Differential Dynamics at Glycosidic Linkages of an Oligosaccharide as Revealed by 13C NMR Spin Relaxation and Stochastic Modeling

Among biomolecules, carbohydrates are unique in that not only can linkages be formed through different positions but the structures may also be branched. The trisaccharide \uf062-D-Glcp-(1\uf0ae3)[\uf062-D-Glcp-(1\uf0ae2)]-\uf061-D-Manp-OMe represents a model of a branched vicinally disubstituted structure. A 13C site-specific isotopologue with labeling in each of the two terminal glucosyl residues enabled acquisition of high-quality 13C NMR relaxation parameters T1, T2 and heteronuclear NOE, with standard deviations of \uf0a3 0.5%. For interpretation of the experimental NMR data a diffusive chain model was used in which the dynamics of the glycosidic linkages is coupled to the global reorientation motion of the trisaccharide. Brownian dynamics simulations relying on the potential of mean force at the glycosidic linkages were employed to evaluate spectral densities of the spin probes. Calculated NMR relaxation parameters showed very good agreement with experimental data, deviating < 3%. The resulting dynamics is described by correlation times of 196 ps and 174 ps for the \uf062-(1\uf0ae2)- and \uf062-(1\uf0ae3)-linked glucosyl residues, respectively, i.e., different and linkage dependent. Notably, the devised computational protocol was performed without any fitting of parameters

Describing general cosmological singularities in Iwasawa variables

Belinskii, Khalatnikov, and Lifshitz (BKL) conjectured that the description of the asymptotic behavior of a generic solution of Einstein equations near a spacelike singularity could be drastically simplified by considering that the time derivatives of the metric asymptotically dominate (except at a sequence of instants, in the `chaotic case') over the spatial derivatives. We present a precise formulation of the BKL conjecture (in the chaotic case) that consists of basically three elements: (i) we parametrize the spatial metric $g_{ij}$ by means of \it{Iwasawa variables} $\beta^a, {\cal N}^a{}_i$); (ii) we define, at each spatial point, a (chaotic) \it{asymptotic evolution system} made of ordinary differential equations for the Iwasawa variables; and (iii) we characterize the exact Einstein solutions $\beta, {\cal{N}}$ whose asymptotic behavior is described by a solution $\beta_{[0]}, {\cal N}_{[0]}$ of the previous evolution system by means of a `\it{generalized Fuchsian system}' for the differenced variables $\bar \beta = \beta - \beta_{[0]}$, $\bar {\cal N} = {\cal N} - {\cal N}_{[0]}$, and by requiring that $\bar \beta$ and $\bar {\cal N}$ tend to zero on the singularity. We also show that, in spite of the apparently chaotic infinite succession of `Kasner epochs' near the singularity, there exists a well-defined \it{asymptotic geometrical structure} on the singularity : it is described by a \it{partially framed flag}. Our treatment encompasses Einstein-matter systems (comprising scalar and p-forms), and also shows how the use of Iwasawa variables can simplify the usual (`asymptotically velocity term dominated') description of non-chaotic systems.Comment: 50 pages, 4 figure

Guide to the Identification of Poplar Cultivars on the Prairies

This paper provides those who work with poplars in the prairies region of Canada with an easy-to-use leaf and twig key and detailed morphological descriptions of the more commonly planted cultivars. Recommendations for their use, notes on growth, natural pruning, susceptibility to insects and diseases, and tolerance to climatic extremes are also provided

Line mixing effects in isotropic Raman spectra of pure N2: A classical trajectory study

International audienceLine mixing effects in the Q branch of pure N2 isotropic Raman scattering are studied at room temperature using a classical trajectory method. It is the first study using an extended modified version of Gordon's classical theory of impact broadening and shift of rovibrational lines. The whole relaxation matrix is calculated using an exact 3D classical trajectory method for binary collisions of rigid N2 molecules employing the most up-to-date intermolecular potential energy surface (PES). A simple symmetrizing procedure is employed to improve off-diagonal cross-sections to make them obeying exactly the principle of detailed balance. The adequacy of the results is confirmed by the sum rule. The comparison is made with available experimental data as well as with benchmark fully quantum close coupling [F. Thibault, C. Boulet, and Q. Ma, J. Chem. Phys. 140, 044303 (2014)] and refined semi-classical Robert-Bonamy [C. Boulet, Q. Ma, and F. Thibault, J. Chem. Phys. 140, 084310 (2014)] results. All calculations (classical, quantum and semi-classical) were made using the same PES. The agreement between classical and quantum relaxation matrices is excellent, opening the way to the analysis of more complex molecular systems

Tyrosine Hydroxylase Expression in Differentiating Neurons of the Rat Arcuate Nucleus: Stimulatory Influence of Serotonin Afferents

The influence of serotonin afferents on tyrosine hydroxylase expression in differentiating neurons of the rat arcuate nucleus was studied in vivo and in vitro. In the in vivo study, pchlorophenylalanine inhibited serotonin synthesis in fetal brain from the 11th to the 20th embryonic day. We then used semiquantitative immunocytochemistry to evaluate tyrosine hydroxylase levels in neurons of the arcuate nucleus in fetuses at the 21st embryonic day or in offspring at the 35th postnatal day. Serotonin depltion significantly decreased the tyrosine hydroxylase content in neurons of males and females at the 21st embryonic day and in males at the 35st postnatal day. For the in vitro study, embryonic neurons of the arcuate nucleus were cocultured with embryonic neurons of the raphe nucleus, the main source of serotonin innervation of the brain, including the arcuate nucleus. Co-culture of the neurons resulted in a genderspecific increase of the tyrosine hydroxylase level in the neurons of the arcuate nucleus. In turn, the neurons of the raphe nucleus showed increased levels .of serotonin in both males and females, with no sexual dimorphism. Thus, our results suggest a stimulatory, long-lasting effect of serotonin afferents on tyrosine hydroxylase expression in the differentiating neurons of the rat arcuate nucleus during prenatal ontogenesis

One size does not fit all: Identifying clusters of physical activity, screen time, and sleep behaviour co-development from childhood to adolescence

Purpose Canada was the first to adopt comprehensive 24-h movement guidelines that include recommendations for physical activity, screen time and sleep to promote health benefits. No studies have investigated the concurrent development of these behaviours in youth. The objectives were to assess adherence to the Canadian 24-h movement guidelines for children and youth and estimate co-development of self-reported moderate-to-vigorous intensity physical activity (MVPA), screen time and sleep during 8-years from childhood to adolescence. Methods Nine hundred and twenty three participants of the MATCH study self-reported their MVPA, screen time and sleep duration at least twice over 8 years. MVPA and screen time were measured three times per year (24 cycles), and sleep was measured once per year (8 cycles). Guideline adherence was dichotomised as meeting each specific health behaviour recommendation or not. Multi-group trajectory modeling was used to identify unique trajectories of behavioural co-development. Analyses were stratified by sex. Results Between 10 and 39% of youth did not meet any recommendation at the various cycles of data collection. More than half of youth met only one or two recommendation, and roughly 5% of participants met all three recommendations at one or more study cycle throughout the 8 years of follow-up. Four different trajectories of behavioural co-development were identified for boys and for girls. For boys and girls, a complier (good adherence to the guideline recommendations; 12% boys and 9% girls), a decliner (decreasing adherence to the guideline recommendations; 23% boys and 18% girls) and a non-complier group (low adherence to the guideline recommendations; 42% boys and 42% girls) were identified. In boys, a MVPA-complier group (high MVPA-low screen time; 23%) was identified, whereas in girls a screen-complier group (moderate screen time-low MVPA; 30%) was identified. Conclusions There is a need to recognise that variations from general trends of decreasing MVPA, increasing screen time and decreasing sleep exist. Specifically, we found that although it is uncommon for youth to adhere to the Canadian 24-h movement guidelines, some youth displayed a high likelihood of attaining one or multiple of the behavioural recommendations. Further, patterns of adherence to the guidelines can differ across different sub-groups of youth

First theoretical global line lists of ethylene (12C2H4) spectra for the temperature range 50-700 K in the far-infrared for quantification of absorption and emission in planetary atmospheres

We present the construction of complete and comprehensive ethylene line lists for the temperatures 50−700 K based on accurate ab initio potential and dipole moment surfaces and extensive first-principle calculations. Three lists spanning the [0−6400] cm-1 infrared region were built at T = 80, 160, and 296 K, and two lists in the range [0−5200] cm-1 were built at 500 and 700 K. For each of these five temperatures, we considered possible convergence problems to ensure reliable opacity calculations. Our final list at 700 K was computed up to J = 71 and contains almost 60 million lines for intensities I > 5 × 10-27 cm/molecule. Comparisons with experimental spectra carried out in this study showed that for the most active infrared bands, the accuracy of band centers in our theoretical lists is better on average than 0.3 cm-1, and the integrated absorbance errors in the intervals relevant for spectral analyses are about 1−3%. These lists can be applied to simulations of absorption and emission spectra, radiative and non-LTE processes, and opacity calculations for planetary and astrophysical applications

Comparison of quantum, semi-classical and classical methods in the calculation of nitrogen self-broadened linewidths

International audienceWe perform dynamical calculations on two robust N2-N2 potential energy surfaces in order to intercompare pressure broadening coefficients derived from close coupling and coupled states quantum dynamical methods, the semi-classical model of Robert and Bonamy and a full classical method. The coupled states and full classical results compare well with the experimental results or with close coupling values when available. This study confirms that the classical method is a good alternative at room and high temperatures to quantum dynamical methods. The results obtained using the semi-classical method however deviate from the other sets of data at all temperatures considered here (77-2400 K)