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Complex Spectra (complex + spectrum)
Selected AbstractsRestricted rotation/tautomeric equilibrium and determination of the site and extent of protonation in bi-imidazole nucleosides by multinuclear NMR and GIAO-DFT calculationsJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 3 2005Jukka Mäki Abstract The restricted rotation about the conjoining bond in a series of 4,-substituted bi-imidazole nucleosides {5-amino-4-[4,-R-imidazol-2,-yl]-1-(,- d -ribofuranosyl)-1H -imidazole; where R=H, methyl, hydroxymethyl, oxalo, formyl} due to intramolecular hydrogen bonding between N-3, and the N-6 protons concomitant with prototropic tautomerism has been examined using multinuclear (1H, 13C and 15N) experimental NMR. Substitution at the 4, position causes the interconversion, whilst still an intramolecular process, to yield complex spectra as the dynamic process consists of a two-site exchange between non-degenerate tautomeric forms (asymmetric sites). The preferred tautomers were identified experimentally in each case and compared with theoretically determined structures geometry optimized using density functional theory (DFT) at the B3LYP/6,31G(d,p) level of theory on which gauge-independent atomic orbital-DFT (GIAO-DFT) computations at the B3LYP/cc-pVTZ level of theory were applied to calculate the chemical shifts of the 1H, 13C and 15N nuclei. Both the site and the extent of protonation of the bi-imidazole nucleosides were also similarly ascertained using the same methodology. Protonation at the pyridine-type nitrogen (N-3,) of the outer imidazole ring, the principle site of protonation, effectively eliminated the barrier to rotation about the conjoining bond yielding time-averaged spectra experimentally. Copyright © 2004 John Wiley & Sons, Ltd. [source] DNA tertiary structure and changes in DNA supercoiling upon interaction with ethidium bromide and gyrase monitored by UV resonance Raman spectroscopyJOURNAL OF RAMAN SPECTROSCOPY, Issue 10 2007U. Neugebauer Abstract The tertiary structure of DNA is important for many of its biological functions. In this work supercoiled and relaxed forms of purified plasmid DNA pBR322 in dilute aqueous solutions are investigated by means of UVRR spectroscopy to assess changes in B-DNA conformation. Spectral variation in the CO and exocyclic NH2 vibration above 1600 cm,1 indicate changes in hydrogen bonding. A minor shift of the CN stretching mode of adenosine and guanosine at 1487 cm,1 supports these findings. Changes in ribose conformation are visible in the spectral region 1320,1360 cm,1 by vibrational coupling of the ribose pucker to the vibrations of the purine and pyrimidine bases. The intercalating phenanthridinium drug ethidium bromide is known to reduce the negative supercoiling of DNA. This change in DNA topology is reflected in variations of the UVRR marker bands of DNA identified above. Principal component analysis helped to extract the features of interest from the complex spectra of the intercalation complex. Within the bacterial cells the change in DNA topology is achieved by the action of topoisomerases. In this work, the DNA-binding subunit GyrA of the enzyme gyrase was extracted from E. coli and applied to relaxed and supercoiled pBR322. The observed changes in the vibrational signature of the relaxed DNA in the presence of GyrA indicate a change of topology towards the supercoiled form. With already supercoiled DNA no further change in DNA topology is observed. Copyright © 2007 John Wiley & Sons, Ltd. [source] Metabolic profile of lettuce leaves by high-field NMR spectraMAGNETIC RESONANCE IN CHEMISTRY, Issue 8 2005Anatoli P. Sobolev Abstract A detailed analysis of the proton high-field NMR spectra of aqueous and organic extracts of lettuce leaves is reported for the first time. A combination of COSY, TOCSY, 1H,13C HSQC, 1H,13C HMBC bidimensional sequences and DOSY was used to assign each spin system and to separate the components of the complex patterns. A large number of water-soluble metabolites belonging to different classes such as carbohydrates, polyols, organic acids and amino acids were fully assigned. Moreover, the complex spectra of metabolites extracted in organic solvents belonging to sterols, fatty acids, diacylglycerophospholipids, galactosyldiacylglycerols, sulpholipids, pheophytins, carotenoids and hydrocarbons were also assigned. Copyright © 2005 John Wiley & Sons, Ltd. [source] Electrical study of InAs/GaAs quantum dots with two different environmentsPHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 9 2008M. Kaniewska Abstract Unusually complex spectra have been obtained for InAs/GaAs quantum dot (QD) structures when studied as a function of applied bias by deep level transient spectroscopy (DLTS). In spite of their complexity, basic processes for electron escape from the QDs have been recognized. We show that due to the variety of transitions involving direct tunneling and more complex thermal transitions, due to QD size fluctuations, and environmental dependent QD carrier population, measurement conditions have to be carefully suited for characterizing transport properties of the QDs. Additionally, on the basis of results of a comparative study under chosen measurement conditions, we conclude that the states of the InAs QDs shift towards the middle of the energy gap if the QDs are capped with a Ga-rich InGaAs insertion. It explains a red-shift of the emission wavelength that was found by photoluminescence measurements (PL). (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Mass spectrometry in the characterization of ambers.RAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 5 2008Amber is a fossil resin constituted of organic polymers derived through complex maturation processes of the original plant resin. A classification of eight samples of amber of different geological age (Miocene to Triassic) and geographical origin is here proposed using direct mass spectrometric techniques, i.e. laser desorption ionization (LDI), atmospheric pressure chemical ionization (APCI) and atmospheric pressure photoionization (APPI), in order to obtain a fingerprint related to the amber origin. Differences and similarities were detected among the spectra with the four methods, showing quite complex spectra, full of ionic species in the mass range investigated (up to m/z 2000). The evaluation required statistical analysis involving multivariate techniques. Cluster analysis or principal component analysis (PCA) generally did not show a clear clustering with respect to the age of samples, except for the APPI method, which allowed a satisfying clustering. Using the total ion current (TIC) obtained by the different analytical approaches on equal quantities of the different amber samples and plotted against the age, the only significant correlation appeared to be that involving APPI. To validate the method, four amber samples from Cretaceous of Spain were analyzed. Also in this case a significant correlation with age was found only with APPI data. PCA obtained with TIC values from all the MS methods showed a fair grouping of samples, according to their age. Three main clusters could be detected, belonging to younger, intermediate and older fossil resins, respectively. This MS analysis on crude amber, either solid or extract, followed by appropriate multivariate statistical evaluation, can provide useful information on amber age. The best results are those obtained by APPI, indicating that the quantity of amber soluble components that can be photoionized decreases with increasing age, in agreement with the formation of highly stable, insoluble polymers. Copyright © 2008 John Wiley & Sons, Ltd. [source] The Heteropolytungstate Core {BW13O46}11, Derived as Monomer, Dimer, and TrimerCHEMISTRY - A EUROPEAN JOURNAL, Issue 25 2007Nathalie Leclerc-Laronze Dr. Abstract A study of the borotungstate system has led to the characterization of new, original compounds based on the unconventional Keggin derivative [H3BW13O46]8, ion (denoted as 1). [H3BW14O48]6, (2) and the dimer [H6B2W26O90]12, (3) crystallize as mixed cesium/ammonium salts and have been characterized by single-crystal X-ray diffraction analysis. Anion 2 reveals an unusual arrangement, consisting of an outer {W3O9} core grafted onto the monovacant [BW11O39]9, Keggin moiety and exhibits an unprecedented distorted square-pyramidal arrangement for a cis -{WO2} core. Elemental analysis, supported by bond distance analysis, is consistent with the presence of three protons distributed over the terminal oxygens of the outer {W3O7} capping fragment. The [H6B2W26O90]12, ion (3) is formally derived from the direct condensation of two [H3BW13O46]8, subunits. The cisoid arrangement of the two [BW11O39]9, subunits, coupled with the antiparallel arrangement of the two quasi-linear OW,,,OWOH2 chains within the central {W4O12} connecting group, breaks any symmetry, thereby resulting in a chiral compound. Polarography and pH-metric titrations reveal the formation of the monomeric precursor [H3BW13O46]8, (anion 1) under stoichiometric conditions. 183W NMR analysis of 2 and 3 in solution gives complex spectra, consistent with the presence of equilibria between several species. In the frame of this study, we also report on a structural re-investigation of the [H6B3W39O132]15, ion (4) based on reliable results obtained in the solid state by means of single-crystal X-ray diffraction analysis, and in solution by means of 1D and 2D COSY 183W NMR. X-ray diffraction analysis revealed the presence of three attached aquo ligands on the central {W6O15} connecting core, generating three OW,,,OWOH2 quasi-linear chains, which are responsible for the chirality of the trimeric assembly. This structural arrangement accounts for the 39-line 183W solution spectrum. The 2D COSY spectrum permits reliable assignments of the six strongly shielded resonances (around ,250 and ,400,ppm) to the six central W atoms, as well as additional assignments. The origin of such strong shielding for these particular W atoms is discussed on the basis of previously published results. Infrared data for compounds 1, 3, and 4 are also presented. [source] Longitudinal evaluation reveals a complex spectrum of virological profiles in hepatitis B virus/hepatitis C virus,coinfected patients,,HEPATOLOGY, Issue 1 2006Giovanni Raimondo Hepatitis B virus (HBV) and hepatitis C virus (HCV) coinfection is often associated with severe forms of liver disease. However, comprehensive studies are lacking, and scant information is available regarding the virological behavior over time in coinfected patients. This study enrolled 133 untreated HBV/HCV-positive patients (male/female = 102/31; median age 51 years [range: 22-83 years]) who were longitudinally followed up for 1 year with bimonthly evaluation of HBV/HCV viremia levels and liver biochemistry. Thirty of these patients had triple infection with hepatitis Delta virus (HDV), while 103 patients were HDV-negative. In the HDV-negative group, active infection with both HBV and HCV was revealed in 24 cases, inactive infection by both viruses was seen in 15 cases, active HBV/inactive HCV was seen in 15 cases, and inactive HBV/active HCV was seen in 49 cases. However, 32 subjects (31%) presented dynamic virological profiles characterized by fluctuation of HBV and/or HCV viremia levels that at different time points were over or under the cutoff limits. Consequently, a correct diagnosis could be performed in these subjects only by serially repeating the virological tests 1 year apart. Similarly, 15 of the 30 HDV-positive subjects showed active HBV and/or HCV infection, with fluctuating virological patterns in 8 cases. In conclusion, this study showed that the virological patterns in HBV/HCV coinfection are widely divergent and have dynamic profiles. A careful longitudinal evaluation of the viremia levels of both viruses is essential for making a correct diagnosis and tailoring the appropriate therapeutic schedule in coinfected patients. (HEPATOLOGY 2005.) [source] ,Robust and Raring to Go?', Judges' Perceptions of Child WitnessesJOURNAL OF LAW AND SOCIETY, Issue 4 2007Fiona E. Raitt This article explores judicial perceptions of child witnesses. It considers the impact of recent legislation in England and Wales as well as in Scotland which classified all child witnesses as vulnerable and introduced a series of special measures to facilitate children's evidence. The article reports the findings of an empirical research study conducted with the judiciary in Scotland which suggests that judicial perceptions of child witnesses extend across a complex spectrum where a child may be viewed as vulnerable but is also likely to be seen as suggestible, reliable or resilient. The article advances two propositions. First, that the statutory conceptualization of children as invariably vulnerable has not displaced established beliefs concerning children's suggestibility and therefore has made little difference to perceptions of their ability to produce reliable testimony. Second, that focusing on children's potential for resilience rather than their vulnerability may prove a more productive conceptualization of children, one which could better support their capability as witnesses. [source] Quantification of hepatic steatosis with MRI: The effects of accurate fat spectral modelingJOURNAL OF MAGNETIC RESONANCE IMAGING, Issue 6 2009Scott B. Reeder MD Abstract Purpose To develop a chemical-shift,based imaging method for fat quantification that accounts for the complex spectrum of fat, and to compare this method with MR spectroscopy (MRS). Quantitative noninvasive biomarkers of hepatic steatosis are urgently needed for the diagnosis and management of nonalcoholic fatty liver disease (NAFLD). Materials and Methods Hepatic steatosis was measured with "fat-fraction" images in 31 patients using a multiecho chemical-shift,based water-fat separation method at 1.5T. Fat-fraction images were reconstructed using a conventional signal model that considers fat as a single peak at ,210 Hz relative to water ("single peak" reconstruction). Fat-fraction images were also reconstructed from the same source images using two methods that account for the complex spectrum of fat; precalibrated and self-calibrated "multipeak" reconstruction. Single-voxel MRS that was coregistered with imaging was performed for comparison. Results Imaging and MRS demonstrated excellent correlation with single peak reconstruction (r2 = 0.91), precalibrated multipeak reconstruction (r2 = 0.94), and self-calibrated multipeak reconstruction (r2 = 0.91). However, precalibrated multipeak reconstruction demonstrated the best agreement with MRS, with a slope statistically equivalent to 1 (0.96 ± 0.04; P = 0.4), compared to self-calibrated multipeak reconstruction (0.83 ± 0.05, P = 0.001) and single-peak reconstruction (0.67 ± 0.04, P < 0.001). Conclusion Accurate spectral modeling is necessary for accurate quantification of hepatic steatosis with MRI. J. Magn. Reson. Imaging 2009;29:1332,1339. © 2009 Wiley-Liss, Inc. [source] The role of aluminium and titanium in the point defects of gamma irradiated natural quartzPHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 1 2005G. O. Sawakuchi Abstract In this work, the origin of the smoky colour acquired by quartz when exposed to extremely high doses (20 kGy) of ionising radiation is studied. Five paramagnetic centres were detected in the electron paramagnetic resonance (EPR) spectrum of irradiated quartz: [AlO4]0, [TiO4,/Li+]0A, [GeO4,/Na+]0A, [GeO4,/Li+]0C, and E,1. Optical absorption revealed a complex spectrum with superposition of bands. With the technique of thermoluminescence, at least three peaks at around 180, 260 and 320 °C were detected. The peak at around 180 ºC has maximum emission at 470 nm and the peaks at around 260 and 320 °C have maximum emissions at 450 nm. Through correlations between the obtained results with these techniques, it was possible to confirm previous results from the literature, i.e., that the smoky colour of quartz is strongly related to the centre [AlO4]0. Besides, it was verified an excellent correlation between the thermal decay of [AlO4]0 and [TiO4,/Li+]0A, suggesting that at a temperature around 200 ºC the Li leaves the Ti centre and recombines with the aluminium centre destroying the smoky colour of irradiated quartz. On the other hand and differently from the literature this process does not correlate to any of the thermoluminescence peaks. (© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Combined use of nuclear magnetic resonance and infrared spectroscopy for studying recognition processes between amphenicolic antibiotics and albuminMAGNETIC RESONANCE IN CHEMISTRY, Issue 7 2003Silvia Martini Abstract Biological reactions are mostly concerned with selective interactions between small ligands and macromolecular receptors. The same ligands may activate responses of different intensities and/or effects in the presence of different receptors. Many approaches based on spectroscopic and non-spectroscopic methods have been used to study interactions between small ligands and macromolecular receptors, including methods based on NMR and IR spectroscopic analysis of the solution behaviour of the ligand in the presence of receptors. In this work, we investigated the interaction between ovine serum albumin with two amphenicolic antibiotics [chloramphenicol (CAP) and thiamphenicol (TAP)], using a combined approach based on NMR and IR methodologies, furnishing complementary information about the recognition process occurring within the two systems. The two ligands, despite their similar structures, showed different affinities towards albumin. NMR methodology is based on the comparison of selective () and non-selective () spin,lattice relaxation rates of the ligands in the presence and absence of macromolecular receptors and and temperature dependence analysis. From these studies, the ligand,receptor binding strength was evaluated on the basis of the ,affinity index.' The derivation of the affinity index from chemical equilibrium kinetics for both the CAP,albumin and TAP,albumin systems allowed a comparison of the abilities of the two amphenicolic antibiotics to interact with the protein. IR methodology is based on the comparison of the ligand,protein ,complex' spectra with those of the non-interacting systems. On the basis of the differences revealed, a more thorough IR analysis was performed in order to understand the structural changes which occurred on both ligand and protein molecules within the interacting system. Copyright © 2003 John Wiley & Sons, Ltd. [source] | |||||||||||||