Asymmetric boronate addition to o-quinone methides: ligand exchange, solvent effects, and Lewis acid catalysis.

Density functional theory calculations suggest that asymmetric boronate addition to o-quinone methides proceeds via a Lewis acid catalyzed process through a closed six-membered transition structure. The BINOL-derived catalyst undergoes an exchange process with the original ethoxide boronate ligands. This activation mode successfully accounts for the sense and level of enantioselectivity observed experimentally. A qualitative model which accurately predicts the observed enantioselectivity has been developed and is consistent with results from our study of ketone propargylation demonstrating the reaction model's generality. The effects of replacing the BINOL framework with H8-BINOL have been rationalized.We thank Girton College, Cambridge (Research Fellowship to M.N.G.), the EPSRC (studentship to M.N.G.), and Unilever for support.This is the final published version. It first appeared at http://pubs.acs.org/doi/abs/10.1021/jo502616a

Finalist essays from the Center for Homeland Defense and Security's First Annual Essay Competition, 2008

The Center for Homeland Defense and Security (CHDS) announces the winner and finalists of its first annual essay contest. CHDS launched the contest last year to provide people from around the country the opportunity to express their opinions on homeland security issues and to suggest new ideas. The winner and four finalists were selected from eighty contest submissions by a committee comprised of CHDS staff, faculty, and alumni. The variety of the essay topics submitted, as well as the backgrounds of the authors, highlights the vast scope of the impact that homeland security policies, programs, and challenges have on our communities and professions. This year’s contestants were asked to answer the question “What single aspect of Homeland Security has been most successful, and what single aspect will be most critical to Homeland Security success?”Naval Posgraduate School, Center for Homeland Defense and Securit

Thermoresponsive reversible behavior of multistimuli pluronic-based pentablock copolymer at the air-water interface

Surface behavior of the pH- and thermoresponsive amphiphilic ABCBA pentablock copolymer has been studied with respect to the environmental conditions. We demonstrate that the pentablock copolymer poly((diethylaminoethyl methacrylate)-b-(ethylene oxide)-b-(propylene oxide)-b-(ethylene oxide)-b-(diethylaminoethyl methacrylate)) possesses reversible temperature changes at the air-water interface in a narrow pH range of the water subphase. Significant diversity in the surface morphology of pentablock copolymer monolayers at different pH and temperatures observed were related to the corresponding reorganization of central and terminal blocks. Remarkable reversible variations of the surface pressure observed for the Langmuir monolayers at pH 7.4 in the course of heating and cooling between 27 and 50°C is associated with conformational transformations of terminal blocks crossing the phase line in the vicinity of the lower critical solution temperature point. The observed thermoresponsive surface behavior can be exploited for modeling of the corresponding behavior of pentablock copolymers adsorbed onto various biointerfaces for intracellular delivery for deeper understanding of stimuli-responsive transformations relevant to controlled drug and biomolecules release and retention

Self-assembly of CdTe tetrapods into network monolayers at the air/water interface

Cadmium telluride (CdTe) tetrapods are synthesized with varying aspect ratios through multiple injections of the Te precursor, which provides an excellent means of controlling and tailoring the optical properties of the tetrapods. The self-assembly of CdTe tetrapods at the air/water interface is explored using the Langmuir-Blodgett (LB) technique due to potential use in solar cells arising from the intriguing tetrapod shape that improves charge transport and the optimum band gap energy of CdTe that enhances light absorption. Interestingly, the Langmuir isotherm shows two pressure plateau regions: one at ∼10 mN/m with the other at the high surface pressure of ∼39 mN/m. LB deposition at various pressures allows the discernment of the unique two-dimensional packing alluded in the isotherm. By placing CdTe at the air/water interface, it is revealed in the deposition that the tetrapods experienced a dewetting phenomenon, forming a ribbon structure at the onset of surface pressure with a height corresponding to the length of one tetrapod arm. With the increase of surface pressure, the ribbons widen to an eventual large-scale percolated network pattern. The packing density of tetrapods is successfully manipulated by controlling the surface pressure, which may find promising applications in optoelectronic devices

Mechanistic insights into a BINOL-derived phosphoric acid-catalyzed asymmetric Pictet-Spengler reaction.

The reaction of tryptamine and (2-oxocyclohexyl)acetic acid can be catalyzed by 3,3'-bis(triphenylsilyl)-1,1'-bi-2-naphthol phosphoric acid to give an asymmetric β-carboline. This reaction was first studied by Holloway et al. ( Org. Lett. 2010 , 12 , 4720 - 4723 ), but their mechanistic work did not explain the high stereoselectivity achieved. This study uses density functional theory and hybrid quantum mechanics/molecular mechanics calculations to investigate this reaction and provide a model to explain its outcome. The step leading to diastereo- and enantioselectivity is an asymmetric Pictet-Spengler reaction involving an N-acyliminium ion bound to the catalyst in a bidentate fashion. This interaction occurs via hydrogen bonds between the two terminal oxygen atoms of the catalyst phosphate group and the hydrogen atoms at N and C2 of the substrate indole group. These bonds hold the transition structure rigidly and thus allow the catalyst triphenylsilyl groups to influence the enantioselectivity.We thank Girton College, Cambridge (research fellowship to M.N.G.), the EPSRC (studentship to M.N.G.), and Unilever for support.The is the final published version. It first appeared at http://pubs.acs.org/doi/abs/10.1021/jo5028134

Particle Physics Implications for CoGeNT, DAMA, and Fermi

Recent results from the CoGeNT collaboration (as well as the annual modulation reported by DAMA/LIBRA) point toward dark matter with a light (5-10 GeV) mass and a relatively large elastic scattering cross section with nucleons (\sigma ~ 10^{-40} cm^2). In order to possess this cross section, the dark matter must communicate with the Standard Model through mediating particles with small masses and/or large couplings. In this Letter, we explore with a model independent approach the particle physics scenarios that could potentially accommodate these signals. We also discuss how such models could produce the gamma rays from the Galactic Center observed in the data of the Fermi Gamma Ray Space Telescope. We find multiple particle physics scenarios in which each of these signals can be accounted for, and in which the dark matter can be produced thermally in the early Universe with an abundance equal to the measured cosmological density.Comment: 4 pages, 2 figure

Getting antimalarials on target: impact of national roll-out of malaria rapid diagnostic tests on health facility treatment in three regions of Tanzania.

OBJECTIVES: Parasitological confirmation of malaria prior to treatment is recommended for patients of all ages, with malaria rapid diagnostic tests (mRDTs) an important tool to target artemisinin-based combination therapies (ACTs) to patients with malaria. To evaluate the impact on case management practices of routine government implementation of mRDTs, we conducted large-scale health facility surveys in three regions of Tanzania before and after mRDT roll-out. METHODS: Febrile patients at randomly selected health facilities were interviewed about care received at the facility, and blood samples were collected for reference blood smears. Health facility staff were interviewed about their qualifications and availability of malaria diagnostics and drugs. RESULTS: The percentage of febrile patients tested for malaria at the facility increased from 15.8% in 2010 to 54.9% in 2012. ACTs were obtained by 65.8% of patients positive by reference blood smear in 2010 and by 50.2% in 2012 (P = 0.0675); no antimalarial was obtained by 57.8% of malaria-negative patients in 2010 and by 82.3% in 2012 (P < 0.0001). Overall, ACT use decreased (39.9-21.3%, P < 0.0001) and antibiotic use increased (31.2-48.5%, P < 0.0001). CONCLUSION: Roll-out of mRDTs in Tanzania dramatically improved diagnostic testing for malaria and reduced overuse of ACTs for patients without parasitemia. However, post-roll-out almost 50% of febrile patients did not receive a diagnostic test, and almost 50% of patients testing positive did not receive ACTs. Stock-outs of ACTs and mRDTs were important problems. Further investigation is needed to determine reasons for not providing ACTs to patients with malaria and potential for inappropriate antibiotic use

Non-relativistic effective theory of dark matter direct detection

Dark matter direct detection searches for signals coming from dark matter scattering against nuclei at a very low recoil energy scale ~ 10 keV. In this paper, a simple non-relativistic effective theory is constructed to describe interactions between dark matter and nuclei without referring to any underlying high energy models. It contains the minimal set of operators that will be tested by direct detection. The effective theory approach highlights the set of distinguishable recoil spectra that could arise from different theoretical models. If dark matter is discovered in the near future in direct detection experiments, a measurement of the shape of the recoil spectrum will provide valuable information on the underlying dynamics. We bound the coefficients of the operators in our non-relativistic effective theory by the null results of current dark matter direct detection experiments. We also discuss the mapping between the non-relativistic effective theory and field theory models or operators, including aspects of the matching of quark and gluon operators to nuclear form factors.Comment: 35 pages, 3 figures, Appendix C.3 revised, acknowledgments and references adde

Cluster randomized trial of text message reminders to retail staff in tanzanian drug shops dispensing artemether-lumefantrine: effect on dispenser knowledge and patient adherence.

Artemisinin combination therapies are available in private outlets, but patient adherence might be compromised by poor advice from dispensers. In this cluster randomized trial in drug shops in Tanzania, 42 of 82 selected shops were randomized to receive text message reminders about what advice to provide when dispensing artemether-lumefantrine (AL). Eligible patients purchasing AL at shops in both arms were followed up at home and questioned about each dose taken. Dispensers were interviewed regarding knowledge of AL dispensing practices and receipt of the malaria-related text messages. We interviewed 904 patients and 110 dispensers from 77 shops. Although there was some improvement in dispenser knowledge, there was no difference between arms in adherence measured as completion of all doses (intervention 68.3%, control 69.8%, p [adjusted] = 0.6), or as completion of each dose at the correct time (intervention 33.1%, control 32.6%, p [adjusted] = 0.9). Further studies on the potential of text messages to improve adherence are needed