An investigation of the self-assembly of neutral, interlaced, triple-stranded molecular braids

The synthesis and structures of six compounds prepared in two different systems have been explored with the purpose of isolating coordination polymers with interlaced triple-stranded molecular braid architectures. The dinuclear paddle-wheel units of [Cu(2)(maa)(4)2 H(2)O] can be rationally tuned to form three classes of isomorphous compounds, namely [Cu(2)(maa)(4)(bpp)] (1) (bpp=1,3-bis(4-pyridyl)propane, Hmaa=2-methylacrylic acid), [Cu(3)(maa)(6)(bpp)(2)] (2), and[Cu(4)(maa)(8)(bpp)(4)(H(2)O)(2)]2 H(2)O (3), with a bridging bpp ligand, at controlled ligand-to-metal molar ratios, and lead to three coordination polymers having similar one-dimensional characteristics but different mono- and dinuclear nodes. Compound 1, with a bpp:[Cu(2)(maa)(4)2 H(2)O] stoichiometry of 1:1, contains a zigzag chain containing dinuclear nodes, whereas polymer 2, with a bpp:[Cu(2)(maa)(4)2 H(2)O] stoichiometry of 1.5:1, also adopts the topology of a zigzag chain but with both mono- and dinuclear nodes. Compound 3, with a bpp:[Cu(2)(maa)(4)2 H(2)O] stoichiometry of 2:1, contains a neutral, interlaced, triple-stranded molecular braid, which is interwoven by three single-stranded meso-helical chains that contain only a mononuclear node. With the three aromatic chelating terminal ligands 2,2':6',2'-terpyridine (tpy), 1,10-phenanthroline (phen), and di(2-pyridyl)amine (dpa) we have also prepared three neutral complexes containing the linear, rigid bridging ligand biphenyl-4,4'-dicarboxylate (bpdc), namely [Cd(bpdc)(tpy)]H(2)O (4), [Cu(bpdc)(phen)(2)]4.25 H(2)O (5), and [Cu(bpdc)(dpa)] (6). An infinite meso-helix is formed initially in 4, and then three of these chains assemble into a triple-stranded braid similar to that of 3. Complexes 5 and 6 have a mononuclear and a looped dinuclear structure, respectively. Compounds 3 and 4 are unusual examples of triple-stranded molecular braid coordination frameworks based on different types of co-ligands.     

Preparation and characterization of a novel organic-inorganic nanohybrid "cerasome" formed with a liposomal membrane and silicate surface

A novel class of organic-inorganic hybrids, the so-called cerasomes, which have a bilayer vesicular structure and a silicate surface, has been synthesized by combination of sol-gel reaction and self-assembly of organoalkoxysilanes with a molecular structure analogous to lipids. We have synthesized two cerasome-forming organoalkoxysilanes, N-[N-(3-triethoxysilyl)propylsuccinamoyl]dihexadecylamine (1) and N,N-dihexadecyl-N (alpha)-[6-[(3-triethoxysilyl)propyldimethylammonio]hexanoyl]glycinamide bromide (2), and investigated the synthetic conditions of the cerasomes and their structural characteristics. For the proamphiphilic 1, the cerasome was obtained under restricted pH conditions where acid-catalyzed hydrolysis of the triethoxysilyl moiety proceeded without disturbing the vesicle formation. In contrast, the amphiphilic 2, additionally having a hydrophilic quaternary ammonium group, formed stable dispersions of the cerasome in a wide pH range. The hydrolysis behavior of the triethoxysilyl groups was monitored by (1)H NMR spectroscopy. Morphology of the cerasomes having the liposomal vesicular structure was confirmed by TEM observations. Extent of the development of siloxane networks through condensation among the silanol groups on the cerasome surface was evaluated by using MALDI-TOF-MS spectrometry. Formation of oligomers of the cerasome-forming lipids in the vesicle was clearly confirmed. Due to the siloxane network formation, the cerasome showed remarkably high morphological stability compared with a reference liposome, as evaluated by surfactant dissolution measurements.     

Designed synthesis of nanostructured siloxane-organic hybrids from amphiphilic silicon-based precursors

This paper reports on recent progress in the synthesis of nanostructured siloxane-organic hybrids based on the self-assembly of amphiphilic silicon-based precursors. A variety of ordered hybrid materials have been obtained by molecular design of the precursors. Alkoxysilanes and chlorosilanes with covalently attached hydrophobic organic tails are hydrolyzed to form amphiphilic molecules containing silanol groups, leading to the formation of layered (lamellar) structures. Transparent and oriented thin films of lamellar hybrids were prepared by the reaction in the presence of tetraalkoxysilane. In addition, the design of molecules having alkyl chains and large oligosiloxane heads led to the formation of mesophases consisting of cylindrical assemblies, providing a direct pathway to ordered porous silica. The synthesis, structural features, and formation processes of these hybrid mesostructures are discussed.