8 resultados para HPLC-DAD-MS
em Indian Institute of Science - Bangalore - Índia
Resumo:
The thermal degradation processes of two sulfur polymers, poly(xylylene sulfide) (PXM) and poly(xylylene disulfide) (PXD), were investigated in parallel by direct pyrolysis mass spectrometry (DPMS) and flash pyrolysis GC/MS (Py-GC/MS). Thermogravimetric data showed that these polymers decompose with two separate steps in the temperature ranges of 250-280 and 600-650 degrees C, leaving a high amount of residue (about 50% at 800 degrees C). The pyrolysis products detected by DPMS in the first degradation step of PXM and PXD were terminated by three types of end groups, -CH3, -CH2SH, and -CH=S, originating from thermal cleavage reactions involving a series of homolytic chain scissions followed by hydrogen transfer reactions, generating several oligomers containing some intact xylylene sulfide repeating units. The presence of pyrolysis compounds containing some stilbene-like units in the first degradation step has also been observed. Their formation has been accounted for with a parallel cleavage involving the elimination of H2S from the PXM main chains. These unsaturated units can undergo cross-linking at higher temperatures, producing the high amount of char residue observed. The thermal degradation compounds detected by DPMS in the second decomposition step at about 600-650 degrees C were constituted of condensed aromatic molecules containing dihydrofenanthrene and fenanthrene units. These compounds might be generated from the polymer chains containing stilbene units, by isomerization and dehydrogenation reactions. The pyrolysis products obtained in the Py-GC/MS of PXM and PXD at 610 degrees C are almost identical. The relative abundance in the pyrolysate and the spectral properties of the main pyrolysis products were found to be in generally good agreement with those obtained by DPMS. Polycyclic aromatic hydrocarbons (PAHs) were also detected by Py-GC/MS but in minor amounts with respect to DPMS. This apparent discrepancy was due to the simultaneous detection of PAHs together with all pyrolysis products in the Py-GC/MS, whereas in DPMS they were detected in the second thermal degradation step without the greatest part of pyrolysis compounds generated in the first degradation step. The results obtained by DPMS and PSI-GC/MS experiments showed complementary data for the degradation of PXM and PXD and, therefore, allowed the unequivocal formulation of the thermal degradation mechanism for these sulfur-containing polymers.
Resumo:
Two new cyclohexadepsipeptides have been isolated from the fungus Isaria. Fungal growth in solid media yielded hyphal strands from which peptide fractions were readily isolable by organic-solvent extraction. Two novel cyclodepsipeptides, isaridin A and isaridin B, have been isolated by reverse-phase HPLC, and characterized by ESI-MS and 1H-NMR. Single crystals of both peptides have been obtained, and their 3D structures were elucidated by X-ray diffraction. The isaridins contain several unusual amino acid residues. The sequences are cyclo(β-Gly-HyLeu-Pro-Phe-NMeVal-NMePhe) and cyclo(β-Gly-HyLeu-β-MePro-Phe-NMeVal-NMePhe), where NMeVal is N-methylvaline, NMePhe N-methylphenylalanine, and HyLeu hydroxyleucine (=2-hydroxy-4-methylpentanoic acid). The two peptides differ from one another at residue 3, isaridin A having an (S)-proline at this position, while β-methyl-(S)-proline (=(2S,3S)-2,3,4,5-tetrahydro-3-methyl-1H-pyrrole-2-carboxylic acid) is found in isaridin B. The solid-state conformations of both cyclic depsipeptides are characterized by the presence of two cis peptide bonds at HyLeu(2)-Pro(3)/HyLeu(2)-β-MePro(3) and NMeVal(5)-NMePhe(6), respectively. In isaridin A, a strong intramolecular H-bond is observed between Phe(4)CO⋅⋅⋅HNβ-Gly(1), and a similar, but weaker, interaction is observed between β-Gly(1)CO⋅⋅⋅HNPhe(4). In contrast, in isaridin B, only a single intramolecular H-bond is observed between β-Gly(1)CO⋅⋅⋅HNPhe(4
Resumo:
Hyoscyamine 6 beta-hydroxylase (H6H; EC 1.14.11.11), an important enzyme in the biosynthesis of tropane alkaloids, catalyzes the hydroxylation of hyoscyamine to give 6 beta-hydroxyhyoscyamine and its epoxidation in the biosynthetic pathway leading to scopolamine. Datura metel produces scopolamine as the predominant tropane alkaloid. The cDNA encoding H6H from D. mete! (DmH6H) was cloned, heterologously expressed and biochemically characterized. The purified recombinant His-tagged H6H from D. mete! (DmrH6H) was capable of converting hyoscyamine to scopolamine. The functionally expressed DmrH6H was confirmed by HPLC and ESI-MS verification of the products, 6 beta-hydroxyhyoscyamine and its derivative, scopolamine; the DmrH6H epoxidase activity was low compared to the hydroxylase activity. The K-m values for both the substrates, hyoscyamine and 2-oxoglutarate, were 50 mu M each. The CD (circular dichroism) spectrum of the DmrH6H indicated a preponderance of alpha-helicity in the secondary structure. From the fluorescence studies, Stern-Volmer constants for hyoscyamine and 2-oxoglutarate were found to be 0.14 M-1 and 0.56 M-1, respectively. These data suggested that the binding of the substrates, hyoscyamine and 2-oxoglutarate, to the enzyme induced significant conformational changes. (C) 2010 Elsevier Masson SAS. All rights reserved.
Resumo:
GC-MS study of two fatty oil fractions from Artabotrys odoratissimus (leaves) indicated the presence of fifteen compounds namely, nonanoic acid; methyl phenyl propanoate; decanoic acid; diethyl phthalate; dibutyl phthalate; 2 - amino-3-ethyl biphenyl; 5-methyl-9-phenylnonan-3-ol; hexadeca-2,7,11-triene; 2,6-dimethyl-1-phenylhepta-1-one; 2,5-dimethyltetradecahydrophenenthrene; 1-phenylundecane; 1-isopropyl-4,6-dimethyl naphthalene; 5-(2-butyl phenyl)pent-3-en-2-ol; 1-phenyideca-1-one and 1-phenylundecan-1-one. Some of the compounds are rare occurring and biologically active.
Resumo:
Degradation of dimethoate under UV irradiation using TiO2/polymer films prepared by the layer-by-layer (LbL) method was investigated. The thin films were fabricated on glass slides and the surface morphology and roughness of the thin films were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The effect of lamp intensity, catalyst loading in the layers, number of bilayers, pH and initial dimethoate concentration on the degradation of dimethoate was systematically studied. The degradation was monitored using high performance liquid chromatography (HPLC) analysis and total organic carbon (TOC) measurements as a function of irradiation time, to see the change in concentration of dimethoate and mineralization, respectively. Complete degradation of dimethoate was achieved under TiO2 optimum loading of 4 g/L at an UV irradiation time of 180 min. Increase in the lamp intensity, catalyst loading and number of bilayers increased the rate of degradation. At a pH of 4.62, complete degradation of dimethoate was observed. The degradation efficiency decreased with increase in initial dimethoate concentration. The degradation byproducts were analyzed and confirmed by gas chromatography-mass spectra (GC-MS). Toxicity of the irradiated samples was measured using the luminescence of bacteria Vibrio fischeri after 30 min of incubation and the results showed more toxicity than the parent compound. Catalyst reusability studies revealed that the fabricated thin films could be repeatedly used for up to ten times without affecting the photocatalytic activity of the films. The findings of the present study are very useful for the treatment of wastewaters contaminated with pesticides. (C) 2011 Elsevier B.V. All rights reserved.
Resumo:
Mass spectrometric analysis of a banyan endophyte, Bacillus subtilis K1, extract showing broad spectrum antifungal activity revealed a complex mixture of lipopeptides, iturins, surfactins, and fengycins. Fractionation by reversed-phase high performance liquid chromatography (HPLC) facilitated a detailed analysis of fengycin microheterogeneity. Matrix assisted laser desorption ionization (MALDI) and electrospray ionization (ESI) mass spectrometric studies permitted the identification of several new fengycin variants. Four major sites of heterogeneity are identified: (1) N-terminus beta-hydroxy fatty acid moiety, where chain length variation and the presence of unsaturation occur, (2) position 6 (Ala/Val/Ile/Leu), (3) position 10 (Val/Ile) within the macrocyclic ring, and (4) Gln to Glu replacement at position 8, resulting in fengycin variants that differ in mass by 1 Da. Diagnostic fragment ions provide a quick method for localizing the sites of variation in the macrocycle or the linear segment. Subsequent establishment of the sequences is achieved by MS/MS analysis of linear fengycin species produced by hydrolysis of the macrocyclic lactone. Unsaturation in the fatty acid chain and the presence of linear precursors in the B. subtilis K1 extract are also established by mass spectrometry. The anomalous distribution of intensities within isotopic multiplets is a diagnostic for Gln/Glu replacements. High resolution mass spectrometry facilitates the identification of fengycin species differing by 1 Da by localizing the variable position (Gln(8)/Glu(8)) in the fengycin variants.
Resumo:
Low power consumption per channel and data rate minimization are two key challenges which need to be addressed in future generations of neural recording systems (NRS). Power consumption can be reduced by avoiding unnecessary processing whereas data rate is greatly decreased by sending spike time-stamps along with spike features as opposed to raw digitized data. Dynamic range in NRS can vary with time due to change in electrode-neuron distance or background noise, which demands adaptability. An analog-to-digital converter (ADC) is one of the most important blocks in a NRS. This paper presents an 8-bit SAR ADC in 0.13-mu m CMOS technology along with input and reference buffer. A novel energy efficient digital-to-analog converter switching scheme is proposed, which consumes 37% less energy than the present state-of-the-art. The use of a ping-pong input sampling scheme is emphasized for multichannel input to alleviate the bandwidth requirement of the input buffer. To reduce the data rate, the A/D process is only enabled through the in-built background noise rejection logic to ensure that the noise is not processed. The ADC resolution can be adjusted from 8 to 1 bit in 1-bit step based on the input dynamic range. The ADC consumes 8.8 mu W from 1 V supply at 1 MS/s speed. It achieves effective number of bits of 7.7 bits and FoM of 42.3 fJ/conversion-step.
Resumo:
The present study examines an improved detoxification and rapid biological degradation of toxic pollutant acrylamide using a bacterium. The acrylamide degrading bacterium was isolated from the soil followed by its screening to know the acrylamide degrading capability. The minimal medium containing acrylamide (30 mM) served as a sole source of carbon and nitrogen for their active growth. The optimization of three different factors was analyzed by using Response Surface Methodology (RSM). The bacteria actively degraded the acrylamide at a temperature of 32 degrees C, with a maximum growth at 30 mM substrate (acrylamide) concentration at a pH of 7.2. The acrylamidase activity and degradation of acrylamide was determined by High Performance Liquid Chromatography (HPLC) and Matrix Assisted Laser Desorption and Ionization Time of Flight mass spectrometer (MALDI-TOF). Based on 168 rRNA analysis the selected strain was identified as Gram negative bacilli Stenotrophomonas acidaminiphila MSU12. The acrylamidase was isolated from bacterial extract and was purified by HPLC, whose mass spectrum showed a molecular mass of 38 kDa. (C) 2014 Elsevier Ltd. All rights reserved.