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81.
Atul Kumar Nagaraj M. Gowda Sushma Gaikwad Archana Pundle 《Journal of photochemistry and photobiology. B, Biology》2009,97(2):65
Penicillin V acylase (PVA), a member of newly evolved Ntn-hydrolase superfamily, is a pharmaceutically important enzyme to produce 6-aminopenicillanic acid. Active site characterization of recently purified monomeric PVA from Rhodotorula aurantiaca (Ra-PVA), the yeast source, showed the involvement of serine and tryptophan in the enzyme activity. Modification of the protein with serine and tryptophan specific reagents such as PMSF and NBS showed partial loss of PVA activity and substrate protection. Ra-PVA was found to be a multi-tryptophan protein exhibiting one tryptophan, in native and, four in its denatured condition. Various solute quenchers and substrate were used to probe the microenvironment of the putative reactive tryptophan through fluorescence quenching. The results obtained indicate that the tryptophan residues of Ra-PVA were largely buried in hydrophobic core of the protein matrix. Quenching of the fluorescence by acrylamide was collisional. Acrylamide was the most effective quencher amongst all the used quenchers, which quenched 71.6% of the total intrinsic fluorescence of the protein, at a very less final concentration of 0.1 M. Surface tryptophan residues were found to have predominantly more electropositively charged amino acids around them, however differentially accessible for ionic quenchers. Denaturation led to shift in λmax from 336, in native state, to 357 nm and more exposed to the solvent, consequently increase in fluorescence quenching with all quenchers. This is an attempt towards the conformational studies of Ra-PVA. 相似文献
82.
Tushar S. Basu Baul Archana Mizar Eleonora Rivarola Michal Hol?apek Ulli Englert 《Journal of organometallic chemistry》2006,691(16):3416-3425
A series of cis-bis{5-[(E)-2-(aryl)-1-diazenyl]quinolinolato}diphenyltin(IV) complexes have been synthesized and characterized by 1H, 13C, 119Sn NMR, ESI-MS, IR and 119mSn Mössbauer spectroscopic techniques in combination with elemental analysis. The structures of a ligand L6H (i.e., 5-[(E)-2-(4-ethoxyphenyl)-1-diazenyl]quinolin-8-ol) and three diphenyltin(IV) complexes, viz., Ph2Sn(L1)2 · (CH3)2CO (1), Ph2Sn(L4)2 (4) and Ph2Sn(L5)2 (5) (L = 5-[(E)-2-(aryl)-1-diazenyl]quinolin-8-ol: aryl = phenyl - (L1H); 4′-methylphenyl - (L4H) and 4′-bromophenyl - (L5H)) were determined by single crystal X-ray diffraction. In general, the complexes were found to adopt a distorted cis-octahedral arrangement around the tin atom. These complexes retain their solid-state structure in non-coordinating solvent as evidenced by 119Sn NMR spectroscopic results. The in vitro cytotoxicity of 1 is reported and compared with Ph2Sn(Ox)2 (Ox = deprotonated quinolin-8-ol) against seven well characterized human tumor cell lines. 相似文献
83.
The principles of the oligoethylene glycol (OEG) mixture synthesis are illustrated with the synthesis of all four possible stereoisomers of a hydroxybutenolide fragment common to murisolin and many other acetogenins. Modified dimethoxybenzyl groups with varying numbers of OEG units (-CH2CH2O-) are used to protect alcohols and serve as codes for configurations at two stereocenters. The encoded isomers are carried through several steps in a sequence of mixing prior to the reaction and then demixing during the separation to give individual pure products. A new tagging scheme is introduced in which a stereocenter bearing a hydroxy group is given two different tags. These initially redundant tags then serve to encode the configuration of another (untagged) stereocenter by appropriate pairwise reactions of the tagged precursors. The experimental features (reaction, analysis, separation, and characterization) of OEG mixture synthesis are detailed and are compared to and contrasted with those of fluorous mixture synthesis. 相似文献
84.
The influence of Reynolds number and blockage ratio on the vortex dynamics of a trapezoidal bluff body placed inside a circular pipe is studied experimentally and numerically. Low aspect ratio, high blockage ratio, curved end conditions (junction of pipe and bluff body), axisymmetric upstream flow with shear and turbulence are some of the intrinsic features of this class of bluff body flows which have been scarcely addressed in the literature. A large range (200:200,000) of Reynolds number (ReD) is covered in this study, encompassing all the three pipe flow regimes (laminar, transition and turbulent). Four different flow regimes are defined based on the distinct features of Strouhal number (St)–ReD relation: steady, laminar irregular, transition and turbulent. The wake in the steady regime is stationary with no oscillations in the shear layer. The laminar regime is termed as irregular owing to irregular vortex shedding. The vortex shedding in this regime is observed to be symmetric. The emergence of separation bubble downstream of the bluff body on either side is another interesting feature of this regime, which is further observed to be symmetric. Two pairs of mean streamwise vortices are noticed in the near-wake regime, which are termed as reverse dipole-type wake topology. Beyond the irregular laminar regime, the Strouhal number falls gradually and vortex shedding becomes more periodic. This regime is named transition and occurs close to the Reynolds number at which transition to turbulence takes place in a fully developed pipe. The turbulent regime is characterised by a nearly constant Strouhal number. Typical Karman-type vortex shedding is noticed in this regime. The convection velocity, wake width formation length and irrecoverable pressure loss are quantified to highlight the influence of blockage ratio. These results will be useful to develop basic understanding of vortex dynamics of confined bluff body flow for several practical applications. 相似文献
85.
Sijo Sebastian Manesh Michael Sreekala G. Anu Varghese Chandu Venugopal 《Brazilian Journal of Physics》2017,47(1):46-54
We have investigated fast- and slow-mode solitary profiles in a five-component plasma consisting of positively and negatively charged pair ions, hydrogen ions, and hotter and colder electrons. Of these, the heavier ions and colder photoelectrons are of cometary origin while the other components are of solar origin; the electrons are described by kappa distributions. The Zakharov-Kuznetsov (ZK) equation is derived, and solutions for fast- and slow-mode solitary structures are plotted for parameters relevant to comet Halley. We found that the presence of hydrogen ions determines the polarity of the fast- and slow-mode solitary structures. Also, variations of equilibrium number density of hydrogen ions and charge numbers on the heavier pair ions act differently on the fast- and slow-mode solitary structures. The addition of hydrogen ions significantly affects the amplitude of the solitary structures for the fast mode. Further, the cyclotron frequency of the lighter and heavier ions has a noticeable effect on the width of the solitary waves. 相似文献
86.
Dhayal V Chaudhary A Choudhary BL Nagar M Bohra R Mobin SM Mathur P 《Dalton transactions (Cambridge, England : 2003)》2012,41(31):9439-9450
[Zr(OPr(i))(4)·Pr(i)OH] reacts with [HOSi(O(t)Bu)(3)] in anhydrous benzene in 1:1 and 1:2 molar ratios to afford alkoxy zirconosiloxane precursors of the types [Zr(OPr(i))(3){OSi(O(t)Bu)(3)}] (A) and [Zr(OPr(i))(2){OSi(O(t)Bu)(3)}(2)] (B), respectively. Further reactions of A or B with glycols in 1:1 molar ratio afforded six chemically modified precursors of the types [Zr(OPr(i))(OGO){OSi(O(t)Bu)(3)}] (1A-3A) and [Zr(OGO){OSi(O(t)Bu)(3)}(2)] (1B-3B), respectively [where G = (-CH(2)-)(2) (1A, 1B); (-CH(2)-)(3) (2A, 2B) and (-CH(2)CH(2)CH(CH(3)-)} (3A, 3B)]. The precursors A and B are viscous liquids, which solidify on ageing whereas the other products are all solids, soluble in common organic solvents. These were characterized by elemental analyses, molecular weight measurements, FAB mass, FTIR, (1)H, (13)C and (29)Si-NMR studies. Cryoscopic molecular weight measurements of all the products, as well as the FAB mass studies of 3A and 3B, indicate their monomeric nature. However, FAB mass spectrum of the solidified B suggests that it exists in dimeric form. Single crystal structure analysis of [Zr{OSi(O(t)Bu)(3)}(4)(H(2)O)(2)]·2H(2)O (3b) (R(fac) = 11.9%) as well as that of corresponding better quality crystals of [Ti(O(t)Bu){OSi(O(t)Bu)(3)}(3)] (4) (R(fac) = 5.97%) indicate the presence of a M-O-Si bond. TG analyses of 3A, B, and 3B indicate the formation of zirconia-silica materials of the type ZrO(2)·SiO(2) from 3A and ZrO(2)·2SiO(2) from B or 3B at low decomposition temperatures (≤200 °C). The desired homogenous nano-sized zirconia-silica materials [ZrO(2)·nSiO(2)] have been obtained easily from the precursors A and B as well as from the glycol modified precursors 3A and 3B by hydrolytic sol-gel process in organic media without using any acid or base catalyst, and these were characterized by powder XRD patterns, SEM images, EDX analyses and IR spectroscopy. 相似文献
87.
Jayaraman Jayabharathi Venugopal Thanikachalam Marimuthu Venkatesh Perumal 《Journal of luminescence》2012,132(3):707-712
The interaction between the imidazole derivative 2-(2,4-difluorophenyl)-1-phenyl-1H-imidazo[4,5-f][1,10]phenanthroline (dfppip) and bovine serum albumin (BSA) was investigated by fluorescence and UV–vis absorbance spectroscopy. From the experimental results, it was found that the imidazole derivative has strong ability to quench the intrinsic fluorescence of BSA by forming complexes. Electrostatic interactions play an important role to stabilize the complex. The binding constants and the number of binding sites have been determined in detail. The distance (r) between the donor and the acceptor was obtained according to fluorescence resonance energy transfer (FRET). Conformational changes of BSA were observed from synchronous fluorescence spectroscopy. The effect of metal ions such as Cu2+, Zn2+, Ca2+, Mg2+, Ni2+, Co2+ and Fe2+ on the binding constants between the imidazole derivative and BSA were also studied. 相似文献
88.
M. Venugopal B. Sankar Reddy C. Devendranath Reddy K. D. Berlin 《Journal of heterocyclic chemistry》2001,38(1):275-279
Several 2‐alkylcarbamato/thiocarbamato/aryloxy/trichloromethyl‐2,3‐dihydro‐5‐propoxy‐1H‐1,3,2‐benzodiazaphosphole 2‐oxides ( 4 and 6 ) were synthesised by reacting 4‐propoxy‐o‐phenylenediamine ( 1 ) with various N‐dichlorophosphinyl carbamates ( 3 ), aryl phosphorodichloridates ( 5a‐f ) and trichloromethyl phosphonic dichloride ( 5g ) in the presence of triethylamine at 45‐65 °C. Their ir, 1H, 13C, 31P nmr and mass spectral data are discussed. The compounds were screened for antifungal activity against Curvularia lunata and Aspergillus niger and for antibacterial activity against Bacillus subtilis and Escherichia coli. Most of these compounds exhibited moderate activity in the assays. 相似文献
89.
Ramkumar Kannan Selvakumar Balasubramaniam Sandeep Kumar Raju Chambenahalli Prof. Eluvathingal D. Jemmis Dr. Ajay Venugopal 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(56):12717-12721
Bismuth compounds are gaining importance as potential alternatives to transition-metal complexes and electron deficient lighter p-block compounds in homogeneous catalysis. Computational analysis on the two-coordinate [(Me2NC6H4)Bi]2+ possessing three electrophilic sites is experimentally evidenced by the isolation of [{Me2NC6H4}Bi{OP(NMe2)3}3][B(3,5-C6H3Cl2)4]2. These observations led us to generate dicationic organobismuth catalyst, [(Me2NC6H4)Bi(L)3]2+ (L=aldehyde/ketone), evidenced by NMR spectroscopy in solution and by single-crystal X-ray diffraction in the solid state. It efficiently catalyzes hydrosilylation of aldehydes and ketones resulting in silyl ethers as the only products in high yields. Our investigations support a carbonyl activation mechanism at the bismuth center followed by Si−H addition. 相似文献
90.
Complexes of Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Pd(II) with di-N-phenyl pyromellitic diimide (PhPMDI) and di-N-pyridyl
pyromellitic diimide (PyPMDI) were prepared and characterized based on analytical, molar conductance, magnetic, IR, PMR, electronic
and ESR data. Based on analytical and molar conductance, the complexes have been formulated as [M(PhPMDA)(H2O)2]n (M = Mn, Fe, Co, Ni), [Cu(PhPMDA)]n [Pd2(PhPMDA)Cl2(H2O)2], [M(PyPMDA)]n (M = Mn, Fe, Co, Ni and Cu) and [Pd2(PyPMDA)Cl2] In all these complexes PhPMDA acts as a mononegative bidentate ligand whereas PyPMDA acts as a mononegative tridentate one
in the form of amide rather than imide. The geometries of the complexes have been proposed based on the electronic spectra.
The various bonding parameters have been calculated from the ESR spectra of Cu(II) complexes. 相似文献