Hybrid Materials Combining Photoactive 2,3-Didecyloxy Anthracene Physical Gels and Gold Nanoparticles

Organic/inorganic hybrid gels have been developed in order to control the three-dimensional structure of photoactive nanofibers and metallic nanoparticles (NPs). These materials are prepared by simultaneous self-assembly of the 2,3-didecyloxyanthracene (DDOA) gelator and of thiol-capped gold nanoparticles (AuNPs). TEM and fluorescence measurements show that alkane-thiol capped AuNPs are homogeneously dispersed and tightly attached to the thermoreversible fibrillar network formed by the organogelator in n-butanol or n-decanol. Rheology and thermal stability measurements reveal moreover that the mechanical and thermal stabilities of the DDOA organogels are not significantly altered and that they remain strong, viscoelastic materials. The hybrid materials display a variable absorbance in the visible range because of the AuNPs, whereas the strong luminescence of the DDOA nanofibers is efficiently quenched by micromolar amounts of AuNPs. Besides, we obtained hybrid aerogels using supercritical CO2. These arc very low-density porous materials showing fibrillar networks oil which fluorinated gold NPs arc dispersed. These hybrid materials are of high interest because of their tunable optical properties and are under investigation for efficient light scattering.

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.

Metal cholate hydrogels: versatile supramolecular systems for nanoparticle embedded soft hybrid materials

This work describes the formation of hydrogels from sodium cholate solution in the presence of a variety of metal ions (Ca2+, Cu2+, Co2+, Zn2+, Cd2+, Hg2+ and Ag+). Morphological studies of the xerogels by electron microscopy reveal the presence of helical nanofibres. The rigid helical framework in the calcium cholate hydrogel was utilised to synthesize hybrid materials (AuNPs and AgNPs). Doping of transition metal salts into the calcium cholate hydrogel brings out the possibility of synthesising metal sulphide nano-architectures keeping the hydrogel network intact. These novel gel-nanoparticle hybrid materials have encouraging application potentials.

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.

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.

Recent advances in purely organic phosphorescent materials

Luminescent organic materials have attracted significant attention in recent times owing to their opportunities in various functional applications. Interestingly, unlike fluorescence, opportunities hidden within the phosphorescence properties of organic compounds have received considerably less attention even until last few years. It is only in the second decade of the 21st century, within a time span of less than last 5 years, that the concepts and prospects of organic compounds as phosphorescent materials have evolved rapidly. The previously perceived limitations of organic compounds as phosphorescent materials have been overcome and several molecules have been designed using old and new concepts, such as heavy atom effects, matrix assisted isolation, hydrogen bonding and halogen bonding, thereby gaining access to a significant number of materials with efficient phosphorescent features. In addition, significant improvements have been made in the development of RTP (room temperature phosphorescent) materials, which can be used under ambient conditions. In this review, we bring together the vastly different approaches developed by various researchers to understand and appreciate this recent revolution in organic luminescent materials.

Polyvinylbutyral based hybrid organic/inorganic films as a moisture barrier material

Flexible and thermally stable, freestanding hybrid organic/inorganic based polymer-composite films have been fabricated using a simple solution casting method. Polyvinylbutyral and amine functionalized mesoporous silica were used to synthesize the composite. An additional polyol-''tripentaerythritol''-component was also used to increase the -OH group content in the composite matrix. The moisture permeability of the composites was investigated by following a calcium degradation test protocol. This showed a reduction in the moisture permeability with the increase in functionalized silica loadings in the matrix. A reduction in permeability was observed for the composites as compared to the neat polymer film. The thermal and mechanical properties of these composites were also investigated by various techniques like thermogravimetric analysis, differential scanning calorimetry, tensile experiments, and dynamic mechanical analysis. It was observed that these properties detonate with the increase in the functionalized silica content and hence an optimized loading is required in order to retain critical properties. This deterioration is due to the aggregation of the fillers in the matrix. Furthermore, the films were used to encapsulate P3HT (poly 3 hexyl thiophene) based organic Schottky structured diodes, and the diode characteristics under accelerated aging conditions were studied. The weathered diodes, encapsulated with composite film showed an improvement in the lifetime as compared to neat polymer film. The initial investigation of these films suggests that they can be used as a moisture barrier layer for organic electronics encapsulation application.

Tunable device properties of free-standing inorganic/organic flexible hybrid structures obtained by exfoliation

We report the fabrication of free-standing flexible inorganic/organic hybrid structures by exfoliating ZnO nanostructured films from the flat indium tin oxide (ITO)/silicon/sapphire substrates using poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS). Strong interaction between ZnO and PEDOT: PSS and the thermomechanical response of PEDOT: PSS are the key issues for the exfoliation to prevail. The performance of the free-standing hybrid structures as rectifiers and photodetectors is better as compared to ITO supported hybrid structures. It is also shown that device properties of hybrid structures can be tuned by using different electrode materials. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4729550]

Hybrid framework iron(II) phosphate-oxalates

Two inorganic-organic hybrid framework iron phosphate-oxalates, I, [N2C4H12](0.5)[Fe-2(HPO4)(C2O4)(1.5)] and II, [Fe-2(OH2)PO4(C2O4)(0.5)] have been synthesized by hydrothermal means and the structures determined by X-ray crystallography. Crystal Data: compound I, monoclinic, spacegroup = P2(1)/c (No. 14), a=7.569(2) Angstrom, b=7.821(2) Angstrom, c=18.033(4) Angstrom, beta=98.8(1)degrees, V=1055.0(4) Angstrom(3), Z=4, M=382.8, D-calc=2.41 g cm(-3) MoK alpha, R-F=0.02; compound II, monoclinic, spacegroup=P2(1)/c (No. 14), a=10.240(1) b=6.375(3) Angstrom, 9.955(1) Angstrom, beta=117.3(1)degrees, V=577.4(1) Angstrom(3), Z=4, M=268.7, D-calc=3.09 g cm(-3) MoK alpha, R-F=0.03. These materials contain a high proportion of three-coordinated oxygens and [Fe2O9] dimeric units, besides other interesting structural features. The connectivity of Fe2O9 is entirely different in the two materials resulting in the formation of a continuous chain of Fe-O-Fe in II. The phosphate-oxalate containing the amine, I, forms well-defined channels. Magnetic susceptibility measurements show Fen to be in the high-spin state (t(2g)(4)e(g)(2)) in II, and in the intermediate-spin state (t(2g)(5)e(g)(1)) in I.

Synthesis and characterization of flexible epoxy nanocomposites reinforced with amine functionalized alumina nanoparticles: a potential encapsulant for organic devices

Research on conducting polymers, organic light emitting diodes and organic solar cells has been an exciting field for the past decade. The challenge with these organic devices is the long term stability of the active material. Organic materials are susceptible to chemical degradation in the presence of oxygen and moisture. The sensitivity of these materials towards oxygen and moisture makes it imperative to protect them by encapsulation. Polymer nanocomposites can be used as encapsulation materials in order to prevent material degradation. In the present work, amine functionalized alumina was used as a cross-linking and reinforcing material for the polymer matrix in order to fabricate the composites to be used for encapsulation of devices. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and Raman spectroscopy were used to elucidate the surface chemistry. Thermogravimetric analysis techniques and CHN analysis were used to quantify grafting density of amine groups over the surface of the nanoparticles. Mechanical characterizations of the composites with various loadings were carried out with dynamic mechanical analyzer. It was observed that the composites have good thermal stability and mechanical flexibility, which are important for an encapsulant. The morphology of the composites was evaluated using scanning electron microscopy and atomic force microscopy.

Multi-component, Self-assembled, Functional Soft Materials

Supramolecular chemistry is an emerging tool for devising materials that can perform specified functions. The self-assembly of facially amphiphilic bile acid molecules has been extensively utilized for the development of functional soft materials. Supramolecular hydrogels derived from the bile acid backbone act as useful templates for the intercalation of multiple components. Based on this, synthesis of gel-nanoparticle hybrid materials, photoluminescent coating materials, development of a new enzyme assay technique, etc. were achieved in the author's laboratory. The present account highlights some of these achievements.

Polymer optoelectronic structures for retinal prosthesis

This commentary highlights the effectiveness of optoelectronic properties of polymer semiconductors based on recent results emerging from our laboratory, where these materials are explored as artificial receptors for interfacing with the visual systems. Organic semiconductors based polymer layers in contact with physiological media exhibit interesting photophysical features, which mimic certain natural photoreceptors, including those in the retina. The availability of such optoelectronic materials opens up a gateway to utilize these structures as neuronal interfaces for stimulating retinal ganglion cells. In a recently reported work entitled ``A polymer optoelectronic interface provides visual cues to a blind retina,'' we utilized a specific configuration of a polymer semiconductor device structure to elicit neuronal activity in a blind retina upon photoexcitation. The elicited neuronal signals were found to have several features that followed the optoelectronic response of the polymer film. More importantly, the polymer-induced retinal response resembled the natural response of the retina to photoexcitation. These observations open up a promising material alternative for artificial retina applications.

Stimuli and shape responsive `boron-containing' luminescent organic materials

Recent advancements of material science and its applications have been immensely influenced by the modern development of organic luminescent materials. Among all organic luminogens, boron containing compounds have already established their stature as one of the indispensable classes of luminescent dyes. Boron, in its various forms e. g. triarylboranes, borate dyes and boron clusters, has attracted considerable attention owing to its several unique and excellent photophysical features. In very recent times, beyond the realms of solution-state studies, luminescent boron-containing compounds have emerged as a large and versatile class of stimuli responsive materials. Based on several fundamental concepts of chemistry, researchers have come up with an admirable variety of boron-containing materials with AIE (aggregation-induced emission), mechano-responsive luminescence, thermoresponsive-luminescence as well as a number of purely organic phosphorescent materials and other standalone examples. The unique chemical as well as physical properties of boron-containing compounds are largely responsible for the development of such materials. In this review these new findings are brought together.