Smart heterostructures for tailoring the optical properties of photochromic hybrid organic-inorganic polyoxometalates

A new concept of photoresponsive composites has been elaborated by intimately connecting a Photochromic Phase (PP), (H(2)DABCO)(2)(HDMA)(0.5)Na(0.75)(H(3)O)(0.75)[Mo(8)O(27)]·3H(2)O (1), with a second hybrid organic-inorganic molybdate material, (H(2)DABCO)(HDABCO)[Fe(OH)(6)Mo(6)O(18)]·4H(2)O (2) acting as an Oxidation Catalytic Phase (OCP) toward the former once photoexcited. The association of both the PP and the OCP in the composite drastically improves the bleaching process of the PP alone because of efficient electronic transfers through the OCP-PP interface without affecting significantly its photoinduced color change characteristic. Two OCP-PP composites with different PP weight percents have been obtained by associating 1 with 2. The optical properties of these composites before and after UV irradiation have been investigated by Diffuse Reflectance Spectroscopy, and the strong impact of the OCP on the fading kinetics of the PP has been clearly highlighted.     

Further studies of intramolecular Michael reactions of nitrosoalkenes for construction of functionalized bridged ring systems

A wide variety of stabilized carbanions have been found to participate as nucleophiles in intramolecular Michael-type conjugate additions to in situ generated nitrosoalkenes to form bridged carbocyclic systems. The vinylnitroso platforms for these cyclizations have been prepared via two key steps involving ring-closing metathesis of vinyl chlorides and regioselective conversion of vinyl chlorides to α-chloroketones with sodium hypochlorite in glacial acetic acid/acetone. An alternative approach to preparation of some cyclization substrates has involved use of more reactive enol ethers as precursors to the requisite α-chloroketones. A sulfonamide anion has also been found to be an effective nucleophile in this type of reaction, leading to formation of a 6-azabicyclo[3.2.1]octane.     

An OFF-ON fluorescent probe for Zn2+ based on a GFP-inspired imidazolone derivative attached to a 1,10-phenanthroline moiety

A green fluorescent protein chromophore inspired chemosenor for Zn(2+) was designed and synthesized. A Zn(2+) specific fluorescence enhancement was observed due to restricted rotation between the 1,10-phenanthroline and imidazolone moieties.     

Application of reversible amide-bond protection to suppress peptide segment epimerisation

Reversible alkylation of the C-terminal amide-bond of a protected peptide segment with 2-hydroxy-4-methoxybenzyl dramatically suppresses epimerisation during activation and coupling. However, due to the formation of a 4,5-dihydro-8-methoxy-1,4-benzoxazepin-2(3H)-one species upon activation the rate of coupling is low. A safety-catch amide-bond protecting group, 6-hydroxy-5-methyl-1,3-benzoxathiolyl, has been designed to suppress epimerisation and couple with excellent yield.     

Aromatization of cyclohexadienes by TEMPO electro-mediated oxidation: Kinetic and structural aspects

Cyclohexadienes are easily converted into the corresponding aromatics in excellent yield (>90%) in the presence of 2,2,6,6-tetramethyl-1-oxopiperidinium ion (TEMPO⁺). The TEMPO radical was used in catalytic amount and was electrochemically regenerated in the presence of 2,6-lutidine as a base in hydro-organic medium (AcCN/H₂O 95/5). This work has been focused on the kinetic aspects. We have demonstrated that the reactivity of different cyclohexadienes is strongly dependent on the configuration of the double bonds and on the nature of the substituents. Competition between allylic functionalization and aromatization has been observed during the oxidation of 1,2-dihydro-4-phenylnaphthalene.     

Children’s use of realistic considerations in problem solving: some English evidence

This is the second of two papers exploring children’s responses to an extended version of a division-with-remainder problem intended to elicit general rather than particular realistic considerations during mathematical problem solving. Responses to two problems are analyzed. The first is a ‘realistically’ contextualised item drawn from national tests in England whose ambiguities have been previously discussed (Cooper, 1992); the second is a version of this problem revised to encourage a wider range of realistic responses. In Cooper and Harries (2002), the responses of children at the end of their first year of secondary schooling were analyzed. Here the responses of children at the end of their primary schooling are analyzed and compared with the previous results. It is shown that many children, given suitable encouragement, are willing and able to enter into an extended form of realistic thinking during problem solving, although the original test item renders this invisible.     

Catalytic enantioselective epoxidation with arabinose-derived uloses containing tunable steric sensors

Readily available arabinose-derived 4-uloses, containing a tunable butane-2,3-diacetal as the steric sensor, displayed increasing enantioselectivity (up to 93% ee) with the size of the acetal alkyl group in catalytic asymmetric epoxidation of trans-disubstituted and trisubstituted alkenes.     

A choice probability characterization of generalized extreme value models

A set of necessary and sufficient conditions is established for the representability of choice probabilities by additive random utility models with generalized extreme value (GEV) distributions of utilities. These conditions yield an operational testing procedure for GEV-representability which does not require explicit construction of the underlying distribution of utilities. In addition, this characterization of GEV models reveals a number of their underlying behavioral features.     

o-quinodimethanes from 3,6-dihydrobenzo[b]-1,2-oxathiin-2-oxides

A two step synthesis of 3,6-dihydrobenzo[b]-1,2-oxathiin-2-oxide 5a from o-tolual-dehyde via the photochemically produced 1-hydroxy-1,3-dihydrobenzo[b]thiophene-2,2-dioxide is described. Analogous syntheses of 3 and 6 substituted derivatives of the benzosultines 5 have also been carried out. The feasibility of using these benzosultines as o-quinodimethane precursors has been tested by thermalizing the phenyl sultine 5c in refluxing cyclohexane in the presence of dimethyl fumarate, dimethyl maleate and methyl crotonate to form cycloadducts, stereospecifically and in good yield. The stereochemistry of addition of maleate appears to be exclusively “exo” in conflict with earlier studies on Diels-Alder reactions of α-aryl-o-quino-dimethanes.     

Overlapping Schwarz methods on unstructured meshes using non-matching coarse grids

Summary. We consider two level overlapping Schwarz domain decomposition methods for solving the finite element problems that arise from discretizations of elliptic problems on general unstructured meshes in two and three dimensions. Standard finite element interpolation from the coarse to the fine grid may be used. Our theory requires no assumption on the substructures that constitute the whole domain, so the substructures can be of arbitrary shape and of different size. The global coarse mesh is allowed to be non-nested to the fine grid on which the discrete problem is to be solved, and neither the coarse mesh nor the fine mesh need be quasi-uniform. In addition, the domains defined by the fine and coarse grid need not be identical. The one important constraint is that the closure of the coarse grid must cover any portion of the fine grid boundary for which Neumann boundary conditions are given. In this general setting, our algorithms have the same optimal convergence rate as the usual two level overlapping domain decomposition methods on structured meshes. The condition number of the preconditioned system depends only on the (possibly small) overlap of the substructures and the size of the coarse grid, but is independent of the sizes of the subdomains. Received March 23, 1994 / Revised version received June 2, 1995