Hierarchically Structured Porous Silica Spheres by Microemulsion/Vesicle Templating for Hydrodesulfurization of Fluid Catalytic Cracking Diesel

A series of hierarchically structured porous silica sphere (HSPSS) materials are successfully fabricated by a facile, one‐step microemulsion/vesicle bimodal method in a multicomponent microemulsion system of P123/n‐butanol/1,3,5‐trimethylbenzene/KCl/H₂O (surfactant/cosurfactant/oil/salt/water). The pore structures of the obtained HSPSS products consist of mesocellular foam and mesostructured vesicles. In contrast to the traditional porous silica materials the new structures combine two separate, distinct mesophases with different‐sized mesovoids in a single porous sphere. Moreover, the proportion of every mesophase in obtained HSPSS can be easily adjusted by tuning the initially added amount of n‐butanol or KCl in this multicomponent microemulsion system. When the molar ratio of KCl/tetraethoxysilane is 2.15, the obtained HSPSS material is turned into uniform mesostructured vesicle silica spheres, which consist of many small diameter vesicle particles. The hydrodesulfurization (HDS) activity of fluid catalytic cracking diesel over the HSPSS was tested. HSPSS‐0.75‐1.43 catalyst support with multiple mesoporous structures shows the highest HDS efficiency (98.5%) among all the studied catalysts.     

Probing organization and communication at layered interfaces

We have investigated the local organization intrinsic to a variety of interfacial structures, by both electrochemical and spectroscopic means. Our focus has been on the design and construction of biomimetic interfaces, where a lipid bilayer or a hybrid bilayer membrane can be bound to an interface. The goal of this work is ultimately to create an interface on a transducer surface that can support an enzyme in its active form. To this point, we have examined the extent of organization that is achievable in monolayers that will be used to bind bilayer structures to a transducer surface. Our electrochemical data point to the important role of the substrate surface in determining adlayer organization. We have also investigated the fluidity and structural heterogeneity of lipid bilayers using time-resolved and steady state fluorescence spectroscopy. Our data point to the highly interactive nature of lipid bilayer constituents, where perturbations introduced to one region have significant consequences on other regions of the bilayer. Such information is directly relevant to the existence and properties of lipid raft structures in both model and biological bilayers.     

Ca2+- and ba2+-ligand coordinated unilamellar, multilamellar, and oligovesicular vesicles

Ca(2+)- and Ba(2+)-coordinated vesicle phases were prepared in mixed aqueous solutions of tetradecyldimethylamine oxide (C(14)DMAO) and calcium oleate (Ca(OA)(2)) or barium oleate (Ba(OA)(2)). At the right mixing ratios, metal-ligand coordination between Ca(OA)(2) or Ba(OA)(2) and C(14)DMAO results in the formation of molecular bilayers due to the reduction in area per head group. Ca(2+) and Ba(2+) tightly associate to the head groups of surfactants and in this system the bilayer membranes are not shielded by excess salts. The structures of the birefringent samples of the Ca(OA)(2)/C(14)DMAO/H(2)O and Ba(OA)(2)/C(14)DMAO/H(2)O systems were determined by freeze-fracture transmission electron microscopy (FF-TEM), small-angle X-ray scattering (SAXS), and rheological measurements to consist of unilamellar, multilamellar, and oligovesicular vesicles. The coordination between C(14)DMAO and Ba(OA)(2) or Ca(OA)(2) plays an important role in the formation of the vesicles, which was easily confirmed by studying the phase behavior of the KOA/C(14)DMAO/H(2)O system in which only the L(1) phase forms, due to the absence of coordination between KOA and C(14)DMAO. A mechanism is proposed that accounts for the formation of these new metal-ligand coordinated vesicles.     

Design of original bioactive formulations based on sugar-surfactant/non-steroidal anti-inflammatory catanionic self-assemblies: a new way of dermal drug delivery

A new kind of catanionic assembly was developed that associates a sugar-based surfactant with a non-steroidal anti-inflammatory drug (NSAID). Three different assemblies using indomethacin, ibuprofen and ketoprofen as NSAIDs were easily obtained in water by an acid-base reaction. These assemblies formed new amphiphilic entities because of electrostatic and hydrophobic effects in water and led to the spontaneous formation of vesicles. These catanionic vesicles were then tested as potential NSAID delivery systems for dermatological application. The anti-inflammatory activity was evaluated in vivo, and this study clearly showed an improved therapeutic effect for NSAIDs that were formulated as catanionic vesicles. These vesicles ensured a slower diffusion of the NSAID through the skin. This release probably increased the time of retention of the NSAID in the targeted strata of the skin. Thus, the present study suggests that this catanionic bioactive formulation could be a promising dermal delivery system for NSAIDs in the course of skin inflammation treatment.     

Lamellar-to-nematic phase transition in a lipid-surfactant mixture

A lyotropic system, consisting of a lecithin (DMPC) and a non-ionic surfactant (C₁₂E₅) in water was studied. The system exhibits a lamellar-to-nematic phase transition. The nematic phase appears as the temperature is decreased and only exists in a very limited temperature and concentration range, for specific lipid-to-surfactant ratios. While a lamellar phase is found at higher temperatures in both mixed and pure C₁₂E₅ systems, the transition to the nematic phase at lower temperatures coincides with a micellar phase in the pure C₁₂E₅ system. The transition appears to be driven by the strong temperature dependence of the surfactant film spontaneous curvature. The structural properties of the lamellar phase close to the lamellar-to-nematic boundary have been studied by polarised light microscopy and small-angle neutron and X-ray scattering experiments. The signature of a helical defect with Burgers vector of magnitude 2 is apparent in our data, close to the lamellar-to-nematic phase transition. The proliferation of screw dislocations in the lamellar phase might be a plausible mechanism for driving this transition. Received 6 July 1999 and Received in final form 17 April 2000     

Interactions between charged rods near salty surfaces

Using both theoretical modeling and computer simulations we study a model system for DNA interactions in the vicinity of charged membranes. We focus on the polarization of the mobile charges in the membranes due to the nearby charged rods (DNA) and the resulting screening of their fields and inter-rod interactions. We find, both within a Debye-Hückel model and in Brownian dynamics simulations, that the confinement of the mobile charges to the surface leads to a qualitative reduction in their ability to screen the charged rods to the degree that the fields and resulting interactions are not finite-ranged as in systems including a bulk salt concentration, but rather decay algebraically and the screening effect is more like an effective increase in the multipole moment of the charged rod. Received 28 September 1999     

Spontaneously Forming Unilamellar Phospholipid Vesicles

Unilamellar vesicles (ULV) consisting of a single lipid bilayer are of special interest as drug delivery vehicles. Here, we report on a spontaneously forming ULV system composed of the short- and long-chain phospholipids, dihexanoyl (DHPC) and dimyristoyl (DMPC) phosphorylcholine, respectively, doped with the negatively charged lipid, dimyristoyl phosphorylglycerol (DMPG). Small-angle neutron scattering (SANS) and dynamic light scattering (DLS) were employed to systematically investigate the effects of lipid concentration, salinity, and time on vesicle stability. It is found that ULV size is practically constant over a range of lipid concentration and temperature. The spontaneously formed ULV are stable for periods of four months, or greater, without the use of stabilizers.     

Synthesis,Characterization and Self‐Assembly of Novel Amphiphilic Block Copolymers with a Polyhedral Oligomeric Silsesquioxanes Moiety Attached at the Junction of the Two Blocks

A novel well‐defined amphiphilic block copolymer, with the polyhedral oligomeric silsesquioxane (POSS) moiety at the junction of the two blocks of polystyrene and poly(ethylene oxide) (PEO), was designed and synthesized. First, a macroinitiator containing a POSS moiety and a PEO chain was prepared and then atom transfer radical polymerization of styrene was carried out in the presence of the macroinitiator in bulk. The polymerization results show that the process bears the characteristics of controlled/living free radical polymerizations. The structure and molecular weight of the polymers were characterized by GPC, ¹H NMR, and FT‐IR spectroscopy. The self‐assembly behaviors of the polymers was investigated by TEM and SEM. It was observed that the polymers can self‐assemble into vesicles in aqueous solution.