Efficiency of connected binary block designs when a single observation is unavailable

In this paper the problem of finding the design efficiency is considered when a single observation is unavailable in a connected binary block design. The explicit expression of efficiency is found for the resulting design when the original design is a balanced incomplete block design or a group divisible, singular or semiregular or regular with ₁>0, design. The efficiency does not depend on the position of the unavailable observation. For a regular group divisible design with ₁>0, the efficiency depends on the position of the unavailable observation. The bounds, both lower and upper, on the efficiency are given in this situation. The efficiencies of designs resulting from a balanced incomplete block design and a group divisible design are in fact high when a single observation is unavailable.The work of the first author is sponsored by the Air Force Office of Scientific Research under Grant AFOSR-90-0092.On leave from Indian Statistical Institute, Calcutta, India. The work of the third author was supported by a grant from the CMDS, Indian Institute of Management, Calcutta.     

Assembly maps,K-theory, and hyperbolic groups

Following Connes and Moscovici, we show that the Baum-Connes assembly map forK _*(C*v) is rationally injective when is word-hyperbolic, implying the Equivariant Novikov conjecture for such groups. Using this result in topologicalK-theory and Borel-Karoubi regulators, we also show that the corresponding generalized assembly map in algebraicK-theory is rationally injective.     

Quantum qualitative dynamics

We describe our work on qualitative methods for visualizing the quantum eigenstates of systems with nonlinear classical dynamics. For two-degree-of-freedom systems, our approach is based on the use of generalized coherent states, and allows systems with nonoscillator kinematics to be investigated. The general approach is illustrated with two examples involving vibration-rotation interaction in polyatomic molecules. We apply the coherent states of the Lie groupH ₄SU(2) to define quantum surfaces of section for a model involving centrifugal coupling of a harmonic bend with molecular rotation, andSU(2)SU(2) coherent states to study two harmonic normal modes coupled to overall molecular rotation through coriolis interaction. In both systems, quantum states are visualized on the rotational surface of section and compared with the corresponding classical phase space structure. Striking classical-quantum correspondence is observed. We then describe recent results on the quantum states of (N 3)-dimensional systems of coupled nonlinear oscillators, which reveal a quantum delocalization that is reminiscent of classical Arnold diffusion.     

Synthesis and characteristics of novel chelate fiber containing amine and amidine groups

A polyacrylonitrile (PAN) fiber was adopted for the backbone of a chelate polymer and poly(acrylo‐amidino ethylene amine) (PAEA) was prepared through a one‐step reaction between the PAN fiber and ethylenediamine (EDA). The maximum removal capacity and degree of substitution were 7.8 meq per gram of dried PAEA and 98%, respectively. The PAEA was tested as an adsorbent in single and two‐component metal aqueous solutions under changing pH. The Cu²⁺ ion accomplished maximum adsorption amount at pH 3 and the order of maximum adsorbed amounts on PAEA is Cu²⁺ > Ag⁺ > Zn²⁺ > Ni²⁺ > Pb²⁺ in molar basis. FT‐IR spectroscopy was employed to characterize the chemical bonding in metal aqueous solutions and surface morphology was examined using atomic force microscopy (AFM) and scanning electron microscopy (SEM). Copyright © 2004 John Wiley & Sons, Ltd.     

Macromonomer synthesis using α‐(2‐methyl‐2‐phenylpropyl)acrylates as addition–fragmentation chain‐transfer agents expelling the cumyl radical

α‐(2‐Methyl‐2‐phenylpropyl)acrylate (RS‐2) was examined as a C? C bond‐cleavage type addition–fragmentation chain transfer (AFCT) agent in the benzene solution polymerizations of styrene (St), ethyl methacrylate (EMA), and cyclohexyl acrylate (CHA) with the objective of achieving efficient macromonomer synthesis by radical polymerization. The AFCT efficiency was evaluated in terms of the decrease in the number‐average molecular weight (M_n) upon the addition of the AFCT agent and the number of unsaturated end groups introduced per chain (f). The AFCT efficiency was rationalized by the consideration of the relative importance of AFCT as an end‐forming event and the competition between ‐fragmentation and crosspropagation as adduct radical reaction pathways. In St and EMA polymerizations at 60 °C, RS‐2 resulted in higher f values and lower M_n values than methyl α‐(2‐methyl‐2‐carbomethoxypropyl)acrylate (MMA‐2), and this suggested the facilitation of ‐fragmentation due to the expulsion of the more stable cumyl radical from the RS‐2 adduct radical. Higher f values were observed for MMA‐2 than for RS‐2 in CHA polymerization because of unsaturated end group formation by ‐fragmentation of midchain radicals. However, RS‐2 resulted in lower M_n values for poly(CHA) than MMA‐2 because of a smaller contribution of crosspropagation. Retardation in the presence of the AFCT agents was affected by the balance between b‐fragmentation and crosspropagation and by the addition rate of the propagating radical to the AFCT agent. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6021–6030, 2004     

Computational combinatorial ligand design: Application to human α-thrombin

Summary A new method is presented for computer-aided ligand design by combinatorial selection of fragments that bind favorably to a macromolecular target of known three-dimensional structure. Firstly, the multiple-copy simultaneous-search procedure (MCSS) is used to exhaustively search for optimal positions and orientations of functional groups on the surface of the macromolecule (enzyme or receptor fragment). The MCSS minima are then sorted according to an approximated binding free energy, whose solvation component is expressed as a sum of separate electrostatic and nonpolar contributions. The electrostatic solvation energy is calculated by the numerical solution of the linearized Poisson-Boltzmann equation, while the nonpolar contribution to the binding free energy is assumed to be proportional to the loss in solvent-accessible surface area. The program developed for computational combinatorial ligand design (CCLD) allows the fast and automatic generation of a multitude of highly diverse compounds, by connecting in a combinatorial fashion the functional groups in their minimized positions. The fragments are linked as two atoms may be either fused, or connected by a covalent bond or a small linker unit. To avoid the combinatorial explosion problem, pruning of the growing ligand is performed according to the average value of the approximated binding free energy of its fragments. The method is illustrated here by constructing candidate ligands for the active site of human -thrombin. The MCSS minima with favorable binding free energy reproduce the interaction patterns of known inhibitors. Starting from these fragments, CCLD generates a set of compounds that are closely related to high-affinity thrombin inhibitors. In addition, putative ligands with novel binding motifs are suggested. Probable implications of the MCSS-CCLD approach for the evolving scenario of drug discovery are discussed.     

Variation of physicochemical properties in the aggregates of structual isomers

The regions of variation of density, enthalpy of formation, and detonation velocity of all of the formally possible structual isomers were determined for several molecular formulas of C,H,N,O-containing explosives. The histograms of the distribution of the structual isomers over these parameters were constructed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 859–862, May, 1995.The authors are grateful to Mrs. I. D. Solodukhina for the design of the graphical material.The work was carried out with the financial support of the Russian Foundation for Basic Research (Project No. 94-03-09323).     

New functional microspheres with active succinimide groups

Radiation-induced polymerization of monomers, for example N-methacryl-oxysuccinimide (MASu) and diethylene glycol dimethacrylate (2G), in ethyl propionate, was performed from +25°C to –78°C. The copoly (MASu/2G) microspheres were obtained in MASu monomer compositions of 30 wt % or below. The average particle diameter of copoly(MASu/2G, 20/80 wt %) microspheres obtained at irradiation temperatures of 25°, 0°, and –43 °C were 0.81±0.29, 0.63±0.26, and 0.90±0.43 m, respectively. No microspheres were formed when irradiated at –78 °C. The reactivity of the succinimide groups on the surface of copoly(MASu/2G, 20/80 wt%) microspheres was checked by reacting with ethylene diamine. The maximal amount of reacting succinimide groups was 9.4±0.5 nol/g, which corresponds to about 1 % of the total number of succinimide groups in the microsphere.     

Regio- and stereoselective reactions of a rhodanine derivative with optically active 2-methyl- and 2-phenyloxirane

The reaction of a rhodanine derivative (=(Z)-5-benzylidene-3-phenyl-2-thioxo-1,3-thiazolidin-4-one; 1) with (S)-2-methyloxirane (2) in the presence of SiO₂ in dry CH₂Cl₂ for 10 days led to two diastereoisomeric spirocyclic 1,3-oxathiolanes 3 and 4 with the Me group at C(2) (Scheme 2). The analogous reaction of 1 with (R)-2-phenyloxirane (5) afforded also two diastereoisomeric spirocyclic 1,3-oxathiolanes 6 and 7 bearing the Ph group at C(3) (Scheme 3). The structures of 3, 4, 6, and 7 were confirmed by X-ray crystallography (Figs. 1 and 2). These results show that oxiranes react selectively with the thiocarbonyl group (CS) in 1. Furthermore, the nucleophilic attack of the thiocarbonyl S-atom at the SiO₂-activated oxirane ring proceeds with high regio- and stereoselectivity via an S_N2-type mechanism.     

锌族和钛族卤化物振动光谱的理论计算

采用ab initio RHF,MP2和B3LYP方法以及LanL2DZ和SDD基组计算了四面体锌族卤素阴离子化合物(MX₄^2-,M=Zn(Ⅱ),Cd(Ⅱ),Hg(Ⅱ);X=F^-,Cl^-,Br^-,I^-)和钛族卤化物(MX₄,M=Ti(Ⅳ),Zr(Ⅳ),Hf(Ⅳ);X=F^-,Cl^-,Br^-,I^-)的几何构型和振动频率。计算结果表明,LanL2DZ基组是合适的基组,能得到合理的电荷分布,几何参数以及振动频率。在锌族卤化物的计算中发现,角弯曲振动频率与实测值相当一致,键伸缩振动频率略为偏低,这主要是由于计算的键长略为偏长所致。MP2方法计算的振动频率更接近于实测值。在钛族卤化物的计算中,三种计算方法都相当地再现了实测值,而以B3LYP方法更为满意。