Antivesiculation and Complete Unbinding of Tail-Tethered Lipids.

We report the effect of tail-tethering on vesiculation and complete unbinding of bilayered membranes. Amphiphilic molecules of a bolalipid, resembling the tail-tethered molecular structure of archaeal lipids, with two identical zwitterionic phosphatidylcholine headgroups self-assemble into a large flat lamellar membrane, in contrast to the multilamellar vesicles (MLVs) observed in its counterpart, monopolar nontethered zwitterionic lipids. The antivesiculation is confirmed by small-angle X-ray scattering (SAXS) and cryogenic transmission electron microscopy (cyro-TEM). With the net charge of zero and higher bending rigidity of the membrane (confirmed by neutron spin echo (NSE) spectroscopy), the current membrane theory would predict that membranes should stack with each other (aka "bind") due to dominant van der Waals attraction, while the outcome of the nonstacking ("unbinding") membrane suggests that the theory needs to include entropic contribution for the nonvesicular structures. This report pioneers an understanding of how the tail-tethering of amphiphiles affects the structure, enabling better control over the final nanoscale morphology.

Uncovering the Optimal Molecular Characteristics of Hydrophobe-Containing Polypeptoids to Induce Liposome or Cell Membrane Fragmentation.

Cellular functions of membrane proteins are strongly coupled to their structures and aggregation states in the cellular membrane. Molecular agents that can induce the fragmentation of lipid membranes are highly sought after as they are potentially useful for extracting membrane proteins in their native lipid environment. Toward this goal, we investigated the fragmentation of synthetic liposome using hydrophobe-containing polypeptoids (HCPs), a class of facially amphiphilic pseudo-peptidic polymers. A series of HCPs with varying chain lengths and hydrophobicities have been designed and synthesized. The effects of polymer molecular characteristics on liposome fragmentation are systemically investigated by a combination of light scattering (SLS/DLS) and transmission electron microscopy (cryo-TEM and negative stained TEM) methods. We demonstrate that HCPs with a sufficient chain length (DPn ≈ 100) and intermediate hydrophobicity (PNDG mol % = 27%) can most effectively induce the fragmentation of liposomes into colloidally stable nanoscale HCP-lipid complexes owing to the high density of local hydrophobic contact between the HCP polymers and lipid membranes. The HCPs can also effectively induce the fragmentation of bacterial lipid-derived liposomes and erythrocyte ghost cells (i.e., empty erythrocytes) to form nanostructures, highlighting the potential of HCPs as novel macromolecular surfactants toward the application of membrane protein extraction.

Aggregation-Enhanced Photoluminescence and Photoacoustics of Atomically Precise Gold Nanoclusters in Lipid Nanodiscs (NANO2).

The authors designed a structurally stable nano-in-nano (NANO2) system highly capable of bioimaging via an aggregation-enhanced NIR excited emission and photoacoustic response achieved based on atomically precise gold nanoclusters protected by linear thiolated ligands [Au25(SC n H2n+1)18, n = 4-16] encapsulated in discoidal phospholipid bicelles through a one-pot synthesis. The detailed morphological characterization of NANO2 is conducted using cryogenic transmission electron microscopy, small/wide angle X-ray scattering with the support of molecular dynamics simulations, providing information on the location of Au nanoclusters in NANO2. The photoluminescence observed for NANO2 is 20-60 times more intense than that of the free Au nanoclusters, with both excitation and emission wavelengths in the near-infrared range, and the photoacoustic signal is more than tripled. The authors attribute this newly discovered aggregation-enhanced photoluminescence and photoacoustic signals to the restriction of intramolecular motion of the clusters' ligands. With the advantages of biocompatibility and high cellular uptake, NANO2 is potentially applicable for both in vitro and in vivo imaging, as the authors demonstrate with NIR excited emission from in vitro A549 human lung and the KB human cervical cancer cells.

Spontaneous Formation of Stable Vesicles and Vesicle Gels in Polar Organic Solvents.

The self-assembly of lipids into nanoscale vesicles (liposomes) is routinely accomplished in water. However, reports of similar vesicles in polar organic solvents like glycerol, formamide, and ethylene glycol (EG) are scarce. Here, we demonstrate the formation of nanoscale vesicles in glycerol, formamide, and EG using the common phospholipid lecithin (derived from soy). The samples we study are simple binary mixtures of lecithin and the solvent, with no additional cosurfactants or salt. Lecithin dissolves readily in the solvents and spontaneously gives rise to viscous fluids at low lipid concentrations (∼2-4%), with structures ∼200 nm detected by dynamic light scattering. At higher concentrations (>10%), lecithin forms clear gels that are strongly birefringent at rest. Dynamic rheology confirms the elastic response of gels, with their elastic modulus being ∼20 Pa at ∼10% lipid. Images from cryo-scanning electron microscopy (cryo-SEM) indicate that concentrated samples are "vesicle gels," where multilamellar vesicles (MLVs, also called "onions"), with diameters between 50 and 600 nm, are close-packed across the sample volume. This structure can explain both the elastic rheology as well as the static birefringence of the samples. The discovery of vesicles and vesicle gels in polar solvents widens the scope of systems that can be created by self-assembly. Interestingly, it is much easier to form vesicles in polar solvents than in water, and the former are stable indefinitely, whereas the latter tend to aggregate or coalesce over time. The stability is attributed to refractive index-matching between lipid bilayers and the solvents, i.e., these vesicles are relatively "invisible" and thus experience only weak attractions. The ability to use lipids (which are "green" or eco-friendly molecules derived from renewable natural sources) to thicken and form gels in polar solvents could also prove useful in a variety of areas, including cosmetics, pharmaceuticals, and lubricants.

Using Microemulsion Phase Behavior as a Predictive Model for Lecithin-Tween 80 Marine Oil Dispersant Effectiveness.

Marine oil dispersants typically contain blends of surfactants dissolved in solvents. When introduced to the crude oil-seawater interface, dispersants facilitate the breakup of crude oil into droplets that can disperse in the water column. Recently, questions about the environmental persistence and toxicity of commercial dispersants have led to the development of "greener" dispersants consisting solely of food-grade surfactants such as l-α-phosphatidylcholine (lecithin, L) and polyoxyethylenated sorbitan monooleate (Tween 80, T). Individually, neither L nor T is effective at dispersing crude oil, but mixtures of the two (LT blends) work synergistically to ensure effective dispersion. The reasons for this synergy remain unexplained. More broadly, an unresolved challenge is to be able to predict whether a given surfactant (or a blend) can serve as an effective dispersant. Herein, we investigate whether the LT dispersant effectiveness can be correlated with thermodynamic phase behavior in model systems. Specifically, we study ternary "DOW" systems comprising LT dispersant (D) + a model oil (hexadecane, O) + synthetic seawater (W), with the D formulation being systematically varied (across 0:100, 20:80, 40:60, 60:40, 80:20, and 100:0 L:T weight ratios). We find that the most effective LT dispersants (60:40 and 80:20 L:T) induce broad Winsor III microemulsion regions in the DOW phase diagrams (Winsor III implies that the microemulsion coexists with aqueous and oil phases). This correlation is generally consistent with expectations from hydrophilic-lipophilic deviation (HLD) calculations, but specific exceptions are seen. This study then outlines a protocol that allows the phase behavior to be observed on short time scales (ca. hours) and provides a set of guidelines to interpret the results. The complementary use of HLD calculations and the outlined fast protocol are expected to be used as a predictive model for effective dispersant blends, providing a tool to guide the efficient formulation of future marine oil dispersants.

Does the Solvent in a Dispersant Impact the Efficiency of Crude-Oil Dispersion?

Dispersants, used in the mitigation of oil spills, are mixtures of amphiphilic molecules (surfactants) dissolved in a solvent. The recent large-scale use of dispersants has raised environmental concerns regarding the safety of these materials. In response to these concerns, our lab has developed a class of eco-friendly dispersants based on blends of the food-grade surfactants, soy lecithin (L) and Tween 80 (T), in a solvent. We have shown that these "L/T dispersants" are very efficient at dispersing crude oil into seawater. The solvent for dispersants is usually selected based on factors like toxicity, volatility, or viscosity of the overall mixture. However, with regard to the dispersion efficiency of crude oil, the solvent is considered to play a negligible role. In this paper, we re-examine the role of solvent in the L/T system and show that it can actually have a significant impact on the dispersion efficiency. That is, the dispersion efficiency can be altered from poor to excellent simply by varying the solvent while keeping the same blend of surfactants. We devise a systematic procedure for selecting the optimal solvents by utilizing Hansen solubility parameters. The optimal solvents are shown to have a high affinity for crude oil and limited hydrophilicity. Our analysis further enables us to identify solvents that combine high dispersion efficiency, good solubility of the L/T surfactants, a low toxicity profile, and a high flash point.

Thermoresponsive Coatings on Hollow Particles with Mesoporous Shells Serve as Stimuli-Responsive Gates to Species Encapsulation and Release.

Nanoscale capsule-type particles with stimuli-respondent transport of chemical species into and out of the capsule are of significant technological interest. We describe the facile synthesis, properties, and applications of a temperature-responsive silica-poly( N-isopropylacrylamide) (PNIPAM) composite consisting of hollow silica particles with ordered mesoporous shells and a complete PNIPAM coating layer. These composites start with highly monodisperse, hollow mesoporous silica particles fabricated with precision using a template-driven approach. The particles possess a high specific surface area (1771 m2/g) and large interior voids that are accessible to the exterior environment through pore channels of the silica shell. An exterior PNIPAM coating provides thermoresponsiveness to the composite, acting as a gate to regulate the uptake and release of functional molecules. Uptake and release of a model compound (rhodamine B) occurs at temperatures below the lower critical solution temperature (LCST) of 32 °C, while the dehydrated hydrophobic polymer layer collapses over the particle at temperatures above the LCST, leading to a shutoff of uptake and release. These transitions are also manifest at an oil-water interface, where the polymer-coated hollow particles stabilize oil-in-water emulsions at temperatures below the LCST and destabilize the emulsions at temperatures above the LCST. Cryogenic scanning electron microscopy indicates patchlike particle structures at the oil-water interface of the stabilized emulsions. The silica-PNIPAM composite therefore couples advantages from both the hollow mesoporous silica structure and the thermoresponsive polymer.

Amphiphilic Polypeptoids Serve as the Connective Glue to Transform Liposomes into Multilamellar Structures with Closely Spaced Bilayers.

We report the ability of hydrophobically modified polypeptoids (HMPs), which are amphiphilic pseudopeptidic macromolecules, to connect across lipid bilayers and thus form layered structures on liposomes. The HMPs are obtained by attaching hydrophobic decyl groups at random points along the polypeptoid backbone. Although native polypeptoids (with no hydrophobes) have no effect on liposomal structure, the HMPs remodel the unilamellar liposomes into structures with comparable diameters but with multiple concentric bilayers. The transition from single-bilayer to multiple-bilayer structures is revealed by small-angle neutron scattering (SANS) and cryo-transmission electron microscopy (cryo-TEM). The spacing between bilayers is found to be relatively uniform at ∼6.7 nm. We suggest that the amphiphilic nature of the HMPs explains the formation of multibilayered liposomes; i.e., the HMPs insert their hydrophobic tails into adjacent bilayers and thereby serve as the connective glue between bilayers. At higher HMP concentrations, the liposomes are entirely disrupted into much smaller micellelike structures through extensive hydrophobe insertion. Interestingly, these small structures can reattach to fresh unilamellar liposomes and self-assemble to form new two-bilayer liposomes. The two-bilayer liposomes in our study are reminiscent of two-bilayer organelles such as the nucleus in eukaryotic cells. The observations have significance in designing new nanoscale drug delivery carriers with multiple drugs on separate lipid bilayers and extending liposome circulation times with entirely biocompatible materials.

Impact of the Charge Ratio on the In Vivo Immunogenicity of Lipoplexes.

PURPOSE: The present study investigated the immunogenic potential of different cationic liposome formulations with a DNA plasmid encoding Pfs25, a malaria transmission-blocking vaccine candidate. METHODS: Pfs25 plasmid DNA was complexed with cationic liposomes to produce lipoplexes at different charge ratios of the cationic lipid head group to the nucleotide phosphate (N:P). The formation of lipoplexes was visualized by Cryogenic-TEM. Confocal microscopy of lipoplexes formed with GFP encoding plasmid DNA, and flow cytometry was used to determine their in vitro transfection capability. Two different lipoplex formulations using plasmid DNA encoding Pfs25 were evaluated for in vivo immunogenicity after intramuscular administration in Balb/c mice. Immune sera were analyzed by ELISA. RESULTS: The results demonstrated that the cationic liposome-mediated DNA immunization with an N:P charge ratio of 1:3 (anionic lipoplexes) is more effective than the use of naked plasmid DNA alone. No antibody response was observed when lipoplexes with a higher N:P charge ratio of 10:3 (cationic lipoplexes) were used. Trehalose was added to some lipoplex formulations as a cryoprotectant and adjuvant, but it did not yield any further improvement of immunogenicity in vivo. CONCLUSIONS: The results suggest that Pfs25 plasmid DNA delivered as lipoplexes at a charge ratio of 1:3 elicited strong immunogenicity in mice and may be improved further to match the immune responses of DNA vaccines administered by in vivo electroporation.

Aggregation of cyclic polypeptoids bearing zwitterionic end-groups with attractive dipole-dipole and solvophobic interactions: a study by small-angle neutron scattering and molecular dynamics simulation.

Aggregation behavior of cyclic polypeptoids bearing zwitterionic end-groups in methanol has been studied using a combination of experimental and simulation techniques. The data from SANS and cryo-TEM indicate that the solution contains small clusters of these cyclic polypeptoids, ranging from a single polypeptoid chain to small oligomers, while the linear counterpart shows no cluster formation. Atomistic molecular dynamics simulations reveal that the driving force for this clustering behavior is due to the interplay between the effective repulsion due to the solvation of the dipoles formed by the charged end-groups in each polypeptoid chain and the attractive forces due to dipole-dipole interactions and the solvophobic effect.

Ablative Focused Ultrasound Synergistically Enhances Thermally Triggered Chemotherapy for Prostate Cancer in Vitro.

High-intensity focused ultrasound (HIFU) can locally ablate biological tissues such as tumors, i.e., induce their rapid heating and coagulative necrosis without causing damage to surrounding healthy structures. It is widely used in clinical practice for minimally invasive treatment of prostate cancer. Nonablative, low-power HIFU was established as a promising tool for triggering the release of chemotherapeutic drugs from temperature-sensitive liposomes (TSLs). In this study, we combine ablative HIFU and thermally triggered chemotherapy to address the lack of safe and effective treatment options for elderly patients with high-risk localized prostate cancer. DU145 prostate cancer cells were exposed to chemotherapy (free and liposomal Sorafenib) and ablative HIFU, alone or in combination. Prior to cell viability assessment by trypan blue exclusion and flow cytometry, the uptake of TSLs by DU145 cells was verified by confocal microscopy and cryogenic scanning electron microscopy (cryo-SEM). The combination of TSLs encapsulating 10 µM Sorafenib and 8.7W HIFU resulted in a viability of less than 10% at 72 h post-treatment, which was significant less than the viability of the cells treated with free Sorafenib (76%), Sorafenib-loaded TSLs (63%), or HIFU alone (44%). This synergy was not observed on cells treated with Sorafenib-loaded nontemperature sensitive liposomes and HIFU. According to cryo-SEM analysis, cells exposed to ablative HIFU exhibited significant mechanical disruption. Water bath immersion experiments also showed an important role of mechanical effects in the synergistic enhancement of TSL-mediated chemotherapy by ablative HIFU. This combination therapy can be an effective strategy for treatment of geriatric prostate cancer patients.

Hydrogel Inverse Replicas of Breath Figures Exhibit Superoleophobicity Due to Patterned Surface Roughness.

The wetting behavior of a surface depends on both its surface chemistry and the characteristics of surface morphology and topography. Adding structure to a flat hydrophobic or oleophobic surface increases the effective contact angle and thus the hydrophobicity or oleophobicity of the surface, as exemplified by the lotus leaf analogy. We describe a simple strategy to introduce micropatterned roughness on surfaces of soft materials, utilizing the template of hexagonally packed pores of breath figures as molds. The generated inverse replicas represent micron scale patterned beadlike protrusions on hydrogel surfaces. This added roughness imparts superoleophobic properties (contact angle of the order of 150° and greater) to an inherently oleophobic flat hydrogel surface, when submerged. The introduced pattern on the hydrogel surface changes morphology as it swells in water to resemble morphologies remarkably analogous to the compound eye. Analysis of the wetting behavior using the Cassie-Baxter approximation leads to estimation of the contact angle in the superoleophobic regime and in agreement with the experimental value.

Tuning the Wettability of Halloysite Clay Nanotubes by Surface Carbonization for Optimal Emulsion Stabilization.

The carbonization of hydrophilic particle surfaces provides an effective route for tuning particle wettability in the preparation of particle-stabilized emulsions. The wettability of naturally occurring halloysite clay nanotubes (HNT) is successfully tuned by the selective carbonization of the negatively charged external HNT surface. The positively charge chitosan biopolymer binds to the negatively charged external HNT surface by electrostatic attraction and hydrogen bonding, yielding carbonized halloysite nanotubes (CHNT) on pyrolysis in an inert atmosphere. Relative to the native HNT, the oil emulsification ability of the CHNT at intermediate levels of carbonization is significantly enhanced due to the thermodynamically more favorable attachment of the particles at the oil-water interface. Cryogenic scanning electron microscopy (cryo-SEM) imaging reveals that networks of CHNT attach to the oil-water interface with the particles in a side-on orientation. The concepts advanced here can be extended to other inorganic solids and carbon sources for the optimal design of particle-stabilized emulsions.

An effective dispersant for oil spills based on food-grade amphiphiles.

Synthetic dispersants such as Corexit 9500A were used in large quantities (∼2 million gallons) to disperse the oil spilled in the ocean during the recent Deepwater Horizon event. These dispersant formulations contain a blend of surfactants in a base of organic solvent. Some concerns have been raised regarding the aquatic toxicity and environmental impact of these formulations. In an effort to create a safer dispersant, we have examined the ability of food-grade amphiphiles to disperse (emulsify) crude oil in seawater. Our studies show that an effective emulsifier is obtained by combining two such amphiphiles: lecithin (L), a phospholipid extracted from soybeans, and Tween 80 (T), a surfactant used in many food products including ice cream. Interestingly, we find that L/T blends show a synergistic effect, i.e., their combination is an effective emulsifier, but neither L or T is effective on its own. This synergy is maximized at a 60/40 weight ratio of L/T and is attributed to the following reasons: (i) L and T pack closely at the oil-water interface; (ii) L has a low tendency to desorb, which fortifies the interfacial film; and (iii) the large headgroup of T provides steric repulsions between the oil droplets and prevents their coalescence. A comparison of L/T with Corexit 9500A shows that the former leads to smaller oil droplets that remain stable to coalescence for a much longer time. The smaller size and stability of crude oil droplets are believed to be important to their dispersion and eventual microbial degradation in the ocean. Our findings suggest that L/T blends could potentially be a viable alternative for the dispersion of oil spills.

Release of surfactant cargo from interfacially-active halloysite clay nanotubes for oil spill remediation.

Naturally occurring halloysite clay nanotubes are effective in stabilizing oil-in-water emulsions and can serve as interfacially-active vehicles for delivering oil spill treating agents. Halloysite nanotubes adsorb at the oil-water interface and stabilize oil-in-water emulsions that are stable for months. Cryo-scanning electron microscopy (Cryo-SEM) imaging of the oil-in-water emulsions shows that these nanotubes assemble in a side-on orientation at the oil-water interface and form networks on the interface through end-to-end linkages. For application in the treatment of marine oil spills, halloysite nanotubes were successfully loaded with surfactants and utilized as an interfacially-active vehicle for the delivery of surfactant cargo. The adsorption of surfactant molecules at the interface serves to lower the interfacial tension while the adsorption of particles provides a steric barrier to drop coalescence. Pendant drop tensiometry was used to characterize the dynamic reduction in interfacial tension resulting from the release of dioctyl sulfosuccinate sodium salt (DOSS) from halloysite nanotubes. At appropriate surfactant compositions and loadings in halloysite nanotubes, the crude oil-saline water interfacial tension is effectively lowered to levels appropriate for the dispersion of oil. This work indicates a novel concept of integrating particle stabilization of emulsions together with the release of chemical surfactants from the particles for the development of an alternative, cheaper, and environmentally-benign technology for oil spill remediation.

The response of carbon black stabilized oil-in-water emulsions to the addition of surfactant solutions.

We use carboxyl-terminated, negatively charged, carbon black (CB) particles suspended in water to create CB-stabilized octane-in-water emulsions, and examine the consequences of adding aqueous anionic (SOS, SDS), cationic (OTAB, DTAB), and nonionic (Triton X-100) surfactant solutions to these emulsions. Depending upon the amphiphile's interaction with particles, interfacial activity, and bulk concentration, some CB particles get displaced from the octane-water interfaces and are replaced by surfactants. The emulsions remain stable through this exchange. Particles leave the octane-water interfaces by two distinct modes that depend on the nature of particle-surfactant interactions. Both happen over time scales of the order of seconds. For anionic and nonionic surfactants that bind to the CB through hydrophobic interactions, individual particles or small agglomerates stream away steadily from the interface. Cationic surfactants bind strongly to the carboxylate groups, reduce the magnitude of the surface potential, and cause the CB particles to agglomerate into easily visible chunks at the droplet interfaces. These chunks then leave the interfaces at discrete intervals, rather than in a steady stream. For the longer chain cationic surfactant, DTAB, the particle ejection mode reverts back to a steady stream as the concentration is increased beyond a threshold. This change from chunks of particles leaving intermittently to steady streaming is because of the formation of a surfactant bilayer on the particles that reverses the particle surface charge and makes them highly hydrophilic. The charge reversal also suppresses agglomeration. Zeta potentials of CB particles measured after exposure to surfactant solutions support this hypothesis. These results are the first systematic observations of different particle release modes from oil-water interfaces produced by variations in interactions between surfactants and particles. They can be generalized to other particle-surfactant systems and exploited for materials synthesis.

Superparamagnetic iron oxide nanoparticles with variable size and an iron oxidation state as prospective imaging agents.

Magnetite nanoparticles in the size range of 3.2-7.5 nm were synthesized in high yields under variable reaction conditions using high-temperature hydrolysis of the precursor iron(II) and iron(III) alkoxides in diethylene glycol solution. The average sizes of the particles were adjusted by changing the reaction temperature and time and by using a sequential growth technique. To obtain γ-iron(III) oxide particles in the same range of sizes, magnetite particles were oxidized with dry oxygen in diethylene glycol at room temperature. The products were characterized by DLS, TEM, X-ray powder diffractometry, TGA, chemical analysis, and magnetic measurements. NMR r(1) and r(2) relaxivity measurements in water and diethylene glycol (for OH and CH(2) protons) have shown a decrease in the r(2)/r(1) ratio with the particle size reduction, which correlates with the results of magnetic measurements on magnetite nanoparticles. Saturation magnetization of the oxidized particles was found to be 20% lower than that for Fe(3)O(4) with the same particle size, but their r(1) relaxivities are similar. Because the oxidation of magnetite is spontaneous under ambient conditions, it was important to learn that the oxidation product has no disadvantages as compared to its precursor and therefore may be a better prospective imaging agent because of its chemical stability.

Design of Nanostraws in Amine-Functionalized MCM-41 for Improved Adsorption Capacity in Carbon Capture.

Polymeric amine encapsulation in high surface area MCM-41 particles for CO2 capture is well established but has the drawback of leaching out the water-soluble polymer upon exposure to aqueous environments. Alternatively, chemical (covalent) grafting amine functional groups from an alkoxysilane such as 3-aminopropyltriethoxysilane (APTES) on MCM-41 offer better stability against this drawback. However, the diffusional restriction exhibited by the narrow uniform MCM-41 pores (2-4 nm) may impede amine functionalization of the available silanol groups within the inner mesoporous core. This leads to incomplete amine functionalization and could reduce the CO2 adsorption capacity in such materials. Our concept to improve access to the MCM-41 interior is based on the incorporation of nanostraws with larger inner diameter (15-30 nm) to create a hierarchical porosity and enhance the molecular transport of APTES. Halloysite nanotubes (HNT) are used as tubular straws that are integrated into the MCM-41 matrix using an aerosol-assisted synthesis method. Characterization results show that the intrinsic structure of MCM-41 remains unaltered after the incorporation of the nanostraws and amine functionalization. At an optimal APTES loading of 0.5 g (X = 2.0), the amine-functionalized composite of MCM-41 with straws (APTES/M40H) has a 20% higher adsorption capacity than the amine-modified MCM-41 (APTES/MCM-41) adsorbent. Furthermore, the CO2 adsorption capacity APTES/M40H doubles that of APTES/MCM-41 when normalized based on the composition of MCM-41 in the composite particle with straws. The facile integration of nanostraws in MCM-41 leading to hierarchical porosities could be effective toward the mitigation of diffusional restriction in porous materials with potential for other catalytic and adsorption technologies.

Lubrication mechanisms of dispersed carbon microspheres in boundary through hydrodynamic lubrication regimes.

HYPOTHESIS: Carbon microspheres have been shown to reduce friction and surface wear at relatively low speeds and high applied loads (i.e., within the boundary lubrication regime). We hypothesize that in dilute colloidal lubricating systems there is an interplay between the size of the carbon microspheres and the lubrication gap size, which determines the dominant lubricating mechanism of the system. EXPERIMENTS: A 60 wt% aqueous glycerol solution was used as the base lubricant and compared to various carbon particle-based lubricant formulations ranging in particle concentrations from 0.05 to 0.30 vol%. The tribological properties of the various lubricant formulations were tested on a pin-on-disk tribometer. A simplified Stribeck plot was produced to understand the changing mechanism of lubrication over a wide range of conditions. FINDINGS: The Stribeck curves show that the carbon microspheres assist lubrication by a rolling mechanism primarily in the boundary lubrication regime. A 0.20 vol% carbon-based lubricant formulation showed the best friction reduction compared to the base lubricant. Increasing speed increases the lubricating gap between the friction pair beyond the size of the particles, thereby nullifying the rolling mechanism of the particles. We introduce a modified specific film thickness parameter to determine the lubrication regime in a particle-lubricant system.

Water-in-trichloroethylene emulsions stabilized by uniform carbon microspheres.

Uniform hard carbon spheres (HCS), synthesized by the hydrothermal decomposition of sucrose followed by pyrolysis, are effective at stabilizing water-in-trichloroethylene (TCE) emulsions. The irreversible adsorption of carbon particles at the TCE-water interface resulting in the formation of a monolayer around the water droplet in the emulsion phase is identified as the key reason for emulsion stability. Cryogenic scanning electron microscopy was used to image the assembly of carbon particles clearly at the TCE-water interface and the formation of bilayers in regions of droplet-droplet contact. The results of this study have potential implications to the subsurface injection of carbon submicrometer particles containing zero-valent iron nanoparticles to treat pools of chlorinated hydrocarbons that are sequestered in fractured bedrock.