Effects of Zinc(II) on the Luminescence of Europium(III) in Complexes Containing β‐Diketone and Schiff Bases

The UV, excitation, and luminescence spectra of tris(pivaloyltrifluoroacetonato)europium(III) ([Eu(pta)₃]; Hpta=1,1,1‐trifluoro‐5,5‐dimethylhexane‐2,4‐dione=HA) were measured in the presence of bis(salicylidene)trimethylenediamine (H₂saltn), bis[5‐(tert‐butyl)salicylidene]trimethylenediamine (H₂(^tBu)saltn), or bis(salicylidene)cyclohexane‐1,2‐diyldiamine (H₂salchn), and the corresponding Zn^II complexes [ZnB] (B=Schiff base). The excitation and luminescence spectra of the solution containing [Eu(pta)₃] and [Zn(salchn)] exhibited much stronger intensities than those of solutions containing the other [ZnB] complexes. The introduction of a ^tBu group into the Schiff base was not effective in sensitizing the luminescence of [Eu(pta)₃]. The luminescence spectrum of [ZnB] showed a band around 450 nm. The intensity decreased in the presence of [Eu(pta)₃], reflecting complexation between [Eu(pta)₃] and [ZnB]. On the basis of the change in intensity against the concentration of [ZnB], stability constants were determined for [Eu(pta)₃Zn(saltn)], [Eu(pta)₃Zn{(^tBu)saltn}], and [Eu(pta)₃Zn(salchn)] as 4.13, 4.9 and 5.56, respectively (log , where =[[Eu(pta)₃ZnB]]([[Eu(pta)₃]][[ZnB]])^?1). The quantum yields of these binuclear complexes were determined as 0.15, 0.11, and 0.035, although [Eu(pta)₃Zn(salchn)] revealed the strongest luminescence at 613 nm. The results of X‐ray diffraction analysis for [Eu(pta)₃Zn(saltn)] showed that Zn^II had a coordination number of five and was bridged with Eu^III by three donor O‐atoms, i.e., two from the salicylidene moieties and one from the ketonato group pta.     

Channel-selective independent sorption and collection of hydrophilic and hydrophobic molecules by Cs2[Cr3O(OOCC2H5)6(H2O)3]2[alpha-SiW12O40] ionic crystal

An ionic crystal of Cs2[Cr3O(OOCC2H5)6(H2O)3]2[alpha-SiW12O40].4H2O 1a with hydrophilic and hydrophobic channels has been designed and successfully synthesized. The guest-free phase 1b sorbs dichloromethane and water in the hydrophobic and hydrophilic channels, respectively. The rate and equilibrium amount of the dichloromethane sorption into the hydrophobic channel and those of water into the hydrophilic channel were independent of each other. The sorption properties can be applied to the channel-selective sorption and collection of hydrophobic (dichloromethane) and hydrophilic (water) molecules from the mixture.     

gamma-1,2-H2SiV2W10O40] immobilized on surface-modified SiO2 as a heterogeneous catalyst for liquid-phase oxidation with H2O2

An organic-inorganic hybrid support has been synthesized by covalently anchoring an N-octyldihydroimidazolium cation fragment onto SiO2 (denoted as 1-SiO2). This modified support was characterized by solid-state 13C, 29Si, and 31P NMR spectroscopy, IR spectroscopy, and elemental analysis. The results showed that the structure of the dihydroimidazolium skeleton is preserved on the surface of SiO2. The modified support can act as a good anion exchanger, which allows the catalytically active polyoxometalate anion [gamma-1,2-H2SiV2W10O40]4- (I) to be immobilized onto the support by a stoichiometric anion exchange (denoted as I/1-SiO2). The structure of anion I is preserved after the anion exchange, as confirmed by IR and 51V NMR spectroscopy. The catalytic performance for the oxidation of olefins and sulfides, with hydrogen peroxide (only one equivalent with respect to substrate) as the sole oxidant, was investigated with I/1-SiO2. This supported catalyst shows a high stereospecificity, diastereoselectivity, regioselectivity, and a high efficiency of hydrogen peroxide utilization for the oxidation of various olefins and sulfides without any loss of the intrinsic catalytic nature of the corresponding homogeneous analogue of I (i.e., the tetra-n-butylammonium salt of I, TBA-I), although the rates decreased to about half that with TBA-I. The oxidation can be stopped immediately by removal of the solid catalyst, and vanadium and tungsten species can hardly be found in the filtrate after removal of the catalyst. These results rule out any contribution to the observed catalysis from vanadium and tungsten species that leach into the reaction solution, which means that the observed catalysis is truly heterogeneous in nature. In addition, the catalyst is reusable for both epoxidation and sulfoxidation without any loss of catalytic performance.     

Piezoelectric immunosensor for bisphenol A based on signal enhancing step with 2-methacrolyloxyethyl phosphorylcholine polymeric nanoparticle

An immunoassay in which BPA competed with a BPA-horseradish peroxidase conjugate for binding to anti-BPA antibodies, coupled to a piezoelectric (PZ) immunosensor, was able to detect 0.1 ng mL(-1) BPA. To enhance the sensitivity of the assay, we tested nanoparticles approximately 200 nm in diameter, coupled to anti-BPA antibodies, to increase the mass change on the surface of the immunosensor and thereby increase the frequency shift detected. This second step, using nanoparticles coated with anti-BPA antibodies, improved the sensitivity of the assay by approximately eight times at BPA concentrations below 10 ng mL(-1). Field emission-scanning electron microscopy (FE-SEM) showed that polymeric 2-methacrolyloxyethyl phosphorylcholine (MPC) nanoparticles coupled to antibodies remained monodisperse on the surface of the immunosensor and therefore produced stable signals in the immunosensors. Since the frequency shift detected in the assay mainly originated from the mass change on the surface of the PZ crystal, the colloidal stability of the antibody-conjugated particles used in the enhancement step played an extremely important role in achieving a stable and highly sensitive signal.     

Mechanism of enantioseparation of DL-pantothenic acid in ligand exchange capillary electrophoresis using a diol-borate system

Borate complexes formed in the ternary system at pH 9.2 containing borate, (S)-3-amino-1,2-propanediol (SAP), and DL-pantothenic acid (DL-PTA) were identified by 13C and 11B NMR, and it is confirmed that the binary complexes, [B(OH)2(SAP)], [B(SAP)2]+ [B(OH)2(D- or L-PTA)]2-, and [B(D- or L-PTA)2]3- (including [B(D-PTA)(L-PTA)]3-), and the ternary complexes, [B(SAP)(D- or L-PTA)]-, coexist at equilibrium in the ternary system. Thermodynamic experiments by variable-temperature 11B NMR revealed that the ternary complex, [B(SAP)(D-PTA)]-, is entropically more stable than [B(SAP)(L-PTA)]-. Because two geometrical isomers are possible for the respective ternary complexes, semi-empirical molecular orbital calculations were performed by PM5, PM3, and AM1 methods in order to obtain the optimized structures. It is indicated from the calculated heats of formation and experimentally obtained thermodynamic parameters that the (S)-isomer is more probable for the respective ternary complexes with D- and L-PTA. In the optimized structure of (S)-[B(SAP)(D-PTA)]- in water, the SAP and D-PTA ligands were oppositely oriented to form a rather linear structure, while the diastereomer, (S)-[B(SAP)(L-PTA)]-, had a folded structure. Because such a difference in the solvated structure of the ternary complexes can give a different electrophoretic velocity in CE, the enantioseparation of DL-PTA in CE is reasonably attributed to a difference in the observed electrophoretic mobility for the equilibrated ternary systems containing the respective ternary complexes.     

Chiral resolution of monosaccharides as 1-phenyl-3-methyl-5-pyrazolone derivatives by ligand-exchange CE using borate anion as a central ion of the chiral selector

Six reducing monosaccharides (mannose, galactose, fucose, glucose, xylose, and arabinose) were derivatized with 1-phenyl-3-methyl-5-pyrazolone (PMP) and chiral resolution of these racemic PMP-monosaccharides was studied by ligand-exchange CE using borate anion as a central ion of the chiral selector and (S)-3-amino-1,2-propanediol (SAP) as a chiral selector ligand. PMP-mannose, PMP-galactose and PMP-fucose were successfully enantioseparated. Lowering the capillary temperature increased the resolution of PMP-mannose system, but decreased that of PMP-galactose and PMP-fucose systems. Whereas the maximum resolution was obtained at pH 8.9 in the PMP-mannose system, resolution increased gradually with pH in the PMP-galactose and PMP-fucose systems. Expecting the formation of the ternary borate complexes with SAP and PMP-monosaccharide in the CE experiments, the optimized structures of the borate diastereomers were obtained by semiempirical molecular orbital calculations to discuss the structural difference of the diastereomers in connection with the enantioseparation behaviors.     

Structural and dynamical aspects of alkylammonium salts of a silicodecatungstate as heterogeneous epoxidation catalysts

The structural and dynamical aspects of alkylammonium salts of a silicodecatungstate [(CH(3))(4)N](4)[γ-SiW(10)O(34)(H(2)O)(2)] [C1], [(n-C(3)H(7))(4)N](4)[γ-SiW(10)O(34)(H(2)O)(2)] [C3], [(n-C(4)H(9))(4)N](4)[γ-SiW(10)O(34)(H(2)O)(2)] [C4], and [(n-C(5)H(11))(4)N](4)[γ-SiW(10)O(34)(H(2)O)(2)] [C5] were investigated. The results of sorption isotherms, XRD analyses, and solid-state NMR spectroscopy show that facile sorption of solvent molecules, flexibility of structures, and high mobility of alkylammonium cations are crucial to the uniform distribution of reactant and oxidant molecules throughout the bulk solid, which are related to the high catalytic activities for epoxidation of alkenes.     

Elucidation of the Active Conformation of Vancomycin Dimers with Antibacterial Activity against Vancomycin‐Resistant Bacteria

Covalently linked vancomycin dimers have attracted a great deal of attention among researchers because of their enhanced antibacterial activity against vancomycin‐resistant strains. However, the lack of a clear insight into the mechanisms of action of these dimers hampers rational optimization of their antibacterial potency. Here, we describe the synthesis and antibacterial activity of novel vancomycin dimers with a constrained molecular conformation achieved by two tethers between vancomycin units. Conformational restriction is a useful strategy for studying the relationship between the molecular topology and biological activity of compounds. In this study, two vancomycin units were linked at three distinct positions of the glycopeptide (vancosamine residue (V), C terminus (C), and N terminus (N)) to form two types of novel vancomycin cyclic dimers. Active NC‐VV‐linked dimers with a stable conformation as indicated by molecular mechanics calculations selectively suppressed the peptidoglycan polymerization reaction of vancomycin‐resistant Staphylococcus aureus in vitro. In addition, double‐disk diffusion tests indicated that the antibacterial activity of these dimers against vancomycin‐resistant enterococci might arise from the inhibition of enzymes responsible for peptidoglycan polymerization. These findings provide a new insight into the biological targets of vancomycin dimers and the conformational requirements for efficient antibacterial activity against vancomycin‐resistant strains.