Water-induced micellar structure change in Pluronic P103/water/o-xylene ternary system

Both laser light scattering (LLS) and small-angle X-ray scattering (SAXS) were used to study the water-induced formation and structure of micelles and supramolecules of Pluronic P103 [(EO)₁₇(PO)₆₀(EO)₁₇] in o-xylene, a selective solvent for the long middle block. In pure o-xylene, P103 molecules exist as unimer coils with an equivalent hard-sphere radius of 1.6 nm even at fairly high concentrations. Micelles with a PEO/water core and a PPO dominated corona were formed in the presence of water when the P103 concentration ≥0.046 g/mL. The size and structure of micelles have been studied as a function of solubilized water content Z (the molar ratio of water to EO units) in micelles. The micelles change from a somewhat open structure with some EO units either dangling out of the micellar core or being incorporated into neighboring micellar cores at low Z values to a flower-like structure with relatively sharp interface at high Z values. At low Z values (< about 2.9), micelles tend to have a structure with part of the poorly solvated PEO blocks present in the corona. With more water added to the core, the PEO blocks in the corona gradually entered into the core, and the PPO blocks backfolded to form loops. With increasing Z, the micellar core radius, R_c, and the hard-sphere volume fraction, ϕ, of micelles increased; the aggregation number, N, kept nearly a constant; but the hydrodynamic radius, 〈R_h〉₀, and the corona thickness, R_s, decreased. At high Z values (> about 2.9), micelles have a flower-like structure with the two end PEO blocks belonging to the small micellar core. With increasing Z, the values of R_c, ϕ, and N increased, while R_s kept nearly a constant. In the concentrated regime (C > 0.30 g/mL), a stiff polymer network at a critical ϕ value of 0.49 was formed. The supramolecular structures with a face-center cubic packing, and a possible hexagonal packing at higher polymer concentrations (i.e. > 0.55 g/mL), were observed, respectively. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 889–900, 1998     

The Role of Ligand Density in the Enzymatic Glycosylation of Carbohydrates Presented on Self-Assembled Monolayers of Alkanethiolates on Gold

The biological activity of immobilized carbohydrates can show a dramatic dependence on the density of carbohydrate. This is the result of investigations with self-assembled monolayers that present N-acetylglucosamine groups as a model substrate for glycosylation by bovine β-1,4-galactosyltransferase (GalTase; see picture). Surface plasmon resonance spectroscopy and carbohydrate-binding lectins were used to characterize the reaction at the interface. UDP-Gal=uridine diphosphogalactose     

Natural Product Synthesis on Polymeric Supports—Synthesis and Biological Evaluation of an Indolactam Library

Potent activators of protein kinase C in fibroblasts: This property was determined for several indolactam V analogues ( 1 ) with a new cell-based assay system. This tumor-promoting indole alkaloid and analogues thereof can be synthesized efficiently on the solid phase. The key steps of the combinatorial approach are a regioselective amination of the indole ring and an enantioselective enzymatic reaction.     

Accelerating electrochemistry with metal nanowires

Scalable, solution-phase syntheses of metal nanowires are enabling their increased use in electrochemical processes. This review highlights recent results demonstrating how metal nanowires can exhibit better durability and higher activity than traditional metal nanoparticle electrocatalysts on carbon supports. Metal nanowires can also form interconnected two-dimensional and three-dimensional (3D) networks that eliminate the need for a carbon support, thus eliminating the detrimental effects of carbon corrosion. Porous 3D networks of nanowires can be used as flow-through electrodes with the highest specific surface areas and mass transport coefficients obtained to date, enabling dramatic increases in the productivity of electrochemical reactions. Nanowire networks are also serving as 3D current collectors that improve the capacity of batteries. The tunable surface structure and dimensions of metal nanowires offer researchers a new opportunity to create electrodes that are tailored from the atomic scale to the microscale to improve electrochemical performance.     

A study of the spatial and temporal evolution of auto-ignition kernels using time-resolved tomographic OH-LIF

In this paper, the spatial and temporal evolution of auto-ignition kernels from methane jets propagating into a NO_x-vitiated, high-turbulence, hot air co-flow was studied by means of time-resolved tomographic laser-induced fluorescence of OH (Tomo OH-LIF). Measurements were performed using a burst dye laser system at 10 kHz for volumetric laser illumination and a multi-camera arrangement (8-views) for detection of the fluorescence signal. Auto-ignition kernels were detected three-dimensionally and tracked using a robust algorithm based on the intensity gradient of the volumetrically reconstructed signals. The size and location of the detected kernels were evaluated for operating conditions with different Reynolds numbers of the fuel jet. Results showed that auto-ignition randomly occurred with high probability in a well defined fairly axisymmetric radial region with strong fluctuations in the main direction of the flow. The increase of the Reynolds number of the fuel jet resulted in a radial spread of the location of auto-ignition events. The statistical evaluation of the orientation and growth of auto-ignition kernels with respect to the mean flow field showed that the kernels were oriented tangentially to the flow and temporally evolve towards this preferential direction as the ignition events progressed.     

Direct Numerical Simulation of Flow over Periodic Hills up to $\text {Re}_{H}= 10{,}595$

We present fully resolved computations of flow over periodic hills at the hill-Reynolds numbers \(\text {Re}_{H}=?5{,}600\) and \(\text {Re}_{H}=?10{,}595\) with the highest fidelity to date. The calculations are performed using spectral incompressible discontinuous Galerkin schemes of \(8^{\text {th}}\) and \(7^{\text {th}}\) order spatial accuracy, \(3^{\text {rd}}\) order temporal accuracy, as well as 34 and 180 million grid points, respectively. We show that the remaining discretization error is small by comparing the results to h- and p-coarsened simulations. We quantify the statistical averaging error of the reattachment length, as this quantity is widely used as an ‘error norm’ in comparing numerical schemes. The results exhibit good agreement with the experimental and numerical reference data, but the reattachment length at \(\text {Re}_{H}=?10{,}595\) is predicted slightly shorter than in the most widely used LES references. In the second part of this paper, we show the broad range of capabilities of the numerical method by assessing the scheme for underresolved simulations (implicit large-eddy simulation) of the higher Reynolds number in a detailed h/p convergence study.