, and squalene were tested, and squalene, a branched hydrocarbon, yielded the highest efficiency.

Novel aqueous foams for suppressing VOC emission.

Reducing volatile organic compound (VOC) emissions from crude oil/gasoline distribution and storage facilities is important in controlling environmental pollution and enhancing workplace safety. Stable aqueous foam formulations are developed to provide a mass transfer barrier to the emission of VOCs during loading of gasoline. Experiments are carried out in a bench-scale foam cell using liquid hexane as oil. The foam columns of 32 cm in height were able to suppress the plateau concentration of hexane vapors in the effluent by 87% under experimental conditions tested. Vapor suppression increased with foam height but was almost insensitive to liquid viscosity. These experiments are then upscaled from bench-scale to a vessel having an exposed surface area of roughly 2 orders of magnitude higher. Gasoline is used as oil in the upscaled experiments, and the concentrations of volatile hydrocarbons in the effluent are measured during oil loading. A 40-cm-thick foam column is found to reduce the emissions by 96% for foams prepared with deionized water and by 93.8% for foams prepared with 3.5 wt % NaCl brine for 10 h of oil loading.

Model for bone strength and osteoporotic fractures.

Inner porous regions play a critical role in the load bearing capability of large bones. We show that an extension of disordered elastic networks [Chung et al., Phys. Rev. B 54, 15 094 (1996)] exhibits analogs of several known mechanical features of bone. The "stress backbones" and histograms of stress distributions for healthy and weak networks are shown to be qualitatively different. A hereto untested relationship between bone density and bone strength is presented.