共查询到20条相似文献,搜索用时 10 毫秒
1.
Kevin W. Plaxco Craig J. Morton Shaun B. Grimshaw Jonathan A. Jones Maureen Pitkeathly Iain D. Campbell Christopher M. Dobson 《Journal of biomolecular NMR》1997,10(3):221-230
The effects of the commonly used denaturant guanidine hydrochloride(GuHCl) on the random coil conformations and NMR chemical shifts of theproteogenic amino acids have been characterized using the peptide seriesAc-Gly-Gly-X-Gly-Gly-NH2. The angle-sensitive couplingconstants, ROESY cross peak intensities and proline cis–trans isomerratios of a representative subset of these peptides are unaffected by GuHCl,which suggests that the denaturant does not significantly perturb intrinsicbackbone conformational preferences. A set of3JHNH values is presented which agreewell with predictions of recently developed models of the random coil. Wehave also measured the chemical shifts of all 20 proteogenic amino acids inthese peptides over a range of GuHCl concentrations. The shifts exhibit alinear dependence on denaturant concentration and we report here correctionfactors for the calculation of random coil 1H chemicalshifts at any arbitrary denaturant concentration. Studies of arepresentative subset of peptides indicate that 13C and15N chemical shifts are also perturbed by the denaturant.These results should facilitate the application of chemical shift-basedanalytical techniques to the study of polypeptides in solution with GuHCl.The effects of the denaturant on the quality of NMR spectra and on chemicalshift referencing are also addressed. 相似文献
2.
Summary Proton chemical shifts of a series of disordered linear peptides (H-Gly-Gly-X-Gly-Gly-OH, with X being one of the 20 naturally
occurring amino acids) have been obtained using 1D and 2D 1H NMR at pH 5.0 as a function of temperature and solvent composition. The use of 2D methods has allowed some ambiguities in
side-chain assignments in previous studies to be resolved. An additional benefit of the temperature data is that they can
be used to obtain ‘random coil’ amide proton chemical shifts at any temperature between 278 and 318 K by interpolation. Changes
of chemical shift as a function of trifluoroethanol concentration have also been determined at a variety of temperatures for
a subset of peptides. Significant changes are found in backbone and side-chain amide proton chemical shifts in these ‘random
coil’ peptides with increasing amounts of trifluoroethanol, suggesting that caution is required when interpreting chemical
shift changes as a measure of helix formation in peptides in the presence of this solvent. Comparison of the proton chemical
shifts obtained here for H-Gly-Gly-X-Gly-Gly-OH with those for H-Gly-Gly-X-Ala-OH [Bundi, A. and Wüthrich, K. (1979) Biopolymers, 18, 285–297] and for Ac-Gly-Gly-X-Ala-Gly-Gly-NH2 [Wishart, D.S., Bigam, C.G., Holm, A., Hodges, R.S. and Sykes, B.D. (1995) J. Biomol. NMR, 5, 67–81] generally shows good agreement for CH protons, but reveals significant variability for NH protons. Amide proton chemical
shifts appear to be highly sensitive to local sequence variations and probably also to solution conditions. Caution must therefore
be exercised in any structural interpretation based on amide proton chemical shifts. 相似文献
3.
The sequence specific 1H, 13C and 15N resonance assignments of hahellin in 8 M urea-denatured state have been accomplished by NMR spectroscopy. Secondary chemical shift analysis reveals the native-like propensities for β-rich conformation in the denatured state. 相似文献
4.
Jenny A.M.T.C. Cromsigt Cees W. Hilbers Sybren S. Wijmenga 《Journal of biomolecular NMR》2001,21(1):11-29
An analysis is presented of experimental versus calculated chemical shifts of the non-exchangeable protons for 28 RNA structures deposited in the Protein Data Bank, covering a wide range of structural building blocks. We have used existing models for ring-current and magnetic-anisotropy contributions to calculate the proton chemical shifts from the structures. Two different parameter sets were tried: (i) parameters derived by Ribas-Prado and Giessner-Prettre (GP set) [(1981) J. Mol. Struct.,
76, 81–92.]; (ii) parameters derived by Case [(1995) J. Biomol. NMR, 6, 341–346]. Both sets lead to similar results. The detailed analysis was carried using the GP set. The root-mean-square-deviation between the predicted and observed chemical shifts of the complete database is 0.16 ppm with a Pearson correlation coefficient of 0.79. For protons in the usually well-defined A-helix environment these numbers are, 0.08 ppm and 0.96, respectively. As a result of this good correspondence, a reliable analysis could be made of the structural dependencies of the 1H chemical shifts revealing their physical origin. For example, a down-field shift of either H2 or H3 or both indicates a high-syn/syn -angle. In an A-helix it is essentially the 5-neighbor that affects the chemical shifts of H5, H6 and H8 protons. The H5, H6 and H8 resonances can therefore be assigned in an A-helix on the basis of their observed chemical shifts. In general, the chemical shifts were found to be quite sensitive to structural changes. We therefore propose that a comparison between calculated and observed 1H chemical shifts is a good tool for validation and refinement of structures derived from NOEs and J-couplings. 相似文献
5.
6.
J. Buellesbach J. Gadau L. W. Beukeboom F. Echinger R. Raychoudhury J. H. Werren T. Schmitt 《Journal of evolutionary biology》2013,26(11):2467-2478
The evolution and maintenance of intraspecific communication channels constitute a key feature of chemical signalling and sexual communication. However, how divergent chemical communication channels evolve while maintaining their integrity for both sender and receiver is poorly understood. In this study, we compare male and female cuticular hydrocarbon (CHC) profiles in the jewel wasp genus Nasonia, analyse their chemical divergence and investigate their role as species‐specific sexual signalling cues. Males and females of all four Nasonia species showed unique, nonoverlapping CHC profiles unambiguously separating them. Surprisingly, male and female phylogenies based on the chemical distances between their CHC profiles differed dramatically, where only male CHC divergence parallels the molecular phylogeny of Nasonia. In particular, N. giraulti female CHC profiles were the most divergent from all other species and very different from its most closely related sibling species N. oneida. Furthermore, although our behavioural assays indicate that female CHC profiles can generally be perceived as sexual cues attracting males in Nasonia, this function has apparently been lost in the highly divergent female N. giraulti CHC profiles. Curiously, N. giraulti males are still attracted to heterospecific, but not to conspecific female CHC profiles. We suggest that this striking discrepancy has been caused by an extensive evolutionary shift in female N. giraulti CHC profiles, which are no longer used as conspecific recognition cues. Our study constitutes the first report of an apparent abandonment of a sexual recognition cue that the receiver did not adapt to. 相似文献
7.
Crystal structures of eight peptide β-hairpins in the sequence Boc-Leu-Phe-Val-Xxx-Yyy-Leu-Phe-Val-OMe revealed that the Phe(2) and Phe(7) aromatic rings are in close spacial proximity, with the centroid-centroid distance (R(cen)) of 4.4-5.4 ? between the two phenyl rings. Proton NMR spectra in chloroform and methanol solution reveal a significant upfield shift of the Phe(7) C(δ,δ') H(2) protons (6.65-7.04 ppm). Specific assignments of the aromatic protons have been carried out in the peptide Boc-Leu-Phe-Val-(D)Pro-(L)Pro-Leu-Phe-Val-OMe (6). The anticipated ring current shifts have been estimated from the aromatic ring geometrics observed in crystals for all eight peptides. Only one of the C(δ,δ') H proton lies in the shielding zone with rapid ring flipping, resulting in averaging between the two extreme chemical shifts. An approximate estimate of the population of conformations, which resemble crystal state orientation, may be obtained. Key nuclear Overhauser effects (NOEs) between facing Phe side chains provide support for close similarity between the solid state and solution conformation. Temperature dependence of aromatic ring proton chemical shift and line widths for peptide 6 (Boc-Leu-Phe-Val-(D)Pro-(L)Pro-Leu-Phe-Val-OMe) and the control peptide Boc-Leu-Val-Val-(D)Pro-Gly-Leu-Phe-Val-OMe establish an enhanced barrier to ring flipping when the two Phe rings are in proximity. Modeling studies suggest that small, conformational adjustment about C(α)-C(β) (χ(1) ) and C(β)-C(γ) (χ(2) ) bonds of both the Phe residues may be required in order to permit unhindered, uncorrelated flipping of both the Phe rings. The maintenance of the specific aromatic ring orientation in organic solvents provides evidence for significant stabilizing interaction. 相似文献
8.
Chet W. Swalina Randy J. Zauhar Michael J. DeGrazia Guillermo Moyna 《Journal of biomolecular NMR》2001,21(1):49-61
The dependence between the anomeric carbon chemical shift and the glycosidic bond , dihedral angles in oligosaccharide and glycopeptide model compounds was studied by Gauge-Including Atomic Orbital (GIAO) ab initio calculations. Complete chemical shift surfaces versus and for d-Glcp-d-Glcp disaccharides with (11), (12), (13), and (14) linkages in both - and -configurations were computed using a 3-21G basis set, and scaled to reference results from calculations at the 6-311G** level of theory. Similar surfaces were obtained for GlcNAcThr and GlcNAcSer model glycopeptides in - and -configurations, using in this case different conformations for the peptide moiety. The results obtained for both families of model compounds are discussed. We also present the determination of empirical formulas of the form 13C=f(,) obtained by fitting the raw ab initio data to trigonometric series expansions suitable for use in molecular mechanics and dynamics simulations. Our investigations are consistent with experimental observations and earlier calculations performed on smaller glycosidic bond models, and show the applicability of chemical shift surfaces in the study of the conformational behavior of oligosaccharides and glycopeptides. 相似文献
9.
Foraging theory suggests that predator responses to potential prey should be influenced by prey chemical defences, but the effects of ontogenetic variation in such defences on prey vulnerability to predators remain unclear. Cane toads (Rhinella marina) are toxic to anurophagous snakes, including the keelback (Tropidonophis mairii, a natricine colubrid that occurs within the toads' invasive range in Australia). Toxin levels and diversity change through toad ontogeny, decreasing from the egg stage to metamorphosis, then increasing in postmetamorphic toads. If the toxin content of a prey item influences predator responses, we predict that keelbacks should exhibit selective predation on toads close to metamorphosis. The results of our laboratory trials on adult (field-collected, and thus toad-experienced) and hatchling (laboratory-incubated, and thus toad-naive) keelbacks supported this prediction. The snakes selectively consumed later-stage rather than earlier-stage tadpoles, and earlier-stage rather than later-stage metamorphs. Our data are thus consistent with the hypothesis that ontogenetic changes in toxin content can affect individuals' vulnerability to predation. 相似文献
10.
The secondary chemical shift experienced by the1H-NMR resonances of the α C?H protons in proteins can be correlated with their backbone torsional angles ψ, which dictate the orientation of the α C?H proton to the adjacent carbonyl group. It is shown that α C?H protons present in β-sheet regions experience downfield secondary shifts , whereas those in α-helix regions experience upfield secondary shifts. The predictive use of this correlation in assignment studies is illustrated for the calcium-binding protein paravalbumin, for which a crystal structure is available, and troponin C, for which no crystallographic data are available. 相似文献
11.
Sukgeun Jung Ig-Chan Pang Joon-ho Lee Ilsu Choi Hyung Kee Cha 《Reviews in Fish Biology and Fisheries》2014,24(2):443-462
Sea surface temperatures in Korean waters have increased by approximately 1 °C during the past 40 years, implying possible range shifts of marine fishes and invertebrates. We analyzed spatially explicit, commercial catch data for 12 major fish species collected from 1984 to 2010 in Korean waters to evaluate and project their range shifts based on climate-driven hydrographic changes simulated by a general circulation model under a climate change scenario. There were significant relationships between the mean latitude of the catch distribution and water temperature for seven of the 12 species examined. Our circulation model projected that temperature stratification in the Korea Strait will disappear by 2030, and our empirical relationships predicted that the ranges of five of the fish species examined will shift poleward by 19–71 km from the 2000s to the 2030s. Compared with studies of demersal fishes in the western North Atlantic and the North Sea, our estimated speeds of shift in mean latitude of fishes were, on average, slower by factors of 2.3 and 5.7, respectively. This suggests that the pattern of range shift of marine species can vary regionally, depending on oceanographic and geomorphologic conditions. International cooperative research among fisheries scientists from countries throughout the region, especially Japan and China, is required to more reliably and comprehensively assess and project the range shifts of fish species. This will provide a scientific basis for the development of fishery policies and their adaptation to climate change in the western North Pacific. 相似文献
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13.
Inhibitive and adsorption properties of Penicillin G, Amoxicillin and Penicillin V potassium were studied using gravimetric, gasometric and quantum chemical methods. The results obtained indicate that these
compounds are good adsorption inhibitors for the corrosion of mild steel in HCl solution. The adsorption of the inhibitors
on mild steel surface is spontaneous, exothermic and supports the mechanism of physical adsorption. From DFT results, the
sites for nucleophilic attacks in the inhibitors are the carboxylic acid functional group while the sites for electrophilic
attacks are in the phenyl ring. There was a strong correlation between theoretical and experimental inhibition efficiencies. 相似文献
14.
15.
Anne Elisabeth Bjune 《Vegetation History and Archaeobotany》2014,23(3):299-308
The modern pollen production of local sub-alpine and alpine vegetation has been monitored over 8 years by using pollen traps situated along an elevational transect crossing the Pinus sylvestris and Betula pubescens elevational limits and continuing into the mid- and high-alpine vegetation in western Norway. The aim of the study is to monitor annual variation in the pollen production and hence the representation of common taxa found at or near the tree-line. The results can be used to derive critical pollen values that can be used to infer the presence of these taxa in the past, and to reconstruct past changes in tree line positions. Nine modified Tauber pollen traps were critically positioned in the vegetation from 663 to 1,347 m a.s.l. Three sub-aquatic traps were located in a small lake at 800 m a.s.l. just above the present-day B. pubescens tree-line. The traps have been sampled from 2004 to 2012. The results display large variations in pollen percentages and pollen accumulation rates from year to year, as well as great differences between the traps placed in the vegetation and in the lake, suggesting that further pollen trapping is needed to get a solid long-term average. The vegetation traps follow the vegetation distribution better and, as expected, give a more local signal than the lake traps. 相似文献
16.
Bernardo Celda Clelia Biamonti Maria Jose Arnau Roberto Tejero Gaetano T. Montelione 《Journal of biomolecular NMR》1995,5(2):161-172
Summary A large portion of the 13C resonance assignments for murine epidermal growth factor (mEGF) at pH 3.1 and 28°C has been determined at natural isotope abundance. Sequence-specific 13C assignments are reported for 100% of the assignable C, 96% of the C, 86% of the aromatic and 70% of the remaining peripheral aliphatic resonances of mEGF. A good correlation was observed between experimental and back-calculated C chemical shifts for regions of regular -sheet structure. These assignments also provide the basis for interpreting 1H–13C heteronuclear NOE (HNOE) values in mEGF at natural isotope abundance. Some of the backbone polypeptide segments with high internal mobility, indicated by these 1H–13C HNOE measurements, correlate with locations of residues involved in the putative mEGF-receptor binding site. Using four families of mEGF structures obtained over the last few years, we demonstrate that standard deviations between experimental and back-calculated C values can be used to monitor the refinement of this protein's structure, particularly for -sheet regions. Improved agreement between calculated and observed values of C is correlated with other measures of structure quality, including lowered values of residual constraint violations and more negative values of conformational energy. These results support the view that experimental conformation-dependent chemical shifts, C, can provide a reliable source of information for monitoring the process of protein structure refinement and are potentially useful restraints for driving the refinement.Abbreviations HSQC
heteronuclear single-quantum coherence spectroscopy
- PFG
pulsed-field gradient
- TOCSY
1H-1H total correlation spectroscopy
- EGF
epidermal growth factor
- mEGF
murine EGF
- hEGF
human EGF
- hTGF
human type- transforming growth factor
- DIPSI
spm-locking pulse sequence
- NOE
nuclear Overhauser effect
- HNOE
heteronuclear Overhauser effect 相似文献
17.
Heikaus S Kempf T Mahotka C Gabbert HE Ramp U 《Apoptosis : an international journal on programmed cell death》2008,13(7):938-949
Activation of the initiator-caspase, caspase-8 is under tight control of multiple antiapoptotic regulators including ARC,
cFlipS, cFlipL and PED/PEA-15. Since there is little data regarding the expression of caspase-8 and its antiapoptotic regulators in human
tumours in vivo, we analysed their expression in renal cell carcinomas (RCCs) to identify which of these genes might be crucial
for the well known impaired apoptosis and—as a result—resistance towards chemotherapy and ionizing radiation of RCCs. Caspase-8,
cFlipS, cFlipL and PED/PEA-15 mRNA expression was significantly increased only in early stages of RCCs compared to non-neoplastic renal
tissue. In contrast, ARC mRNA expression was significantly increased in RCCs of all stages without differences between the
tumour stages and grades. Importantly, the relative mRNA expression ratio between ARC and caspase-8 was significantly increased
during carcinogenesis and tumour progression. In contrast, the relative mRNA expression ratio between cFlipS, cFlipL or PED/PEA-15 and caspase-8 remained constant during all tumour stages. In conclusion, our analysis revealed that ARC is
the only caspase-8 inhibiting regulator being constantly overexpressed in RCCs. Furthermore, the balance between antiapoptotic
ARC and proapoptotic caspase-8 is the only one to be disturbed during carcinogenesis and tumour progression of RCCs. This
inhibition of Caspase-8 might therefore be one example for the multiple antiapoptotic functions of ARC in RCCs possibly contributing
to the marked resistance of RCCs towards radio- and chemotherapy and reflects a shift of gene expression towards a more antiapoptotic
context in RCCs.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
18.
Fluctuations of "computer time" provided by the PC quartz generator were studied. It was shown that variations in the yearly course of the quartz generator frequency occur with periodicities of 13-15 days and 28-30 days. Regular fluctuations with periods of 0.5 and 1.0 min are typical of the short-term spectral component. Impulses of sharp and intense deceleration of "computer time" are often observed against the background of these regular fluctuations. The conclusion is made that fluctuations of "computer time" are of cosmophysical origin. 相似文献
19.
Miles MF 《Nature reviews. Neuroscience》2001,2(6):441-443
Microarray expression profiling is instrumental to our understanding of the function of the genome. Resolution of functionally relevant expression patterns will require the analysis of large data sets compiled from multiple investigators. For this and other reasons, I argue that it is crucial for array data to be publicly shared in a format as close to the 'raw data' as possible. Issues such as protection of intellectual property, ensuring quality of the data, and the format and timing for sharing array data are also discussed. 相似文献
20.