Solvent‐induced enantioselectivity reversal in a chiral metal organic framework

Solvent-induced enantioselectivity reversal is a rarely reported phenomenon in porous homochiral materials. Similar behavior has been studied in chiral high performance liquid chromatography, where minor modifications to the mobile phase can induce elution order reversal of two enantiomers on a chiral stationary phase column. We report the first instance of solvent-induced enantioselectivity reversal in a homochiral metal organic framework. Further, we highlight the complex enantioselectivity behavior of homochiral metal organic frameworks toward racemic mixtures in the presence of solvents through racemate-solvent enantioselectivity and loading experiments as well as enantiopure-solvent loading experiments. We hypothesize that this interesting selectivity reversal behavior is likely to be observed in other competitive adsorption, nonchiral selective processes involving a solvent

A Scenario-based Parametric Analysis of the Army Personnel-to-assignment Matching Problem

This study aims to compare linear programming and stable marriage approaches to the personnel assignment problem under conditions of uncertainty. Robust solutions should exhibit reduced variability of solutions in the presence of one or more additional constraints or problem perturbations added to some baseline problems.Several variations of each approach are compared with respect to solution speed, solution quality as measured by officer-to-assignment preferences and solution robustness as measured by the number of assignment changes required after inducing a set of representative perturbations or constraints to an assignment instance. These side constraints represent the realistic assignment categorical priorities and limitations encountered by army assignment managers who solve this problem semiannually, and thus the synthetic instances considered herein emulate typical problem instances

Price Discovery and the Accuracy of Consolidated Data Feeds in the U.S. Equity Markets

Both the scientific community and the popular press have paid much attention to the speed of the Securities Information Processor, the data feed consolidating all trades and quotes across the US stock market. Rather than the speed of the Securities Information Processor, or SIP, we focus here on its accuracy. Relying on Trade and Quote data, we provide various measures of SIP latency relative to high-speed data feeds between exchanges, known as direct feeds. We use first differences to highlight not only the divergence between the direct feeds and the SIP, but also the fundamental inaccuracy of the SIP. We find that as many as 60 percent or more of trades are reported out of sequence for stocks with high trade volume, therefore skewing simple measures such as returns. While not yet definitive, this analysis supports our preliminary conclusion that the underlying infrastructure of the SIP is currently unable to keep pace with the trading activity in today's stock market.Comment: 18 pages, 20 figures, 2 table

Neural Level Set Topology Optimization Using Unfitted Finite Elements

To facilitate widespread adoption of automated engineering design techniques, existing methods must become more efficient and generalizable. In the field of topology optimization, this requires the coupling of modern optimization methods with solvers capable of handling arbitrary problems. In this work, a topology optimization method for general multiphysics problems is presented. We leverage a convolutional neural parameterization of a level set for a description of the geometry and use this in an unfitted finite element method that is differentiable with respect to the level set everywhere in the domain. We construct the parameter to objective map in such a way that the gradient can be computed entirely by automatic differentiation at roughly the cost of an objective function evaluation. The method produces optimized topologies that are similar in performance yet exhibit greater regularity than baseline approaches on standard benchmarks whilst having the ability to solve a more general class of problems, e.g., interface-coupled multiphysics.Comment: 16 pages + refs, 10 fig

Priming bias versus post-treatment bias in experimental designs

Conditioning on variables affected by treatment can induce post-treatment bias when estimating causal effects. Although this suggests that researchers should measure potential moderators before administering the treatment in an experiment, doing so may also bias causal effect estimation if the covariate measurement primes respondents to react differently to the treatment. This paper formally analyzes this trade-off between post-treatment and priming biases in three experimental designs that vary when moderators are measured: pre-treatment, post-treatment, or a randomized choice between the two. We derive nonparametric bounds for interactions between the treatment and the moderator in each design and show how to use substantive assumptions to narrow these bounds. These bounds allow researchers to assess the sensitivity of their empirical findings to either source of bias. We extend the basic framework in two ways. First, we apply the framework to the case of post-treatment attention checks and bound how much inattentive respondents can attenuate estimated treatment effects. Second, we develop a parametric Bayesian approach to incorporate pre-treatment covariates in the analysis to sharpen our inferences and quantify estimation uncertainty. We apply these methods to a survey experiment on electoral messaging. We conclude with practical recommendations for scholars designing experiments.Comment: 32 pages (main text), 18 pages (supplementary materials), 4 figure

Photoionization of High Altitude Gas in a Supernova-Driven Turbulent Interstellar Medium

We investigate models for the photoionization of the widespread diffuse ionized gas in galaxies. In particular we address the long standing question of the penetration of Lyman continuum photons from sources close to the galactic midplane to large heights in the galactic halo. We find that recent hydrodynamical simulations of a supernova-driven interstellar medium have low density paths and voids that allow for ionizing photons from midplane OB stars to reach and ionize gas many kiloparsecs above the midplane. We find ionizing fluxes throughout our simulation grids are larger than predicted by one dimensional slab models, thus allowing for photoionization by O stars of low altitude neutral clouds in the Galaxy that are also detected in Halpha. In previous studies of such clouds the photoionization scenario had been rejected and the Halpha had been attributed to enhanced cosmic ray ionization or scattered light from midplane H II regions. We do find that the emission measure distributions in our simulations are wider than those derived from Halpha observations in the Milky Way. In addition, the horizontally averaged height dependence of the gas density in the hydrodynamical models is lower than inferred in the Galaxy. These discrepancies are likely due to the absence of magnetic fields in the hydrodynamic simulations and we discuss how magnetohydrodynamic effects may reconcile models and observations. Nevertheless, we anticipate that the inclusion of magnetic fields in the dynamical simulations will not alter our primary finding that midplane OB stars are capable of producing high altitude diffuse ionized gas in a realistic three-dimensional interstellar medium.Comment: ApJ accepted. 17 pages, 7 figure

Effect of ovariectomy on the progression of chronic kidney disease-mineral bone disorder (CKD-MBD) in female Cy/+ rats

Male Cy/+ rats have shown a relatively consistent pattern of progressive kidney disease development that displays multiple key features of late stage chronic kidney disease-mineral bone disorder (CKD-MBD), specifically the development of cortical bone porosity. However, progression of disease in female Cy/+ rats, assessed in limited studies, is more heterogeneous and to date has failed to show development of the CKD-MBD phenotype, thus limiting their use as a practical model of progressive CKD-MBD. Animal and human studies suggest that estrogen may be protective against kidney disease in addition to its established protective effect on bone. Therefore, in this study, we aimed to determine the effect of ovariectomy (OVX) on the biochemical and skeletal manifestations of CKD-MBD in Cy/+ female rats. We hypothesized that OVX would accelerate development of the biochemical and skeletal features of CKD-MBD in female Cy/+ rats, similar to those seen in male Cy/+ rats. Female Cy/+ rats underwent OVX (n = 8) or Sham (n = 8) surgery at 15 weeks of age. Blood was collected every 5 weeks post-surgery until 35 weeks of age, when the rats underwent a 4-day metabolic balance, and the tibia and final blood were collected at the time of sacrifice. OVX produced the expected changes in trabecular and cortical parameters consistent with post-menopausal disease, and negative phosphorus balance compared with Sham. However, indicators of CKD-MBD were similar between OVX and Sham (similar kidney weight, plasma blood urea nitrogen, creatinine, creatinine clearance, phosphorus, calcium, parathyroid hormone, and no cortical porosity). Contrary to our hypothesis, OVX did not produce evidence of development of the CKD-MBD phenotype in female Cy/+ rats

Hyperoxia Causes Mitochondrial Fragmentation in Pulmonary Endothelial Cells by Increasing Expression of Pro-Fission Proteins

Objective—We explored mechanisms that alter mitochondrial structure and function in pulmonary endothelial cells (PEC) function after hyperoxia. Approach and Results—Mitochondrial structures of PECs exposed to hyperoxia or normoxia were visualized and mitochondrial fragmentation quantified. Expression of pro-fission or fusion proteins or autophagy-related proteins were assessed by Western blot. Mitochondrial oxidative state was determined using mito-roGFP. Tetramethylrhodamine methyl ester estimated mitochondrial polarization in treatment groups. The role of mitochondrially derived reactive oxygen species in mt-fragmentation was investigated with mito-TEMPOL and mitochondrial DNA (mtDNA) damage studied by using ENDO III (mt-tat-endonuclease III), a protein that repairs mDNA damage. Drp-1 (dynamin-related protein 1) was overexpressed or silenced to test the role of this protein in cell survival or transwell resistance. Hyperoxia increased fragmentation of PEC mitochondria in a time-dependent manner through 48 hours of exposure. Hyperoxic PECs exhibited increased phosphorylation of Drp-1 (serine 616), decreases in Mfn1 (mitofusion protein 1), but increases in OPA-1 (optic atrophy 1). Pro-autophagy proteins p62 (LC3 adapter–binding protein SQSTM1/p62), PINK-1 (PTEN-induced putative kinase 1), and LC3B (microtubule-associated protein 1A/1B-light chain 3) were increased. Returning cells to normoxia for 24 hours reversed the increased mt-fragmentation and changes in expression of pro-fission proteins. Hyperoxia-induced changes in mitochondrial structure or cell survival were mitigated by antioxidants mito-TEMPOL, Drp-1 silencing, or inhibition or protection by the mitochondrial endonuclease ENDO III. Hyperoxia induced oxidation and mitochondrial depolarization and impaired transwell resistance. Decrease in resistance was mitigated by mito-TEMPOL or ENDO III and reproduced by overexpression of Drp-1. Conclusions—Because hyperoxia evoked mt-fragmentation, cell survival and transwell resistance are prevented by ENDO III and mito-TEMPOL and Drp-1 silencing, and these data link hyperoxia-induced mt-DNA damage, Drp-1 expression, mt-fragmentation, and PEC dysfunction