02637nas a2200289 4500008004100000022001400041245011800055210006900173260007300242300001000315490000800325520165900333653000601992653002301998653001302021653001602034653000802050653000802058653001502066653002102081653001102102653004602113100001902159700001802178700002802196856012302224 2005 eng d a1381-116900aOxidation of norbornene over vanadium-substituted phosphomolybdic acid catalysts and spectroscopic investigations0 aOxidation of norbornene over vanadiumsubstituted phosphomolybdic aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcMAR a37-450 v2273 a

Oxidation of norbornene has been carried out over mono-, di- and tri-vanadium-substituted phosphomolybdic acid catalysts with aqueous hydrogen peroxide (aq. H2O2) as an oxidant in different solvents. Monovanadium-substituted phosphomolybdic acid catalyst was found to be better than other catalysts for the above reaction and acetonitrile was the suitable solvent. At the optimum temperature of 60 degreesC, the norbornene conversion was 70% and the selectivity for 2,3-epoxy norbornane was 58%. The side products were norborneols and 2-norbornanone. The lower selectivity of 2,3-epoxy norbornane with aq. H2O2 is attributed to the simultaneous formation of other products, norborneols and 2-norbornanone. The norborneols are formed from norbornene by acid-catalyzed reaction. Other oxidants like urea-hydrogen peroxide adduct (UHP) and tert-butyl hydrogen peroxide (TBHP) were also tested for norbornene oxidation reaction. With UHP, the conversion was almost same (69%) as that of aq. H2O2 reaction; however, 2,3-epoxy norbornane was the main product with >97% selectivity. Thus, the overall yield was 66.9% at 60 degreesC after 4 h. The high selectivity with UHP is attributed to the controlled release of H2O2, absence of water and less acidic nature of UHP. With TBHP the selectivity for the epoxide was >96%; however, the conversion was low (27%). A mechanism for the norbornene oxidation is believed to be proceeding via V(5+)-peroxo and V(4+)-superoxo intermediates. NMR, EPR and UV-vis spectroscopic techniques were employed to understand the reaction intermediates and reaction pathways. (C) 2004 Elsevier B.V. All rights reserved.

10a210a3-epoxy norbornane10aaq. H2O210aepoxidation10aEPR10aNMR10anorbornene10aurea-H2O2 adduct10aUV-Vis10avanadium-substituted phosphomolybdic acid1 aRaj, N., K. K.1 aRamaswamy, A.1 aManikandan, Palanichamy uhttps://library.ncl.res.in/content/oxidation-norbornene-over-vanadium-substituted-phosphomolybdic-acid-catalysts-and-002154nas a2200265 4500008004100000022001400041245005700055210005600112260006900168300001200237490000800249520136900257653002001626653000801646653000801654653001501662653000801677100002401685700001301709700001701722700002201739700001901761700002101780856008701801 2008 eng d a0925-400500aEPR and DRS evidence for NO2 sensing in Al-doped ZnO0 aEPR and DRS evidence for NO2 sensing in Aldoped ZnO aPO BOX 564, 1001 LAUSANNE, SWITZERLANDbELSEVIER SCIENCE SAcMAR a668-6730 v1303 a

Zinc oxide (ZnO) is a well-known semiconducting multifunctional material wherein properties right from the morphology to gas sensitivity can be tailor-made by doping or surface modification. Aluminum (Al)-incorporated porous zinc oxide (AI:ZnO) exhibits good response towards NO2 at low-operating temperature. The NO2 gas concentration as low as 20 ppm exhibits S = 17% for 5 wt. % Al-incorporated ZnO. The NO2 response increases with operating temperature and concentration and reaches to its maximum at 300 degrees C without any interference from other gases such as SO3, HCl, LPG and alcohol. Physico-chemical characterization likes differential thermogravimetric analysis (TG-DTA) electron paramagnetic resonance (EPR) and diffused reflectance spectroscopy (DRS) have been used to understand the sensing behavior for pure and A]-incorporated ZnO. The TG-DTA depicts formation of ZnO phase at 287 degrees C. The EPR study reveals distinct variation for O- (g=2.003) and Zn interstitial (g = 1.98) defect sites in pure and Al:ZnO. The DRS studies elucidate signature of adsorbed NO, species in aluminium-incorporated zinc oxide indicating its tendency to adsorb these species even at low temperatures. This paper is an attempt to correlate the gas sensing behavior with the physico-chemical studies such as EPR and DRS. (c) 2007 Published by Elsevier B.V.

10aaluminum doping10aDRS10aEPR10aNO2 sensor10aZnO1 aNavale, Shalaka, C.1 aRavi, V.1 aSrinivas, D.1 aMulla, Imtiaz, S.1 aGosavi, S., W.1 aKulkarni, S., K. uhttps://library.ncl.res.in/content/epr-and-drs-evidence-no2-sensing-al-doped-zno-001909nas a2200217 4500008004100000022001400041245009100055210006900146260005700215300001200272490000800284520113100292653002601423653000801449653001101457653004201468653002801510100001401538700001701552856012201569 2009 eng d a1011-372X00aSelective oxidation of benzyl alcohol over copper phthalocyanine immobilized on MCM-410 aSelective oxidation of benzyl alcohol over copper phthalocyanine a233 SPRING ST, NEW YORK, NY 10013 USAbSPRINGERcMAR a434-4420 v1283 a

Copper phthalocyanine (CuPc) complexes immobilized on ``neat'' and Ti(4+) and Al(3+) containing MCM-41 mimic the functionality of metalloenzymes. These novel materials catalyze the oxidation of benzyl alcohol to selectively benzaldehyde at moderate temperatures using peroxides and molecular oxygen as oxidant. Electron paramagnetic resonance and X-ray photoelectron spectroscopic studies revealed that the acidity of the support (MCM-41) influences the electronic structure of the immobilized CuPc. On acidic supports a part of copper in CuPc got reduced from a ``formal'' +2 to +1 oxidation state. This reduction of copper in its oxidation state on different supports decreased in the order: Al-MCM-41 (Bronsted and strong Lewis acid sites) > MCM-41 (silanol sites) > Ti-MCM-41 (weak Lewis acid sites). A linear variation in catalytic activity with the concentration of Cu(1+) ions in different catalyst samples was observed. The study reveals that by suitably modifying the acidic properties of the support one can, in principle, fine-tune the electronic and catalytic properties of the active oxidation sites.

10aCopper phthalocyanine10aEPR10aMCM-4110aSelective oxidation of benzyl alcohol10aUV-visible spectroscopy1 aHamza, A.1 aSrinivas, D. uhttps://library.ncl.res.in/content/selective-oxidation-benzyl-alcohol-over-copper-phthalocyanine-immobilized-mcm-41-002052nas a2200265 4500008004100000022001400041245015900055210006900214260007300283300001000356490000900366520105300375653001601428653002001444653000801464653002101472653001201493653003201505100002701537700002101564700001901585700002601604700002601630856013001656 2012 eng d a0022-286000aSingle crystal X-ray structure of lawsone anion: evidence for coordination of alkali metal ions and formation of naphthosemiquinone radical in basic media0 aSingle crystal Xray structure of lawsone anion evidence for coor aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcFEB a38-450 v10103 a

2-hydroxy-1,4-naphthoquinone; Lawsone (Lw) is a natural compound found in henna leaves. The reaction of lawsone with `Na' metal (Lw-1), CH3COONa (Lw-2), NaOH (Lw-3), KOH (Lw-4), K2CO3 (Lw-5) and Tris(hydroxymethyl)aminomethane (Lw-6) were studied. Red orange solids obtained for Lw-1 to Lw-6 are characterized by Elemental Analysis, FTIR, (HNMR)-H-1 and EPR studies. The results reveal the coordination of alkali metals `Na' and `K' to lawsone anion. The single crystal X-ray structure of Lw-6 was solved and it crystallizes in triclinic space group P-1 with extensive hydrogen bonding network of C-H center dot center dot center dot O, N-H center dot center dot center dot O and O-H center dot center dot center dot O between cations and anions. Polycrystalline powder X-band EPR spectra of Lw-1 to Lw-5 shows signals similar to 2.004 at 133 K, while Lw-6 is EPR silent. The naphthosemiquinone (NSQ) radical formed in Lw-2 to Lw-5, is due to disproportion reaction of catechol and naphthoquinone. (C) 2011 Elsevier B.V. All rights reserved.

10a2-Hydroxy-110a4-naphthoquione10aEPR10ahydrogen bonding10aLawsone10aNaphthosemiquinone radicals1 aSalunke-Gawali, Sunita1 aKathawate, Laxmi1 aShinde, Yogesh1 aPuranik, Vedavati, G.1 aWeyhermueller, Thomas uhttps://library.ncl.res.in/content/single-crystal-x-ray-structure-lawsone-anion-evidence-coordination-alkali-metal-ions-and-0