Girish Kumar,K; Pearl,Augustine; Sareena, John; Beena,Saraswathyamma(Department of Applied Chemistry, June 12, 2006)
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Abstract:
new PVC membrane ion selective electrode which is highly selective towards Ni(II) ions was constructed using a
Schiff base containing a binaphthyl moiety as the ionophore. The sensor exhibited a good Nernstian response for nickel
ions over the concentration range 1.0 × 10–1 – 5.0 × 10–6 M with a lower limit of detection of 1.3 × 10–6 M. It has a fast
response time and can be used for a period of 4 months with a good reproducibility. The sensor is suitable for use in
aqueous solutions in a wide pH range of 3.6 – 7.4 and works satisfactorily in the presence of 25% (v/v) methanol or
ethanol. The sensor shows high selectivity to nickel ions over a wide variety of cations. It has been successfully used as
an indicator electrode in the potentiometric titration of nickel ions against EDTA and also for the direct determination of
nickel content in real samples: effluent samples, chocolates and hydrogenated oils.
PVC supported liquid membrane and carbon paste potentiometric sensors incorporating an Mn(III)-porphyrin
complex as a neutral host molecule were developed for the determination of paracetamol. The measurements were
carried out in solution at pH 5.5. Under such conditions paracetamol exists as a neutral molecule. The mechanism of
molecular recognition between the Mn(III)-porphyrin and paracetamol, leading to potentiometric signal generation,
is discussed.The sensitivity and selectivity toward paracetamol of carbon paste and polymeric liquid membrane electrodes
incorporating an Mn(III)-porphyrin host were compared. The applicability of these sensors to the direct
determination of paracetamol was checked by performing a recovery test in human plasma.
Sreekumar, K; Rani, Joseph; Pramitha, V; Sudha Kartha, C(Indian Academy of Sciences, December , 2010)
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Abstract:
Plane-wave transmission gratings were stored in the same location of silver-
doped photopolymer ¯lm using peristrophic multiplexing techniques. Constant and vari-
able exposure scheduling methods were adopted for storing gratings in the ¯lm using
He{Ne laser (632.8 nm). The role of recording geometry on the dynamic range of the ma-
terial was studied by comparing the results obtained from both techniques. Peristrophic
multiplexing with rotation of the ¯lm in a plane normal to the bisector of the incident
beams resulted in better homogenization of di®raction e±ciencies and larger M/# value.
Girish Kumar,K; Saji John,Konnully(Department of Applied Chemistry, August 1, 2006)
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Abstract:
Salicylaldehyde Schiff base of amino-methylated
polystyrene has been developed as a novel reagent for the removal
of Fe(III) from solutions. The selectivity of the metal
ion uptake over a wide range of different concentrations of
metal ion, effect of pH, ligand concentration and the influence
of other foreign ions were studied. A very good selectivity
was achieved for the removal of the ion. It was found
that 0.01 g of the ligand was sufficient to achieve about 96%
removal of the metal ion in terms of concentration (ppm)
from a 30 ppm solution in acidic pH.
A new photopolymerizable recording media is introduced based on poly
(vinyl alcohol) and vinyl acetate sensitized with methylene blue. It is observed
that this MBPVA/VAc system can be reused a number of times without
significant decrease in diffraction efficiency. The PVA-VAc ratio was optimized
at 2:1. Diffraction efcienc4y of 6.3% was obtained without any fixing at a dye
concentration of 9.3 x 10- mol/l at an exposure of 750mJ/cm2. The material is
attractive on account of its reusability.
A new photopolymerizable recording media is introduced based on poly
(vinyl alcohol) and vinyl acetate sensitized with methylene blue. It is observed
that this MBPVA/VAc system can be reused a number of times without
significant decrease in diffraction . The PVA-VAc ratio was optimized
at 2:1. Diffraction efficiency of 6.3% was obtained without any fixing at a dye
concentration of 9.3 10 4 mol/l at an exposure of 750 mJ/cm2. The material is
attractive on account of its reusability.
Mohammed Yusuff, K K; Pearly Sebastian, Chittilappilly; Sridevi, N(Elsevier,Journal of Molecular Catalysis A: Chemical 286 (2008) 92–97, February 5, 2008)
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Abstract:
Zeolite Y-encapsulated ruthenium(III) complexes of Schiff bases derived from 3-hydroxyquinoxaline-2-carboxaldehyde and 1,2-
phenylenediamine, 2-aminophenol, or 2-aminobenzimidazole (RuYqpd, RuYqap and RuYqab, respectively) and the Schiff bases derived from
salicylaldehyde and 1,2-phenylenediamine, 2-aminophenol, or 2-aminobenzimidazole (RuYsalpd, RuYsalap and RuYsalab, respectively) have
been prepared and characterized. These complexes, except RuYqpd, catalyze catechol oxidation by H2O2 selectively to 1,2,4-trihydroxybenzene.
RuYqpd is inactive. A comparative study of the initial rates and percentage conversion of the reaction was done in all cases. Turn over frequency
of the catalysts was also calculated. The catalytic activity of the complexes is in the order RuYqap > RuYqab for quinoxaline-based complexes and
RuYsalap > RuYsalpd > RuYsalab for salicylidene-based complexes. The reaction is believed to proceed through the formation of a Ru(V) species.
Sugunan, S; Benny, Thomas(Indian Journal of Chemistry, February , 1995)
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Abstract:
The Setschenow parameter and thermodynamic
parameters of transfer of 2- and 4- hydroxybenzoic acids
from water to salt solutions have been reported. The data
have been rationalised by considering the structure
breaking effects of the ions of the salts, the localized
hydrolysis model, the internal pressure theory and the
theory of water structure due to Symons.
The Setschenow parameter and thermodynamic parameters of transfer of 2-, 3-, and 4-methylbenzoic acids
from water to salt solutions have been reported. The data have been rationalized by considering the structure breaking
effects of the ions of the salts, the localized hydrolysis model, and the internal pressure theory.
Sugunan, S; Benny, Thomas(Journal of Solution Chemistry, 1994)
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Abstract:
The Setschenow parameter and thermodynamic parameters of transfer of
2-, 3- and 4-fluorobenzoic acid from water to salt solution are reported.
The data have been rationalized by considering the structure breaking effects of the ions of the salts, the localized hydrolysis model and the internal
pressure theory.
Sugunan, S; Anantaraman, R(Indian Journal of Chemistry, December , 1982)
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Abstract:
Kinetics of mercuric chloride catalysed solvolysis of l-butyl
chloride, benzyl chloride. p-methylbenzyl chloride, l-phenylethyl
chloride and triethylcarbinyl chloride have been studied in aq.
DMSO, aq. acetonitrile and aq. ethanol. The kinetic data fit a second
order rate equation in aq. DMSO. The calculated values of the
second order rate coefficients increase in the case of aq. acetonitrile
and aq. ethanol. The order in catalyst in 95%(v/v) aq. DMSO is less
than unity.
Nishamol, K; Rahna, K S; Sugunan, S(Elsevier, 2004)
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Abstract:
Various compositions of chromium manganese ferrospinels were tested as catalysts for the vapour phase alkylation of aniline with methanol. The samples were prepared by room temperature co-precipitation technique and characterized by various physico-chemical methods. The acidity–basicity determination revealed that the samples possess greater amount of basic sites than acidic sites. All the ferrite samples proved to be selective and active for N-monoalkylation of aniline leading to N-methyl aniline; Cr0.6Mn0.4Fe2O4, Cr0.8Mn0.2Fe2O4 and CrFe2O4 exhibited cent percent selectivity for N-methyl aniline. Neither C-alkylated products nor any other side products were detected for all catalyst samples. The catalytic activity of the samples studied in this reaction is related to their acid–base properties and also on the cation distribution. Under the optimized reaction conditions all the systems showed constant activity for a long duration.
Iron and mixed iron aluminium pillared montmorillonites prepared by partial hydrolysis method was subjected to room temperature exchange with transition metals of the first series. The materials exhibit good structural as well as thermal stability. Exchanged metals were found to be present inside the porous network, in the environs of the pillars. Mixed pillaring resulted in the intercalation of Al 13 like polymers in which Al is partially substituted by Fe. The acidic structure was followed by temperature programmed desorption of ammonia and cumene cracking test reaction. Weak and medium sites overshadow the strong sites in all systems. However, exchange with metals increases the number of strong sites. The prepared materials are efficient catalysts for gas phase MTBE synthesis. The catalytic activity can be well correlated with the total amount of weak and medium acid sites.
Sreekumar, K; Raja, T; Kiran, B P; Sugunan, S; Rao, B S(Elsevier, 1999)
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Abstract:
The reaction of aniline with methanol was carried out over Zn1-xNixFe2O4 (x= 0, 0.2, 0.5, 0.8 and 1) type systems in a
fixed-bed down-flow reactor. It was observed that systems possessing low ``x'' values are highly selective and active for mono
N-alkylation of aniline leading to N-methyl aniline. Selectivity for N-methyl aniline over ZnFe2O4 was more than 99% under
the optimized reaction conditions. Even at methanol to aniline molar ratio of 2, the yield of N-methyl aniline was nearly
55.5%, whereas its yield exceeded 67% at the molar ratio of 7. The Lewis acid sites of the catalysts are mainly responsible for
the good catalytic performance. Cation distribution in the spinel lattice influences their acido-basic properties, and hence,
these factors have been considered as helpful to evaluate the activity and stability of the systems.
Sreekumar, K; Jyothi, T M; Talawar, M B; Kiran, B P; Rao, B S(Elsevier, 2000)
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Abstract:
A series of ferrites having the general formula Zn1-xCoxFe2O4 (x=0, 0.2, 0.5, 0.8 and 1.0)were prepared by soft
chemical route. The materials were characterized by adopting various physico-chemical methods. The reaction of aniline
with methanol was studied in a fixed-bed reactor system as a potential source for the production of various methyl anilines.
It was observed that systems possessing low ‘ x’ values are highly selective and active for N-monoalkylation of aniline
leading to N-methylaniline. Reaction parameters were properly varied to optimize the reaction conditions for obtaining
N-methylaniline selectively and in better yield. Among the systems Zn0.8Co0.2Fe2O4 is remarkable due to its very high
activity and excellent stability. Under the optimized conditions N-methylaniline selectivity exceeded 98%. Even at a
methanol to aniline molar ratio of 2, the yield of N-methylaniline was nearly 50%, whereas its yield exceeded 71% at the
molar ratio of 5. ZnFe2O4, though executed better conversion than Zn0.8Co0.2Fe2O4 in the initial period of the run,
deactivates quickly as the reaction proceeds. The Lewis acidity of the catalysts is mainly responsible for the good
performance. Cation distribution in the spinel lattice influences their acido-basic properties and, hence, these factors have
been considered as helpful parameters to evaluate the activity of the systems.
The 2,4,6-triphenylthiapyrylium ion has been obtained imprisoned inside the supercages of the tridirectional,
large pore zeolites Y and beta via ship-in-a-bottle synthesis from chalcone and acetophenone in the presence of
hydrogen sulfide. The resulting solids are efficient and robust photocatalysts that are able to degrade phenol and
aniline in water with a higher efficiency than the P-25 TiO2 standard. Preliminary tests have shown that these
encapsulated dye materials are also efficient photocatalysts for the oxidative degradation of malodorous sulfurcontaining
molecules.
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.