Structure of hydrated Na-Nafion polymer membranes

We use molecular dynamics simulations to investigate the structure of the hydrated Na-Nafion membranes. The membrane is "prepared" by starting with the Nafion chains placed on a cylinder having the water inside it. Minimizing the energy of the system leads to a filamentary hydrophilic domain whose structure depends on the degree of hydration. At 5 wt % water the system does not have enough water molecules to solvate all the ions that could be formed by the dissociation of the -SO3Na groups. As a result, the -SO3Na groups aggregate with the water to form very small droplets that do not join into a continuous phase. The size of the droplets is between 5 and 8 A. As the amount of water present in the membrane is increased, the membrane swells, and SO3Na has an increasing tendency to dissociate into ions. Furthermore, a transition to a percolating hydrophilic network is observed. In the percolating structure, the water forms irregular curvilinear channels branching in all directions. The typical dimension of the cross section of these channels is about 10-20 A. Calculated neutron scattering from the simulated system is in qualitative agreement with experiment. In all simulations, the pendant sulfonated perfluorovinyl side chains of the Nafion hug the walls of the hydrophilic channel, while the sulfonate groups point toward the center of the hydrophilic phase. The expulsion of the side chains from the hydrophilic domain is favored because it allows better interaction between the water molecules. We have also examined the probability of finding water molecules around the Na+ and the -SO3(-) ions as well as the probability of finding other water molecules next to a given water molecule. These probabilities are much broader than those found in bulk water or for one ion in bulk water (calculated with the potentials used in the present simulation). This is due to the highly inhomogeneous nature of the material contained in the small hydrophilic pores.     

Quadratically constrained least squares and quadratic problems

Summary We consider the following problem: Compute a vectorx such that Ax–b₂=min, subject to the constraint x₂=. A new approach to this problem based on Gauss quadrature is given. The method is especially well suited when the dimensions ofA are large and the matrix is sparse.It is also possible to extend this technique to a constrained quadratic form: For a symmetric matrixA we consider the minimization ofx ^T A x–2b ^T x subject to the constraint x₂=.Some numerical examples are given.This work was in part supported by the National Science Foundation under Grant DCR-8412314 and by the National Institute of Standards and Technology under Grant 60NANB9D0908.     

Determination of butyltins in environmental samples using sodium tetraethylborate derivatisation: characterisation and minimisation of interferences

Interferences affecting the determination of butyltin species by sodium tetraethylborate (STEB) derivatisation followed by purge-trap preconcentration were systematically studied using synthetic solutions, natural water samples and sediment extracts. Substances that did not cause interferences included most common cations (apart from those metal ions listed below), anions, metalloids and polar organic compounds. Natural organic matter (NOM) specifically interfered with tributyltin (TBT) due to a mechanism involving partitioning of the butyltin to the hydrophobic portions of the NOM. The metal ions Ag(I) (≥2 μM), Cd(II) (≥2 μM), Cu(II) (≥0.5 μM) interfered predominantly with the determination of monobutyltin (MBT) due to catalytic degradation of the STEB reagent. Pb(II) (≥14 μM) interfered with butyltin determination by an unknown mechanism. Other interferences to the purge-trap method were shown to occur in the presence of chelating agents (e.g. EDTA) or hydrophobic liquids such as diesel fuel. A mixture comprising methanol (MeOH), EDTA and Mn(II) was used to partially mask the effect of interfering NOM and metals. Spike recoveries (mean±S.D. of n=7 different samples) of MBT, dibutyltin (DBT) and TBT in contaminated natural water samples were improved from 70±36,90±11 and 91±24 to 102±10,98±3 and 98±4%, respectively. Spike recoveries (mean±S.D. of n=5 different samples) of MBT, DBT and TBT in aliquots of sediment extracts were improved from 86±17,79±18 and 59±32 to 97±6.2,103±3.6 and 103±5.0%, respectively. The ability to analyse larger aliquots of sediment extracts in the presence of the masking mixture improved the detection limit four-fold if MBT and DBT determination was required and 10-fold if only TBT determination was required.     

Competitive hydrogen bonding of cyclopropenium ions: Implications of an anion switch

This work demonstrates how modulating hydrogen bonding between intermolecular, bifurcated, and intramolecular interactions can be used to tune the structural, electronic, and photophysical properties of cyclopropenium ions and their respective fluorophores. The basis of this switchability was examined using X-ray diffraction analysis, ¹H NMR spectroscopy, DFT calculations, and fluorescence spectroscopy.     

D-bar Operators on Quantum Domains

We study the index problem for the d-bar operators subject to Atiyah- Patodi-Singer boundary conditions on noncommutative disk and annulus.     

Highly Stereoselective Synthesis of a C2-Symmetric 2,2′-Bipyridine Derived from Glucose

2-Bromo-6-lithiopyridine adds stereoselectively to the β-face of 1,2;5,6-di-O-isopropylidene-α-D-glucofuranos-3-ulose (2) to provide compound 5 in 50% yield as a single diastereomer. Compound 5 can be coupled to form novel C₂-symmetric 2,2′-bipyridine 7, the first example of a C₂-symmetric bipyridine that derives chirality from glucose.     

Alternating Current Electrohydrodynamics Induced Nanoshearing and Fluid Micromixing for Specific Capture of Cancer Cells

We report a new tuneable alternating current (ac) electrohydrodynamics (ac‐EHD) force referred to as “nanoshearing” which involves fluid flow generated within a few nanometers of an electrode surface. This force can be externally tuned via manipulating the applied ac‐EHD field strength. The ability to manipulate ac‐EHD induced forces and concomitant fluid micromixing can enhance fluid transport within the capture domain of the channel (e.g., transport of analytes and hence increase target–sensor interactions). This also provides a new capability to preferentially select strongly bound analytes over nonspecifically bound cells and molecules. To demonstrate the utility and versatility of nanoshearing phenomenon to specifically capture cancer cells, we present proof‐of‐concept data in lysed blood using two microfluidic devices containing a long array of asymmetric planar electrode pairs. Under the optimal experimental conditions, we achieved high capture efficiency (e.g., approximately 90 %; % RSD=2, n=3) with a 10‐fold reduction in nonspecific adsorption of non‐target cells for the detection of whole cells expressing Human Epidermal Growth Factor Receptor 2 (HER2). We believe that our ac‐EHD devices and the use of tuneable nanoshearing phenomenon may find relevance in a wide variety of biological and medical applications.