Synthesis of a Molecular Charm Bracelet via Click Cyclization and Olefin Metathesis Clipping

We describe the synthesis of a polycatenated cyclic polymer, a structure that resembles a molecular charm bracelet. Ruthenium-catalyzed ring-opening metathesis polymerization of an aminocontaining cyclic olefin monomer in the presence of a chain transfer agent generated an α,ω-diazide functionalized polyamine. Cyclization of the resulting linear polyamine using pseudo-high-dilution coppercatalyzed click cyclization produced a cyclic polymer in 19% yield. The click reaction was then further employed to remove linear contaminants from the cyclic polymer using azide- and alkyne-functionalized scavenging resins, and the purified cyclic polymer product was characterized by gel permeation chromatography, ^1H NMR spectroscopy, and IR spectroscopy. Polymer hydrogenation and conversion to the corresponding polyammonium species enabled coordination and interlocking of diolefin polyether fragments around the cyclic polymer backbone using ruthenium-catalyzed ring-closing olefin metathesis to afford a molecular charm bracelet structure. This charm bracelet complex was characterized by ^1H NMR spectroscopy, and the catenated nature of the small rings was confirmed using two-dimensional diffusion-ordered NMR spectroscopy

Ways to Reduce Peak Electrical Demand in South Louisiana

This study analyses alternatives for coping with the peak electrical demand of hot summer afternoons. Economic and Political aspects, as well as technical feasibility, are included. It is concluded that South Louisiana may indeed be able to trim peak demand to 5% below what is anticipated by 1980 , thus making one of the coal fired stations scheduled then unnecessary. However, the contingencies (Natural Gas Shortage, Another Oil Embargo) would make a coal-fired station very desirable

Prevalence of Mental Health Disorder Symptoms and Rates of Help-seeking Among University-Enrolled, Black Men

Background. Black men in college represent a subgroup of emerging adults who are at increased risk of developing mental health disorders (MHDs), such as anxiety and depression. Such risk has been attributed to disproportionate experiences with everyday racial discrimination and high levels of psychological distress. Despite being at higher risk, university-enrolled, Black men are not utilizing mental health or health resources at optimal rates. The current evidence base describing prevalence of MHDs and health services utilization among Black men in college is limited. The present study addresses this by examining mental health prevalence among university-enrolled, Black men and their rates of health services utilization. Methods. We analyzed data (N ~ 2500) from a student survey, Spit for Science, a longitudinal, ongoing, research study at a mid-Atlantic, public university. Participants are given surveys in their freshman year and follow-up surveys every spring thereafter. Measures included: mental health disorders (depression and anxiety, as measured by the Symptom Checklist 90) and campus health service utilization (counseling center, health services, wellness center, and recreational sports). We conducted descriptive analyses to determine MHD symptom prevalence and utilization rates; Mann Whitney U tests to compare prevalence rates to White men and Black women; and, Chi-squared tests to compare rates of utilization among groups. Results. During their Freshman year, greater than 60% of students from each ethnic group reported at least one anxiety symptom and greater than 80% reported at least one depressive symptom. By senior year, reporting rates decreased significantly for Black men (49.6%) but remained high for White men (69.1%) and Black women (63%); p \u3c0.000. For depression, results were similar; however, only significant differences between Black men (72.7%) and Black women (87.1%); p\u3c0.000. Black men (20.4%), though reporting high levels of symptoms, still utilized counseling services at lower rates compared to White men (37.76%); p = 0.024. Conclusion. Findings suggest that Black men underutilize available campus health resources despite reporting one or more symptoms associated with anxiety and depression. Further research and prevention efforts are needed to improve help-seeking among this vulnerable population.https://scholarscompass.vcu.edu/gradposters/1077/thumbnail.jp

Framing and visual type: Effect on future Zika vaccine uptake intent

Introduction: The Zika virus is associated with the birth defect microcephaly, and while a vaccine was not available in early- 2017, several were under development. This study’s purpose was to identify effective communication strategies to promote uptake of a new vaccine, particularly among women of reproductive age.Design and methods: In order to study the effects of Zika message framing (gain vs. loss) and visual type (photo vs. infographic) on future Zika vaccine uptake intent, a 2×2 between-subjects experiment was performed via an online survey in 2017 among 339 U.S. women of reproductive age (18-49 years). Participants were exposed to one of four messages, all resembling Instagram posts: gain-framed vs. loss-framed infographic, and gain-framed vs. loss-framed photo. These messages were followed by questions about Zika vaccine uptake intent as well as intermediate psychosocial variables that could lead to intent. Results: There was no interaction between framing and visual type (P=0.116), and there was no effect for framing (P=0.185) or visual type (P=0.724) on future Zika vaccine uptake intent, which is likely indicative of insufficient dosage of the intervention. However, when focusing on intermediate psychosocial constructs that are known to influence behavior and intent, gain-framed messages were more effective in increasing subjective norms (P=0.005) as related to a future Zika vaccine, as well as perceived benefits (P=0.016) and self-efficacy (P=0.032). Conclusions: Gain-framed messages seem to be more effective than loss-framed messages to increase several constructs that could, in turn, affect future Zika vaccine uptake intent. This is a novel finding since, traditionally, loss-framed messages are considered more beneficial in promoting vaccine-related health behaviors

"Pair" Fermi contour and repulsion-induced superconductivity in cuprates

The pairing of charge carriers with large pair momentum is considered in connection with high-temperature superconductivity of cuprate compounds. The possibility of pairing arises due to some essential features of quasi-two-dimensional electronic structure of cuprates: (i) The Fermi contour with strong nesting features; (ii) The presence of extended saddle point near the Fermi level; (iii) The existence of some ordered state (for example, antiferromagnetic) close to the superconducting one as a reason for an appearing of "pair" Fermi contour resulting from carrier redistribution in momentum space. In an extended vicinity of the saddle point, momentum space has hyperbolic (pseudoeuclidean) metrics, therefore, the principal values of two-dimensional reciprocal reduced effective mass tensor have unlike signs. Rearrangement of holes in momentum space results in a rise of "pair" Fermi contour which may be defined as zero-energy line for relative motion of the pair. The superconducting gap arises just on this line. Pair Fermi contour formation inside the region of momentum space with hyperbolic metrics results in not only superconducting pairing but in a rise of quasi-stationary state in the relative motion of the pair. Such a state has rather small decay and may be related to the pseudogap regime of underdoped cuprates. It is concluded that the pairing in cuprates may be due to screened Coulomb repulsion. In this case, the superconducting energy gap in hole-doped cuprates exists in the region of hole concentration which is bounded both above and below. The superconducting state with positive condensation energy exists in more narrow range of doping level inside this region. Such hole concentration dependence correlates with typical phase diagram of cuprates.Comment: 23 pages, 11 figures. Submitted to Phys. Rev.

Outcomes in patients with gunshot wounds to the brain.

Introduction:Gunshot wounds to the brain (GSWB) confer high lethality and uncertain recovery. It is unclear which patients benefit from aggressive resuscitation, and furthermore whether patients with GSWB undergoing cardiopulmonary resuscitation (CPR) have potential for survival or organ donation. Therefore, we sought to determine the rates of survival and organ donation, as well as identify factors associated with both outcomes in patients with GSWB undergoing CPR. Methods:We performed a retrospective, multicenter study at 25 US trauma centers including dates between June 1, 2011 and December 31, 2017. Patients were included if they suffered isolated GSWB and required CPR at a referring hospital, in the field, or in the trauma resuscitation room. Patients were excluded for significant torso or extremity injuries, or if pregnant. Binomial regression models were used to determine predictors of survival/organ donation. Results:825 patients met study criteria; the majority were male (87.6%) with a mean age of 36.5 years. Most (67%) underwent CPR in the field and 2.1% (n=17) survived to discharge. Of the non-survivors, 17.5% (n=141) were considered eligible donors, with a donation rate of 58.9% (n=83) in this group. Regression models found several predictors of survival. Hormone replacement was predictive of both survival and organ donation. Conclusion:We found that GSWB requiring CPR during trauma resuscitation was associated with a 2.1% survival rate and overall organ donation rate of 10.3%. Several factors appear to be favorably associated with survival, although predictions are uncertain due to the low number of survivors in this patient population. Hormone replacement was predictive of both survival and organ donation. These results are a starting point for determining appropriate treatment algorithms for this devastating clinical condition. Level of evidence:Level II

I Spy Transits and Pulsations: Empirical Variability in White Dwarfs Using Gaia and the Zwicky Transient Facility

We present a novel method to detect variable astrophysical objects and transient phenomena using anomalous excess scatter in repeated measurements from public catalogs of Gaia DR2 and Zwicky Transient Facility (ZTF) DR3 photometry. We first provide a generalized, all-sky proxy for variability using only Gaia DR2 photometry, calibrated to white dwarf stars. To ensure more robust candidate detection, we further employ a method combining Gaia with ZTF photometry and alerts. To demonstrate the efficacy, we apply this latter technique to a sample of roughly $12,100$ white dwarfs within 200 pc centered on the ZZ Ceti instability strip, where hydrogen-atmosphere white dwarfs are known to pulsate. Through inspecting the top $1\%$ samples ranked by these methods, we demonstrate that both the Gaia-only and ZTF-informed techniques are highly effective at identifying known and new variable white dwarfs, which we verify using follow-up, high-speed photometry. We confirm variability in all 33 out of 33 ($100\%$) observed white dwarfs within our top $1\%$ highest-ranked candidates, both inside and outside the ZZ Ceti instability strip. In addition to dozens of new pulsating white dwarfs, we also identify five white dwarfs highly likely to show transiting planetary debris; if confirmed, these systems would more than triple the number of white dwarfs known to host transiting debris.Comment: 30 pages, 14 figures, revised and accepted to ApJ on March 11, 202

Single-Particle and Collective Motion for Proton-Rich Nuclei on the Astrophysical rp-Process Path

Based on available experimental data, a new set of Nilsson parameters is proposed for proton-rich nuclei with proton or neutron numbers $28\leq N\leq 40$. The resulting single-particle spectra are compared with those from relativistic and non-relativistic mean field theories. Collective excitations in some even--even proton-rich nuclei in the upper $pf$ shell are investigated using the Projected Shell Model with the new Nilsson basis. It is found that the regular bands are sharply disturbed by band crossings involving $1g_{9/2}$ neutrons and protons. Physical quantities for exploring the nature of the band disturbance and the role of the $1g_{9/2}$ single-particle are predicted, which may be tested by new experiments with radioactive beams.Comment: 4 pages, 3 figures, accepted by Phys. Rev. C, Rapid Communicatio

Reduced Stability and Increased Dynamics in the Human Proliferating Cell Nuclear Antigen (PCNA) Relative to the Yeast Homolog

Proliferating Cell Nuclear Antigen (PCNA) is an essential factor for DNA replication and repair. PCNA forms a toroidal, ring shaped structure of 90 kDa by the symmetric association of three identical monomers. The ring encircles the DNA and acts as a platform where polymerases and other proteins dock to carry out different DNA metabolic processes. The amino acid sequence of human PCNA is 35% identical to the yeast homolog, and the two proteins have the same 3D crystal structure. In this report, we give evidence that the budding yeast (sc) and human (h) PCNAs have highly similar structures in solution but differ substantially in their stability and dynamics. hPCNA is less resistant to chemical and thermal denaturation and displays lower cooperativity of unfolding as compared to scPCNA. Solvent exchange rates measurements show that the slowest exchanging backbone amides are at the β-sheet, in the structure core, and not at the helices, which line the central channel. However, all the backbone amides of hPCNA exchange fast, becoming undetectable within hours, while the signals from the core amides of scPCNA persist for longer times. The high dynamics of the α-helices, which face the DNA in the PCNA-loaded form, is likely to have functional implications for the sliding of the PCNA ring on the DNA since a large hole with a flexible wall facilitates the establishment of protein-DNA interactions that are transient and easily broken. The increased dynamics of hPCNA relative to scPCNA may allow it to acquire multiple induced conformations upon binding to its substrates enlarging its binding diversity

Earnings smoothing and CEO cash bonus compensation: The role of mandatory derivatives disclosure policy

© 2018 Macmillan Publishers Ltd., part of Springer Nature. Motivated by intense controversy over mandatory derivative instruments disclosure required by the Statement of Financial Accounting Standard No. 133 (SFAS 133), this study is to examine whether the sensitivity of CEOs compensation to earnings smoothing changes following the adoption of SFAS 133. Moreover, the study investigates whether the sensitivity of CEOs compensation to earnings smoothing after the implementation of SFAS 133 varies with the level of market volatility. Using the correlation between the changes in discretionary accruals and the changes in pre-discretionary income as a measure of earnings smoothing and dollar value of a bonus earned by the CEOs during the year as a measure of CEOs compensation, the empirical evidence reveals that while earnings smoothing and CEOs compensation are positively related, the positive relation is stronger after the adoption of SFAS 133. The study also finds that the positive association between earnings smoothing and CEOs compensation after the adoption of SFAS 133 is larger when the market volatility is higher. This study provides direct evidence on the impact of the adoption of SFAS 133 on the sensitivity of CEO compensation to earnings smoothing and sheds light on current literature on the effects of accounting regulations, earnings smoothing, and compensation plan. Moreover, this study helps standard setters to better understand the trade-off between transparency and compensation plans