Shukun Shen

Liposil-supported lipid bilayers as a hybrid platform for drug delivery

We report a hybrid drug delivery system inspired by the functional compartmentalization of cell, isolating properties of cargo encapsulation, targeting, stability, biocompatibility, and permeability into discrete multilamellar organic-inorganic–organic design consisting of two differently functionalized lipid bilayers sandwiching a nanoporous silica layer.

A green synthesis of CTAB–PTP/PAM microhydrogel and its application in oxidation of DBT

Polyacrylamide (PAM) microgels covered with hexadecyltrimethylammonium (CTAB)-peroxotungstophosphate (PTP) complexes were synthesized and characterized by scanning electron microscopy and Fourier transform infrared. The results indicate the CTAB–PTP/PAM composite microsphere with surface-wrinkling morphology and PAM microgel core/CTAB–PTP shell structure. The surface-wrinkling structure changed with the amount of CTAB–PTP supported on the PAM microgels. The results based on CTAB–PTP/PAM composite microspheres used in oxidation of dibenzothiophene demonstrated that the resulting microspheres have high catalytic performance and could be reused three times with a small decrease in activity. The proposed method is commonly significant for construction of reusable catalyst used in diphase catalysis.

Substituent-Dominated Structure Evolution during Sol−Gel Synthesis: A Comparative Study of Sol−Gel Processing of 3-Glycidoxypropyltrimethoxysilane and Methacryloxypropyltrimethoxysilane

The sol-gel processes of 3-glycidoxypropyltrimethoxysilane (GPTMS) and methacryloxypropyltrimethoxysilane (MAPTMS) have been followed by fluorescence spectroscopy with pyranine as a photophysical probe. The experimental results showed that this probe is sensitive to the structural evolution and microenvironment polarity. The specific comparison of the structural evolution in two substituted organotrialkoxysilanes, namely, MAPTMS and GPTMS, illustrates the ability of the substituents to interact with the microenvironment via electrostatic interactions. Interestingly, these interactions determine the kinds of intermediate supramolecular structures that form during the sol-gel process and hence control the structure of the ensuing sol-gel end product. In particular, the amphiphile-like character of the MAPTMS intermediates contrasts with the biamphiphilic character of their GPTMS counterparts, driving distinctly different transient and local molecular organizations, which in turn modulate the hydrolysis and condensation reactions during the sol-gel process.

Amino Acid Catalyzed Bulk-Phase Gelation of Organoalkoxysilanes via a Transient Co-operative Self-Assembly

We report acceleration in the rate of bulk phase gelation of an organoalkoxysilane, 3-methacryloxypropyltrimethoxysilane (MAPTMS), in the presence of an amphiphilic additive, N-phenyl glycine (NPG). The MAPTMS gelation occurs within 30 min in the presence of 0.5 wt % NPG, which took several months in the absence of NPG. Using a combination of ATR-FT IR, (29)Si NMR, (1)H NMR, viscosity analysis, SEM, UV-vis, and pi-A isotherm measurements, we elucidate the molecular-level details of the structural changes during NPG-catalyzed MPTMS gelation rate. On the basis of these results, we propose a gelation mechanism in which a transient cooperative self-assembly process fosters hydrolysis and retards early condensation thereby promoting the formation of extended three-dimensionally cross-linked gels. Specifically, the amphiphilic character of the hydrolysis product of MAPTMS, consisting of a hydrophobic tail R = -CH(2)CH(2)CH(2)O(CO)C(CH(3)) horizontal lineCH(2) and a hydrophilic Si-OH headgroup, promotes micelle formation at high MAPTMS/water ratio. NPG readily inserts within these micelles thus retarding the topotactic condensation of silanols at the micellar surface. This in turn allows for a more complete hydrolysis of Si-OCH(3) groups prior to condensation in MAPTMS. With increased silanol concentration at the micellar periphery, a delayed condensation phase initiates. This formation of a covalently bonded Si-O-Si framework (and possibly also the formation of the methanol byproduct) likely destabilizes the micellar motif thus promoting its transformation into condensed mesophases (e.g., lamellar microstructure) upon gelation. Because of the generality of this transient and co-operative organic-inorganic self-assembly between hydrolyzed amphiphilic organoalkoxysilanes and surfactant-like amino acid additives, we envisage applications in controlling bulk phase gelation of many chain-substituted organoalkoxysilanes.

A New Route to Liposil Formation by an Interfacial Sol–Gel Process Confined by Lipid Bilayer

We report a new and simple approach to prepare a class of silica-reinforced liposomes with hybrid core-shell nanostructures. The amphiphilic natural structure of lipids was exploited to sequester hydrophobic molecules, namely precursor TEOS and pyrene, in the hydrophobic midplane of liposomal bilayer assemblies in the aqueous phase. Subsequent interfacial hydrolysis of TEOS at the bilayer/water interface and ensuing condensation within the hydrophobic interstices of the lipid bilayer drives silica formation in situ, producing a novel class of silica-lipid hybrid liposils. Structural characterization by scanning- and transmission electron microscopy confirm that the liposils so generated preserve closed topologies and size-monodipersity of the parent lecithin liposomes, and DSC-TGA and XRD measurements provide evidence for the silica coating. Monitoring fluorescence measurements using embedded pyrene yield detailed information on microenvironment changes, which occur during sol-gel process and shed light on the structural evolution during silica formation. We envisage that liposils formed by this simple, new approach, exploiting the hydrophobic core of the lipid bilayer to spatially localize silica-forming precursors enables preparation of stable liposils exhibiting capacity for cargo encapsulation, bicompatibility, and fluorescence monitoring, more generally opening a window for construction of stable, functional hybrid materials.