Phosphate Tether-Mediated Ring-Closing Metathesis Studies to Complex 1,3-anti-Diol-Containing Subunits

This is the peer reviewed version of the following article: Chegondi, R., Maitra, S., Markley, J. L., & Hanson, P. R. (2013). Phosphate Tether-Mediated Ring-Closing Metathesis Studies to Complex 1,3-anti-Diol-Containing Subunits. Chemistry (Weinheim an Der Bergstrasse, Germany), 19(25), 10.1002/chem.201300913. http://doi.org/10.1002/chem.201300913, which has been published in final form at doi.org/10.1002/chem.201300913. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.An array of examples of diastereoselective, phosphate tether-mediated ring-closing metathesis reactions, which highlight the importance of product ring size and substrate stereochemical compatibility, as well as complexity, is reported. Studies focus primarily on the formation of bicyclo[n.3.1]phosphates, involving the coupling of C2-symmetric dienediol subunits with a variety of simple, as well as complex alcohol cross-partners

Phosphate Tether-Mediated Ring-Closing Metathesis for the Generation of Medium to Large, P-Stereogenic Bicyclo[n.3.1]phosphates

A phosphate tether-mediated ring-closing metathesis study towards the synthesis of P-stereogenic bicyclo[6.3.1]-, bicyclo[7.3.1]-, and bicyclo[8.3.1]phosphates is reported. This study demonstrates expanded utility of phosphate tether-mediated desymmetrization of C2-symmetric, 1,3-anti-diol dienes in generating complex medium to large, P-stereogenic bicyclo[n.3.1]phosphates.

Anisotropic Brane Cosmology with Variable GG and Λ\Lambda

In this work, the cosmological implications of brane world scenario are investigated when the gravitational coupling $G$ and the cosmological term $\Lambda$ are not constant but rather there are time variation of them. From observational point of view, these time variations are taken in the form $\frac{\dot{G}}{G}\sim H$ and $\Lambda \sim H^{2}$. The behavior of scale factors and different kinematical parameters are investigated for different possible scenarios where the bulk cosmological constant $\Lambda_{5}$ can be zero, positive or negative.Comment: RevTex, 7 figures, 16 page

Do olfactory and gustatory psychophysical scores have prognostic value in COVID-19 patients? A prospective study of 106 patients

Background: The lack of objective data makes it difficult to establish the prognostic value of chemosensitive disorders in coronavirus disease 2019 (COVID-19) patients. We aimed to prospectively monitor patients diagnosed with COVID-19 to see if the severity of olfactory and gustatory dysfunction associates with subsequent disease severity. Methods: Multicentre prospective study that recruited 106 COVID-19 subjects at diagnosis. Chemosensitive functions were assessed with psychophysical tests within 4 days of clinical onset, at 10 and 20 days. Daily body temperature and oxygen saturation were recorded as markers of disease severity alongside need for hospitalisation. The correlation between olfactory and gustatory scores and disease severity was assessed with linear regression analysis. Results: At T0, 71 patients (67%) presented with olfactory dysfunction while gustatory impairment was detected in 76 cases (65.6%). Chemosensitive disorders gradually improved over the observation period. No significant correlations were found between T0 chemosensitive scores and final disease severity. The correlation between olfactory scores and fever proved significant at T2 (p = 0.05), while the relationship with gustatory scores was significant at T1 (p = 0.01) and T2 (p < 0.001), however neither was clinically relevant. The correlation between chemosensitive scores and oxygen saturation was significant only for taste at T2 (p < 0.001). Logistic regression analysis found significant correlations between olfactory impairment severity and need for hospitalization at T2 (OR 3.750, p = 0.005). Conclusions: Initial objective olfactory and gustatory scores do not seem to have a significant prognostic value in predicting the severity of the COVID-19 course; however, persistence of olfactory dysfunction at 20 days, associated with a more severe course. Unfortunately, olfactory and gustatory dysfunction do not seem to hold prognostic value at the time of initial diagnosis

Effect of pre-existing baryon inhomogeneities on the dynamics of quark-hadron transition

Baryon number inhomogeneities may be generated during the epoch when the baryon asymmetry of the universe is produced, e.g. at the electroweak phase transition. The regions with excess baryon number will have a lower temperature than the background temperature of the universe. Also the value of the quark hadron transition temperature $T_c$ will be different in these regions as compared to the background region. Since a first-order quark hadron transition is very susceptible to small changes in temperature, we investigate the effect of the presence of such baryonic lumps on the dynamics of quark-hadron transition. We find that the phase transition is delayed in these lumps for significant overdensities. Consequently, we argue that baryon concentration in these regions grows by the end of the transition. We briefly discuss some models which may give rise to such high overdensities at the onset of the quark-hadron transition.Comment: 16 pages, no figures, minor changes, version to appear in Phys. Rev.

Non-renewal statistics in the catalytic activity of enzyme molecules at mesoscopic concentrations

Recent fluorescence spectroscopy measurements of single-enzyme kinetics have shown that enzymatic turnovers form a renewal stochastic process in which the inverse of the mean waiting time between turnovers follows the Michaelis-Menten equation. Under typical physiological conditions, however, tens to thousands of enzymes react in catalyzing thousands to millions of substrates. We study enzyme kinetics at these physiologically relevant conditions through a master equation including stochasticity and molecular discreteness. From the exact solution of the master equation we find that the waiting times are neither independent nor are they identically distributed, implying that enzymatic turnovers form a non-renewal stochastic process. The inverse of the mean waiting time shows strong departures from the Michaelis-Menten equation. The waiting times between consecutive turnovers are anti-correlated, where short intervals are more likely to be followed by long intervals and vice versa. Correlations persist beyond consecutive turnovers indicating that multi-scale fluctuations govern enzyme kinetics.Comment: 5 pages, 4 figures, to appear in Physical Review Letter

Search for nucleon decays with EXO-200

A search for instability of nucleons bound in $^{136}$Xe nuclei is reported with 223 kg$\cdot$yr exposure of $^{136}$Xe in the EXO-200 experiment. Lifetime limits of 3.3$\times 10^{23}$ and 1.9$\times 10^{23}$ yrs are established for nucleon decay to $^{133}$Sb and $^{133}$Te, respectively. These are the most stringent to date, exceeding the prior decay limits by a factor of 9 and 7, respectively

Baryon inhomogeneity generation via cosmic strings at QCD scale and its effects on nucleosynthesis

We have earlier shown that cosmic strings moving through the plasma at the time of a first order quark-hadron transition in the early universe can generate large scale baryon inhomogeneities. In this paper, we calculate detailed structure of these inhomogeneities at the quark-hadron transition. Our calculations show that the inhomogeneities generated by cosmic string wakes can strongly affect nucleosynthesis calculations. A comparison with observational data suggests that such baryon inhomogeneities should not have existed at the nucleosynthesis epoch. If this disagreement holds with more accurate observations, then it will lead to the conclusions that cosmic string formation scales above $10^{14} - 10^{15}$ GeV may not be consistent with nucleosynthesis and CMBR observations. Alternatively, some other input in our calculation should be constrained, for example, if the average string velocity remains sufficiently small so that significant density perturbations are never produced at the QCD scale, or if strings move ultra-relativistically so that string wakes are very thin, trapping negligible amount of baryons. Finally, if quark-hadron transition is not of first order then our calculations do not apply.Comment: 24 pages, 5 figures, minor changes, version to appear in Phys. Rev.

Cosmic string induced sheet like baryon inhomogeneities at quark-hadron transition

Cosmic strings moving through matter produce wakes where density is higher than the background density. We investigate the effects of such wakes occurring at the time of a first order quark-hadron transition in the early universe and show that they can lead to separation of quark-gluon plasma phase in the wake region, while the region outside the wake converts to the hadronic phase. Moving interfaces then trap large baryon densities in sheet like regions which can extend across the entire horizon. Typical separation between such sheets, at formation, is of the order of a km. Regions of baryon inhomogeneity of this nature, i.e. having a planar geometry, and separated by such large distance scales, appear to be well suited for the recent models of inhomogeneous nucleosynthesis to reconcile with the large baryon to photon ratio implied by the recent measurements of the cosmic microwave background power spectrum.Comment: 8 pages, 3 figure