Synthesis of Optically Active endo,endo Bicyclo[2.2.2]octane-2,5-diol, Bicyclo[2.2.2]octane-2,5-dione, and Related Compounds

Optically active C(2)-symmetric (1S,2S,4S,5S)-bicyclo[2.2.2]octane-2,5-diol ((+)-12; 98% ee) and several selectively protected optically active intermediates useful for synthetic transformations were synthesized via a 1,2-carbonyl transposition route starting from the easily available optically active (1R,4S,6S)-6-hydroxybicyclo[2.2.2]octan-2-one ((-)-2). The synthetic route also allowed the preparation of optically active (1S,4S)-bicyclo[2.2.2]octane-2,5-dione ((+)-14; 98% ee).     

The roles of template complexation and ligand binding conditions on recognition in bupivacaine molecularly imprinted polymers

A model for the molecular basis for ligand recognition in bupivacaine imprinted methacrylic acid-ethylene glycol dimethacrylate co-polymers has been developed based upon a series of (1)H-NMR studies in conjunction with HPLC and radioligand binding analyses. (1)H-NMR studies indicated that functional monomer-template complexes survive the polymerisation process, at least up until the stage of gelation. Polymers were synthesised and characterised by surface area analysis (BET), FT-IR and SEM. A combination of zonal and frontal chromatographic studies in aqueous and non-polar media indicate that selectivity arises from a combination of hydrophobic and electrostatic interactions. However, in the concentration regime employed for LC-based studies, ligand recognition in aqueous media was shown to be predominantly non-specific and hydrophobic in character. Radioligand binding studies, in lower ligand binding concentration regimes, permitted closer examination of the higher affinity binding sites. It was shown that the presence of a polar modifier in a non-polar solvent, or an organic modifier in water, produced enhanced selectivity. Variable temperature studies showed that the temperature of binding influences selectivity as well as the apparent number of sites available and that this effect is different in organic and aqueous environments. This indicates that the system studied is more complex in character than is generally appreciated. A comparison of the techniques employed here indicates that although chromatographic studies provide a valuable first-round screen for polymer-ligand selectivities, the level of detail obtainable using radioligand binding studies (lower concentrations and true equilibrium binding) makes them superior for detailed evaluations of molecularly imprinted polymers.     

A novel palladium-catalyzed synthesis of β-carbolines: application in total synthesis of naturally occurring alkaloids

Two naturally occurring β-carbolines, 6-methoxy-2-methyl-1,2,3,4-tetrahydro-β-carboline and bauerine A, have been prepared using a Stille-type coupling, followed by a palladium-phosphine catalyzed N-heteroannulation as the key steps.     

Elimination of bremsstrahlung in activation analysis by the deflection of β-particles in a magnetic field

The structureless background at X-ray and low energy -ray region, resulting from bremsstrahlung due to the stopping of -radiations, causes serious problems in nuclear spectroscopy. In this study, in order to reduce the background and therefore to increase the sensitivity of the nuclear analytical technique and the number of elements observable, a methodology is developed to deflect the -particles by a magnetic field. The experimental setup consists of a permanent magnet /1 kG/, Ge/Li/ solid-state detector, and multichannel analyzer.     

Cyclodextrin Solubilization of the Antibacterial Agents Triclosan and Triclocarban: Effect of Ionization and Polymers

The natural β-cyclodextrin (βCD) and its complexes have limited solubility in aqueous solutions. This low aqueous solubility, as well as low aqueous solubility of the guest molecule (i.e. triclosan or triclocarban (TCC)), can result in low complexation efficiency (CE). The purpose of this study was to enhance the apparent intrinsic solubility (S ₀) of the guest molecule and its βCD complexes through ionization and addition of auxiliary compounds such as polymers, amino acids and metal ions. Both triclosan (pK _a 7.9) and TCC (pK _a 12.7) are weak acids. Addition of ethanol to the complexation medium enhanced S ₀ of both triclosan and TCC but at the same time ethanol lowered the stability constant (K _c ) of their βCD complexes resulting in overall lowering of CE. Addition of small amount of water-soluble polymers enhanced the βCD solubilization of both guests, and addition lysine enhanced the solubilization of TCC. Ionization of triclosan resulted in significant enhancement of CE and enhanced triclosan release from tablets containing triclosan/βCD complex. The effect of ionization was not as pronounced in the case of TCC.This revised version was published online in July 2005 with a corrected issue number.     

Removal of strontium ions by a crosslinked copolymer containing methacrylic acid functional groups</p> </p>

Summary A tail-made polymer matrix is proposed to remove strontium ions from aqueous solutions. The removal behavior of strontium ions on a crosslinked copolymer containing methacrylic acid as functional groups was investigated as a function of sorptive concentration, time, temperature and pH. It was observed that an increase of these parameters enhanced the removal of Sr(II) ions from aqueous solution. It is found that a maximum adsorption of Sr(II) ions can be obtained on the crosslinked copolymer after 30 minutes and at pH 8. The increase of Sr(II) ion concentration in the solution resulted in an increase in the amount of Sr(II) ions adsorbed on the crosslinked copolymer containing methacrylic acid as functional groups. However, after a maximum of Sr(II) concentration in the solution, the percentage of adsorbed Sr(II) ions decreased. The adsorption data are well represented by the Freundlich, Langmuir and Dubinin-Radushkevich (D-R) isotherms. The adsorption capacity of the copolymer and the free energy change were calculated by using the D-R isotherm. For the adsorption of Sr(II) ions on the crosslinked copolymer the thermodynamic parameters (DH°,DS° andDG°) were calculated.</p> </p>     

Structure and properties of the dendron-encapsulated polyoxometalate (C(52)H(60)NO(12))(12)[(Mn(H(2)O))(3)(SbW(9)O(33))(2)], a first generation dendrizyme

Combining analytical and theoretical methods, we present a detailed study of a heteropolytungstate cluster encapsulated in a shell of dendritically branching surfactants, namely (C(52)H(60)NO(12))(12)[(Mn(H(2)O))(3)(SbW(9)O(33))(2)], 3. This novel surfactant-encapsulated cluster (SEC) self-assembles spontaneously from polyoxometalate-containing solutions treated with a stoichiometric amount of dendrons. Compound 3 exhibits a discrete supramolecular architecture in which a single polyoxometalate anion resides in a compact shell of dendrons. Our approach attempts to combine the catalytic activity of polyoxometalates with the steric properties of tailored dendritic surfactants into size-selective catalytic systems. The structural characterization of the SEC is based on analytical ultracentrifugation (AUC) and small-angle neutron scattering (SANS). The packing arrangement of dendrons at the cluster surface is gleaned from molecular dynamics (MD) simulations, which suggests a highly porous shell structure due to the dynamic formation of internal clefts and cavities. From analysis of the MD trajectory of 3, a theoretical neutron-scattering function is derived that is in good agreement with experimental SANS data. Force field parameters used in MD simulations are partially derived from a quantum mechanical geometry optimization of [(Zn(H(2)O))(3)(SbW(9)O(33))(2)](12)(-), 2b, at the density functional theory (DFT) level. DFT calculations are corroborated by X-ray structure analysis of Na(6)K(6)[(Zn(H(2)O))(3)(SbW(9)O(33))(2)].23H(2)O, which is isostructural with the catalytically active Mn derivative 2a. The combined use of theoretical and analytical methods aims at rapidly prototyping smart catalysts ("dendrizymes"), which are structurally related to naturally occurring metalloproteins.     

Determination of trace elements in Na-bentonitic clay by INAA in Turkey

Instrumental neutron activation analysis was applied to the determination of trace elements in a Na-bentonitic clay. The irradiation was done in the Triga Mark II type reactor of ITU Nuclear Energy Institute. The sample was irradiated in two steps for short- and long- lived isotopes. After irradiation, spectra were taken using a germanium detector, multichannel analyzer Canberra System 100 and a fitting program called Sampo 90. The spectra of short-lived isotopes were analyzed to determine Al, Mg, Na, K, Ca, Ti elements and Mn, V trace elements. The spectra of long-lived isotopes were analyzed to determine Sc, Br, Sb, Cs, La, Ce, Sm, Yb, Hf, Pa, Np trace elements.     

Determination of average degree of polymerisation and distribution of oligosaccharides in a partially acid-hydrolysed homopolysaccharide: a comparison of four experimental methods applied to mannuronan

The average degree of polymerisation (DP) and distribution of oligosaccharides in partially acid hydrolysed mannuronans were quantitatively evaluated by 1H NMR, electrospray ionisation mass spectrometry (ESI-MS), micellar electrokinetic capillary chromatography with UV detection (MEKC-UV), and high-pressure anion-exchange chromatography with pulsed amperometric detection (HPAEC-PAD). Our investigation shows that 1H NMR, MEKC-UV and, in particular, HPAEC-PAD can be used as quantitative tools to aid the investigation of polysaccharide structure, function and synthesis. For the latter two techniques, especially, this represents a significant new development as it enables calculation of the quantity of individual oligomers of nominal DP by direct analysis of a defined oligomer mixture. Appropriate statistical averages of number and weight distributions were also calculated and found to fit very well to predicted Kuhn distributions that assume random depolymerisation.