Oxygen-17 hyperfine structures in the pure rotational spectra of SrO, SnO, BaO, HfO and ThO

Hyperfine structures arising from the couplings of the nuclear spin angular momentum of (17)O (I = 5/2) with the end over end rotation of several metal-containing diatomic monoxides have been observed using a Fourier transform microwave spectrometer. The molecules have been produced by reacting (17)O(2) with laser ablated metal atoms. The oxygen-17 nuclear quadrupole coupling constants have been determined for the title molecules and are interpreted in terms of a simple Townes-Dailey model. Also, the oxygen-17 nuclear spin-rotation constants have been determined and used to calculate the oxygen-17 shieldings for each molecule.     

A study of comparability in amplified fragment length polymorphism profiling using a simple model system

A simple amplified fragment length polymorphism (AFLP) model, using the bacteriophage lambda genome, was developed to test the reproducibility of this technique in an international comparative study. Using either non-selective or selective primers, nine fragments or subsets of two or three fragments, respectively, were predicted using in silico software. Under optimized conditions, all predicted fragments were experimentally generated. The reproducibility of the AFLP model was tested by submitting both "unknown" DNA template that had been restricted and ligated with AFLP linkers (R/L mixture) and corresponding primer pairs to nine laboratories participating in the study. Participants completed the final PCR step and then used either slab gel electrophoresis or CE to detect the AFLP fragments. The predicted fragments were identified by the majority of participants with size estimates consistently up to 3 base pair (bp) larger for slab gel electrophoresis than for CE. Shadow fragments, 3 bp larger than the predicted fragments, were often observed by study participants and organizers. The nine AFLP fragments exhibited relative intensities ranging from less than 3% to 22% and, apart from the two weakest fragments, with a % CV of 16 to 25. Fragments containing the highest guanine-cytosine (GC) content of 50-56% showed the greatest stability in the AFLP profiles.     

Complete (1)H and (13)C assignments of the four major saponins from Dioscorea villosa (wild yam)

Complete (1)H and (13)C spectral assignments for the four major steroidal saponins isolated by methanolic extraction of the roots of Dioscorea villosa, collected in North Carolina, United States (in summer and autumn), are presented in this paper. The structures were determined by a combination of (1)H, (13)C and 2D NMR techniques and were found to be ((3beta,25R)-26-(beta-D-glucopyranosyloxy)-22-methoxyfurost-5-en-3-yl-O-beta-D-glucopyranosyl-(1 --> 3)-O-beta-D-glucopyranosyl-(1 --> 4)-O-[alpha-L-rhamnopyranosyl-(1 --> 2)]-beta-D-glucopyranoside (1) (or methyl parvifloside), ((3beta,25R)-26-(beta-D-glucopyranosyloxy)-22 methoxyfurost-5-en-3-yl-O-alpha-L-rhamnopyranosyl-(1 --> 2)-O-[beta-D-gluco- pyranosyl-(1 --> 4)]-beta-D-glucopyranoside (2) (or methyl protodeltonin), (3beta,25R)-spirost-5-en-3-yl-O-beta-D-glucopy ranosyl-(1 --> 3)-O-beta-D-glucopyranosyl-(1 --> 4)-O-[alpha-L-rhamnopyranosyl-(1 --> 2)]-beta-D-glucopyranoside (3) (or Zingiberensis saponin I) and (3beta,25R)-spirost-5-en-3-yl-O-alpha-L-rhamnopyranosyl-(1 --> 2)-O-[beta-Ds-glucopyranosyl -(1 --> 4)]-beta-D-glucopyranoside (4) (or deltonin).     

On the potential limitations of conventional sound metrics in quantifying perception of nonlinearly propagated noise

The use of conventional metrics to quantify the perception of nonlinearly propagated noise has been studied. Gaussian noise waveforms have been numerically propagated both linearly and nonlinearly, and from the resulting waveforms, several metrics are calculated. These metrics are overall, A-, C-, and D-weighted sound pressure levels, perceived noise level, Stevens Mark VII perceived loudness, Zwicker loudness, and sharpness. Informal listening demonstrations indicate that perceived differences in annoyance between linearly and nonlinearly propagated waveforms are substantial. Because the metrics studied seem inadequate in representing the perceived differences, rigorous subjective testing is encouraged to properly quantify and understand these differences.     

Tandem aza-Claisen rearrangement and ring-closing metathesis reactions: the stereoselective synthesis of functionalised carbocyclic amides

A one-pot, tandem process has been developed for the efficient synthesis of functionalised carbocyclic amides. A substituted cyclopentenyl trichloroacetamide was synthesised using a tandem thermal aza-Claisen rearrangement and RCM process, while an analogous cyclohexenyl trichloroacetamide was generated with high diastereoselectivity using a tandem MOM-ether directed metal-catalysed aza-Claisen rearrangement and RCM process.     

Analysis of isotope ratios in vitamin K1 (phylloquinone) from human plasma by gas chromatography/mass spectrometry

Vitamin K(1) is a fat-soluble vitamin required for the gamma-carboxylation of vitamin K-dependent proteins. Recent work has suggested an important role for vitamin K(1) in bone health beyond its more established function in the control and regulation of blood coagulation. However, current UK recommended intakes do not reflect this recent evidence. The use of stable isotopes provides a powerful tool to investigate vitamin K kinetics, turnover and absorption in man, although published methods have reported difficulties in the extraction and analysis of isotope ratios of vitamin K in human plasma. In this paper, we report a new methodology for the extraction and measurement of isotope ratios in vitamin K(1). Sample clean-up is achieved with liquid-liquid extraction, enzyme hydrolysis with lipase and cholesterol esterase, and solid-phase extraction. Isotopic analysis of the pentafluoropropionyl derivative of vitamin K(1) is performed by gas chromatography/mass spectrometry (GC/MS). The limit of quantitation is equivalent to at least 0.3 nmol/L and the method is demonstrated to be linear over a range of enrichments. This method provides a robust alternative to previous work requiring the use of semi-preparative high-performance liquid chromatography (HPLC).     

Finite deformation analysis of slip-induced crystalline rotations during tensile and compressive tests on bcc iron crystals

This work compares slip-induced lattice rotations calculated from double-slip, finite-deformation analytical solutions to electron-back-scattering-diffraction (EBSD) rotation measurements from SEM in situ, room temperature straining of bcc iron crystals. The finite-deformation modelling assumes slip proportionality between the two dominant active systems. Four experimental cases from a recently published work (2015) are examined, two in axial tension and two in axial compression. They correspond to mixed double-slip on {110} and {112} planes, with slip on the latter in both ‘easy’ and ‘hard’ orientations. In the experiments, EBSD rotation measurements were made on three faces of the iron samples and the dominant active systems were identified from slip traces. Here the relative contributions of the two systems for the best match with available rotation data are determined for each case, and the results discussed in relation to initial shear stress and (probable) critical shear-strength ratios. The analyses provide insight into achievable accuracy in crystal-slip quantification, based on slip-trace observations and rotation measurements of a sample’s load and lateral axes, and some assessment of the relative hardening of active slip systems.     

A Collaboration-based Approach to CFD Model Validation and Uncertainty Quantification (VUQ) Using Data from a Laminar Helium Plume

An effective approach to the model VUQ process by means of direct collaboration between computationalist and experimental data analyst is proposed. An analysis of data from a laminar helium plume experiment provides a demonstration of the proposed collaboration process. Consistency analysis serves a central role in the collaboration. It takes the data and uncertainties from both analyst and computationalist and provides an objective and quantifiable measure of agreement between the two. Despite the simplicity of the laminar helium system and the computational model, certain phenomena brought to light in the collaboration process make it difficult to find quantitative agreement in the data. These phenomena include the unsteady behavior of air flow in an open room, and the presence of helium permeation to the region near the plume. Important sources of error in the simulation include uncertainty in the room temperature (295.15 to 305.15 K), uncertainty in the helium inlet velocity (0.1215 \(\frac {m}{s}\) to 0.1415 \(\frac {m}{s}\)), and uncertainty in local helium permeation (0 % to 3 % by mass.) The collaboration process allows for a better understanding of the phenomena affecting the plume and the relative sensitivies of the system to these phenomena.     

Exploitation of the Ornithine Effect Enhances Characterization of Stapled and Cyclic Peptides

A method to facilitate the characterization of stapled or cyclic peptides is reported via an arginine-selective derivatization strategy coupled with MS/MS analysis. Arginine residues are converted to ornithine residues through a deguanidination reaction that installs a highly selectively cleavable site in peptides. Upon activation by CID or UVPD, the ornithine residue cyclizes to promote cleavage of the adjacent amide bond. This Arg-specific process offers a unique strategy for site-selective ring opening of stapled and cyclic peptides. Upon activation of each derivatized peptide, site-specific backbone cleavage at the ornithine residue results in two complementary products: the lactam ring-containing portion of the peptide and the amine-containing portion. The deguanidination process not only provides a specific marker site that initiates fragmentation of the peptide but also offers a means to unlock the staple and differentiate isobaric stapled peptides.

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