Hydrogen bonding in the gas-phase: the molecular structures of 2‑hydroxybenzamide (C7H7NO2) and 2‑methoxybenzamide (C8H9NO2), obtained by gas-phase electron diffraction and theoretical calculations

The structures of 2-hydroxybenzamide(C7H7NO2) and 2-methoxybenzamide (C8H9NO2) have been determined in the gas-phase by electron diffraction using results from quantum chemical calculations to inform restraints used on the structural parameters. Theoretical methods (HF and MP2/6-311+G(d,p)) predict four stable conformers for both 2-hydroxybenzamide and 2-methoxybenzamide. For both compounds, evidence for intramolecular hydrogen bonding is presented. In 2-hydroxybenzamide, the observed hydrogen bonded fragment is between the hydroxyl and carbonyl groups, while in 2-methoxybenzamide, the hydrogen bonded fragment is between one of the hydrogen atoms of the amide group and the methoxy oxygen atom.

Preparation and ring-opening reactions of N-diphenylphosphinyl vinyl aziridines

Predominantly (E)-N-diphenylphosphinyl vinyl aziridines are prepared by a reaction of N-diphenylphosphinyl imines with α-bromoallyllithium in the presence of freshly fused ZnCl2. These aziridines undergo a ring-opening reaction with a variety of carbon and heteronucleophiles, in good yield, and generally with good regioselectivity.

Comparison of the open-closed separatrix in a global magnetospheric simulation with observations: the role of the ring current

The development of global magnetospheric models, such as Space Weather Modeling Framework (SWMF), which can accurately reproduce and track space weather processes has high practical utility. We present an interval on 5 June 1998, where the location of the polar cap boundary, or open-closed field line boundary (OCB), can be determined in the ionosphere using a combination of instruments during a period encompassing a sharp northward to southward interplanetary field turning. We present both point- and time-varying comparisons of the observed and simulated boundaries in the ionosphere and find that when using solely the coupled ideal magnetohydrodynamic magnetosphere-ionosphere model, the rate of change of the OCB to a southward turning of the interplanetary field is significantly faster than that computed from the observational data. However, when the inner magnetospheric module is incorporated, the modeling framework both qualitatively, and often quantitatively, reproduces many elements of the studied interval prior to an observed substorm onset. This result demonstrates that the physics of the inner magnetosphere is critical in shaping the boundary between open and closed field lines during periods of southward interplanetary magnetic field (IMF) and provides significant insight into the 3-D time-dependent behavior of the Earth's magnetosphere in response to a northward-southward IMF turning. We assert that during periods that do not include the tens of minutes surrounding substorm expansion phase onset, the coupled SWMF model may provide a valuable and reliable tool for estimating both the OCB and magnetic field topology over a wide range of latitudes and local times.

Ruminal dry matter and nitrogen degradation in relation to condensed tannin and protein molecular structures in sainfoin (Onobrychis viciifolia) and lucerne (Medicago sativa).

Sainfoin is a temperate legume that contains condensed tannins (CT), i.e. polyphenols that are able to bind proteins and thus reduce protein degradation in the rumen. A reduction in protein degradation in the rumen can lead to a subsequent increase in amino acid flow to the small intestine. The effects of CT in the rumen and the intestine differ according to the amount and structure of CT and the nature of the protein molecular structure. The objective of the present study was to investigate the degradability in the rumen of three CT-containing sainfoin varieties and CT-free lucerne in relation to CT content and structure (mean degree of polymerization, proportion of prodelphinidins and cis-flavanol units) and protein structure (amide I and II bands, ratio of amide I-to-amide II, α-helix, β-sheet, ratio of α-helix-to-β-sheet). Protein molecular structures were identified using Fourier transform/infrared-attenuated total reflectance (FT/IR-ATR) spectroscopy. The in situ degradability of three sainfoin varieties (Ambra, Esparcette and Villahoz) was studied in 2008, during the first growth cycle at two harvest dates (P1 and P2, i.e. 5 May and 2 June, respectively) and at one date (P3) during the second growth cycle (2 June) and these were compared with a tannin-free legume, lucerne (Aubigny). Loss of dry matter (DMDeg) and nitrogen (NDeg) in polyester bags suspended in the rumen was measured using rumen-fistulated cows. The NDeg of lucerne compared with sainfoin was 0·80 v. 0·77 at P1, 0·78 v. 0·65 at P2 and 0·79 v. 0·70 at P3, respectively. NDeg was related to the rapidly disappearing fraction (‘a’) fraction (r=0·76), the rate of degradation (‘c’) (r=0·92), to the content (r=−0·81) and structure of CT. However, the relationship between NDeg and the slowly disappearing fraction (‘b’) was weak. There was a significant effect of date and species×date, for NDeg and ‘a’ fraction. The secondary protein structure varied with harvest date (species×date) and was correlated with the fraction ‘b’. Both tannin and protein structures influenced the NDeg degradation. CT content and structure were correlated to the ‘a’ fraction and to the ‘c’. Features of the protein molecular secondary structure were correlated to the ‘b’ fraction.

Primary evolving networks and the comparative analysis of robust and fragile structures

In this paper we consider the structure of dynamically evolving networks modelling information and activity moving across a large set of vertices. We adopt the communicability concept that generalizes that of centrality which is defined for static networks. We define the primary network structure within the whole as comprising of the most influential vertices (both as senders and receivers of dynamically sequenced activity). We present a methodology based on successive vertex knockouts, up to a very small fraction of the whole primary network,that can characterize the nature of the primary network as being either relatively robust and lattice-like (with redundancies built in) or relatively fragile and tree-like (with sensitivities and few redundancies). We apply these ideas to the analysis of evolving networks derived from fMRI scans of resting human brains. We show that the estimation of performance parameters via the structure tests of the corresponding primary networks is subject to less variability than that observed across a very large population of such scans. Hence the differences within the population are significant.

The vertical structure of oceanic Rossby waves: a comparison of high-resolution model data to theoretical vertical structures

Tests of the new Rossby wave theories that have been developed over the past decade to account for discrepancies between theoretical wave speeds and those observed by satellite altimeters have focused primarily on the surface signature of such waves. It appears, however, that the surface signature of the waves acts only as a rather weak constraint, and that information on the vertical structure of the waves is required to better discriminate between competing theories. Due to the lack of 3-D observations, this paper uses high-resolution model data to construct realistic vertical structures of Rossby waves and compares these to structures predicted by theory. The meridional velocity of a section at 24° S in the Atlantic Ocean is pre-processed using the Radon transform to select the dominant westward signal. Normalized profiles are then constructed using three complementary methods based respectively on: (1) averaging vertical profiles of velocity, (2) diagnosing the amplitude of the Radon transform of the westward propagating signal at different depths, and (3) EOF analysis. These profiles are compared to profiles calculated using four different Rossby wave theories: standard linear theory (SLT), SLT plus mean flow, SLT plus topographic effects, and theory including mean flow and topographic effects. Our results support the classical theoretical assumption that westward propagating signals have a well-defined vertical modal structure associated with a phase speed independent of depth, in contrast with the conclusions of a recent study using the same model but for different locations in the North Atlantic. The model structures are in general surface intensified, with a sign reversal at depth in some regions, notably occurring at shallower depths in the East Atlantic. SLT provides a good fit to the model structures in the top 300 m, but grossly overestimates the sign reversal at depth. The addition of mean flow slightly improves the latter issue, but is too surface intensified. SLT plus topography rectifies the overestimation of the sign reversal, but overestimates the amplitude of the structure for much of the layer above the sign reversal. Combining the effects of mean flow and topography provided the best fit for the mean model profiles, although small errors at the surface and mid-depths are carried over from the individual effects of mean flow and topography respectively. Across the section the best fitting theory varies between SLT plus topography and topography with mean flow, with, in general, SLT plus topography performing better in the east where the sign reversal is less pronounced. None of the theories could accurately reproduce the deeper sign reversals in the west. All theories performed badly at the boundaries. The generalization of this method to other latitudes, oceans, models and baroclinic modes would provide greater insight into the variability in the ocean, while better observational data would allow verification of the model findings.

The joint influence of personal achievement goals and classroom goal structures on achievement-relevant outcomes

The authors provide an analytic framework for studying the joint influence of personal achievement goals and classroom goal structures on achievement-relevant outcomes. This framework encompasses 3 models (the direct effect model, indirect effect model, and interaction effect model), each of which addresses a different aspect of the joint influence of the 2 goal levels. These 3 models were examined together with a sample of 1,578 Japanese junior high and high school students from 47 classrooms. Results provided support for each of the 3 models: Classroom goal structures were not only direct, but also indirect predictors of intrinsic motivation and academic self-concept, and some cross-level interactions between personal achievement goals and classroom goal structures were observed (indicating both goal match and goal mismatch effects). A call is made for more research that takes into consideration achievement goals at both personal and structural levels of representation. (PsycINFO Database Record (c) 2012 APA, all rights reserved)(journal abstract)

Syntheses, spectroelectrochemical studies, and molecular and electronic structures of ferrocenyl ene-diynes

The readily available complex 1,1-dibromo-2-ferrocenylethylene provides a convenient entry point for the preparation of a wide range of cross-conjugated 1,1-bis(alkynyl)-2-ferrocenylethenes through simple Pd(0)/Cu(I)-mediated cross-coupling reactions with 1-alkynes. The ferrocene moiety in compounds of the general form FcCHC(CCR)2 is essentially electronically isolated from the cross-conjugated π system, as evidenced by IR and UV−vis spectroelectrochemical experiments and quantum chemical calculations. In contrast to the other examples which give stable ferrocenium derivatives upon electrochemical oxidation, the aniline derivatives [FcCHC(CCC6H4NH2-4)2]+ and [FcCHC(CCC6H4NMe2-4)2]+ proved to be unstable on the time scale of the spectroelectrochemical experiments, leading to passivation of the electrode surface over time. There is no significant thermodynamic stabilization of the radical anion [FcCHC(CCC6H4NO2-4)2]− relative to the neutral and dianionic analogues, although the dianion [FcCHC(CCC6H4NO2- 4)2]2− could be studied as a relatively chemically stable species and is well described in terms of two linked nitrophenyl radicals. The capacity to introduce a relatively isolated point charge at the periphery of the cross-conjugated π system appears to make these complexes useful templates for the construction of electrochemically gated quantum interference transistors.

Relationship between condensed tannin structures and their ability to precipitate feed proteins in the rumen

Abstract BACKGROUND Tannins can bind to and precipitate protein by forming insoluble complexes resistant to fermentation and with a positive effect on protein utilisation by ruminants. Three protein types, Rubisco, rapeseed protein and bovine serum albumin (a single high-molecular weight protein), were used to test the effects of increasing concentrations of structurally different condensed tannins on protein solubility/precipitation. RESULTS Protein type (PT) influenced solubility after addition of condensed tannins (P < 0.001) in the order: Rubisco < rapeseed < BSA (P < 0.05). The type of condensed tannin (CT) affected protein solubility (P = 0.001) with a CT × PT interaction (P = 0.001). Mean degree of polymerisation, proportions of cis- versus trans-flavanol subunits or prodelphinidins versus procyanidins among CTs could not explain precipitation capacities. Increasing tannin concentration decreased protein solubility (P < 0.001) with a PT × CT concentration interaction. The proportion of low-molecular weight rapeseed proteins remaining in solution increased with CT concentration but not with Rubisco. CONCLUSIONS Results of this study suggest that PT and CT type are both of importance for protein precipitation but that the CT structures investigated did not allow identification of parameters that contribute most to precipitation. It is possible that the three-dimensional structures of tannins and proteins may be more important factors in tannin–protein interactions. © 2013 Society of Chemical Industry

Flavonoid inhibitory pharmacodynamics on platelet function in physiological environments

The complex relationship between flavonoid-based nutrition and cardiovascular disease may be dissected by understanding the activities of these compounds in biological systems. The aim of the present study was to explore a hierarchy for the importance of dietary flavonoids on cardiovascular health by examining the structural basis for inhibitory effects of common, dietary flavonoids (quercetin, apigenin, and naringenin) and the plasma metabolite, tamarixetin. Understanding flavonoid effects on platelets in vivo can be informed by investigations of the ability of these compounds to attenuate the function of these cells. Inhibition of platelet function in whole blood and plasma was structure-dependent. The order of potency was apigenin > tamarixetin > quercetin = naringenin indicating that in vivo, important functional groups are potentially a methylated B ring, and a non-hydroxylated, planar C ring. Apigenin and the methylated metabolite of quercetin, tamarixetin significantly reduced thrombus volume at concentrations (5 μM) that suggested their reported physiological levels (0.1-1 μM) may exert low levels of inhibition. Flavonoid interactions with erythrocytes, leukocytes and human serum albumin in whole blood reduce their inhibitory activities against platelet function. The diminished inhibitory activity of flavonoids that we observed in whole blood and plasma indicated that these interactions do not overcome the attenuating effects of these compounds. Furthermore, inhibition of platelet aggregation by flavonoids was enhanced with increases in exposure time, indicating the potential for measurable inhibitory effects during resident plasma times. We conclude that flavonoid structures may be a major influence of their activities in vivo with methylated metabolites and those of flavones being more potent than those of flavonols and flavanones.

Investigating flavonoids as molecular templates for the design of small-molecule inhibitors of cell signaling

Epidemiological and clinical trials reveal compelling evidence for the ability of dietary flavonoids to lower cardiovascular disease risk. The mechanisms of action of these polyphenolic compounds are diverse, and of particular interest is their ability to function as protein and lipid kinase inhibitors. We have previously described structure-activity studies that reinforce the possibility for using flavonoid structures as templates for drug design. In the present study, we aim to begin constructing rational screening strategies for exploiting these compounds as templates for the design of clinically relevant, antiplatelet agents. We used the platelet as a model system to dissect the structural influence of flavonoids, stilbenes, anthocyanidins, and phenolic acids on inhibition of cell signaling and function. Functional groups identified as relevant for potent inhibition of platelet function included at least 2 benzene rings, a hydroxylated B ring, a planar C ring, a C ring ketone group, and a C-2 positioned B ring. Hydroxylation of the B ring with either a catechol group or a single C-4' hydroxyl may be required for efficient inhibition of collagen-stimulated tyrosine phosphorylated proteins of 125 to 130 kDa, but may not be necessary for that of phosphotyrosine proteins at approximately 29 kDa. The removal of the C ring C-3 hydroxyl together with a hydroxylated B ring (apigenin) may confer selectivity for 37 to 38 kDa phosphotyrosine proteins. We conclude that this study may form the basis for construction of maps of flavonoid inhibitory activity on kinase targets that may allow a multitargeted therapeutic approach with analogue counterparts and parent compounds.

Assessing the quality of modelled 3D protein structures using the ModFOLD server

Model quality assessment programs (MQAPs) aim to assess the quality of modelled 3D protein structures. The provision of quality scores, describing both global and local (per-residue) accuracy are extremely important, as without quality scores we are unable to determine the usefulness of a 3D model for further computational and experimental wet lab studies.Here, we briefly discuss protein tertiary structure prediction, along with the biennial Critical Assessment of Techniques for Protein Structure Prediction (CASP) competition and their key role in driving the field of protein model quality assessment methods (MQAPs). We also briefly discuss the top MQAPs from the previous CASP competitions. Additionally, we describe our downloadable and webserver-based model quality assessment methods: ModFOLD3, ModFOLDclust, ModFOLDclustQ, ModFOLDclust2, and IntFOLD-QA. We provide a practical step-by-step guide on using our downloadable and webserver-based tools and include examples of their application for improving tertiary structure prediction, ligand binding site residue prediction, and oligomer predictions.

Diversity of condensed tannin structures affects rumen in vitro methane production in sainfoin (Onobrychis viciifolia) accessions

Sainfoin is a non-bloating temperate forage legume with a moderate-to-high condensed tannin (CT) content. This study investigated whether the diversity of sainfoin accessions in terms of CT structures and contents could be related to rumen in vitro gas and methane (CH4) production and fermentation characteristics. The aim was to identify promising accessions for future investigations. Accessions differed (P < 0·0001) in terms of total gas and CH4 productions. Fermentation kinetics (i.e. parameters describing the shape of the gas production curve and half-time gas production) for CH4 production were influenced by accession (P ≤ 0·038), but not by PEG. Accession, PEG and time affected (P < 0·001) CH4 production, but accession and PEG interaction showed only a tendency (P = 0·08). Increase in CH4 due to PEG addition was not related to CT content. Further analysis of the relationships among multiple traits (nutritional composition, CT structure and CH4 production) using principal component analysis (PCA) based on optimally weighted variables revealed differences among accessions. The first two principal component axes, PC1 (57·6%) and PC2 (18·4%), explained 76·0% of the total variation among accessions. Loading of biplots derived from both PCAs made it possible to establish a relationship between the ratio of prodelphinidin:procyanidin (PD:PC) tannins and CH4 production in some accessions. The PD:PC ratio seems to be an important source of variation that is negatively related to CH4 production. These results suggested that sainfoin accessions collected from across the world exhibited substantial variation in terms of their effects on rumen in vitro CH4 production, revealing some promising accessions for future investigations.

Structures and relationships: women partners' careers in Germany and the UK

Purpose – This paper aims to highlight differences in women's experiences of advancement to partnership in accountancy firms in Germany and the UK and consider the ways in which such differences may be constituted by the institutional context in which they occurred. Design/methodology/approach – This research is based on 60 semi-structured interviews with women partners in Germany and the UK. Techniques adopted from grounded theory were applied. Research limitations/implications – This qualitative research is context-specific and given its cross-national, interdisciplinary nature is limited to the extent that findings cannot be generalised beyond the studied scope. Practical implications – The study points to cross-national differences in women's career advancement in accountancy firms. The findings support extant research suggesting that structured performance evaluation and hiring systems – while not without flaws – are likely more gender-neutral. In addition, the study highlights the potential of headhunters and recruitment agents as an important tool for women to navigate their way out of career culs-de-sac. Originality/value – This research provides unique insights into women partners' experiences of career advancement and, through its interdisciplinary nature, demonstrates the usefulness of employing institutional frameworks in qualitative in-depth studies of this kind