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Minor Shifts (minor + shift)
Selected AbstractsDNA 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] RELIABILITY OF SENSORY ASSESSORS: ISSUES OF COMPLEXITYJOURNAL OF SENSORY STUDIES, Issue 1 2009JANNA BITNES ABSTRACT The objective of this study was to investigate whether the sensory performance of assessors in a sensory panel maybe explained by complexity of evaluated product. We aimed to investigate whether we could observe a decline in sensory performance when increasing the complexity of the product. The products increased in number of constituents from mixtures of sucrose, sodium chloride, citric acid and caffeine in water, to the foods ice tea and tomato soup constituting different levels of the same substances. Candidates who succeeded evaluating one product were not always successful evaluating others. Few subjects were successful in everything. The conclusion was that there is only minor systematic decline with increasing complexity of products. The authors emphasize that definition of complexity involves more than just counting number of constituents and taste sensations, and suggest that minor differences in the task given to the assessor might explain different performances. PRACTICAL APPLICATIONS Practical use of the research presented in the present paper is in a sensory evaluation context. It is important for the users of sensory data to find out how the profiling should be organized to achieve optimum output, and in specific, the need for extensive training when dealing with a more complex product. The present study hypothesized that sensory assessors would have more difficulties evaluating a more complex product. However, the results showed that panel leaders should be more concerned with the task variables in the sensory evaluation. Even a minor shift in task variables had a stronger impact on the performance and reliability of the assessors than increasing number of constituents and/or stimuli sensations of the product. This study did not demonstrate a need for extensive training when dealing with a more complex product as hypothesized. [source] Systematic Studies on Photoluminescence of Oligo(arylene-ethynylene)s: Tunability of Excited States and Derivatization as Luminescent Labeling Probes for ProteinsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 14 2006Yong-Gang Zhi Abstract Functionalized oligo(phenylene-ethynylene)s (OPEs) with different conjugation lengths, p -X(C6H4C,C)nSiMe3 (n = 1,4; X = NH2, NMe2, H) were synthesized by Sonogashira coupling of (phenylene-ethynylene)s and 1-iodo-4-(trimethylsilylethynyl)benzene, followed by desilylation of the p -substituted (trimethylsilylethynyl)benzenes with potassium hydroxide. The photoluminescent properties for the OPE series with different chain lengths and their solvatochromic responses were examined. The absorption maxima were red-shifted with increasing numbers of ,(C6H4C,C), units (n), and a linear plot of the absorption energy maxima vs. 1/n was obtained for each series. The emission spectra in dichloromethane showed a broad and structureless band, the energies of which (in wavenumbers) also fit linearly with 1/n. Both the absorption and emission wavelength maxima of the NH2 - and NMe2 -substituted OPEs exhibited significant solvent dependence, whereas the parent OPEs (X = H) showed only minor shifts of the ,max values in different solvents. Substituent effects upon the photoluminescent characteristics of the OPEs and the tunability of the excited states were examined with the p -X(C6H4C,C)nSiMe3 (n = 2, 3; X = NH2, NMe2, H, SMe, OMe, OH, and F) series. The H- and F-substituted counterparts exhibited high-energy vibronically structured emissions attributed to the 3(,,*) excited states of the (arylene-ethynylene) backbone. For compounds bearing NH2 and NMe2 groups, a broad red-shifted emission with a remarkable Stokes shift from the respective absorption maximum was observed, which can be assigned to an n , ,* transition. The n , ,* assignment was supported by MO calculations on the model compounds p -X(C6H4C,C)2SiH3 (X = NH2, H). Functionalization of the oligo(arylene-ethynylene)s with the N -hydroxysuccinimidyl (NHS) moiety enabled covalent attachment of the fluorophore to HSA protein molecules. A series of fluorescent labels, namely p -X(C6H4C,C)nC6H4NHS, (n = 1, X = NH2, NMe2, SMe, OMe, OH, F; n = 2, X = NH2, NMe2) and p -Me2NC6H4C,C(C4H2S)C,CC6H4NHS were synthesized, and their conjugates with HSA (human serum albumin) were characterized by MALDI-TOF mass spectrometry, UV/Vis absorption spectroscopy, and gel electrophoresis. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] 4- and 4,5-Substituted N -Methoxythiazole-2(3H)-thiones , Preparation,UV/Vis Spectra, and Assignment of Electronic Transitions in Comparison to N -Methoxypyridine-2(1H)-thione Using Time-Dependent Density Functional Theory CalculationsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 5 2005Jens Hartung Abstract Experimentally observed absorptions in UV/Vis spectra of N -methoxy-4-methylthiazole-2(3H)-thione, N -methoxy-5-(p -methoxyphenyl)-4-methylthiazole-2(3H)-thione, N -methoxypyridine-2(1H)-thione, and selected N -hydroxy derivatives thereof have been assigned to ,,,*-type transitions as dominating character, using the results from ab initio calculations [time-dependent density functional theory (TD)RI-BLYP/TZVPP]. Theory further predicts that electronic excitations in N -methoxythiazole-2(3H)-thiones on one side and N -meth-oxypyridine-2(1H)-thione on the other side differ significantly with respect to character and statistical weight of contributing transitions. These effects originate predominantly from contributions of the endocyclic sulfur atom onto orbital energies and shapes in thiazole-2(3H)-thiones, and may be intensified by substituents such as a p -methoxyphenyl group located in position 5. Since the majority of the calculated spectral differences between thiazole- and pyridinethiones refers to excitations of low intensity, the findings from the present study correlate with two important experimental facts: (i) Apart from minor shifts in the exact spectral location of UV/Vis absorptions, electronic spectra of N -hydroxy- or N -methoxy-substituted pyridine-2(1H)-thiones and thiazole-2(3H)-thiones are surprisingly similar in shape. (ii) N -alkoxypyridine-2(1H)-thiones and N -alkoxythiazole-2(3H)-thiones liberate upon UV/Vis excitation oxygen-centered radicals with a comparable efficiency. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Paradoxical Solvent Effects on the Absorption and Emission Spectra of Amino-Substituted Perylene Monoimides,CHEMPHYSCHEM, Issue 8 2005Peter D. Zoon Abstract In N -(2,5-di- tert -butylphenyl)-9-pyrrolidinoperylene-3,4-dicarboximide (5PI) the absorption and emission spectra display large solvatochromic shifts, but, remarkably, the Stokes shift is practically independent of solvent polarity. This unique behavior is caused by the extraordinarily large ground-state dipole moment of 5PI, which further increases upon increasing the solvent polarity, whereas the excited-state dipole moment is less solvent dependent. In the corresponding piperidine compound, 6PI, this effect is much less important owing to the weaker coupling between the amino group and the aromatic imide moiety, and in the corresponding naphthalimide, 5NI, it is absent. The latter shows the conventional solvatochromic behavior of a push,pull substituted conjugated system, that is, minor shifts in absorption and a larger change in the emission energy with solvent polarity. [source] | ||||||||||