Soft Functional Materials Induced by Fibrillar Networks of Small Molecular Photochromic Gelators

Low-molecular-mass organogelators (LMOGs) based on photochromic molecules aggregate in selected solvents to form gels through various spatio-temporal interactions. The factors that control the mode of aggregation of the chromophoric core in the LMOGs during gelation, gelation-induced changes in fluorescence, the formation of stacked superstructures of extended pi-conjugated systems, and so forth are discussed with selected examples. Possible ways of generating various light-harvesting assemblies are proposed, and some unresolved questions, future challenges, and their possible solutions on this topic are presented.

Re-entrant Phase Behavior of a Concentrated Anionic Surfactant System with Strongly Binding Counterions

The phase behavior of the anionic surfactant sodium dodecyl sulfate (SDS) in the presence of the strongly binding counterion p-toluidine hydrochloride (PTHC) has been examined using small-angle X-ray diffraction and polarizing microscopy. A hexagonal-to-lamellar transition on varying the PTHC to SDS molar ratio (alpha) occurs through a nematic phase of rodlike micelles (N-C) -> isotropic (I) -> nematic of disklike micelles (N-D) at a fixed surfactant concentration (phi). The lamellar phase is found to coexist with an isotropic phase (l') over a large region of the phase diagram. Deuterium nuclear magnetic resonance investigations of the phase behavior at phi = 0.4 confirm the transition from N-C to N-D on varying alpha. The viscoelastic and flow behaviors of the different phases were examined. A decrease in the steady shear viscosity across the different phases with increasing alpha suggests a decrease in the aspect ratio of the micellar aggregates. From the transient shear stress response of the N-C and N-D nematic phases in step shear experiments, they were characterized to be tumbling and now aligning, respectively. Our studies reveal that by tuning the morphology of the surfactant micelles strongly binding counterions modify the phase behavior and rheological properties of concentrated surfactant solutions.

Choice of the End Functional Groups in Tri(p-phenylenevinylene) Derivatives Controls Its Physical Gelation Abilities

New supramolecular organogels based on all-trans-tri(p-phenylenevinylene) (TPV) systems possessing different terminal groups, e.g., oxime, hydrazone, phenylhydrazone, and semicarbazone have been synthesized. The self-assembly properties of the compounds that gelate in specific organic solvents and the aggregation motifs of these molecules in the organogels were investigated using UV−vis, fluorescence, FT-IR, and 1H NMR spectroscopy, electron microscopy, differential scanning calorimetry (DSC), and rheology. The temperature variable UV−vis and fluorescence spectroscopy in different solvents clearly show the aggregation pattern of the self-assemblies promoted by hydrogen bonding, aromatic π-stacking, and van der Waals interactions among the individual TPV units. Gelation could be controlled by variation in the number of hydrogen-bonding donors and acceptors in the terminal functional groups of this class of gelators. Also wherever gelation is observed, the individual fibers in gels change to other types of networks in their aggregates depending on the number of hydrogen-bonding sites in the terminal functions. Comparison of the thermal stability of the gels obtained from DSC data of different gelators demonstrates higher phase transition temperature and enthalpy for the hydrazone-based gelator. Rheological studies indicate that the presence of more hydrogen-bonding donors in the periphery of the gelator molecules makes the gel more viscoelastic solidlike. However, in the presence of more numbers of hydrogen-bonding donor/acceptors at the periphery of TPVs such as with semicarbazone a precipitation as opposed to gelation was observed. Clearly, the choice of the end functional groups and the number of hydrogen-bonding groups in the TPV backbone holds the key and modulates the effective length of the chromophore, resulting in interesting optical properties.

Jump Reorientation of Water Molecules Confined in Narrow Carbon Nanotubes

We used molecular dynamics (MD) simulations to study the reorientational dynamics of water molecules confined inside narrow carbon nanotubes immersed in a bath of water. Our simulations show that the confined water molecules exhibit bistability in their reorientational relaxation, which proceeds by angular jumps between the two stable states. The angular jump of a water molecule in the bulk involves the breaking of a hydrogen bond with one of its neighbors and the formation of a hydrogen bond with a different neighbor. In contrast, the angular jump of a confined water molecule corresponds to an interchange of the two hydrogen atoms that can form a hydrogen bond with the same neighbor. The free energy barrier between these two states is a few k(B)T. The analytic solution of a simplified two-state jump model that qualitatively explains the reorientational behavior observed in simulations is also presented.

Chlorinated Hypoelectronic Dimetallaborane Clusters: Synthesis, Characterization, and Electronic Structures of (eta(5)-C5Me5W)(2)B5HnClm (n=7, m=2 and n=8, m=1)

Pyrolysis of (eta(5)-C5Me5WH3)B4H8, 1, in the presence of excess BHCl2 center dot SMe2 in toluene at 100 degrees C led to the isolation of (eta(5)-C5Me5W)(2)B5H9, 2, and B-Cl inserted (eta(5)-C5Me5W)(2)B5H8Cl, 3, and (eta(5)-C5Me5W)(2)B5H7Cl2, (four isomers). All the Chlorinated tungstaboranes were isolated as red and air and moisture sensitive solids. These new compounds have been characterized in solution by H-1, B-11, C-13 NMR, and the structural types were unequivocally established by crystallographic analysis of compounds 3, 4, and 7. Density functional theory (DFT) calculations were carded out on the model molecules of 3-7 to elucidate the actual electronic structures of these chlorinated species. On grounds of DFT calculations we demonstrated the role of transition metals, bridging hydrogens, and the effect of electrophilic substitution of hydrogens at B-H vertices of metallaborane structures.

In Situ Phase Separation Following Dehydration in Bimetallic Sulfates: A Variable-Temperature X-Ray Diffraction Study

Phase separation resulting in a single-crystal-single-crystal transition accompanied by a polycrystalline phase following the dehydration of hydrated bimetallic sulfates [Na2Mn1.167(SO4)(2)S0.33O1.167 center dot 2H(2)O and K4Cd3-(SO4)(5)center dot 3H(2)O] has been investigated by in situ variable-temperature single-crystal X-ray diffraction. With two examples, we illustrate the possibility of generating structural frameworks following dehydration in bimetallic sulfates, which refer to the possible precursor phases at that temperature leading to the mineral formation. The room-temperature structure of Na2Mn1.167(SO4)(2)S0.33O1.167 center dot 2H(2)O is trigonal, space group R (3) over bar. On heating the crystal in situ on the diffractometer, the diffraction images display spherical spots and concentric rings suggesting phase separation, with the spherical spots getting indexed in a monoclinic space group, C2/c. The structure determination based on this data suggests the formation of Na2Mn(SO4)(2). However, the diffraction images from concentric rings could not be indexed. In the second example, the room-temperature structure is determined to be K4Cd3(SO4)(5)center dot 3H(2)O, crystallizing in a monoclinic space group, P2(1)/n. On heating the crystal in situ, the diffraction images collected also have both spherical spots and diffuse rings. The spherical spots could be indexed to a cubic crystal system, space group P2(1)3, and the structure is K4Cd3(SO4)(3). The possible mechanism for the phase transition in the dehydration regime resulting in this remarkable single-crystal to single-crystal transition with the appearance of a surrogate polycrystalline phase is proposed.

Nondeactivating Nanosized Ionic Catalysts for Water-Gas Shift Reaction

The water-gas shift reaction (WGS) is an important reaction to produce hydrogen. In this study, we have synthesized nanosized catalysts where Pt ion is substituted in the +2 state in TiO2, CeO2, and Ce1-xTixO2-delta. These catalysts have been characterized by X-ray diffraction and X-ray photoelectron spectroscopy (XPS), and it has been shown that Pt2+ in these reducible oxides result in solid solutions like Ti0.99Pt0.01O2-delta, Ce0.8Ti0.15Pt0.02O2-delta, and Ce0.98Pt0.02O2-delta. These catalysts were tested for the water gas shift reaction both ill the presence and absence of hydrogen. It was shown that Ti0.99Pt0.01O2-delta exhibited higher catalytic activity than Ce0.83Ti0.15Pt0.02O2-delta and Ce0.98Pt0.02O2-delta. Further, experiments were conducted to determine the deactivation of these catalysts. There was no sintering of Pt and no carbonate formation; therefore, the catalyst did not deactivate even after prolonged reaction. There was no carbonate formation because of the highly acidic nature of Ti4+ ions in the catalysts.

Association between endometriosis and the interleukin 1A (IL1A) locus

STUDY QUESTION Are single-nucleotide polymorphisms (SNPs) at the interleukin 1A (IL1A) gene locus associated with endometriosis risk? SUMMARY ANSWER We found evidence for strong association between IL1A SNPs and endometriosis risk. WHAT IS KNOWN ALREADY Genetic factors contribute substantially to the complex aetiology of endometriosis and the disease has an estimated heritability of ∼51%. We, and others, have conducted genome-wide association (GWA) studies for endometriosis, which identified a total of nine independent risk loci. Recently, two small Japanese studies reported eight SNPs (rs6542095, rs11677416, rs3783550, rs3783525, rs3783553, rs2856836, rs1304037 and rs17561) at the IL1A gene locus as suggestively associated with endometriosis risk. There is also evidence of a link between inflammation and endometriosis. STUDY DESIGN, SIZE, DURATION We sought to further investigate the eight IL1A SNPs for association with endometriosis using an independent sample of 3908 endometriosis cases and 8568 controls of European and Japanese ancestry. The study was conducted between October 2013 and July 2014. PARTICIPANTS/MATERIALS, SETTING, METHODS By leveraging GWA data from our previous multi-ethnic GWA meta-analysis for endometriosis, we imputed variants in the IL1A region, using a recent 1000 Genomes reference panel. After combining summary statistics for the eight SNPs from our European and Japanese imputed data with the published results, a fixed-effect meta-analysis was performed. An additional meta-analysis restricted to endometriosis cases with moderate-to-severe (revised American Fertility Society stage 3 or 4) disease versus controls was also performed. MAIN RESULTS AND THE ROLE OF CHANCE All eight IL1A SNPs successfully replicated at P < 0.014 in the European imputed data with concordant direction and similar size to the effects reported in the original Japanese studies. Of these, three SNPs (rs6542095, rs3783550 and rs3783525) also showed association with endometriosis at a nominal P < 0.05 in our independent Japanese sample. Fixed-effect meta-analysis of the eight SNPs for moderate-to-severe endometriosis produced a genome-wide significant association for rs6542095 (odds ratio = 1.21; 95% confidence interval = 1.13–1.29; P = 3.43 × 10−8). LIMITATIONS, REASONS FOR CAUTION The meta-analysis for moderate-to-severe endometriosis included results of moderate-to-severe endometriosis cases from our European data sets and all endometriosis cases from the Japanese data sets, as disease stage information was not available for endometriosis cases in the Japanese data sets. WIDER IMPLICATIONS OF THE FINDINGS SNP rs6542095 is located ∼2.3 kb downstream of the IL1A gene and ∼6.9 kb upstream of cytoskeleton-associated protein 2-like (CKAP2L) gene. The IL1A gene encodes the IL1a protein, a member of the interleukin 1 cytokine family which is involved in various immune responses and inflammatory processes. These results provide important replication in an independent Japanese sample and, for the first time, association of the IL1A locus in endometriosis patients of European ancestry. SNPs within the IL1A locus may regulate other genes, but if IL1A is the target, our results provide supporting evidence for a link between inflammatory responses and the pathogenesis of endometriosis. STUDY FUNDING/COMPETING INTEREST(S) The research was funded by grants from the Australian National Health and Medical Research Council and Wellcome Trust. None of the authors has competing interests for the study.

Genetic burden associated with varying degrees of disease severity in endometriosis

Endometriosis is primarily characterized by the presence of tissue resembling endometrium outside the uterine cavity and is usually diagnosed by laparoscopy. The most commonly used classification of disease, the revised American Fertility Society (rAFS) system to grade endometriosis into different stages based on disease severity (I to IV), has been questioned as it does not correlate well with underlying symptoms, posing issues in diagnosis and choice of treatment. Using two independent European genome-wide association (GWA) datasets and top-level classification of the endometriosis cases based on rAFS [minimal or mild (Stage A) and moderate-to-severe (Stage B) disease], we previously showed that Stage B endometriosis has greater contribution of common genetic variation to its aetiology than Stage A disease. Herein, we extend our previous analysis to four endometriosis stages [minimal (Stage I), mild (Stage II), moderate (Stage III) and severe (Stage IV) disease] based on the rAFS classification system and compared the genetic burden across stages. Our results indicate that genetic burden increases from minimal to severe endometriosis. For the minimal disease, genetic factors may contribute to a lesser extent than other disease categories. Mild and moderate endometriosis appeared genetically similar, making it difficult to tease them apart. Consistent with our previous reports, moderate and severe endometriosis showed greater genetic burden than minimal or mild disease. Overall, our results provide new insights into the genetic architecture of endometriosis and further investigation in larger samples may help to understand better the aetiology of varying degrees of endometriosis, enabling improved diagnostic and treatment modalities.

Oriented Nanocrystal Arrays of Selectable Polymorphs by Chemical Sculpture

Growing crystals with selected structure and preferred orientations oil seed substrates is crucial for a wide variety of applications. Although epitaxial or textured film growth of a polymorph whose structure resembles the seed crystal structure is well-known, growing oriented nanocrystal arrays or more than one polymorph, selectable one at a time, from the same seed has not been realized. Here, we demonstrate for the first time the exclusive growth of oriented nanocrystal arrays of two titania polymorphs from a titanate crystal by chemically activating respective polymorph-mimicking crystallographic facets in the seed. The oriented titania nanocrystal arrays exhibit significantly higher photocatalytic activity than randomly oriented polymorphs. Our approach of chemically sculpting oriented nanocrystal polymorph arrays could be adapted to other materials systems to obtain novel properties.

Ce1-xRuxO2-delta (x=0.05, 0.10): A New High Oxygen Storage Material and Pt, Pd-Free Three-Way Catalyst

Nanocrystalline Ce1-xRuxO2-delta (x = 0.05 and 0.10) of 8-10 nm sizes have been synthesized by hydrothermal method using melamine as complexing agent. Compounds have been characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and energy-dispersive X-ray analysis (EDX) and their structures have been refined by the Rietveld method.The compounds crystallize in fluorite structure and the composition is Ce1-xRuxO2-x/2 where Ru is in +4 state and Ce is in mixed-valence (+3, +4) state. Substitution of Ru4+ ion in CeO2 activated the lattice oxygen. Ce1-xRuxO2-x/2 reversibly releases 0.22[O] and 0.42[O] for x = 0.05 and 0.10, respectively, which is higher than the maximumpossible OSC of 0.22 [O] observed for Ce0.50Zr0.50O2. Utilization of Higher OSC of Ce1-xRuxO2-delta (x = 0.05 and 0.10) is also reflected in terms of low-temperature CO oxidation with these catalysts, both in the presence and absence of feed oxygen. The Ru4+ ion acts as an active center for reducing molecules (CO, hydrocarbon ``HC'') and oxide ion vacancy acts as an active center for O-2 and NO, leading to low-temperature NO conversion to N-2. Thus due to Ru4+ ion, Ce1-xRuxO2-delta is not just a high oxygen storage material but also shows high activity toward CO, hydrocarbon ``HC'' oxidation, and NO reduction by CO at low temperature with high N-2 selectivity for three-way catalysis.

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.

Synthesis and spectroscopic data of 3,3',5,5'-tetrabromo-4,4'-diaminodiphenyldibromomethane

3,3',5,5'-Tetrabromo-4,4'-dlaminodlphenyMhane has been synthedzed and Its spectral and thermal characterlstlcs have been examined.

Fluctuation Theory Of The Specific-Heat Of Normal Liquid-3He

The measured specific heat of normal liquid 3He shows a plateau for 0.15<1 K; below 0.15 K and above 1 K, it rises linearly with temperature. However, the slope on the high-temperature side is very much reduced compared with the free-Fermi-gas value. We explain these features through a microscopic, thermal spin- and density-fluctuation model. The plateau is due to spin fluctuations which have a low characteristic energy in 3He. Because of the low compressibility, the density fluctuations are highly suppressed; this leads to a reduced slope for CV(T) for high temperatures.