Hybrid EuIII Coordination Luminophore Standing on Two Legs on Silica Nanoparticles for Enhanced Luminescence

In this study, we have demonstrated a two-legged, upright molecular design method for monochromatic and bright red luminescent Ln^III-silica nanomaterials. A novel Eu^III-silica hybrid nanoparticle was developed by using a doubly binding TPPO−Si(OEt)₃ (TPPO: triphenyl phosphine oxide) linker. The TPPO−Si(OEt)₃ was confirmed by ¹H, ³¹P, ²⁹Si NMR spectroscopy and single-crystal X-ray analysis. Luminescent Eu(hfa)₃ and Eu(tfc)₃ moieties (hfa: hexafluoroacetylacetonate, tfc: 3-(trifluoromethylhydroxymethylene)camphorate) were fixed onto TPPO−Si(OEt)₃-modified silica nanoparticles, producing Eu(hfa)₃(TPPO−Si)₂-SiO₂ and Eu(tfc)₃(TPPO−Si)₂-SiO₂, respectively. Eu(hfa)₃(TPPO−Si)₂−SiO₂ exhibited the higher intrinsic luminescence quantum yield (93 %) and longer emission lifetime (0.98 ms), which is much larger than those of previously reported Eu^III-based hybrid materials. Eu(tfc)₃(TPPO−Si)₂−SiO₂ showed an extra-large intrinsic emission quantum yield (54 %), although the emission quantum yield for the precursor Eu(tfc)₃(TPPO−Si(OEt)₃)₂ was found to be 39 %. These results confirmed that the TPPO−Si(OEt)₃ linker is a promising candidate for development of Eu^III-based luminescent materials.     

Experimental study for adsorption and photocatalytic reaction of ethyl methylphosphonate molecule as organophosphorus compound adsorbed at surface of titanium dioxide under UV irradiation in ambient condition

The adsorption and photocatalytic degradation of Ethyl methylphosphonate (EMPA) on powdery TiO₂ film has experimentally investigated using attenuated total reflection-infrared Fourier transform spectroscopy (ATR-FTIR) in ambient condition. Characteristic IR frequency as P-O-C vibration mode as EtO was observed by EMPA adsorbed at the surface of TiO₂. By TiO₂ photocatalysis, the adsorbed EMPA was decomposed to methyl phosphonic acid and phosphoric acid. The increment of IR intensity of which is assigned to Ti–O-P-O-Ti of EMPA was accompanied with increasing the IR peak intensity assigned to MPA. About that, we suggest that the appearance of the Ti–O-P-O-Ti of EMPA by the TiO₂ photocatalysis is regarded as acceleration of the hydrolysis of EMPA by the surface OH groups of TiO₂. The plausible adsorption structure and the photocatalytic reaction mechanism of EMPA at the surface of TiO₂ photocatalyst were elucidated.

     

An optical resolution of racemic organophosphorous esters by phosphotriesterase-catalyzing hydrolysis

Conclusion  We have shown that PTE chiral recognition is limited to organophosphorous esters having the chiral center on the phosphorous atoms, which is attacked with nucleophile, not having the chiral center on the other atoms of the leaving group. Therefore, PTE can be utilized for the synthesis of their chiral organophosphorous esters.     

Second-derivative spectrophotometric study on the interactions of chlorpromazine and triflupromazine with bovine serum albumin

The second-derivative spectra of chlorpromazine (CPZ) or triflupromazine (TFZ) in buffer solutions (pH 7.4) containing various amounts of BSA (the reference solutions contained the same amount of BSA) showed derivative isosbestic points. The residual background signals derived from incomplete suppression of BSA signals can be entirely eliminated in the second-derivative spectra and BSA has spectrophotometrically one kind of binding site for CPZ or TFZ. The fractions of the drugs bound to BSA were calculated from the derivative intensity differences (ΔD values) of CPZ or TFZ before and after the addition of BSA. Scatchard plot experiments suggested that the binding of the drugs to BSA could be explained as a partition like non-specific binding model. The association constants (K) of CPZ or TFZ with BSA were calculated from the ΔD values according to the non-specific binding model by a nonlinear least-squares method. The K values were almost constant for all of the drug concentrations studied, and good reproducibility was obtained. The fractions predicted by the K values were in good coincidence to the observed values. These results confirm the usefulness of the proposed derivative method which does not need any separation procedures.     

Structures and stabilities of 3d-transition metal-benzene organometallic clusters

In the gas phase, we have successfully synthesized organometallic clusters, M_n(benzene)_m (M=3d transition metal atoms), by using a laser vaporization method. The measurements of mass spectra and ionization energies (E_i) have revealed that the organometallic clusters can take two types of structures; layered sandwich structures (m = n + 1) and metal clusters saturatedly covered with benzenes. For early transition metals of Sc, Ti, and V, only the multiple decker sandwich structure clusters were preferentially produced, in which benzene and metal atoms are alternately piled up. For late transition metals of Co and Ni, the metal clusters saturatedly surrounded by benzenes were also produced as well as the sandwich clusters. Furthermore, the E_is of M₁(benzene)₂ (M = Sc-Ni) were systematically measured and their electronic properties will be discussed.     

General Mechanism for Chiral Recognition by Native and Modified Cyclodextrins

A general mechanism for chiral recognition by native and modified cyclodextrins hasbeen proposed by reconsidering the data reported so far. Cyclodextrins in aqueoussolution adopt asymmetrically twisted structures, which seems to be the origin of chiralrecognition.     

Two-dimensional self-organization of phthalocyanine and porphyrin: dependence on the crystallographic orientation of Au

By immersing Au substrate into a benzene solution containing both cobalt(II) phthalocyanine (CoPc) and copper(II) tetraphenyl-21H,23H-porphine (CuTPP), a two-dimensional alternate bimolecular structure was formed on the reconstructed Au(100)-(hex) surface.     

Synthesis of new peptidic glycoclusters derived from β-alanine

The synthesis of an asymmetric glycocluster 1 has been achieved by coupling of a sugar unit with the β-alanine polypeptide, the principal chain, and combining a carbohydrate chain with the side chain causing it to branch from the N terminal. The synthesis of this side chain multivalent ligands is based on the scaffolding of some ω-amino acid (glycine, β-alanine, and GABA) derivatives. This method facilitated the synthesis of the cluster, of which the length of each unit differs.     

Characterization of p-aminobenzamidine-based sorbent and its use for high-performance affinity chromatography of trypsin-like proteases

An affinity sorbent, hydrophilic polymer-based carrier of different pore size (Toyopearl) with immobilized p-aminobenzamidine (ABA), has been prepared. Its basic properties and some applications for protein purification were studied. ABA, which is a synthetic inhibitor for trypsin-like proteases, was covalently immobilized to Toyopearl by reductive amination. The ligand density and binding capacity for porcine trypsin varied depending on the pore size of Toyopearl. The maximum binding capacity of the immobilized p-aminobenzamidine Toyopearl (ABA-Toyopearl) for trypsin was more than 40 mg/ml gel. ABA-Toyopearl thus obtained was very stable below pH 8 and was successfully used for high-performance affinity chromatography of trypsin-like proteases such as trypsin, thrombin, tissue-type plasminogen activator or urokinase in a single step at 25 degrees C.     

Signal denoising and baseline correction by discrete wavelet transform for microchip capillary electrophoresis

Signal denoising and baseline correction using discrete wavelet transform (DWT) are described for microchip capillary electrophoresis (MCE). DWT was performed on an electropherogram describing a separation of nine tetramethylrohodamine-5-isothiocyanate labeled amino acids, following MCE with laser-induced fluorescence detection, using Daubechies 5 wavelet at a decomposition level of 6. The denoising efficiency was compared with, and proved to be superior to, other commonly used denoising techniques such as Fourier transform, Savitzky-Golay smoothing and moving average, in terms of noise removal and peak preservation by directly visual inspection. Novel strategies for baseline correction were proposed, with a special interest in baseline drift that frequently occurred in chromatographic and electrophoretic separations.