Shear-induced orientation of a rigid surfactant mesophase

An optically clear, crystalline, gel-like mesophase is formed by the addition of water to a micellar solution consisting of a mixture of 0.85 M anionic surfactant sodium bis(2-ethylhexyl) sulfosuccinate (AOT) and a 0.42 M zwitterionic surfactant phosphatidylcholine (lecithin) in isooctane. At 25 degrees C and water to AOT molar ratio of 70, the system has a columnar hexagonal microstructure with randomly oriented domains. The shear-induced orientation and subsequent relaxation of this structure were investigated by rheological characterization and small-angle neutron scattering (SANS). The rheological response implies that the domains align under shear, and remain aligned for several hours after cessation of shear. Shear-SANS confirms this picture. The sheared gel mesophase retains its alignment as the temperature is increased to 57 degrees C, indicating the potential to conduct templated polymer and polymer-ceramic composite materials synthesis in aligned systems.     

Structural evolution of a two-component organogel

Dry reverse micelles of AOT in isooctane spontaneously undergo a microstructural transition to an organogel upon the addition of a phenolic dopant, p-chlorophenol. This microstructural evolution has been studied through a combination of light scattering, small-angle neutron scattering (SANS), NMR, and rheology. Several equilibrium stages between the system of dry reverse micelles of AOT and a 1:1 AOT/p-chlorophenol (molar ratio) gel in isooctane have been examined. To achieve this, p-chlorophenol is added progressively to the dilute solutions of AOT in isooctane, and this concentration series is then analyzed. The dry micelles of AOT in isooctane do not undergo any detectable structural change up to a certain p-chlorophenol concentration. Upon a very small increment in the concentration of p-chlorophenol beyond this "threshold" concentration, large strandlike aggregates are observed which then evolve to the three-dimensional gel network.     

Metallaboranes of the Early Transition Metals: Direct Synthesis and Characterization of [{(eta5-C5Me5)Ta}2BnHm] (n=4, m=10; n=5, m=11), [{(eta5-C5Me5)Ta}2B5H10(C6H4CH3)], and [{(eta5-C5Me5)TaCl}2B5H11

Reaction of [Cp*TaCl4] (Cp*=eta5-C5Me5) with a sixfold excess of LiBH(4)thf followed by BH3thf in toluene at 100 degrees C led to the isolation of hydrogen-rich metallaboranes [(Cp*Ta)2B4H10] (1), [(Cp*Ta)2B5H11] (2), [(Cp*Ta)2B5H10(C6H4CH3)] (3), and [(Cp*TaCl)2B5H11] (4) in modest yield. Compounds 1-3 are air- and moisture-sensitive but 4 is reasonably stable in air. Their structures are predicted by the electron-counting rules to be a bicapped tetrahedron (1), bicapped trigonal bipyramids (2, 3), and a nido structure based on a closo dodecahedron 4. Yellow tantalaborane 1 has a nido geometry with C2v symmetry and is isostructural with [(Cp*M)2B4H8] (M=Cr and Re); whereas 2 and 3 are C3v-symmetric and isostructural with [(Cp*M)2B5H9] (M=Cr, Mo, W) and [(Cp*ReH)2B5Cl5]. The most remarkable feature of 4 is the presence of a hydride ligand bridging the ditantalum center to form a symmetrical tantalaborane cluster with a long Ta--Ta bond (3.22 A). Cluster 4 is a rare example of electronically unsaturated metallaborane containing four TaHB bonds. All these new metallaboranes have been characterized by mass spectrometry, 1H, 11B, and 13C NMR spectroscopy, and elemental analysis, and the structural types were unequivocally established by crystallographic analysis of 1-4.     

Hypervalent iodine mediated intramolecular cyclization of thioformanilides: expeditious approach to 2-substituted benzothiazoles

A new, mild, and efficient method has been developed for the synthesis of 2-substituted benzothiazoles via the intramolecular cyclization of thioformanilides by using hypervalent iodine reagents in CH2Cl2 at ambient temperature. The reaction proceeds via a thiyl radical in high yields to give the novel compound oxybis benzothiazole and is also amenable to generating combinatorial libraries of heterocyclic compounds by solid-phase synthesis.     

Characterization and Analysis of the Electrochemical Proper-ties of the Polyaniline Synthesized by Emulsion Polymerization in Constant Magnetic Field(0.4 T)

A new, convenient and economical method was established firstly, which took loaded polyaniline (PANI) carbon paper as the working electrode to real‐time characterize and analyze the electrochemical properties of the PANI synthesized by emulsion polymerization in constant magnetic field (MF, 0.4 T). The characterization results of the electrochemical properties of the PANI had been proved by contrast analysis of the thermal stability of conductivity, FT‐IR, XRD and TGA of the PANI. The experimental results of cyclic voltammogram, AC impedance, Tafel curve and electrochemical stability showed that the PANI synthesized in the presence of the MF had larger redox current, smaller charge resistance, higher corrosion potential and better electrochemical stability. The PANI thermal stability of conductivity had been measured in the temperature range from 20 to 140°C, and the results showed that the PANI synthesized in the presence of the MF had better thermal stability of conductivity. The results of FT‐IR, XRD and TGA indicated that the characteristic peaks of FT‐IR spectra of the PANI synthesized in the presence of the MF shifted to the lower wavenumbers, and its crystallinity and thermal stability were also improved.     

Development of core‐shell structure aided by SiC‐coated MWNT in ABS/LCP blend

Agglomeration is an issue of major concern for unmodified multi‐walled carbon nanotubes (MWNTs)‐aided polymeric composites. To overcome the above‐mentioned problem, multi‐walled carbon nanotubes (MWNTs) are modified by polycarbosilane (PCS)‐derived Silicone carbide (SiC). Acrylonitrile Butadiene Styrene (ABS)/Liquid Crystalline polymer (LCP)/MWCNT nanocomposites are prepared through melt blending in a twin screw extruder. X‐Ray Diffraction (XRD) studies authenticate the creation of ß‐SiC particles. Field Emission Scanning Electron Microscopy (FESEM) and Transmission Electron Microscopy (TEM) studies reveal the formation of core–shell morphology involving MWNT as the core and SiC‐coated MWNT as the shell. The degree of dispersion of MWNT is far better when it has been coated with SiC. As viewed from Thermo‐gravimetric analysis (TGA), the thermal stability is substantially increased in SiC‐aided nanocomposite in comparison to ABS/LCP/unmodified CNT blend. Glass transition temperature as well as mechanical properties are improved significantly (in the presence of SiC‐coated MWNT) as a result of homogeneous dispersion exhibited by MWNT. Copyright © 2009 John Wiley & Sons, Ltd.     

Gas‐Sensing Properties of Needle‐Shaped Ni‐Doped SnO2 Nanocrystals Prepared by a Simple Sol–Gel Chemical Precipitation Method

The preparation of needle‐shaped SnO₂ nanocrystals doped with different concentration of nickel by a simple sol–gel chemical precipitation method is demonstrated. By varying the Ni‐dopant concentration from 0 to 5 wt %, the phase purity and morphology of the SnO₂ nanocrystals are significantly changed. Powder XRD results reveal that the SnO₂ doped with a nickel concentration of up to 1 wt % shows a single crystalline tetragonal rutile phase, whereas a slight change in the crystallite structure is observed for samples with nickel above 1 wt %. High resolution scanning electron microscopy (HRSEM) results reveal the change in morphology of the materials from spherical, for SnO₂, to very fine needle‐like nanocrystals, for Ni‐doped SnO₂, annealed at different temperatures. The gas sensing properties of the SnO₂ nanocrystals are significantly enhanced after the nickel doping.     

Role of sugar in controlling reaction pattern: A comparative study with adenine and 2′-deoxyadenosine

Interaction between 2-methyl-1,4-naphthoquinone (MQ) and adenine (A) and 2′-deoxyadenosine (dA) reveals interesting differences with respect to electron transfer (ET) and hydrogen abstraction (HA). In our case A and dA exhibited ET from different sites, which has been associated to the presence of a sugar unit in dA. Sugar unit has also reduced the rate of ET from dA. We have utilized an external magnetic field in conjunction with our laser flash photolysis set-up to establish our data. In a polar MeCN/H₂O medium A and dA are found to promote ET but HA from dA is seen to be insignificant. However shifting to a heterogeneous micellar medium has been found to have a marked effect in increasing the HA rate for dA only. Separate experiments with 2′-deoxyribose sugar have revealed sugar moiety to be more susceptible to HA in SDS medium.     

Photocatalytic Au–Bi2S3 Heteronanostructures

Au–Bi₂S₃ heteronanostructure photocatalysts were designed in which the coupling of a metal plasmon and a semiconductor exciton aids the absorption of solar light, enhances charge separation, and results in improved catalytic activity. Furthermore, these nanostructures show a unique pattern of structural combination, with Au nanoparticles positioned at the center of Bi₂S₃ nanorods. The chemistry of formation of these nanostructures, their epitaxy at the junction, and their photoconductance were studied, as well as their photoresponse properties.     

Decolorization of Distillery Effluent Using Poly(Vinyl Chloride) and Cellulose Acetate Phthalate as Adsorbents

Decolorization of distillery effluents, using low cost polymer adsorbents, is one of the challenging areas for environmental technologists. Untreated distillery effluents are harmful to the environment, causing foul smell, spoiling fresh water sources and killing aquatic life. The color of distillery effluents have been decolorized by using polymer based adsorbents, such as poly(vinyl chloride) (PVC) and cellulose acetate phthalate (CAP), which are water insoluble, easily available, and cheap. In the present article, special emphasis is given to studies such as the effect of contact time, dosage amount, dilution, and the variation in the amount of sample on the degree of decolorization of the effluent. The decolorization of a distillery effluent was monitored by using UV/Visible spectroscopy and Fourier transform infrared spectroscopy (FTIR). From these studies, it was noticed that moderate to fair results were obtained and it was also found that CAP was a better adsorbent, compared to PVC, for decolorization of distillery effluents.