Electrospray ionization tandem mass spectrometry in high-throughput screening of homogeneous catalysts

The frontispiece shows an illustration by John Tenniel and an excerpt from the 1865 edition of Lewis Carroll's "Alice in Wonderland". Because everything in Wonderland runs counter to logic, the Queen of Hearts declares in Alice's trial "Sentence first-verdict afterwards". High-throughput screening of catalysts, as it is conventionally practiced, does "Synthesis first-screening afterwards" which, as is argued in this review, also backwards. Given the particular constraints present in organometallic complexes, it is more efficient to develop a selective synthesis only when it has already been determined that a structure is likely to be better. The consequence is that screening methods must be able to handle ill-defined mixtures. Electrospray ionization tandem mass spectrometry is presented as a technical solution to this problem.     

High‐throughput characterization of pattern formation in symmetric diblock copolymer films

Surface‐pattern formation in thin block copolymer films was investigated by utilizing a high‐throughput methodology to validate the combinatorial measurement approach and to demonstrate the value of the combinatorial method for scientific investigation. We constructed measurement libraries from images of subregions of block copolymer films having gradients in film thickness and a range of molecular mass, M. A single gradient film covers a wide range of film morphologies and contains information equivalent to a large number of measurements of films having a fixed thickness, h. Notably, the scale of the surface patterns is generally much larger than the molecular dimensions so that the interpretation of the patterns is more subtle than ordering in bulk block copolymer materials, and there is no predictive theory of this type of surface‐pattern formation. We observed a succession of surface patterns that repeat across the film with increasing h [extended smooth regions, regions containing circular islands, labyrinthine (“spinodal”) patterns, holes, and smooth regions again]. The extended smooth regions and the labyrinthine patterns appear to be novel features revealed by our combinatorial study, and these patterns occurred as bands of h that were quantized by integral multiples of the bulk lamellar period, L_o. The magnitude of the height gradient influenced the width of the bands, and the smooth regions occupied an increasing fraction of the film‐surface area with an increasing film gradient. The average size of the spinodal patterns, λ, was found to scale as λ ～ L or λ ～ M^?1.65 and reached a limiting size at long annealing times. The hole and island features had a size comparable to λ, and their size likewise decreased with increasing M. The smooth regions were attributed to an increase in the surface‐chain density in the outer brushlike block copolymer layer with increasing h, and the scaling of λ with M was interpreted in terms of the increasing surface elasticity with M. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2141–2158, 2001     

An Adaptive Algorithm for Vector Partitioning

The vector partition problem concerns the partitioning of a set A of n vectors in d-space into p parts so as to maximize an objective function c which is convex on the sum of vectors in each part. Here all parameters d, p, n are considered variables. In this paper, we study the adjacency of vertices in the associated partition polytopes. Using our adjacency characterization for these polytopes, we are able to develop an adaptive algorithm for the vector partition problem that runs in time O(q(L)v) and in space O(L), where q is a polynomial function, L is the input size and v is the number of vertices of the associated partition polytope. It is based on an output-sensitive algorithm for enumerating all vertices of the partition polytope. Our adjacency characterization also implies a polynomial upper bound on the combinatorial diameter of partition polytopes. We also establish a partition polytope analogue of the lower bound theorem, indicating that the output-sensitive enumeration algorithm can be far superior to previously known algorithms that run in time polynomial in the size of the worst-case output.     

An Intersection Theorem on an Unbounded Set and Its Application to the Fair Allocation Problem

We prove the following theorem. Let m and n be any positive integers with mn, and let be a subset of the n-dimensional Euclidean space ⁿ . For each i=1, . . . , m, there is a class of subsets M _i ^j of ^Tn . Assume that for each i=1, . . . , m, that M _i ^j is nonempty and closed for all i, j, and that there exists a real number B(i, j) such that and its jth component _{xjB(i, j)} imply . Then, there exists a partition of {1, . . . , n} such that for all i and We prove this theorem based upon a generalization of a well-known theorem of Birkhoff and von Neumann. Moreover, we apply this theorem to the fair allocation problem of indivisible objects with money and obtain an existence theorem.     

Design of Stacked Self-Healing Rings Using a Genetic Algorithm

Ring structures in telecommunications are taking on increasing importance because of their self-healing properties. We consider a ring design problem in which several stacked self-healing rings (SHRs) follow the same route, and, thus, pass through the same set of nodes. Traffic can be exchanged among these stacked rings at a designated hub node. Each non-hub node may be connected to multiple rings. It is necessary to determine to which rings each node should be connected, and how traffic should be routed on the rings. The objective is to optimize the tradeoff between the costs for connecting nodes to rings and the costs for routing demand on multiple rings. We describe a genetic algorithm that finds heuristic solutions for this problem. The initial generation of solutions includes randomly-generated solutions, complemented by seed solutions obtained by applying a greedy randomized adaptive search procedure (GRASP) to two related problems. Subsequent generations are created by recombining pairs of parent solutions. Computational experiments compare the genetic algorithm with a commercial integer programming package.     

New type of biosensor based on magnetic nanoparticle detection

A new type of biosensor has been developed based on detection of nanosized superparamagnetic particles that serve as labels in bioreactions. The method is based on non-linear magnetic material detection by a magnetic field having components at two frequencies f₁ and f₂. The response is measured at the combinatorial frequencies f_i=mf₁+nf₂, where m and n are integers, e.g., f_i=f₁±2f₂. Several highly sensitive readers of superparamagnetic particles have been designed and used for development of various formats of immunoassays, including those compatible with immunoconcentration and magnetic enrichment of antigens.     

A combinatorial approach to jumping particles: The parallel TASEP

In this article, we continue the combinatorial study of models of particles jumping on a row of cells which we initiated with the standard totally asymmetric simple exclusion process or TASEP (Duchi and Schaeffer, Journal of Combinatorial Theory, Series A, 110(2005), 1–29). We consider here the parallel TASEP, in which particles can jump simultaneously. On the one hand, the interest in this process comes from highway traffic modeling: it is the only solvable special case of the Nagel‐Schreckenberg automaton, the most popular model in that context. On the other hand, the parallel TASEP is of some theoretical interest because the derivation of its stationary distribution, as appearing in the physics literature, is harder than that of the standard TASEP. We offer here an elementary derivation that extends the combinatorial approach we developed for the standard TASEP. In particular, we show that this stationary distribution can be expressed in terms of refinements of Catalan numbers. © 2008 Wiley Periodicals, Inc. Random Struct. Alg., 2008     

Synthesis of a Resorcylic Acid Lactone (RAL) Library Using Fluorous‐Mixture Synthesis and Profile of its Selectivity Against a Panel of Kinases

A library of resorcylic acid lactones (RAL) containing a cis‐enone moiety targeting kinases bearing a cysteine residue within the ATP‐binding pocket was prepared using a fluorous‐mixture synthesis and evaluated against a panel of 19 kinases thus providing important structure–activity trends. Two new analogues were then profiled for their selectivity against a panel of 402 kinases providing the broadest evaluation of this pharmacophores’ selectivity.