Molecular dynamics simulation of hydrated DPPC monolayers using charge equilibration force fields

We present results of molecular dynamics simulations of a model DPPC-water monolayer using charge equilibration (CHEQ) force fields, which explicitly account for electronic polarization in a classical treatment of intermolecular interactions. The surface pressure, determined as the difference between the monolayer and pure water surface tensions at 323 K, is predicted to be 22.92 ±1.29 dyne/cm, just slightly below the broad range of experimental values reported for this system. The surface tension for the DPPC-water monolayer is predicted to be 42.35 ±1.16 dyne/cm, in close agreement with the experimentally determined value of 40.9 dyne/cm. This surface tension is also consistent with the value obtained from DPPC monolayer simulations using state-of-the-art nonpolarizable force fields. The current results of simulations predict a monolayer-water potential difference relative to the pure water-air interface of 0.64 ±0.02 Volts, an improved prediction compared to the fixed-charge CHARMM27 force field, yet still overestimating the experimental range of 0.3 to 0.45 Volts. As the charge equilibration model is a purely charge-based model for polarization, the current results suggest that explicitly modeled polarization effects can offer improvements in describing interfacial electrostatics in such systems.     

Molecular Modeling and Nuclear Overhauser Enhancement Spectroscopy (NOESY): Tools for Studying the Regioselective Bromination of 3-Bromoanisole

The use of molecular modeling for predicting chemical reactivity has been highly successful in the industrial and academic research communities. For this reason, increased emphasis has been placed on molecular modeling in the undergraduate curriculum. In the described experiment, the bromination of 3-bromoanisole, students are encouraged to use molecular modeling software as a tool for predicting chemical reactivity. Besides introducing students to molecular modeling, this experiment incorporates the use of nontraditional, less hazardous reagents and solvents for electrophilic aromatic bromination reactions. Lastly, nuclear Overhauser enhancement spectroscopy (NOESY) is introduced as a tool for structural elucidation. Although there are a number of aspects to this experiment, two 3-hour laboratory periods are sufficient because the results from semiempirical (AMI) geometry optimizations, which are complete in seconds, were almost identical to the higher order, more time-intensive ab initio (3-21G*) calculations. In addition, the experimental time was greatly shortened by the discovery that catalytic HCl(aq) reduces the reaction time from 5 hours to 18 minutes.     

Heawood's empire problem

Heawood's map color theorem is generalized to maps of empires on surfaces.     

Mössbauer spectroscopy as a tool in astrobiology

Two miniaturized Mössbauer spectrometers are part of the Athena instrument package of the NASA Mars Exploration Rovers, Spirit and Opportunity. The primary objectives of their science investigation are to explore two sites on the surface of Mars where water may once have been present, and to assess past environmental conditions at those sites and their suitability for life. Aqueous minerals – jarosite at Meridiani Planum, Opportunity’s landing site, and goethite in the Columbia Hills in Gusev Crater, Spirit’s landing site – were identified by Mössbauer spectroscopy, thus providing in situ proof of water being present at those sites in the past. The formation of jarosite in particular puts strong constraints on environmental conditions during the time of formation and hence on the evaluation of potential habitability. On Earth Mössbauer spectroscopy was used to investigate microbially induced changes in Fe oxidation states and mineralogy at the Loihi deep sea mount, a hydrothermal vent system, which might serve as an analogue for potential habitats in the Martian subsurface and the sub-ice ocean of Jupiter’s icy moon Europa.     

The Global Dimension of Rings of Differential Operators on Projective Spaces

We compute the global dimension of the twisted rings of globaldifferential operators D on complex projective n-space. As varies through the complex numbers, this global dimension takeson the values n, 2n and infinity. We also study the embeddingof D in the Weyl algebra A_n in the cases when the global dimensionis infinite. In these cases, we see that the flat dimensionof A_n as a D-module is infinite as well.     

The atomic number revolution in chemistry: a Kuhnian analysis

This paper argues that the field of chemistry underwent a significant change of theory in the early twentieth century, when atomic number replaced atomic weight as the principle for ordering and identifying the chemical elements. It is a classic case of a Kuhnian revolution. In the process of addressing anomalies, chemists who were trained to see elements as defined by their atomic weight discovered that their theoretical assumptions were impediments to understanding the chemical world. The only way to normalize the anomalies was to introduce new concepts, and a new conceptual understanding of what it is to be an element. In the process of making these changes, a new scientific lexicon emerged, one that took atomic number to be the defining feature of a chemical element.     

Total synthesis of (-)-bafilomycin A(1)

A highly stereoselective total synthesis of (-)-bafilomycin A(1), the naturally occurring enantiomer of this potent vacuolar ATPase inhibitor, is described. The synthesis features the highly stereoselective aldol reaction of methyl ketone 8b and aldehyde 60c and a Suzuki cross-coupling reaction of the highly functionalized advanced intermediates 12 and 39. Vinyl iodide 12 was synthesized by a 14-step sequence starting from the readily available beta-alkoxy aldehyde 14, while the vinylboronic acid component 39 was synthesized by a nine-step sequence from beta-hydroxy-alpha-methyl butyrate 44 via a sequence involving the alpha-methoxypropargylation of chiral aldehyde 49 with the alpha-methoxypropargylstannane reagent 54. Syntheses of fragments 12 and 39 also feature diastereoselective double asymmetric crotylboration reactions to set several of the critical stereocenters. The Suzuki cross-coupling of 12 and 39 provided seco ester 40, which following conversion to the seco acid underwent smooth macrolactonization to give 41. The success of the macrocyclization required that C(7)-OH be unprotected. The Mukaiyama aldol reaction between aldehyde 60c and the TMS enol ether generated from 8b provided aldol 65 with high diastereoselectivity. Finally, all silicon protecting groups were removed by treatment of the penultimate intermediate 65 with TAS-F (tris(dimethylamino)sulfonium difluorotrimethylsilicate), thereby completing the total synthesis of (-)-bafilomycin A(1).     

Sensitive through-space dipolar correlations between nuclei of small organic molecules by partial alignment in a deuterated liquid solvent

Through-space residual dipolar correlations in NMR spectra can be measured between nuclei of small organic molecules by partially aligning them with respect to the magnetic field in a pure deuterated liquid solvent, 4-pentyl-4'-cyanobiphenyl. A simple temperature change of this liquid phase enables spectra to be compared between samples under isotropic tumbling conditions and weakly oriented anisotropic states. This should provide access of a number of small nonpolar molecules to more sensitive through-space nuclear correlations than possible through NOE experiments, depending on the net orientation of specific nuclear pairs with respect to the magnetic field and the specific coherence transfers employed.