The quantum yields of singlet oxygen production and
lifetimes at the gas–solid interface in silica gel material
are determined. Different photosensitizers (PS) are encapsulated
in parallelepipedic xerogel monoliths (PS-SG). PS were chosen according
to their known photooxidation properties: 9,10-dicyanoanthracene
(DCA), 9,10-anthraquinone (ANT), and a benzophenone
derivative, 4-benzoyl benzoic acid (4BB). These experiments
are mainly based on time-resolved 1O2 phosphorescence detection,
and the obtained FD and tD values are compared with
those of a reference sensitizer for production, 1H-phenalen-1-
one (PN), included in the same xerogel. The trend between their
ability to oxidize organic pollutants in the gas phase and their efficiency
for production is investigated through photooxidation
experiments of a test pollutant dimethylsulfide (DMS). The
FD value is high for DCA-SG relative to the PN reference, whereas
it is slightly lower for 4BB-SG and for ANT-SG. FD is related to
the production of sulfoxide and sulfone as the main oxidation
products for DMS photosensitized oxidation. Additional mechanisms,
leading to C!S bond cleaveage, appear to mainly occur
for the less efficient singlet oxygen sensitizers 4BB-SG and ANTSG.
Rare earth metal ion exchanged (La3+, Ce3+, RE3+) KFAU-Y zeolites were prepared by simple ion-exchange methods and have
been characterized using different physico-chemical techniques. In this paper a novel application of solid acid catalysts in the dehydration/
Beckmann rearrangement of aldoximes; benzaldoxime and 4-methoxybenzaldoxime is reported. Dehydration/Beckmann
rearrangement reactions of benzaldoxime and 4-methoxybenzaldoxime is carried out in a continuous down flow reactor at
473K. 4-Methoxybenzaldoxime gave both Beckmann rearrangement product (4-methoxyphenylformamide) and dehydration product
(4-methoxybenzonitrile) in high overall yields. The difference in behavior of the aldoximes is explained in terms of electronic
effects. The production of benzonitrile was near quantitative under heterogeneous reaction conditions. The optimal protocol allows
nitriles to be synthesized in good yields through the dehydration of aldoximes. Time on stream studies show a fast decline in the
activity of the catalyst due to neutralization of acid sites by the basic reactant and product molecules.
Sugunan, S(Indian Journal of Chemistry, February , 1983)
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Abstract:
Solubilities of 4-nitrobenzoic acid at 25°, 35° and 42°C have
been determined in water and in the presence of several concentrations
of electrolytes. The free energies, enthalpies and entropies
of transfer are also reported. The data have been rationalized
by considering the structure-breaking effects of the ions of
the salts and the requirement of the localized hydrolysis model.
The theory of Symons is not satisfactory to rationalise the
experimental data.
Seena, E B; Prathapachandra Kurup, M R(Elsevier, 2007)
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Abstract:
Three copper(II) complexes of salicylaldehyde N(4)-phenyl thiosemicarbazone (H2L1) and two copper(II) complexes of N(4)-cyclohexyl thiosemicarbazone (H2L2) have been synthesized and characterized by different physicochemical techniques like magnetic studies and electronic, infrared and EPR spectral studies. The complexes View the MathML source and [(CuL2)2] (4) having dimeric structure. The thiosemicarbazones bind to the metal as dianionic ONS donor ligand in all the complexes, except in the complex [Cu(HL1)2] · H2O (2). In complex 2, the ligand moieties are coordinated as monoanionic (HL−) ones. Two of the complexes [CuL1dmbipy] · H2O (3) and [CuL2dmbipy] (5) have been found to possess the stoichiometry [CuLB], where B = 4,4′-dimethyl-2,2′-bipyridine (dmbipy). The coordination geometry around copper(II) in 5 is trigonal bipyramidal distorted square based pyramidal (TBDSBP), as obtained by X-ray diffraction studies.
Girish Kumar,K; Muthuselvi,R(Department of Applied Chemistry, March 30, 2005)
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Abstract:
A spectrophotometric method employing 2-hydroxybenzaldiminoglycine (HBIG) is proposed for
the determination of chromium(III). The results of the determinations are compared with the standard diphenyl
carbazide method. The presently developed method is direct, simple, rapid, selective, sensitive and precise.
Girish Kumar,K; Devala Rao, G; Chowdary, K P R(Indian Journal Of Pharmaceutical Sciences, February 7, 2001)
[+]
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Abstract:
Two simple and sensitive spectrophotometric methods(A and B) in the visible region have been developed for the determination of cefotaxime sodium (DFTS) in bulk and in dosage forms. Method A is based on the reaction of CFTS with nitrous acid under alkaline conditions to form a stable violet colored chromogen with absorption maximum of 560 nm and method B is based on the reaction of CFTS with1,10-phenanthroline and ferric chloride to form a red colored chromogen with the absorption maximum of 520 mm.The color obeyed Beer’s law in the concentration range of 100-500 µg/ml for method A and 1.6-16 µg/ml for method B, respectively.When pharmaceutical preparations containing CFTS were analysed, the results obtained by the proposed methods are in good agreement with the labeled amounts and are comparable with the results obtained using a UV spectrophotometric method.
Rice husk silica was utilized as the promoter of ceria for preparing supported vanadia catalysts. Effect of vanadium content was investigated with 2–10 wt.% V2O5 loading over the support. Structural characterization of the catalysts was done by various techniques like energy dispersive X-ray (EDX), X-ray diffraction (XRD), BET surface area, thermal analysis (TGA/DTA), FT-infrared spectroscopy (FT-IR), UV–vis diffused reflectance spectroscopy (DR UV–vis), electron paramagnetic spectroscopy (EPR) and solid state magnetic resonance spectroscopies (29Si and 51V MASNMR). Catalytic activity was studied towards liquid-phase oxidation of benzene. Surface area of ceria enhanced upon rice husk silica promotion, thus makes dispersion of the active sites of vanadia easier. Highly dispersed vanadia was found for low V2O5 loading and formation of cerium orthovanadate (CeVO4) occurs as the loading increases. Spectroscopic investigation clearly confirms the formation of CeVO4 phase at higher loadings of V2O5. The oxidation activity increases with vanadia loading up to 8 wt.% V2O5, and further increase reduces the conversion rate. Selective formation of phenol can be attributed to the presence of highly dispersed active sites of vanadia over the support.
Seven bis(ligand) Co(III) complexes {[CoL21] NO3 · H2 O (1), [CoL21] Cl · 2 H2 O (2),[CoL21] ClO4 (3), [CoL22] NO3 (4), [CoL22] Cl · 2 H2 O (5), [CoL23] Br · 2 H2 O (6), [CoL23] ClO4 · H2 O (7)} of three thiosemicarbazone ligands {pyridine-2-carbaldehyde-N(4)-p-methoxyphenyl thiosemicarbazone [HL1], pyridine-2-carbaldehyde-N(4)-2-phenylethyl thiosemicarbazone [HL2] and pyridine-2-carbaldehyde-N(4)-(methyl),N(4)-(phenyl) thiosemicarbazone [HL3]} were synthesized and physico-chemically characterized. All complexes are assigned octahedral geometries on the basis of spectral studies. The ligands deprotonate and coordinate by means of pyridine nitrogen, azomethine nitrogen, and thiolate sulfur atoms. The single crystal X-ray structures of HL3 and two nitrate compounds are discussed. The structural studies corroborate the spectral characterization.
Manoj, N(American chemical society, August 7, 2006)
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Abstract:
A combined experimental and theoretical study of the absorption spectra of a group of closely related pyrylium
perchlorates 1-11 are presented. Minor changes in the position of the substituents lead to drastic changes in
the absorption spectra in this series of compounds. We have attempted to explain the observed changes using
the x,y-band notation developed by Balaban and co-workers. Absorption spectra of all compounds are compared
with results from time-dependent density functional theory (TDDFT) and Zerner’s intermediate neglect of
differential overlap (ZINDO/S) level calculations. Results of the calculations are in good agreement with
experimental observations and an interesting correlation between Balaban’s notations and the MO transitions
are obtained for simple derivatives. It is suggested that for more complex systems such as R- and â-naphthyl
substituted systems, the empirical method is not appropriate.
Mohammed Yusuff, K K; Mayadevi, S; Preetha, G Prasad(Taylor & Francis, May 5, 2003)
[+]
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Abstract:
Two series of transition metal complexes of Schiff bases derived from
quinoxaline-2-carboxaldehyde with semicarbazide (QSC) and furfurylamine
(QFA) were synthesised and characterised by elemental analyses,
molar conductance and magnetic susceptibility measurements, IR, electronic
and EPR spectral studies. The QSC complexes have the general
formula [M(QSC)Cl2]. A tetrahedral structure has been assigned for the
Mn(II), Co(II) and Ni(II) complexes and a square-planar structure for the
Cu(II) complex. The QFA complexes have the formula [M(QFA)2Cl2].
An octahedral structure has been assigned for these complexes. All of
the complexes exhibit catalytic activity towards the oxidation of 3,5-di-tert-butylcatechol (DTBC) to 3,5-di-tert-butylquinone (DTBQ) using
atmospheric oxygen. The cobalt(II) complex of the ligand QFA was
found to be the most active catalyst.
Ramankutty, C G; Sugunan, S; Bejoy, Thomas(Elsevier, September 9, 2002)
[+]
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Abstract:
Preparation of simple and mixed ferrospinels of nickel, cobalt and copper and their sulphated analogues by the room temperature coprecipitation method yielded fine particles with high surface areas. Study of the vapour phase decomposition of cyclohexanol at 300 °C over all the ferrospinel systems showed very good conversions yielding cyclohexene by dehydration and/or cyclohexanone by dehydrogenation, as the major products. Sulphation very much enhanced the dehydration activity over all the samples. A good correlation was obtained between the dehydration activities of the simple ferrites and their weak plus medium strength acidities (usually of the Brφnsted type) determined independently by the n-butylamine adsorption and ammonia-TPD methods. Mixed ferrites containing copper showed a general decrease in acidities and a drastic decrease in dehydration activities. There was no general correlation between the basicity parameters obtained by electron donor studies and the ratio of dehydrogenation to dehydration activities. There was a leap in the dehydrogenation activities in the case of all the ferrospinel samples containing copper. Along with the basic properties, the redox properties of copper ion have been invoked to account for this added activity.
Sunajadevi, K R; Sugunan, S(Elsevier, September , 2005)
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Abstract:
Titania, sulfated titania and chromium loaded sulfated titania were prepared by sol–gel method and characterized using different technique. Phenol is nitrated regioselectively by nitric acid using chromium loaded sulfated titania catalysts. A remarkable ortho selectivity is observed in solid state nitration to yield exclusively ortho-nitrophenol. Compared to the conventional process, phenol nitration over solid acid catalyst is a clean and environment friendly process. Catalytic activity well correlates with the Brönsted acid sites of these catalysts.
Sugunan, S; Rahna, K S(Indian Journal of Chemistry, July , 2002)
[+]
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Abstract:
The incorporation of transition metal oxide pillars such as those of iron and chromium along with Al2O3, pillars within
the interlayers of a montmorillonite clay is investigated. The surface acidity of these catalysts has been evaluated for the first
time employing the equilibrium adsorption of an electron donor, perylene, and the results are compared with those obtained
by temperature programmed desorption of ammonia. The principle is based on the ability of a catalyst surface site to accept
a single electron from an electron donor like perylene to form charge transfer complexes and the amount of adsorbed species
is measured quantitatively by UV-vis spectroscopy. Fina1ly, an attempt has been made to correlate the acidity determined by
the two independcnt methods and the catalytic activity of present systems in the benzoylation of toluene with benzoyl
chloride. Incorporation of Fe and Cr has changed the properties of AI pitlared montmorillonite. Fe pillared systems have
been found to be vcry good catalysts for benzoylation reaction
Sugunan, S; Kumaree Seena, C R(Indian Journal of Chemistry, May , 1998)
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Abstract:
We have investigated the changes in surface acidity/basicity
and catalytic pro~erties of samarium oxide due to surface modification
by SO42- ion. The acidity/basicity of the catalysts is
determined by titration method using Hammett indicators.
Esterification of acetic acid by n-butanol is chosen as a test
reaction. Sm203, owing to its high basicity and low acidity, does
not catalyze the reaction. But sulphated Sm20J catalyzes the
esterification reaction effectively. Activation temperature does
not have much effect on the acidity of sulphated samaria.
Sugunan, S; Anto, Paul(Indian Journal of Chemistry, April , 1997)
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Abstract:
The surface acidity/basicity of binary oxides of Zr and La and the ternary oxides of Zr, La and Al are
reported. The data have been correlated with their catalytic activity towards liquid phase reduction of
cyclohexanone.
Sugunan, S; Bindhu, Jacob(Indian Journal of Engineering & Materials Sciences, June , 1997)
[+]
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Abstract:
The surface acidity and basicity of ternary oxides of
AI, Ce and Dy have been determined using a set of
Hammett indicators. The data have been correlated
with the catalytic activity of these oxides towards the
liquid phase reduction of cyclohexanone in 2-propanol.
The reaction is favoured by the higher basicity of
the ternary oxide.
Sugunan, S; Ampili, S; Bindhu, Jacob; Rani, Varghese(Indian Journal of Chemistry, February , 1996)
[+]
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Abstract:
The surface acidity and basicity of ternary oxides of
La, Ce and AI have been determined using a set of
Hammett indicators. The data have been correlated
with the catalytic activity of these oxides towards the
liquid phase reduction of cycIohexanone in 2-propanol.
Sugunan, S; Sunitha, Kurur; Anto, Paul(Indian Journal of Chemistry, December , 1994)
[+]
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Abstract:
The surface acidity and basicity of oxides of Sm and Zr
and their mixed oxides have been determined using a set of
Hammett indicators. The data have been correlated with
the catalytic activity of these oxides towards the liquid
phase reduction of cyclo-hexanone in 2-propanol.