Nanocrystalline Janus films of inorganic materials prepared at the liquid-liquid interface

The interface between toluene and water has been employed to prepare ultrathin Janus nanocrystalline films of metal oxides, metal chalcogenides and gold, wherein the surface on the organic-side is hydrophobic and the aqueous-side is hydrophilic. We have changed the nature of the metal precursor or capping agent in the organic layer to increase the hydrophobicity. The strategy employed for this purpose is to increase the length of the alkane chain in the precursor or use a perfluroalkane derivative as precursor or as a capping agent. The hydrophobicity and hydrophilicity of the Janus films have been determined by contact angle measurements. The morphology of hydrophobic and hydrophilic sides of the film have been examined by field emission scanning electron microscopy.

Reactivity of Cationic Terminal Borylene Complexes: Novel Mechanisms for Insertion and Metathesis Chemistry Involving Strongly Lewis Acidic Ligand Systems

The reactions of terminal borylene complexes of the type [CpFe(CO)(2)(BNR2)](+) (R = `Pr, Cy) with heteroallenes have been investigated by quantum-chemical methods, in an attempt to explain the experimentally observed product distributions. Reaction with dicyclohexylcarbodiimide (CyNCNCy) gives a bis-insertion product, in which 1 equiv of carbodiimide is assimilated into each of the Fe=B and B=N double bonds to form a spirocyclic boronium system. In contrast, isocyanates (R'NCO, R' = Ph, 2,6-wXy1, CY; XYl = C6H3Me2) react to give isonitrile complexes of the type [CpFe(CO)(2)(CNR')]+, via a net oxygen abstraction (or formal metathesis) process. Both carbodiimide and socyanate substrates are shown to prefer initial attack at the Fe=B bond rather than the B=N bond of the borylene complex. Further mechanistic studies reveal that the carbodiimide reaction ultimately leads to the bis-insertion compounds [CpFe(CO)(2)C(NCy)(2)B(NCY)(2)CNR2](+), rather than to the isonitrile system [CpFe(CO)(2)(CNCy)](+), on the basis of both thermodynamic (product stability) and kinetic considerations (barrier heights). The mechanism of the initial carbodiimide insertion process is unusual in that it involves coordination of the substrate at the (borylene) ligand followed by migration of the metal fragment, rather than a more conventional process: i.e., coordination of the unsaturated substrate at the metal followed by ligand migration. In the case of isocyanate substrates, metathesis products are competitive with those from the insertion pathway. Direct, single-step metathesis reactivity to give products containing a coordinated isonitrile ligand (i.e. [CpFe(CO)(2)(CNR')](+)) is facile if initial coordination of the isocyanate at boron occurs via the oxygen donor (which is kinetically favored); insertion chemistry is feasible when the isocyanate attacks initially via the nitrogen atom. However, even in the latter case, further reaction of the monoinsertion product so formed with excess isocyanate offers a number of facile (low energetic barrier) routes which also generate ['CpFe(CO)(2)(CNR')](+), rather than the bis-insertion product [CpFe(CO)(2)C(NR')(O)B(NR')(O)CNR2](+) (i.e., the direct analogue of the observed products in the carbodiimide reaction).

Site-Specific Functionalization of Hyperbranched Polymers Using ``Click'' Chemistry

Different strategies for functionalization of the core region and periphery of core-shell type hyperbranched polymers (HBP) using the ``click'' reaction have been explored. For achieving periphera functionalization, an AB(2) + A-R-1 + A-R-2 type copolymerization approach was used, where A-R-1 is heptaethylene glycol monomethyl ether (HPEG-M) and A-R-2 is tetraethylene glycol monopropargyl ether (TEG-P). A very small mole fraction of the propargyl containing monomer, TEG-P, was used to ensure that the water-solubility of the hyperbranched polymer is minimally affected. Similarly, to incorporate propargyl groups in the core region, a new propargyl group bearing B-2-typ monomer was designed and utilized in an AB(2) + A(2) + B-2 + A-R-1 type copolymerization, such that the total mole fraction of B-2 + A(2) is small and their mole-ratio is 1: 1. Further, using a combination of both the above approaches, namely AB(2) + A(2) + B-2 + A-R-1 + A-R-2, hyperbranched structures that incorporate propargyl groups both at theperiphery and within the core were synthesized. Since the AB(2) monomer carries a hexamethylene spacer (C-6) and the periphery is PEGylated all the derivatized polymers form core-shell type structures in aqueous solutions. Attempts were made to ascertain and probe the location of the propargyl groups in these HBP's, by ``clicking'' azidomethylpyrene, onto them. However, the fluorescence spectra of aqueous solutions of the pyrene derivatized polymers were unable to discriminate between the various locations, possibly because the relatively hydrophobic pyrene units insert themselves into the core region to minimize exposure to water.

ESR studies of non-silicate inorganic glasses through their glass transformation ranges

ESR spectra of three inorganic glasses doped with Mn2+ and Fe3+ have been studied through their glass transition temperatures (Tg). Spectral features in each case have been discussed with reference to site symmetries. The intensity of the ESR signal has been bound to decrease in the region of Tg. An attempt has been made to explain this interesting feature on the basis of a two-state model.

Some features of solid propellant chemistry

Abstract is not available.

Nanostructured Peptide Fibrils Formed at the Organic-Aqueous Interface and Their Use as Templates To Prepare Inorganic Nanostructures

Formation of fibril-type nanostructures of the Alzheimer's beta-amyloid diphenylalanine (L-Phe-L-Phe, FF) at the organic-aqueous interface and the factors affecting their structures have been investigated. Such nanostructures are also formed by bovine serum albumin and bovine pancreas insulin. The concentration of the precursor taken in the aqueous layer plays an important role in determining the morphology of the nanostructures, The addition of curcumin to the organic layer changes the structure of the self-assembled one-dimensional aggregates of diphenylalanine. By coating the diphenylalanine dipeptide fibrils with appropriate precursors followed by calcination in air, it has been possible to obtain one-dimensional nanostructures of inorganic materials.

Metal-organic framework structures - how closely are they related to classical inorganic structures?

Metal-organic frameworks (MOFs) have emerged as an important family of compounds for which new properties are increasingly being found. The potential for such compounds appears to be immense, especially in catalysis, sorption and separation processes. In order to appreciate the properties and to design newer frameworks it is necessary to understand the structures from a fundamental perspective. The use of node, net and vertex symbols has helped in simplifying some of the complex MOF structures. Many MOF structures are beginning to be described as derived from inorganic structures. In this tutorial review, we have provided the basics of the node, the net and the vertex symbols and have explained some of the MOF structures. In addition, we have also attempted to provide some leads towards designing newer structures/topologies.

Three-component assembly of a metal-inorganic 3D Co(II) polymer containing bridging hydrazine

Three-component metal-inorganic assembly of a Co(II) network representing the first example of a 3D coordination polymer containing a hydrazine bridging ligand, has been synthesized and characterized.

Novel organic-inorganic composite polymer-electrolyte membranes for DMFCs

Organic-inorganic composite membranes comprising Nation with inorganic materials such as silica, mesoporous zirconium phosphate (MZP) and mesoporous titanium phosphate (MTP) are fabricated and evaluated as proton-exchange-membrane electrolytes for direct methanol fuel cells (DMFCs). For Nation-silica composite membrane, silica is impregnated into Nation matrix as a sol by a novel water hydrolysis process precluding the external use of an acid. Instead, the acidic nature of Nation facilitates in situ polymerization reaction with Nation leading to a uniform composite membrane. The rapid hydrolysis and polymerization reaction while preparing zirconia and titania sols leads to uncontrolled thickness and volume reduction in the composite membranes, and hence is not conducive for casting membranes. Nafion-MZP and Nafion-MTP composite membranes are prepared by mixing pre-formed porous MZP and MTP with Nation matrix. MZP and MTP are synthesised by co-assembly of a tri-block co-polymer, namely pluronic-F127, as a structure-directing agent, and a mixture of zirconium butoxide/titanium isopropoxide and phosphorous trichloride as inorganic precursors. Methanol release kinetics is studied by volume-localized NMR spectroscopy (employing ``point resolved spectroscopy'', PRESS), the results clearly demonstrating that the incorporation of inorganic fillers in Nation retards the methanol release kinetics under osmotic drag. Appreciable proton conductivity with reduced methanol permeability across the composite membranes leads to improved performance of DMFCs in relation to commercially available Nafion-117 membrane.

Adsorption-desorption and photocatalytic properties of inorganic-organic hybrid cadmium thiosulfate compounds

Three inorganic-organic hybrid framework cadmium thiosulfate phases have been investigated for adsorption and photodegradation of organic dye molecules. Different classes of organic dyes, viz., triaryl methane, azo, xanthene, anthraquinone, have been studied. The anionic dyes with sulfonate groups appear to readily adsorb on the cadmium thiosulfate compounds in an aqueous medium. The adsorption of the dye molecules, however, does not create any structural changes on the cadmium thiosulfate compounds, though weak electronic interactions have been observed. The adsorbed dyes have been desorbed partially in an alcoholic medium, suggesting possible applications in scavenging specific anionic dyes from the aqueous solutions. Langmuir adsorption/desorption isotherms have been used to model this behavior. UV-assisted (lambda(max) = 365 nm) photocatalytic decomposition studies on the cationic dyes indicate reasonable activity comparable with that of Degussa P-25 (TiO2) catalyst. Sunlight assisted photocatalyti studies have been carried out in detail employing hybrid framework compounds. The Langmuir-Hinshelwood kinetics model, employed to follow the degradation profile of the organic dyes, indicates that the photocatalytic degradation follows the order: triaryl methane > azo > xanthene.

Synthesis, Structure, and Transformation Studies in a Family of Inorganic-Organic Hybrid Framework Structures Based on Indium

Eight new open-framework inorganic-organic hybrid compounds based on indium have been synthesized employing hydrothermal methods. All of the compounds have InO6, C2O4, and HPO3/HPO4/SO4 units connected to form structures of different dimensionality Thus, the compounds have zero- (I), two- (II, III, IV, V, VII, and VIII), and three-dimensionally (VI) extended networks. The formation of the first zero-dimensional hybrid compound is noteworthy In addition, concomitant polymorphic structures have been observed in the present study. The molecular compound, I, was found to be reactive, and the transformation studies in the presence of a base (pyridine) give rise to the polymorphic structures of II and III, while the addition of an acid (H3PO3) gives rise to a new indium phosphite with a pillared layer structure (T1). Preliminary density functional theory calculations suggest that the stabilities of the polymorphs are different, with one of the forms (II) being preferred over the other, which is consistent with the observed experimental behavior. The oxalate units perform more than one role in the present structures. Thus, the oxalate units connect two In centers to satisfy the coordination requirements as well as to achieve charge balance in compounds II, IV, and VI. The terminal oxalate units observed in compounds I, IV, and V suggest the possibility of intermediate structures. Both in-plane and out-of-plane connectivity of the oxalate units were observed in compound VI. The 31 compounds have been characterized by powder X-ray diffraction, IR spectroscopy, thermogravimetric analysis, and P-31 NMR studies.

Melting of an Anchored Bilayer: Phase Transitions in the Organic-Inorganic Hybrid Pervoskite (CH3NH3)(CH3(CH2)(n)NH3)(2)Pb2I7 (n=11, 13, 15, 17)

The conformation, organization, and phase transitions of alkyl chains in organic-inorganic hybrids based on the double pervoskite-slab lead iodides, (CH3NH3)(CH3(CH2)(n)NH3)(2)Pb2I7 (n = 11, 13, 15, 17) have been investigated by X-ray diffraction, calorimetry, and infrared vibrational spectroscopy. In these hybrid solids, double pervoskite (CH3NH3)Pb2I7 slabs are interleaved with alkyl ammonium chains with the anchored alkyl chains arranged as tilted bilayers and adopting a planar all-trans conformation at room temperature. The (CH3NH3)(CH3(CH2)(n)NH3)(2)Pb2I7 compounds exhibit a single reversible phase transition above room temperature with the associated enthalpy change varying linearly with alkyl chain length. This transition corresponds to the melting in two-dimensions of the alkyl chains of the anchored bilayer and is characterized by increased conformational disorder of the methylene units of the chain and loss of tilt angle coherence leading to an increase in the interslab spacing. By monitoring features in the infrared spectra that are characteristic of the global conformation of the alkyl chains, a quantitative relation between conformational disorder and melting of the anchored bilayer is established. It is found that, irrespective of the alkyl chain length, melting occurs when at least 60% of the chains in the anchored bilayer of (CH3NH3)(CH3(CH2)(n)NH3)(2)Pb2I7 have one or more gauche defects. This concentration is determined by the underlying lattice to which the alkyl chains are anchored.

Highly stable Ag nanoparticles in agar-agar matrix as inorganic-organic hybrid

A novel synthesis of inorganic-organic hybrid films containing well dispersed and almost uniform size Ag nanoparticles in agar-agar matrix has been reported. The films are found to be highly stable for more than a year. The colloidal particles of Ag can be obtained in large quantities in the form of a film or in the gel form when dispersed in agar-agar or by dissolving in a suitable solvent as solution. Characterization has been done by UV-visible spectroscopy and TEM. The hybrid may be of interest to study third-order non-linear susceptibility.