Single-step preparation and catalytic activity of mesoporous MCM-41 and SBA-15 silicas functionalized with perfluoroalkylsulfonic acid groups analogous to Nafion

Preparation of hybrid organic-inorganic MCM-41 and SBA-15 silicas functionalized with perfluoroalkylsulfonic acid groups has been achieved in a single step by reacting the mesoporous silicas with 1,2,2-trifluoro-2-hydroxy-1-trifluoromethylethane sulfonic acid beta-sultone; the catalysts showed higher activity than commercial Nafion-silica composite for the esterification of long chain fatty acids with ethanol.     

The effect of grass fiber filler on curing characteristics and mechanical properties of natural rubber

Natural rubber is reinforced with a novel type of grass fiber (Cyperus Tegetum Rox b). The effects of fiber loading of different mesh sizes on curing characteristics and mechanical properties of grass fiber filled natural rubber composite are studied. Since 400 mesh grass fiber loaded natural rubber composite shows superior mechanical properties, therefore the effect of silane coupling agent was studied for this particular composite. Here composites were prepared by using water leached grass fiber. Optimum cure time increases with the increase in fiber loading but the change in scorch time is less. The same trend of increase in optimum cure time is observed in the presence of Si69. But the value is higher compared to that of rubber composite without Si69. With increase in the fiber loading, modulus and hardness of the composite increases but tensile strength decreases. The mechanical properties of the composite, namely moduli at 200 and 300% elongation and hardness increase in the presence of Si69 but tensile strength is less compared to that of the composite without Si69. Elongation at break is not much affected due to the presence of Si69. Copyright © 2004 John Wiley & Sons, Ltd.     

The first examples of anthracene capped chiral carbohydrate derived dendrimers: synthesis, fluorescence and chiroptical properties

The first examples of anthracene capped chiral dendrimers derived from a 1,3,5-trisubstituted aromatic core and carbohydrate units in the interior and periphery are described. Excimer formation was evident from the fluorescence spectrum, and both fluorescence and chiroptical properties indicated that the dendrimer does not undergo aggregation in the ground state.     

Intramolecular 1,3-dipolar nitrone and nitrile oxide cycloaddition of 2- and 4-O-allyl and propargyl glucose derivatives: a versatile approach to chiral cyclic ether fused isoxazolidines, isoxazolines and isoxazoles

2-O- and 4-O-Allyl and -propargyl glucose and the corresponding oxime derivatives were prepared from readily available glucose dithioacetals. Intramolecular 1,3-dipolar cycloaddition of the N-benzyl and N-methyl nitrones of the above acyclic 2-O-allyl glucose derivatives led to the diastereoselective formation of chiral isoxazolidines incorporating the tetrahydrofuran ring. The EI mass spectra revealed a characteristic cleavage of the C-alkyl group adjacent to the furan oxygen atom. An enantiopure trisubstituted tetrahydrofuran was obtained by the reductive cleavage of the isoxazolidine ring of one of the cycloadducts. In contrast, the nitrile oxide cycloaddition of the 2-O-allyl derivatives afforded diastereomeric mixtures of the corresponding dihydroisoxazolines, the stereochemistry of which was tentatively assigned on the basis of the principle of optical superposition. The exclusive formation of a tetrahydrofuran ring from pentaallyl nitrone or nitrile oxide demonstrated the preferred formation of a five-membered ring to that of six or seven-membered rings. The nitrile oxide generated from a 3,4,5,6,7-pentaallyloxy-1-nitroheptane derivative obtained from pentaallylglucose underwent diastereoselective cycloaddition to give an isoxazoline fused to a pyran ring. Enantiopure isoxazoles containing tetrahydrofuran and oxepane rings were also prepared in good yields by the nitrile oxide cycloaddition of the 2-O- and 4-O-propargyl derivatives.     

Complexes of NS and NSO donor ligands. Nickel(II), copper(II) and cobalt(II) complexes of glyoxal bis(morpholineN-thiohydrazone) and diacetyl bis(morpholineN-thiohydrazone)

Summary Reactions of glyoxal bis(morpholineN-thiohydrazone), H₂gbmth, with NiCl₂·6H₂O, Ni(OAc)₂·4H₂O, Ni(acac)₂· H₂O, CuCl₂·2H₂O, Cu(OAc)₂·H₂O, Cu(acac)₂, CoCl₂· 6H₂O, Co(OAc)₂·4H₂O and Co(acac)₂·2H₂O yield complexes of the type [M(gbmth)], [M=Ni^II, Cu^II or Co^II]. Diacetyl reacts with morpholineN-thiohydrazide in the presence of nickel salts to yield [Ni^II(dbmth)], [Ni^II(dmth)(OAc)]H₂O and [Ni^II(Hdmth)(NH₃)Cl₂] involving N₂S₂ and NSO donor ligands. Copper and cobalt complexes of N₂S₂ and NSO donor ligands with compositions [Cu^II(dbmth)], [Co^II(dbmth)]·4H₂O and [Co^II(H₂dbmth)]Cl₂, have been isolated. The compounds have been characterised by elemental analyses, magnetic moments, molar conductance values and spectroscopic (electronic and infrared) data.     

One-step synthesis and characterization of difunctionalized N-confused tetraphenylporphyrins

Three disubstituted N-confused porphyrins (2-4) were prepared in ca. 4% yield using a one-pot synthesis. These porphyrins bear 3,5-di-tert-butylphenyl groups substituted at the C(5) and C(20) meso positions and para-substituted (Br, NO(2), ethynyl) phenyl groups at the C(10) and C(15) meso positions. The specific orientation of the aryl rings around the macrocycle in porphyrin 2 was definitively determined using a combination of 1D ((1)H and (13)C) and 2D (gHMQC and gHMBC) NMR spectroscopy. The absorption spectra of 2-4 in CH(2)Cl(2) and dimethylacetamide are similar to those of N-confused tetraphenylporphyrin in the same solvents but have Soret and Q-bands that are shifted to lower energies. Steady-state fluorescence measurements revealed Q(x)(0,0) and Q(x)(0,1) bands similar in energy to the unsubstituted NCPs 1i and 1e. The fluorescence quantum yield results for two of these NCPs (2, 4) are atypical of porphyrin behavior and are being further investigated by time-resolved spectroscopy.     

A New Bismuth Nitrate–Catalyzed Electrophilic Substitution of Indoles with Carbonyl Compounds Under Solvent-Free Conditions

An expeditious synthetic method for the preparation of bis(indollyl)methane derivatives has been developed through a bismuth nitrate-catalyzed reaction of indole with various carbonyl compounds in mortar and pastle under solvent-free conditions.     

Highly chemoselective reduction of azides to amines by Fe(0) nanoparticles in water at room temperature

A highly chemoselective reduction of aryl, heteroaryl, acyl and sulfonyl azides to the corresponding amines has been achieved by Fe(0) nanoparticles in water at room temperature in the absence of external hydride source. Several readily reducible functionalities including alkene, alkyne, S-S linkage, OTBDMS remain unaffected during reduction.     

“Dial-In” Emission from a Unique Flexible Material with Polarization Tuneable Spectral Intensity

The development of organic photoluminescent materials, which show promising roles as catalysts, sensors, organic light-emitting diodes, logic gates, etc., is a major demand and challenge for the global scientific community. In this context, a photoclick polymerization method is adopted for the growth of a unique photoluminescent three-dimensional (3D) polymer film, E, as a model system that shows emission tunability over the range 350–650 nm against the excitation range 295–425 nm. The DFT analysis of energy calculations and π-stacking supports the spectroscopic observations for the material exhibiting a broad range of emission owing to newly formed chromophoric units within the film. Full polarization spectroscopic Mueller matrix studies were employed to extract and quantify the molecular orientational order of both the ground (excitation) and excited (emission) state anisotropies through a set of newly defined parameters, namely the fluorescence diattenuation and fluorescence polarizance. The information contained in the recorded fluorescence Mueller matrix of the organic polymer material provided a useful way to control the spectral intensity of emission by using pre- and post-selection of polarization states. The observation was based on the assumption that the longer lifetime of the excited dipolar orientation is attributed to the compactness of the film.