The electron-donor properties of Sm2O3 activated at 300, 500, and 800°C are reported from studies on the adsorption of electron acceptors of various electron affinities (electron affinity values in eV are given in parentheses): 7,7,8,8-tetracyanoquino-dimethane (2.84), 2,3,5,6-tetrachloro-1,4-benzoquinone (2.40), p-dinitrobenzene (1.77), and m-dinitrobenzene (1.26) in acetonitrile and 1,4-dioxane. The extent of electron transfer during the adsorption was determined from magnetic measurements. The acid-base properties of Sm2O3 at different activation temperatures are reported using a set of Hammett indicators. Electron donor-acceptor interactions at interfaces are important in elucidating the adhesion forces.
Sugunan, S; Jalaja, J M(Indian Journal of Chemistry, March , 1995)
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Abstract:
The electron donating properties of Ce02 and its mixed
oxides with alumina have been determined from the studies
of adsorption of electron acceptors of various electron
affinities on the surface of these oxides. The catalytic
activity of these oxides towards some reactions such as
oxidation of alcohols and reduction of ketones have been
Correlated with their surface electrondonor properties. The
surface acidity/basicity of these oxides have also been
determined by titration method using a set of Hammett
indicators.
The catalytic activity of Perovskite-type mixed oxides (LaCo03 . PrCo03 and SmCo03 ) for the
reduction of cyclohexanone to cyclohexanol with 2-propanol (Meerwein-Ponndorf-Verley reduction)
has been studied. The data have been correlated with the surface electron donor properties
of these mixed oxides.
Sugunan, S; Devika Rani, G(Indian Journal of Chemistry, November , 1993)
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Abstract:
The adsorption of electron acceptors, viz.,7,7,8,8-tetracyanoquinodimethane(TCNQ), 2,3,5,6-tetrachloro-p-
benzoquinone (chloranil) and p-dinitrobenzene
(PDNB) on the surface of three rare earth oxides Y2O3,
Nd203 and Pr6O11 has been studied in acetonitrile and
dioxan. From the radical concentration on the surface
determined using ESR spectral data, the electron donor
strength of the rare earth oxides are reported.
Invertase was adsorbed onto micro-porous acid-activated montmorillonite clay (K-10) by two procedures, namely adsorption and covalent binding. The immobilized enzymes were characterized by XRD, surface area measurements and 27Al NMR. XRD measurements revealed an expansion of clay layers due to immobilization which suggests that intercalation had taken place. Surface area measurements also support this observation. 27Al NMR showed that interaction of enzyme with tetrahedral and octahedral Al changes with the immobilization procedure. Sucrose hydrolysis was performed in a batch reactor. The immobilized enzymes showed enhanced pH and thermal stabilities. Optimum pH and temperature were found to increase upon immobilization. The effectiveness factor (η) and Michaelis constant (Km) suggest that diffusional resistances play a major role in the reaction. The immobilized invertase could be stored in buffer of pH 5 and 6 at 5 °C without any significant loss in activity for 20 days.
The differaction efficiency,sensitivity and storage life of Methylene blue sensitized poly(vinyl chloride) film was improved by the addition of an electron donor in the matrix. The
addition of pyridine enhanced the diffraction efficiency by two times and storage life of the
gratings was increased to 2-3 days.
Thomas Lee, S; Suresh, Kumar P; Unnikrishnan, K P; Nampoori, V P N; Girijavallabhan, C P; Sugunan, S; Radhakrishnan, P(Department of Applied Chemistry, May 15, 2003)
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Abstract:
In this communication, we discuss the details of fabricating an off-line fibre
optic sensor (FOS) based on evanescent wave absorption for detecting trace
amounts of Fe3+ in water. Two types of FOS are developed; one type uses
the unclad portion of a multimode silica fibre as the sensing region whereas
the other employs the microbent portion of a multimode plastic fibre as the
sensing region. Sensing is performed by measuring the absorption of the
evanescent wave in a reagent medium surrounding the sensing region. To
evaluate the relative merits of the two types of FOS in Fe3+ sensing, a
comparative study of the sensors is made, which reveals the superiority of
the latter in many respects, such as smaller sensing length, use of a double
detection scheme (for detecting both core and cladding modes) and higher
sensitivity of cladding mode detection at an intermediate range of
concentration along with the added advantage that plastic fibres are
inexpensive. A detection limit of 1 ppb is observed in both types of fibre and
the range of detection can be as large as 1 ppb–50 ppm. All the
measurements are carried out using a LabVIEW set-up.
Sreekumar, K(Optical society of America, June 20, 2004)
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Abstract:
A methylene-blue-sensitized polymer blend of polyvinyl alcohol and polyacrylic acid is fabricated and
tested for holographic recording. It was found to have good characteristics such as high sensitivity,
storage stability, ease of fabrication, and environmental stability. Optimization of the ratio of polyvinyl
alcohol polyacrylic acid, the sensitizer concentration, pH, energy, diffraction efficiency measurements,
etc., have been done. pH is found to have a great influence on the recovery of the dye in this matrix.
The results of experimental investigations into the properties of this new material are reported.
The fabrication and analytical applications of two types of potentiometric
sensors for the determination of ketoconazole (KET) are described. The
sensors are based on the use of KET-molybdophosphoric acid (MPA) ion pair
as electroactive material. The fabricated sensors include both polymer membrane
and carbon paste electrodes. Both sensors showed a linear, stable and near
Nernstian slope of 57.8mV=decade and 55.2mV=decade for PVC membrane
and carbon paste sensors respectively over a relatively wide range of KET concentration
(1×10-2-5×10-5 and 1×10-2-1×10-6). The sensors showed a fast
response time of <30 sec and <45 sec. A useful pH range of 3–6 was obtained
for both types of sensors. A detection limit of 2.96 10 5M was obtained for
PVC membrane sensor and 6.91 10 6M was obtained for carbon paste sensor.
The proposed sensors proved to have a good selectivity for KET with respect to a
large number of ions. The proposed sensors were successfully applied for the
determination of KET in pharmaceutical formulations. The results obtained
are in good agreement with the values obtained by the standard method.
Sreekumar, Krishnapillai; Rajesh Krishnan, G(Eur. J. Org. Chem, August , 2008)
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Abstract:
This paper describes the first use of polystyrene-supported
poly(amidoamine) (PAMAM) dendrimers as heterogeneous
basic organocatalysts for carbon–carbon bond formation.
Polystyrene-supported PAMAM dendrimers of first, second
and third generations have been used as reusable base catalysts
in Knoevenagel condensations of carbonyl compounds
with active methylene compounds. The reactions proceed in short periods of time and with 100% selectivity. This novel
catalyst eliminates the use of aromatic and halogenated solvents,
as well as complex purification processes. The catalysts
can be recycled ten times.
Invertase was immobilized on acid activated montmorillonite via two independent procedures, adsorption and covalent binding. The immobilized enzymes were characterized by XRD, NMR and N2 adsorption measurements and their activity was tested in a fixed bed reactor. XRD revealed that the enzyme was situated on the periphery of the clay and the side chains of different amino acid residues were involved in intercalation with the clay matrix. NMR demonstrated that tetrahedral Al was linked to the enzyme during adsorption and the octahedral Al was involved during covalent binding. Secondary interaction of the enzyme with Al was also observed. N2 adsorption studies showed that covalent binding of enzymes caused pore blockage since the highly polymeric species were located at the pore entrance. The fixed bed reactor proved to be efficient for the immobilized invertase. The optimum pH and pH stability improved upon immobilization. The kinetic parameters calculated also showed an enhanced efficiency of the immobilized systems. They could be used continuously for long period. Covalently bound invertase demonstrated greater operational stability.
Prathapachandra Kurup, M R; Manoj, E; Rohith, John P; Nethaji, M; Alex, Punnoose(Elsevier, July 16, 2009)
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Abstract:
An unusual copper(II) complex [Cu(L1a)2Cl2] CH3OH H2O H3O+Cl (1a) was isolated from a solution of a
novel tricopper(II) complex [Cu3(HL1)Cl2]Cl3 2H2O (1) in methanol, where L1a is 3-(2-pyridyl)triazolo
[1,5-a]-pyridine, and characterized with single crystal X-ray diffraction study. The tricopper(II) complex
of potential ligand 1,5-bis(di-2-pyridyl ketone) carbohydrazone (H2L1) was synthesized and physicochemically
characterized, while the formation of the complex 1a was followed by time-dependant monitoring
of the UV–visible spectra, which reveals degradation of ligand backbone as intensity loss of bands
corresponding to O?Cu(II) charge transfer
Glucoamylase was immobilized on acid
activated montmorillonite clay via two different procedures
namely adsorption and covalent binding. The
immobilized enzymes were characterized by XRD,
NMR and N2 adsorption measurements and the
activity of immobilized glucoamylase for starch
hydrolysis was determined in a batch reactor. XRD
shows intercalation of enzyme into the clay matrix
during both immobilization procedures. Intercalation
occurs via the side chains of the amino acid residues,
the entire polypeptide backbone being situated at the
periphery of the clay matrix. 27Al NMR studies
revealed the different nature of interaction of enzyme
with the support for both immobilization techniques.
N2 adsorption measurements indicated a sharp drop in
surface area and pore volume for the covalently bound
glucoamylase that suggested severe pore blockage.
Activity studies were performed in a batch reactor. The
adsorbed and covalently bound glucoamylase retained
49% and 66% activity of the free enzyme respectively.
They showed enhanced pH and thermal stabilities. The
immobilized enzymes also followed Michaelis–Menten
kinetics. Km was greater than the free enzyme that was
attributed to an effect of immobilization. The immobilized
preparations demonstrated increased reusability
as well as storage stability.
Glucoamylase from Aspergillus Niger was immobilized on montmorillonite clay (K-10) by two procedures, adsorption and covalent binding. The immobilized enzymes were characterized using XRD, surface area measurements and 27Al MAS NMR and the activity of the immobilized enzymes for starch hydrolysis was tested in a fixed bed reactor (FBR). XRD shows that enzyme intercalates into the inter-lamellar space of the clay matrix with a layer expansion up to 2.25 nm. Covalently bound glucoamylase demonstrates a sharp decrease in surface area and pore volume that suggests binding of the enzyme at the pore entrance. NMR studies reveal the involvement of octahedral and tetrahedral Al during immobilization. The performance characteristics in FBR were evaluated. Effectiveness factor (η) for FBR is greater than unity demonstrating that activity of enzyme is more than that of the free enzyme. The Michaelis constant (Km) for covalently bound glucoamylase was lower than that for free enzyme, i.e., the affinity for substrate improves upon immobilization. This shows that diffusional effects are completely eliminated in the FBR. Both immobilized systems showed almost 100% initial activity after 96 h of continuous operation. Covalent binding demonstrated better operational stability.
The effect of residual cations in rare earth metal modified faujasite–Y zeolite has been monitored using magic angle spinning NMR spectral analysis and catalytic activity studies. The second metal ions being used are Na+, K+ and Mg+. From a comparison of the spectra of different samples, it is concluded that potassium and magnesium exchange causes a greater downfield shift in the 29Si NMR peaks. Also, lanthanum exchanged samples show migration behavior from large cages to small cages, which causes the redistribution of second counter cations. It is also observed that Mg2+ causes the most effective migration of lanthanum ions due to its greater charge. The prepared systems were effectively employed for the alkylation of benzene with 1-octene in the vapor phase. From the deactivation studies it is observed that the as-exchanged zeolites possess better stability towards reaction condition over the pure HFAU zeolite.
Suja, H; Deepa, C S; Sreeja Rani, K; Sugunan, S(Indian Journal of Chemistry, August , 2003)
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Abstract:
The present work attempts a systematic examination of the effect of sulphate content on the physico-chemical properties
and catalytic activity of sulphated zirconia and iron promoted sulphated zirconia systems. Sulphate content is estimated by
EDX analysis. The amount of sulphate incorporated has been found to influence the surface area, crystal structure and the
acid strength distribution. Ammonia TPD and adsorption studies using perylene have enabled the determination of surface
acidic properties. The results are supported by the thermodesorption studies using pyridine and 2,6-dimethylpyridine. The
catalytic activity towards benzoylation reaction has been correlated with the surface acidity of the systems.
Cyclohexanol decomposition activity of supported vanadia catalysts is ascribed to the high surface area, total acidity and interaction between supported vanadia and the amorphous support. Among the supported catalysts, the effect of vanadia over various wt% V2O5 (2–10) loading indicates that the catalyst comprising of 6 wt% V2O5 exhibits higher acidity and decomposition activity. Structural characterization of the catalysts has been done by techniques like energy dispersive X-ray analysis, X-ray diffraction and BET surface area. Acidity of the catalysts has been measured by temperature programmed desorption using ammonia as a probe molecule and the results have been correlated with the activity of catalysts.
Invertase was immobilised on microporous montmorillonite K-10 via adsorption and covalent binding. The immobilised enzymes were tested for sucrose hydrolysis activity in a batch reactor. Km for immobilised systems was greater than free enzyme. The immobilised forms could be reused for 15 continuous cycles without any loss in activity. After 25 cycles, 85% initial activity was retained. A study on leaching of enzymes showed that 100% enzyme was retained even after 15 cycles of reuse. Leaching increased with reaction temperature. Covalent binding resisted leaching even at temperatures of 70 °C.