Lower Bounds for Local Versions of Dimension Reductions

We consider the problem of embedding vectors from an arbitrary Euclidean space into a low-dimensional Euclidean space while preserving, up to a small distortion, a subset of the distances. In particular, preserving only the distance of each vector to a small number of its nearest neighbors. We show that even when the subset of distances we wish to preserve is very small, the problem does not become easier than when one is required to preserve all the distances. Supported in part by the Israel Science Foundation.     

Coordination‐Directed Growth of Transition‐Metal–Crystalline‐Carbon Composites with Controllable Metal Composition

Transition‐metal–carbon (CTM) composites show ample activity in many catalytic reactions. However, control of composition, distribution, and properties is challenging. Now, a straightforward path for the synthesis of transition‐metal nanoparticles engulfed in crystalline carbon is presented with excellent control over the metal composition, amount, ratio, and catalytic properties. This approach uses molten monomers that coordinate metals ions at high temperature. At high temperatures, strong coordination bonds direct the growth of carbon material with homogeneous metals distribution and with negligible losses, owing to the liquid‐like reaction compared to the traditional solid‐state reaction. The strength of the approach is demonstrated by the synthesis of mono, binary, and trinary transition‐metal–crystalline‐carbon composites with tunable and precise elemental composition as well as good electrochemical properties as oxygen evolution reaction electrocatalysts.     

On iterative methods for solving nonlinear least squares problems over convex sets

Nonlinear least squares problems over convex sets inR ⁿ are treated here by iterative methods which extend the classical Newton, gradient and steepest descent methods and the methods studied recently by Pereyra and the author. Applications are given to nonlinear least squares problems under linear constraint, and to linear and nonlinear inequalities. Part of the research underlying this report was undertaken for the Office of Naval Research, Contract Nonr-1228(10), Project NR047-021, and for the U.S. Army Research Office — Durham, Contract No. DA-31-124-ARO-D-322 at Northwestern University. Reproduction of this paper in whole or in part is permitted for any purpose of the United States Government.     

Designing a multiroute synthesis scheme in combinatorial chemistry

Solid-phase mix-and-split combinatorial synthesis is often used to produce large arrays of compounds to be tested during the various stages of the drug development process. This method can be represented by a synthesis graph in which nodes correspond to grow operations and arcs to beads transferred among the different reaction vessels. In this work, we address the problem of designing such a graph which maximizes the number of produced target compounds (namely, compounds out of an input library of desired molecules), given constraints on the number of beads used for library synthesis and on the number of reaction vessels available for concurrent grow steps. We present a heuristic based on a discrete search for solving this problem, test our solution on several data sets, explore its behavior, and show that it achieves good performance.     

Active loading and tunable release of doxorubicin from block copolymer vesicles

Vesicles are spherical bilayers that offer a hydrophilic reservoir, suitable for the incorporation of water-soluble molecules, as well as a hydrophobic wall that protects the loaded molecules from the external solution. The permeability of a vesicle wall made from polystyrene can be enhanced by adding a plasticizer such as dioxane. Tuning the wall permeability allows loading and release of molecules from vesicles to be controlled. In this study, vesicles are prepared from polystyrene(310)-b-poly(acrylic acid)(36) and used as model carriers for doxorubicin (DXR), a weak amine and a widely used anticancer drug. To increase the wall permeability, different amounts of dioxane are added to the vesicle solution. A pH gradient is created across the vesicle wall (inside acidic) and used as an active loading method to concentrate the drug inside the vesicles. The results show that a pH gradient of ca. 3.8 units can enhance the loading level up to 10-fold relative to loading in the absence of the gradient. After loading, the release of DXR from vesicles is followed as a function of the wall permeability. The diffusion coefficient of doxorubicin through polystyrene (D) is evaluated from the initial slope of the release curves; the value of D ranges from 8 x 10(-17) to 6 x 10(-16) cm(2)/s, depending on the degree of plasticization of the vesicle wall.     

How do electronic carriers cross Si-bound alkyl monolayers?

Electron transport through Si-C bound alkyl chains, sandwiched between and Hg, is characterized by two distinct types of barriers, each dominating in a different voltage range. At low voltage, the current depends strongly on temperature but not on molecular length, suggesting transport by thermionic emission over a barrier in the Si. At higher voltage, the current decreases exponentially with molecular length, suggesting transport limited by tunneling through the molecules. The tunnel barrier is estimated, from transport and photoemission data, to be approximately 1.5 eV with a 0.25m(e) effective mass.     

Remarkable dendritic effect in the polymer-supported catalysis of the Heck arylation of olefins

[reaction: see text] Phosphine-palladium complexes, immobilized on polystyrene, demonstrated a remarkable increase in catalytic activity and selectivity in the Heck reaction upon the introduction of a dendritic spacer between the support and phosphine. For some reactions an up to 5-fold increase in yield is observed.