Cyclotetrabenzoin: Facile Synthesis of a Shape‐Persistent Molecular Square and Its Assembly into Hydrogen‐Bonded Nanotubes

Cyanide‐catalyzed benzoin condensation of terephthaldehyde produces a cyclic tetramer, which we propose to name cyclotetrabenzoin. Cyclotetrabenzoin is a square‐shaped macrocycle ornamented with four α‐hydroxyketone functionalities pointing away from the central cavity, the dimensions of which are 6.9×6.9 Å. In the solid state, these functional groups extensively hydrogen bond, resulting in a microporous three‐dimensional organic framework with one‐dimensional nanotube channels. This material exhibits permanent—albeit low‐porosity, with a Langmuir surface area of 52 m² g^?1. Cyclotetrabenzoin’s easy and inexpensive synthesis and purification may inspire the creation of other shape‐persistent macrocycles and porous molecular crystals by benzoin condensation.     

Theoretical characterization of four distinct isomer types in hydrated-electron clusters, and proposed assignments for photoelectron spectra of water cluster anions

Water cluster anions, (H(2)O)(N)(-), are examined using mixed quantum/classical molecular dynamics based on a one-electron pseudopotential model that incorporates many-body polarization and predicts vertical electron detachment energies (VDEs) with an accuracy of ~0.1 eV. By varying the initial conditions under which the clusters are formed, we are able to identify four distinct isomer types that exhibit different size-dependent VDEs. On the basis of a strong correlation between the electron's radius of gyration and its optical absorption maximum, and extrapolating to the bulk limit (N → ∞), our analysis supports the assignment of the "isomer Ib" data series, observed in photoelectron spectra of very cold clusters, as arising from cavity-bound (H(2)O)(N)(-) cluster isomers. The "isomer I" data reported in warmer experiments are assigned to surface-bound isomers in smaller clusters, transitioning to partially embedded isomers in larger clusters. The partially embedded isomers are characterized by a partially formed solvent cavity at the cluster surface, and they are spectroscopically quite similar to internalized cavity isomers. These assignments are consistent with various experimental data, and our theoretical characterization of these isomers sheds new light on a long-standing assignment problem.     

Electrically driven oxygen separation through gadolinia-doped ceria using PrBaCo2O5?+?x and NdBaCo2O5?+?x electrodes

Oxygen gas can be electrochemically separated from ambient air with very high purity and compressed by using a solid-electrolyte ion-transport membrane. An electrolyte with high ionic conductivity such as gadolinium-doped ceria (CGO) and mixed conducting electrodes are used to construct the electrochemical cell. To achieve high oxygen flux, the electrodes must exhibit very fast electrode kinetics. Here, we report the performances of mixed conducting PrBaCo₂O_5 + x and NdBaCo₂O_5 + x electrodes in oxygen separation in a planar CGO electrolyte-supported cell. The properties of the electrode materials were evaluated using potentiostatic and potentiodynamic measurements and alternating current impedance spectroscopy. The oxygen flux was also measured using gas chromatography to confirm the absence of gas leaks. The electrodes demonstrated very low polarization resistances as a result of very high cathodic and anodic reaction rates at temperatures of 600–800 °C. High oxygen gas flow rates were observed on applying potentials up to 1 V with an almost linear relationship between the applied potential and the molar flow rate of oxygen gas.     

Sequential stochastic assignment under uncertainty: estimation and convergence

This paper generalizes the sequential stochastic assignment problem, involving the assignment of workers to sequentially arriving jobs, by introducing uncertainty into the job value distribution. Three estimators are presented that address various levels of uncertainty while simultaneously improving worker assignments. Specifically, each estimator is designed to utilize the unbiased and consistent properties of the sample mean to estimate the expected job value, while suppressing high variance effects during start-up. The key contribution is that closed-loop decision policies involving past job value observations can responsively adapt to changing environments and improve the overall reward resulting from pairing workers with jobs. Examples of applications that can benefit from these results include aviation passenger screening and the real estate market, as well as applications of the stochastic knapsack problem.     

Using an Integer Programming Model to Determine the Price of Combination Vaccines for Childhood Immunization

The Recommended Childhood Immunization Schedule has become sufficiently crowded that the prospect of adding additional vaccines to this schedule may not be well received by either health-care providers or parents/guardians. This has encouraged vaccine manufacturers to develop combination vaccines that can permit new vaccines to be added to the schedule without requiring children to be exposed to an unacceptable number of injections during a single clinic visit. This paper develops an integer programming model to assess the economic premium that exists in having combination vaccines available. The results of this study suggest that combination vaccines provide a cost effective alternative to individual vaccines and that further developments and innovations in this area by vaccine manufacturers can provide significant economic and societal benefits.     

The Galois group of a radical extension of the rationals

The Galois group of the splitting field of an irreducible binomialx ^2e −a overQ is computed explicitly as a full subgroup of the holomorph of the cyclic group of order 2 ^e . The general casex ⁿ −a is also effectively computed.     

On graphs having domination number half their order

In this paper we present a characterization of connected graphs of order 2n with domination numbern. Using this class of graphs, we determine an infinite class of graphs with the property that the domination number of the product of any two is precisely the product of the domination numbers.