Noncovalent ligand-to-ligand interactions alter sense of optical chirality in luminescent tris(β-diketonate) lanthanide(III) complexes containing a chiral bis(oxazolinyl) pyridine ligand

Highly luminescent tris[β-diketonate (HFA, 1,1,1,5,5,5-hexafluoropentane-2,4-dione)] europium(III) complexes containing a chiral bis(oxazolinyl) pyridine (pybox) ligand--[(Eu(III)(R)-Ph-pybox)(HFA)(3)], [(Eu(III)(R)-i-Pr-pybox)(HFA)(3)], and [(Eu(III)(R)-Me-Ph-pybox)(HFA)(3)])--exhibit strong circularly polarized luminescence (CPL) at the magnetic-dipole ((5)D(0) → (7)F(1)) transition, where the [(Eu(III)(R)-Ph-pybox)(HFA)(3)] complexes show virtually opposite CPL spectra as compared to those with the same chirality of [(Eu(III)(R)-i-Pr-pybox)(HFA)(3)] and [(Eu(III)(R)-Me-Ph-pybox)(HFA)(3)]. Similarly, the [(Tb(III)(R)-Ph-pybox)(HFA)(3)] complexes were found to exhibit CPL signals almost opposite to those of [(Tb(III)(R)-i-Pr-pybox)(HFA)(3)] and [(Tb(III)(R)-Me-Ph-pybox)(HFA)(3)] complexes with the same pybox chirality. Single-crystal X-ray structural analysis revealed ligand-ligand interactions between the pybox ligand and the HFA ligand in each lanthanide(III) complex: π-π stacking interactions in the Eu(III) and Tb(III) complexes with the Ph-pybox ligand, CH/F interactions in those with the i-Pr-pybox ligand, and CH/π interactions in those with the Me-Ph-pybox ligand. The ligand-ligand interactions between the achiral HFA ligands and the chiral pybox results in an asymmetric arrangement of three HFA ligands around the metal center. The metal center geometry varies depending on the types of ligand-ligand interaction.     

Reversed-phase HPLC separation of the enantiomers of denopamine after derivatization with GITC chiral reagent

Summary A reversed-phase high-performance liquid chromatographic (HPLC) method was developed to determine the optical purity of denopamine, which is a new cardiotonic agent having an asymmetric carbon in a molecule. The enantiomers were converted to diastereomeric thiourea derivatives using 2,3,4,6-Tetra-O-acetyl--D-glucopyranosyl isothiocyanate (GITC) reagent. Separation of the enantiomers of denopamine as diastereomers was successfully achieved by reversed-phase HPLC within 10 min using an ODS column and UV detection. Derivatization of denopamine proceeded rapidly under the alkaline conditions and the ambient temperature. This method was applied to the determination of the optical purity of denopamine drug substances and those in tablets. The favorable UV absorption of the derivatives enabled the optical antipode to be determined down to the 0.2% level.     

In Situ Processing of Nano Crystalline Oxide Particles/Polymer Hybrid

Nano sized crystalline particles/polymer hybrids were synthesized form designed metal-organic precursors. The newly developed method is composed of the synthesis of organic matrix by polymerization and the in situ nucleation and growth of crystalline oxide particles in the organic matrix below 100°C. The design of metal-organic precursor modified with polymerizable ligand and the selection of reaction conditions does influence the size and crystallinity of ceramic particles in organic matrix. The nano-sized magnetic particle/polymer hybrid exhibits the interesting feature of superparamagnetism and quantum size effect. The crystalline particles of BaTiO₃/, PbTiO₃/, and KNbO₃/polymer hybrids behave to be dielectric and show the typical electro-rheological behavior.     

Determination of ethylenediaminetetraacetic acid in sea water by solid-phase extraction and high-performance liquid chromatography

The chelating agent EDTA is widely used, and as a result is showing up widely in the aquatic environment. Here we describe a preconcentration procedure for measuring EDTA concentration in sea water samples by HPLC. The procedure consists of forming an Fe(III) complex followed by solid-phase extraction using an activated carbon cartridge. After the preconcentration, EDTA was quantified by HPLC with ultraviolet detection (260 nm). The enrichment permitted the determination of EDTA at concentrations as low as 1 nM. Good recoveries were obtained for both brackish and full-strength sea water with high repeatability (RSD < 6%). The method was applied to sea water samples taken from near the mouth of the Oyabe River in Japan.     

Factors affecting physicochemical properties of liposomes prepared with hydrogenated purified egg yolk lecithins by the microencapsulation vesicle method

We examined hydrogenated purified egg yolk lecithins, having practical advantages over non-hydrogenated ones, as liposomal membrane materials. Liposomes were prepared by the microencapsulation vesicle (MCV) method in which liposomes are formed through two-step emulsification and dispersion. Three types of purified egg yolk lecithins with different iodine values were examined after being dissolved in one of three lipid solvents. The liposome size increased as the temperature during the second emulsification increased, being closer to the boiling temperature of the solvent. The preparation temperature in relation to the transition temperature of each lecithin was also a factor affecting liposome sizes. As for the encapsulation efficiencies of the model compound calcein in liposomes, they differed mainly depending on the solubility of each lecithin in a lipid solvent and it was more obvious in hydrogenated lecithins. A high preparation temperature resulted in lower encapsulation efficiencies, suggesting that leakage of encapsulated calcein was facilitated at high temperature in the MCV methods. There was a significant correlation between liposome sizes and encapsulation efficiencies in non-hydrogenated purified egg yolk lecithin but not in hydrogenated ones. When using hydrogenated purified egg yolk lecithins as liposomal membrane materials, it was suggested that a lipid solvent should be chosen so that a lecithin completely dissolves under the preparation condition in order to achieve a higher encapsulation efficiency. Smaller liposome particles were obtained when the second emulsification was performed at a lower temperature compared with the boiling point of the lipid solvent. These findings can be applied to control encapsulation efficiencies and particle sizes in each particular liposome preparation enclosing therapeutic agents.     

Organometallic Rotaxanes with a Triazole Group in the Axle Component and Their Behavior as Ligands of PtII Complexes

Two ferrocenylmethyl ammonium salts were used as axle components of pseudorotaxanes with dibenzo[24]crown‐8. The pseudorotaxane with an alkyne terminal group in the axle component underwent a Cu‐catalyzed Huisgen coupling reaction (click reaction) with an alkyl azide to afford cationic [2]rotaxanes with a triazole group in the axle molecule. The rotaxane reacted with Ac₂O to produce neutral rotaxanes with an amide group in the axle component. Both cationic and neutral rotaxanes were treated with K[PtCl₃(CH₂?CH₂)] to form the Pt^II‐containing rotaxanes.     

Stereocontrolled synthesis of 8,11-dideoxytetrodotoxin,unnatural analogue of puffer fish toxin

[structure: see text] 8,11-Dideoxytetrodotoxin, an unnatural tetrodotoxin analogue, was synthesized in a highly stereoselective manner from a common intermediate in our synthetic studies on tetrodotoxin. The synthesis features neighboring group participation of trichloroacetamide for stereoselective hydroxylation, protection of ortho ester, and guanidine installation with Boc-protected isothiourea.     

Application of non-thermal atmospheric pressure ac plasmas to the carbon dioxide reforming of methane

Methane conversions of 11.9%, yields of hydrogen as high as 23.3% and energy yields of 1.0 mol H₂/kWh have been achieved from CO₂ reforming of CH₄ in non-thermal, atmospheric pressure plasma reactors with Pt coated electrodes. Two reactors have been studied. A novel fan type reactor consisting of a movable rotor and immobile stator produced the highest yields in contrast to a tube type (silent discharge) reactor with a glass dielectric barrier. Conversions, yields of hydrogen and energy yields (expressed as mol H₂/kWh) were studied for CO₂/CH₄ concentrations of 1.1% and 5.0% in He as a function of flow rate and input voltage. Hydrogen yields are observed to increase as the input voltage is increased from 411 V to 911 V and the flow rate is decreased from 100 cc/min to 30 cc/min. Energy yields vary only slightly with input voltage and flow rate. Hydrogen yields show little dependence on CO₂/CH₄ concentrations, but energy yields are approximately five times greater for the 5.0% mixture than the 1.1% mixture. Selectivities to H₂, CO, coke, and low molecular weight hydrocarbons were also evaluated and compared to data obtained without CO₂ in the feed. Hydrogen selectivities of nearly 100% were obtained, with small amounts of ethane and propane as the only observed side products and the selectivites were approximately the same whether CO₂ was present or absent in the mixture. However, the reaction proceeds much more cleanly when CO₂ is present, producing CO. The syngas product has an H₂ : CO ratio of 1.5 with the fan type reactor and 0.67 with the tubular reactor. In the absence of CO₂, coke is the main carbonaceous product. Under all conditions studied the fan type reactor demonstrated higher methane conversions (up to 11.9%) and selectivities to hydrogen.     

One- or two-dimensional organometallic arrays containing PdIr2(μ3-S)2 mixed-metal sulfido cluster units connected via the nicotinamide or isonicotinamide ligands on their Pd sites through hydrogen-bonding interactions

Mixed-metal sulfido cluster [(PdCl₂)(Cp*Ir)₂(μ₃-S)₂] (Cp*=η⁵-C₅Me₅) dissolved in CH₂Cl₂ reacted with two equivalent of L (L=nicotinamide, isonicotinamide, or N-methylnicotinamide) in the presence of AgBF₄ to give the cationic clusters [(PdL₂)(Cp*Ir)₂(μ₃-S)₂][BF₄]₂. The single-crystal X-ray diffraction studies of these products have disclosed that in the solid state the PdIr₂S₂ cores are self-assembled to form one-dimensional chains through the intermolecular hydrogen-bonding between the amide groups for L=nicotinamide or two-dimensional sheets via the hydrogen-bonding between the amide groups and the BF₄ anions for L=isonicotinamide, whereas no organization of the cluster cores is observed for L=N-methylnicotinamide.     

Synthesis of 3-hydroxyindolin-2-one alkaloids, (±)-donaxaridine and (±)-convolutamydines A and E, through enolization-Claisen rearrangement of 2-allyloxyindolin-3-ones

Claisen rearrangement triggered by enolization of 2-allyloxyindolin-3-ones with DBU was performed in order to prepare 3-allyl-3-hydroxyindolin-2-ones. Total synthesis of 3-hydroxyindolin-2-one alkaloids, (±)-donaxaridine, as well as (±)-convolutamydines A and E, was achieved by transformation of the allyl moiety of 3-allyl-3-hydroxyindolin-2-ones.