Concerted [4 + 2] and Stepwise (2 + 2) Cycloadditions of Tetrafluoroethylene with Butadiene: DFT and DLPNO-UCCSD(T) Explorations.

Tetrafluoroethylene and butadiene form the 2 + 2 cycloadduct under kinetic control, but the Diels-Alder cycloadduct is formed under thermodynamic control. Borden and Getty showed that the preference for 2 + 2 cycloaddition is due to the necessity for syn-pyramidalization of the two CF2 groups in the 4 + 2 transition state. We have explored the full potential energy surface for the concerted and stepwise reactions of tetrafluoroethylene and butadiene with density functional theory, DFT (B3LYP and M06-2X), DLPNO-UCCSD(T), and CASSCF-NEVPT2 methods and with the distortion/interaction-activation strain model to explain the energetics of different pathways. The 2 + 2 cycloadduct is formed by an anti-transition state followed by two rotations and a final bond formation transition state. Energetics are compared to the reaction of maleic anhydride and ethylene

Review of Outcome Information in 46,XX Patients with Congenital Adrenal Hyperplasia Assigned/Reared Male: What Does It Say about Gender Assignment?

There is ample historical verification of 46,XX congenital adrenal hyperplasia (CAH) patients being born with essentially male genitaliawhile outcome information is scant. Prior to glucocorticoid therapy, most patients died very young from adrenal insufficiency. Most available reports from laterchildhood, contain little information concerning sexual identity. Reports on older individuals lack adequate information about sexual identity and quality of life. The difficulty in assessing the relative impact of multiple dynamic environmental factors on the development of sexual identity, self- and body esteem and overall adjustment to life is clear. Nevertheless, it remains unclear whether those infants whose masculine genitalia at birth resulted in an initial male assignment would have enjoyed a better adult outcome had they been allowed to remain male rather than the female reassignment that most received. Further, one could ask whether a male sex of rearing should be considered in 46,XX CAH infants with male external genitalia. After reviewing available literature, we conclude that because those extremely virlized 46,XX CAH patients who were reared male with healthy social support demonstrated satisfactory levels of social and sexual function as adults a male sex assignment should be considered in these types of infants when social and cultural environment are supportive

The Role of Support Groups, Advocacy Groups, and Other Interested Parties in Improving the Care of Patients with Congenital Adrenal Hyperplasia: Pleas and Warnings

In the era of advocacy groups, it seems appropriate to contemplate how best to utilize them for patient benefit in the management of those with disorders of sex development (DSD), including those with congenital adrenal hyperplasia (CAH). Such interactions, to be constructive, require a spirit of cooperation to optimize outcomes. A traditional view of advocacy groups as a type of defender of patients' rights appears outdated and it is time that the benefits of their participation be fully realized. Open dialogue with all patients/families, including those who feel harmed by prior care are paramount. We discuss several recent examples of interactions that illustrate how dialogue in the name of “advocacy” can have a negative impact on developing a framework for ongoing constructive dialogue and actions. Such approaches completely change the dynamics of subsequent interactions. Physicians involved in the care of individuals with DSD, including those with CAH, and patients should be aware of confrontational techniques and legal implications that may be used by some advocacy groups. Hopefully recent efforts to promote a multidisciplinary care approach for patients with DSD/CAH will continue to foster mutual cooperation between team members, where the common goal is improving patient/family outcomes and quality of life

The search for habitable worlds: 1. The viability of a starshade mission

As part of NASA's mission to explore habitable planets orbiting nearby stars, this paper explores the detection and characterization capabilities of a 4-m space telescope plus 50-m starshade located at the Earth-Sun L2 point, a.k.a. the New Worlds Observer (NWO). Our calculations include the true spectral types and distribution of stars on the sky, an iterative target selection protocol designed to maximize efficiency based on prior detections, and realistic mission constraints. We carry out both analytical calculations and simulated observing runs for a wide range in exozodiacal background levels ({\epsilon} = 1 - 100 times the local zodi brightness) and overall prevalence of Earth-like terrestrial planets ({\eta}\oplus = 0.1 - 1). We find that even without any return visits, the NWO baseline architecture (IWA = 65 mas, limiting FPB = 4\times10-11) can achieve a 95% probability of detecting and spectrally characterizing at least one habitable Earth-like planet, and an expectation value of ~3 planets found, within the mission lifetime and {\Delta}V budgets, even in the worst-case scenario ({\eta}\oplus = 0.1 and {\epsilon} = 100 zodis for every target). This achievement requires about one year of integration time spread over the 5 year mission, leaving the remainder of the telescope time for UV-NIR General Astrophysics. Cost and technical feasibility considerations point to a "sweet spot" in starshade design near a 50-m starshade effective diameter, with 12 or 16 petals, at a distance of 70,000-100,000 km from the telescope.Comment: Refereed and accepted to PASP, scheduled for publication in the May 2012 issue (Vol. 124, No. 915

A catalog of visual double and multiple stars with eclipsing components

A new catalog of visual double systems containing eclipsing binaries as one component is presented. The main purpose of this catalog is to compile a complete list of all known multiples of this variety, both for current analysis and to highlight those in need of additional observations. All available photometric and astrometric data were analyzed, resulting in new orbits for eight systems and new times of minimum light for a number of the eclipsing binaries. Some of the systems in the catalog have acceptable solutions for their visual orbits, although in most cases their orbital periods are too long for simultaneous analysis. Also included, however, are a number of systems which currently lack an orbital solution but which may be suitable for simultaneous analysis in the future.Comment: 15 pages, 8 figures, 4 tables, published in A

Neurology

Contains research objectives and reports on three research projects.Office of Naval Research (Nonr-609(39))U. S. Air Force (AF33(616)-7282)Army Chemical Corps (DA-18-108-405-Cml-942)U.S. Public Health Service (B-3055)U. S. Air Force (AF49(638)-1130)U.S. Public Health Service (B-3090

Water Quality and Herbivory Interactively Drive Coral-Reef Recovery Patterns in American Samoa

BACKGROUND: Compared with a wealth of information regarding coral-reef recovery patterns following major disturbances, less insight exists to explain the cause(s) of spatial variation in the recovery process. METHODOLOGY/PRINCIPAL FINDINGS: This study quantifies the influence of herbivory and water quality upon coral reef assemblages through space and time in Tutuila, American Samoa, a Pacific high island. Widespread declines in dominant corals (Acropora and Montipora) resulted from cyclone Heta at the end of 2003, shortly after the study began. Four sites that initially had similar coral reef assemblages but differential temporal dynamics four years following the disturbance event were classified by standardized measures of 'recovery status', defined by rates of change in ecological measures that are known to be sensitive to localized stressors. Status was best predicted, interactively, by water quality and herbivory. Expanding upon temporal trends, this study examined if similar dependencies existed through space; building multiple regression models to identify linkages between similar status measures and local stressors for 17 localities around Tutuila. The results highlighted consistent, interactive interdependencies for coral reef assemblages residing upon two unique geological reef types. Finally, the predictive regression models produced at the island scale were graphically interpreted with respect to hypothesized site-specific recovery thresholds. CONCLUSIONS/SIGNIFICANCE: Cumulatively, our study purports that moving away from describing relatively well-known patterns behind recovery, and focusing upon understanding causes, improves our foundation to predict future ecological dynamics, and thus improves coral reef management

An unexpected Ireland–Claisen rearrangement cascade during the synthesis of the tricyclic core of Curcusone C: Mechanistic elucidation by trial-and-error and automatic artificial force-induced reaction (AFIR) computations

In the course of a total synthesis effort directed toward the natural product curcusone C, the Stoltz group discovered an unexpected thermal rearrangement of a divinylcyclopropane to the product of a formal Cope/1,3-sigmatropic shift sequence. Since the involvement of a thermally forbidden 1,3-shift seemed unlikely, theoretical studies involving two approaches, the “trial-and-error” testing of various conceivable mechanisms (Houk group) and an “automatic” approach using the Maeda–Morokuma AFIR method (Morokuma group) were applied to explore the mechanism. Eventually, both approaches converged on a cascade mechanism shown to have some partial literature precedent: Cope rearrangement/1,5-sigmatropic silyl shift/Claisen rearrangement/retro-Claisen rearrangement/1,5-sigmatropic silyl shift, comprising a quintet of five sequential thermally allowed pericyclic rearrangements

Correlation Between the Deuteron Characteristics and the Low-energy Triplet np Scattering Parameters

The correlation relationship between the deuteron asymptotic normalization constant, $A_{S}$, and the triplet np scattering length, $a_{t}$, is investigated. It is found that 99.7% of the asymptotic constant $A_{S}$ is determined by the scattering length $a_{t}$. It is shown that the linear correlation relationship between the quantities $A_{S}^{-2}$ and $1/a_{t}$ provides a good test of correctness of various models of nucleon-nucleon interaction. It is revealed that, for the normalization constant $A_{S}$ and for the root-mean-square deuteron radius $r_{d}$, the results obtained with the experimental value recommended at present for the triplet scattering length $a_{t}$ are exaggerated with respect to their experimental counterparts. By using the latest experimental phase shifts of Arndt et al., we obtain, for the low-energy scattering parameters ($a_{t}$, $r_{t}$, $P_{t}$) and for the deuteron characteristics ($A_{S}$, $r_{d}$), results that comply well with experimental data.Comment: 19 pages, 1 figure, To be published in Physics of Atomic Nucle