Rhodium complexes with a new chiral nitrogen‐containing BINOL‐based diphosphite or phosphonite ligand: synthesis and application to hydroformylation of styrene and/or hydrogenation of prochiral olefins

Two new cationic rhodium(I) complexes with a chiral nitrogen‐containing BINOL‐based diphosphite or phosphonite ligand have been synthesized. Chiral diphosphite was prepared by the reaction of N‐phenyldiethanolamine with two equivalents of [(R)‐(1,1′‐binaphthalene‐2,2′‐diyl)]chlorophosphite. In its rhodium complex the ligand is bound to the metal via both phosphorus atoms, and a Rh–N interaction is also possible. Synthesis of the chiral phosphonite was achieved by the reaction of 2‐(N,N‐dimethylaminophenyl)‐bis(diethylamino)phosphine with one equivalent of R‐BINOL. In its rhodium complex, the ligand is P,N‐bonded, forming a five‐membered chelate ring. The first complex was applied to hydroformylation of styrene and displayed high activity and chemo‐ and regioselectivity, but unfortunately no asymmetric induction was found. Both complexes were evaluated in the hydrogenation of prochiral olefins with moderate activities and low enantioselectivities. Copyright © 2005 John Wiley & Sons, Ltd.     

Excitonic Bands in the Spectra of Some Organic-Inorganic Hybrid Compounds Based on Metal Halide Units

Summary.  The optical absorption, photoluminescence, and photoconductivity spectra of some compounds of the formulas [R(CH₂) _n NH₃] _x M _y X _z , [R(CH₂) _n NH(CH₃)₂] _x M _y X _z , [R(CH₂) _n S(CH₃)₂] _x M _y X _z , [R(CH₂) _n SC(NH₂)₂] _x M _y X _z , and [R(CH₂) _n SeC(NH₂)₂] _x M _y X _z (R = organic residue; M = Bi(III), Pb(II), Sn(II), Cu(I), Ag(I) etc; X = I, Br, Cl; n, x, y, z = 0, 1, 2, 3, …) are briefly reviewed, and some new results are reported. The position, intensity, and shape of the excitonic bands depend on the dimensionality and size of the inorganic network as well as on the nature of the M, X, R, and onium moieties. Received June 23, 2000. Accepted August 1, 2000     

Design of cellular manufacturing systems using Latent Semantic Indexing and Self Organizing Maps

A new, efficient clustering method for solving the cellular manufacturing problem is presented in this paper. The method uses the part-machine incidence matrix of the manufacturing system to form machine cells, each of which processes a family of parts. By doing so, the system is decomposed into smaller semi-independent subsystems that are managed more effectively improving overall performance. The proposed method uses Self Organizing Maps (SOMs), a class of unsupervised learning neural networks, to perform direct clustering of machines into cells, without first resorting to grouping parts into families as done by previous approaches. In addition, Latent Semantic Indexing (LSI) is employed to significantly reduce the complexity of the problem resulting in more effective training of the network, significantly improved computational efficiency, and, in many cases, improved solution quality. The robustness of the method and its computational efficiency has been investigated with respect to the dimension of the problem and the degree of dimensionality reduction. The effectiveness of grouping has been evaluated by comparing the results obtained with those of the k-means classical clustering algorithm.AMS classification: 62H30     

Monte Carlo study of the coil-to-globule transition of a model polymeric system

Monte Carlo computer simulations of single, flexible, self-avoiding chains on a cubic lattice have been performed upon conditions of increasing segment–segment cohesive energy (deteriorating solvent quality). The simulations spanned a wide range of chain lengths (20–10,000, i.e., up to molecular weights of a few millions) and cohesive energies (0.0–0.45k_BT, i.e., from athermal to very poor solvents). The chain length dependence of the chain size in poor solvents was characterized by a wide plateau of almost null growth for intermediate chain lengths. This plateau was linked to the development of the incipient constant density core, while genuine power law dependence (1/3) was not reached even for the longest chains and poorest solvents simulated here. The mere appearance of a core required substantial chain lengths (higher than 1000; molecular weights of a few hundred thousands), while short chains underwent a gradual densification devoid of any qualitative changes in the density distribution. Sufficiently long chains became more but not quite spherical and underwent a reasonably sharp second order phase transition. The findings were generally in agreement with predictions of mean-field theory and with the use of the standard scaling variables, despite slight inconsistencies. Nevertheless, the results stress the fact that short chains never form a constant density core and that core-dominance on the globule's properties (“volume approximation”) is only valid for extraordinarily long chains [molecular weight of O(10⁹)], an effect linked to the relatively diffuse nature of the surface layer and originating from chain connectivity in conjunction with spherical geometry. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3651–3666, 2006     

The Structure of Lattice-Subspaces

In Polyrakis (1983; Math. Proc. Cambridge Phil. Soc. 94, 519) it is proved that each infinite-dimensional, closed lattice-subspace of . . .₁ is order-isomorphic to . . .₁ and in Polyrakis (1987; Math. Anal. Appl. 184, 1) that each separable Banach lattice is order isomorphic to a closed lattice-subspace of C[0,1]. Therefore . . .₁ contains only one lattice-subspace but C[0,1] contains all the separable Banach lattices. In the first section of this article we study the kind of the order embeddability of a separable Banach lattice in C[0,1]. We show that the AM spaces have the ``best' behavior and the AL-spaces the ``worst'. In the second section we prove that the closure of a lattice-subspace is not necessarily a lattice-subspace and in the least one we study lattice-subspaces with positive bases.     

Factors affecting primary health care centers’ economic and production efficiency

Little is known about the efficiency of health centers, despite their central role in primary health care strategy for several countries. This study evaluates the health centers in Greece, and identifies factors impeding the achievement of efficiency, with the aim of determining how their efficiency could be improved. Two alternative conceptual models are used to ensure the consistency of the efficiency results: one model is focusing on production efficiency and the other on economic efficiency. Subsequently a second stage analysis is performed to account for the impact of explanatory variables on efficiency. The use of DEA models alongside with bootstrap techniques allows calculating more accurately the efficiency scores that can reflect the performance of health centers more properly. The main drivers of health centers’ technical efficiency for both conceptual models were the location characteristics, the population growth, the mortality rate and the competition. The scale efficiency of health centers in production model is reflected by the size of their respective covered populations, the location characteristics and the mortality rate while the economic model is affected by their size, the location characteristics and the percentage of population working in agriculture. Determining how these variables influence on efficiency is essential for determining performance improvement strategies.     

Remainder Estimates for the Long Range Behavior of the van der Waals Interaction Energy

The van der Waals–London’s law, for a collection of atoms at large separation, states that their interaction energy is pairwise attractive and decays proportionally to one over their distance to the sixth. The first rigorous result in this direction was obtained by Lieb and Thirring (Phys Rev A 34(1):40–46, 1986), by proving an upper bound which confirms this law. Recently the van der Waals–London’s law was proven under some assumptions by Anapolitanos and Sigal (arXiv:1205.4652v2). Following the strategy of Anapolitanos and Sigal (arXiv:1205.4652v2) and reworking the approach appropriately, we prove estimates on the remainder of the interaction energy. Furthermore, using an appropriate test function, we prove an upper bound for the interaction energy, which is sharp to leading order. For the upper bound, our assumptions are weaker, the remainder estimates stronger and the proof is simpler. The upper bound, for the cases it applies, improves considerably the upper bound of Lieb and Thirring. Their bound holds in a much more general setting, however. Here we consider only spinless Fermions.