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1.
Mithilesh Kumar Mishra Thenkrishnan Kumaraguru Gurrala Sheelu Nitin W. Fadnavis 《Tetrahedron: Asymmetry》2009,20(24):2854-2860
The general properties of Lecitase® Ultra, a phospholipase manufactured and marketed by Novozymes, Denmark, have been studied after purification by ultrafiltration. The enzyme has a molecular mass of 35 KD, pH-optimum of 8.5, and appears to possess a single active site which exhibits both the lipase and phospholipase activities that increase in the presence of Ca2+ and Mg2+ ions. The enzyme is inhibited by heavy metal ions and surfactants, and does not accept p-nitrophenyl acetate and glycerol triacetate. Substrates, such as glycerol tributyrate and p-nitrophenyl palmitate, esters of N-acetyl-α-amino acids and α-hydroxy acids are readily accepted. Amino acids with aliphatic residues, such as alanine, isoleucine, and methionine, are hydrolyzed with high enantioselectivity for the l-enantiomer (E >100), but amino acids with aromatic residues such as phenylalanine and phenylglycine, and esters of α-hydroxy acids are hydrolyzed with low enantioselectivity (E = 1–5). Immobilization of the enzyme in a gelatin matrix (gelozyme) leads to a marginal improvement in the enantioselectivity for these substrates. However, a dramatic improvement in enantioselectivity is observed for ethyl 2-hydroxy-4-oxo-4-phenylbutyrate (E value increases from 4.5 to 19.5 with S-selectivity). Similarly, glycidate esters, such as ethyl trans-(±)-3-phenyl glycidate and methyl trans-(±)-3-(4-methoxyphenyl) glycidate, are selectively hydrolyzed with a remarkable selectivity towards the (2S,3R)-enantiomer providing unreacted (2R,3S)-glycidate esters (ee >99%, conversion 52–55%) by the immobilized enzyme. 相似文献
2.
Shekhar Putta Annem Mallikarjun Reddy Gurrala Sheelu B.V. Subba Reddy Thenkrishnan Kumaraguru 《Tetrahedron》2018,74(46):6673-6679
Photooxidation of cyclopentadiene has been carried out in methanol using white light of LED lamp, rose bengal as photo initiator, and compressed air at 0?°C. Under conditions of [thiourea] ? [cyclopentadiene], the consumption of thiourea follows a pseudo-first-order reaction kinetics with half life of 75?±?10?min; corr. coeff. r?=?0.989. Slow addition of the monomer and maintaining excess thiourea concentration in reaction mass improves the yield. cis-3,5-Dihydroxy-1-cyclopentene is acetylated without isolation to obtain cis-3,5-Diacetoxy-1-cyclopentene of high purity (>99%) with overall isolated yield of 30%. Desymmetrization of the diacetate to (1R,4S)-4-hydroxycyclopent-2-en-1-yl acetate has been carried out via enzymatic transesterification with methanol in methyl tert-butyl ether (MTBE) at 5?°C using Novozym-435®. The enantiomerically pure monoacetate (e.e. >99%) was obtained in 95% isolated yield. The recovered enzyme was reused for more than 10 times without loss in yield and selectivity. The entire protocol does not require purification of final product by chromatography. 相似文献
3.
The critical micelle concentration (CMC) of four kinds of metallosurfactants of the type halogeno(dodecyl/cetylamine)‐bis(ethylenediamine)cobalt(III) has been studied in n‐alcohol and in formamide at different temperatures by electrical conductivity method. Specific conductivity data (at 293–313 K) served for the evaluation of temperature‐dependent CMC and the thermodynamic parameters such as standard Gibbs free energy changes (ΔG), enthalpies (ΔH), and entropies (ΔS) of micelle formation. CMCs have also been measured as a function of percentage concentration of alcohol added. It is suggested that alcohol addition leads to increase in formamide penetration into micellar interface that depends on the alcohol chain length. The results have been discussed in terms of increased hydrophobic effect (solvophobic interaction), dielectric constant of the medium, and the chain length of the alcohols, the surfactant in the solvent mixture. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 39: 22–31, 2007 相似文献
4.
P. Raja A. S. Faritha N. Kumaraguru R. Renganathan 《Research on Chemical Intermediates》2003,29(4):393-405
The kinetics of the oxidation of ascorbic acid (AH2) by peroxomonosulphate (PMS) were determined in aqueous medium in acidic (pH 4.4), neutral (pH 7.0) and alkaline (pH 9.0) conditions over the temperature range 13-28°C. The reactions were found to obey total second-order kinetics, first-order each with respect to peroxomonosulphate and ascorbic acid concentration, obeying-d[AH2]/dt = k
2[PMS][AH2]. Dehydroascorbic acid was detected as the product of the reaction. The stoichiometry of the reaction, [peroxomonosulphate]/[ascorbicacid] = 1 : 1, indicated the absence of self-decomposition of peroxomonosulphate. The influence of neutral salt (NaClO4) was found to increase the reaction rate. Evidence for the formation of radical intermediates was obtained. A mechanism involving the formation of hydroxyl, sulphate and ascorbate free radicals as intermediates is proposed. The rate and activation parameters were evaluated to substantiate the mechanism proposed. A comparison is made with the corresponding reactions of the similar peroxides, S2O8
2- and P2O8
4-. 相似文献
5.
In the present communication, the unglazed cylindrical solar adsorber module is suggested for refrigeration and theoretical models for the heat and mass transfer in the cylindrical adsorber with heat balance equations in the collector components have been developed. It has been found that, both the SCP and COPsolar raises with increasing the evaporation temperature and drop off with the increase of the condensation temperature. The COPsolar increased from 0.15 to 0.52 with the increase of the total solar energy absorbed by the collector while the COPcycle varied in the range of 0.57–0.73. The efficiency of unglazed solar collector varied from 36 to 44 %. The cost of current unglazed adsorption refrigeration system is compared with the glazed system, and it is 33 to 50 % less than the cost of glazed system. 相似文献
6.
Narayanasamy Kumaraguru Sankarlingam Arunachalam Mahadevimanglam Narayanasamy Arumugham Kannappan Santhakumar 《Transition Metal Chemistry》2006,31(2):250-255
A number of mixed ligand chromium(III)–surfactant coordination complexes, of the type cis-[Cr(en)2(A)X]2+ and cis-α-[Cr(trien)(A)X]2+ (A = Dodecyl or Cetylamine; X = F−, Cl−, Br−) were synthesized from the corresponding dihalogeno complexes by ligand substitution. These compounds form foam in aqueous
solution when shaken. The critical micelle concentration (CMC) values of these surfactant metal complexes in aqueous solution
were obtained from conductance measurements. Specific conductivity data (at 303, 308 and 313 K) served for evaluation of the
temperature-dependent critical micelle concentration (cmc) and the thermodynamics of micellization (Δ Gm0, Δ Hm0 and Δ Sm0). 相似文献
7.
Kannappan Santhakumar Narayanasamy Kumaraguru Sankarlingam Arunachalam Mahadevimanglam Narayanasamy Arumugham 《Transition Metal Chemistry》2006,31(4):475-481
The kinetics and mechanism of iron(II) reduction of cis- α-chloro/bromo(cetylamine)(triethylenetetramine) cobalt(III) surfactant complex ions were studied spectrophotometrically
in an aqueous acid medium by following the disappearance of CoIII using an excess of the reductant under pseudo-first-order conditions: [FeII = 0.25 mol dm−3, [H+ = 0.1 mol dm−3, [μ = 1.0 mol dm−3 ionic strength in a nitrogen atmosphere at 303, 308 and 313 K. The reaction was found to be second order and showed acid
independence in the range [H+ = 0.05−0.25 mol dm−3. The second order rate constant increased with CoIII concentration and the presence of aggregation of the complex itself altered the reaction rate. The effects of [FeII], [H+] and [ μ] on the rate were determined. Activation and thermodynamic parameters were computed. It is suggested that the reaction of
Fe2+(aq) with CoIII complex proceeds by an inner-sphere mechanism. 相似文献
8.
Thenkrishnan Kumaraguru Tirunagari Harini Shalini Basetty 《Tetrahedron: Asymmetry》2017,28(11):1612-1617
Lecitase® Ultra was immobilized on epoxy-activated polymer (DILBEAD-VWR) functionalized with polyethyleneimine via adsorption and crosslinking with glutaraldehyde. The resolution of methyl trans-(±)-3-(4-methoxyphenyl) glycidate was carried out in xylene (e.e. >99%, conversion 50%). The enzyme is not inhibited by the 4-methoxy phenyl acetaldehyde produced during hydrolysis and the immobilized enzyme with 7% moisture content works efficiently in an organic phase. While the immobilized enzyme can be recycled several times, the polymer support can also be recycled after removing the immobilized enzyme by washing with 1?M HCl. 相似文献
9.
Marimuthu Sangavi Narayanasamy Kumaraguru Ray J. Butcher Colin D. McMillen 《Acta Crystallographica. Section C, Structural Chemistry》2024,80(2):30-36
Three new compounds, namely, 5-fluorocytosine–urea (2/1), 2C4H4FN3O·CH4N2O, (I), 5-fluorocytosine–5-fluorocytosinium 3,5-dinitrosalicylate–water (2/1/1), 2C4H4FN3O·C4H5FN3O+·C7H2N2O7−·H2O, (II), and 2-amino-4-chloro-6-methylpyrimidine–6-chloronicotinic acid (1/1), C6H4ClNO2·C5H6ClN3, (III), have been synthesized and characterized by single-crystal X-ray diffraction. In compound (I), 5-fluorocytosine (5FC) molecules A and B form two different homosynthons [R22(8) ring motif], one formed via N—H…O hydrogen bonds and the second via N—H…N hydrogen bonds. In addition to this interaction, a sequence of fused-ring motifs [R21(6), R33(8), R22(8), R43(10) and R22(8)] are formed, generating a supramolecular ladder-like hydrogen-bonded pattern. In compound (II), 5FC and 5-fluorocytosinium are linked by triple hydrogen bonds, generating two fused-ring motifs [R22(8)]. The neutral 5FC and protonated 5-fluorocytosinum cation form a dimeric synthon [R22(8) ring motif] via N—H…O and N—H…N hydrogen bonds. On either side of the dimeric synthon, the neutral 5FC, 5-fluorocytosinium cation, 3,5-dinitrosalicylate anion and water molecule are hydrogen bonded through N—H…O, N—H…N, N—H…OW and OW—HW…O hydrogen bonds, forming a large ring motif [R1010(56)], leading to a three-dimensional supramolecular network. In compound (III), 2-amino-4-chloro-6-methylpyrimidine (ACP) interacts with the carboxylic acid group of 6-chloronicotinic acid via N—H…O and O—H…O hydrogen bonds, generating an R22(8) primary ring motif. Furthermore, the ACP molecules form a base pair via N—H…N hydrogen bonds. The primary motif and base pair combine to form tetrameric units, which are further connected by Cl…Cl interactions. In addition to this hydrogen-bonding interaction, compounds (I) and (III) are further enriched by π–π stacking interactions. 相似文献
10.
N. Kumaraguru K. Santhakumar S. Kalyanasundharam 《Journal of solution chemistry》2011,40(10):1673-1686
The critical micelle concentration (CMC) of surfactant–Cr(III)–dodecylamine complexes of the type cis-α-[Cr(trien)(C12H25NH2)X]2+ (where trien = triethylenetetramine; X = F−, Cl−, Br−) has been studied in n-alcohol and in formamide at different temperatures, by electrical conductivity measurements. From the CMC values as a function
of temperature, various thermodynamic properties have been evaluated: standard Gibbs energy changes (Δmic
G
0), standard enthalpy changes (Δmic
H
0) and standard entropy changes (Δmic
S
0) for micellization. Critical micelle concentrations have also been measured as a function of the percentage composition of
alcohol added. The solvent composition dependences of these thermodynamic parameters were determined. It is suggested that
alcohol addition leads to an increase in formamide penetration into the micellar interface that depends on the alcohol’s chain
length. The results are discussed in terms of an increased hydrophobic effect, dielectric constant of the medium, the chain
length of the alcohols, and the surfactant in the solvent mixture. 相似文献