Stereochemical effects in supramolecular self-assembly at surfaces: 1-D versus 2-D enantiomorphic ordering for PVBA and PEBA on Ag(111)

We present investigations on noncovalent bonding and supramolecular self-assembly of two related molecular building blocks at a noble metal surface: 4-[trans-2-(pyrid-4-yl-vinyl)]benzoic acid (PVBA) and 4-[(pyrid-4-yl-ethynyl)]benzoic acid (PEBA). These rigid, rodlike molecules comprising the same complementary moieties for hydrogen bond formation are comparable in shape and size. For PVBA, the ethenylene moiety accounts for two-dimensional (2-D) chirality upon confinement to a surface; PEBA is linear and thus 2-D achiral. Molecular films were deposited on a Ag(111) surface by organic molecular beam epitaxy and characterized by scanning tunneling microscopy. At low temperatures (around 150 K), both species form irregular networks of flat lying molecules linked via their endgroups in a diffusion-limited aggregation process. In the absence of kinetic limitations (adsorption or annealing at room temperature), hydrogen-bonded supramolecular assemblies form which are markedly different. With PVBA, enantiomorphic twin chains in two mirror-symmetric species running along a high-symmetry direction of the substrate lattice form by diastereoselective self-assembly of one enantiomer. The chirality signature is strictly correlated between neighboring twin chains. Enantiopure one-dimensional (1-D) supramolecular nanogratings with tunable periodicity evolve at intermediate coverages, reflecting chiral resolution in micrometer domains. In contrast, PEBA assembles in 2-D hydrogen-bonded islands, which are enantiomorphic because of the orientation of the supramolecular arrangements along low-symmetry directions of the substrate. Thus, for PVBA, chiral molecules form 1-D enantiomorphic supramolecular structures because of mesoscopic resolution of a 2-D chiral species, whereas with PEBA, the packing of an achiral species causes 2-D enantiomorphic arrangements. Model simulations of supramolecular ordering provide a deeper understanding of the stability of these systems.     

Synthesis of thiol chelating resins and their adsorption properties toward heavy metal ions

A series of chelating resins, derived from a macroreticular styrene-divinylbenzene (2%) copolymer beads grafted with various poly(ethylene glycols) HO? (? CH₂? CH₂? O? )_n? H(n = 0, 4, 9, 13) and containing thiol groups as chelating functions, have been synthesized in a three-step reaction sequence. The structure of the functionalized resins was confirmed by IR spectrophotometry, elemental analysis, and differential scanning calorimetry. The complexation behavior of these thiol resins was investigated towards Hg(II), Cu(II), and Pb(II) ions in aqueous solution by a batch equilibration technique. The influence of pH on adsorption capacity was also examined. The adsorption values for metal ions' intake followed the order Hg(II) > Cu(II) > Pb(II). The affinity of these polymers towards Hg(II) ions was so high that the total mercury level in the liquid decreased from 20 ppm to below 10 ppb after 2 h of treatment. Polymers can be regenerated by washing with a solution of hydrochloric acid (6N) and 10% by weight of an aqueous solution of thiourea. © 1994 John Wiley & Sons, Inc.     

Liquid—liquid extraction and determination of uranium(IV) with 2,6-diacetylpyridine bis(benzoylhydrazone)

2,6-Diacetylpyridine bis(benzoylhydrazone) (H₂DPBH) is proposed as a ligand for the extraction of uranium(VI). Complete extraction from aqueous solutions into dichloromethane is achieved with a ligand/metal mole ratio of < for 10^?5?10^?4 M uranyl ion. Potentiometric measurements indicate that the extracted species is UO₂ (DPBH). Uranium can be determined in the extract by spectrophotometric measurements at 420 nm and by differentail pulse polarography (E_p = ?0.67 V) with tetraethylammonium bromide as supporting electrolyte. For both methods, the detection limit is about 2 × 10^?6 M in the extract.     

Electronic structure of paramagnetic clusters of transition metal ions. 3. Magnetic properties and scattered wave description of the electronic structure of the hexanuclear octahedral cluster [Fe6(μ3−S)8(PEt3)6] (BPh4)2

Spin-polarized Xα–SW calculations of [Fe₆(μ₃?S)₈(PH₃)₆]²⁺ as a model of the cluster [Fe₆(μ₃?S)₈(PEt₃)₆] (BPh₄)₂ have been performed. The highest occupied energy levels are well separated from empty levels, and up to a maximum of eight electrons can be unpaired, giving a maximum spin state with S = 4. This electronic state is consistent with the magnetic data of [Fe₆(μ₃?S)₈(PEt₃)₆](BPh ₄)₂, which have been interpreted using the Heisenberg–Dirac–Van Vleck exchange spin Hamiltonian. The S = 4 state arises from the magnetic coupling between five low-spin (S_i = 1/2) and one intermediate-spin (S = 3/2) iron(III) center. © 1994 John Wiley & Sons, Inc.     

A generic framework for time-stepping partial differential equations (PDEs): general linear methods,object-oriented implementation and application to fluid problems

Time-stepping algorithms and their implementations are a critical component within the solution of time-dependent partial differential equations (PDEs). In this article, we present a generic framework – both in terms of algorithms and implementations – that allows an almost seamless switch between various explicit, implicit and implicit–explicit (IMEX) time-stepping methods. We put particular emphasis on how to incorporate time-dependent boundary conditions, an issue that goes beyond classical ODE theory but which plays an important role in the time-stepping of the PDEs arising in computational fluid dynamics. Our algorithm is based upon J.C. Butcher's unifying concept of general linear methods that we have extended to accommodate the family of IMEX schemes that are often used in engineering practice. In the article, we discuss design considerations and present an object-oriented implementation. Finally, we illustrate the use of the framework by applications to a model problem as well as to more complex fluid problems.     

A simple,efficient, regioselective and one-pot preparation of N-hydroxy- and N–O-protected hydroxyindoles via cycloaddition of nitrosoarenes with alkynes. Synthetic scope,applications and novel by-products

The thermal reaction between nitrosoarenes and alkynes under alkylating conditions produces N-alkoxyindoles as the major products in moderate to good yields and excellent regioselectivity. Various electrophiles are used affording different N–O-protected hydroxyindoles in a multi-component fashion. Privileged acetylenic substrates used in reactions with substituted nitrosoarenes are arylalkynes or propiolates. Potentially bioactive compounds and other classes of highly functionalizable indole products were prepared. Reactions between o-carbomethoxy-nitrosoarenes and arylacetylenes provided tricyclic compounds containing an acylaziridine indoline skeleton.