Near-IR Luminescent YbIII Coordination Polymers Composed of Pyrene Derivatives for Thermostable Oxygen Sensors

Oxygen-sensitive and near-infrared (NIR) luminescent Yb^III coordination polymers incorporating ligands based on pyrene derivatives were synthesized: Yb^III–TBAPy and Yb^III–TIAPy (TBAPy: 1,3,6,8-tetrakis(p-benzoate)pyrene; TIAPy: 1,3,6,8-tetrakis(3,5-isophthalic acid)pyrene). The coordination structures of these materials have been characterized by means of electrospray ionization mass spectrometry, X-ray diffraction analysis, and thermogravimetric analysis. Moreover, the porous structure of Yb^III–TIAPy has been evaluated by measuring its N₂ adsorption isotherm. The NIR luminescence properties of Yb^III–TBAPy and Yb^III–TIAPy have been examined by acquiring emission spectra and determining emission lifetimes under air or argon and in vacuo. Yb^III–TIAPy exhibited high thermal stability (with a decomposition temperature of 400 °C), intense luminescence (with an emission quantum yield under argon of 6.6 %), and effective oxygen-sensing characteristics. These results suggest that NIR luminescent Yb^III coordination polymers prepared using pyrene derivatives could have applications in novel thermo-stable oxygen sensors.     

Saccharide Recognition by a Three-Arm-Shaped Host Having Preorganized Three-Dimensional Hydrogen-Bonding Sites

Generally, cage-shaped hosts for saccharides can bind strongly to guest molecules because of the three-dimensional preorganized hydrogen-bonding sites. However, the preparation of cage molecules is often difficult because of the low yield of the macrocyclization step. Here, we report a three-arm-shaped molecule possessing pyridine-acetylene-phenol units as a new kind of host having a preorganized three-dimensional hydrogen-bonding site. This three-arm-shaped host was readily prepared compared to a cage-shaped analogue. This host associated with lipophilic glycosides to form chiral complexes, and the association constants were sufficiently high as to be comparable to those of the cage-shaped analogue. Furthermore, this host extracted native monosaccharides into a lipophilic solvent.     

Design of Chitosan-5Fu Conjugate Exhibiting Antitumor Activity

In order to provide a macromolecular prodrug of 5-fluorouracil (5FU) reducing the side effects, having an affinity for tumor cells, and exhibiting strong antitumor activity, the covalent attachments of 5FUs to chitosan and chitosamino-oligosaccharide (COS) through hexamethylene spacer groups via urea, urea bonds were carried out. The effect of prolongation of life was tested in vivo against p388 lyrnphocytic leukemia in female CDF, mice by intra-peritoneal (i.p.) transplantation/i.p. injection and the growth-inhibitory effect on Meth-A fibrosarcoma or MH-134Y heputoma was evaluated in vivo in SPF-C3H/He scl male or Balb/c male mice by subcutaneous (s.c.) implantation/intravenous (i.v.) injection. The effects of the degree of polymerization of chitosan and     

Design,Synthesis, and Properties of Substituted Polyacetylenes

This article reviews recent topics on the polymerization of substituted acetylenes, focusing on the synthesis of poly(diphenylacetylenes) and the living polymerization of phenylacetylenes. Diphenylacetylene (DPA) polymerizes with TaCl_s-n-Bu₄Sn to give a polymer which is thermally very stable but insoluble in any solvents. DPAs with various groups (e.g.,p-Me₃Si,m-Me₃Ge, p-t-Bu,and_p-PhO) polymerize similarly. These polymers are soluble and their M¯_w's reach 1 × 10⁶ to 3 × 10⁶. Some of them are more gas-permeable than poly(dimethylsiloxane). Several acetylenes (e.g., ClC -n-C₆H₁₃ and HCUC-t-Bu) have been found to undergo living polymerization with MoOCl₄-n-Bu₄Sn-EtOH. Whereas phenylacetylene (PA) does not polymerize in a living fashion, ortho-substituents in PA more or less suppress termination and chain transfer. PAs with bulky ortho groups (e.g., CF₃ and Me₃Ge) especially undergo virtually ideal living polymerization.     

Theory of docking scores and its application to a customizable scoring function

In general, the docking scoring tends to have a size dependence related to the ranking of compounds. In this paper, we describe a novel method of parameter optimization for docking scores which reduce the size dependence and can efficiently discriminate active compounds from chemical databases. This method is based on a simplified theoretical model of docking scores which enables us to utilize large amounts of data of known active and inactive compounds for a particular target without requiring large computational resources or a complicated procedure. This method is useful for making scoring functions for the identification of novel scaffolds using the knowledge of active compounds for a particular target or a customized scoring function for an interesting family of drug targets.     

Examination of an absolute quantity of less than a hundred nanograms of proteins by amino acid analysis

We developed an ultra-sensitive method of amino acid analysis (AAA) for the absolute quantification of less than 100 ng of proteins, in solution or on polyvinylidene difluoride (PVDF) membranes using an oxygen-free chamber for protein hydrolysis. We used a pre-label method with 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate for fluorescence detection, ion-pair chromatography with a reversed-phase column, and an ultra-high-pressure high-performance liquid chromatography. We optimized both handling- and instrument-dependent factors for accurate quantification and showed that the least amount of proteins to quantify was determined by handling accuracy rather than instrumental limit for quantification which was 0.6 fmol/amino acid. As a new evaluation method for the handling accuracy, we adopted the protein identification by the obtained amino acid compositions by AAA and the Swiss-Prot database search without the restriction of species. As a result, the least amount of starting material for AAA was 16 ng (0.24 pmol) for a solution of bovine serum albumin (BSA), 33 ng (0.50 pmol) for BSA on a PVDF membrane, and 44 ng (0.15 pmol) for thyroglobulin on a PVDF membrane. These results demonstrate that the ultra-sensitive AAA developed in this study is feasible for absolute quantification of biological significant protein.

Regioselective Alkylation of Thiazolylsulfonamides: Direct and Efficient Synthesis of 3‐Alkylthiazolidene Derivatives

Various N‐3‐alkylated thiazolidenesulfonamide derivatives were efficiently prepared by the direct endo‐selective alkylation of thiazolylsulfonamides. The effects of different bases and solvents were investigated, and the NaH–THF combination was found to be the most effective at conferring high yields and endo‐selectivity.     

Officinatrione: an unusual (17S)-17,18-seco-lupane skeleton,and four novel lupane-type triterpenoids from the roots of Taraxacum officinale

Novel 5 lupane-type of triterpenois, i.e., 3β-acetoxy-18α,19α-epoxylupan-21β-ol (1), 18α,19α-epoxy-21β-hydroxylupan-3-one (2), lup-18-ene-3,21-dione (3), lupa-18,21-dien-3β-yl acetate (4), and (17S)-17,18-seco-lup-19(21)-ene-3,18,22-trione (5), named officinatrione, as well as 16 known compounds from the roots of Taraxacum officinale collected in Takatsuki city, Osaka, Japan. Of the above compounds, 5 was the first lupane-type triterpene, of which the D-ring was open to form a nine-membered ring. Compounds 2 and 5 exhibited moderate cytotoxic activities against L1210 cell line (IC₅₀ 10.5 and 10.1 μM).     

Accurate measurement of uranium isotope ratios in soil samples using thermal ionization mass spectrometry equipped with a warp energy filter

A chemical and mass-spectrometric procedure for uranium isotopic analysis using a thermal ionisation mass spectrometer equipped with a Wide Aperture Retardation Potential energy filter has been developed and applied to uranium isotopic measurements for various soil samples. Soil samples were digested using a microwave digestor. Uranium was isolated from soil samples by the chemical separation procedure based on the use of anion-exchange resin and UTEVA extraction chromatography column. The isotope ratios were measured for two certified reference materials by using a VG Sector 54-30 thermal ionisation mass spectrometer in dynamic mode with Faraday cup and Daly ion counting system. Replicates of standard reference materials showed excellent analytical agreement with established values supporting the reliability and accuracy of the method. Precision of the ²³⁵U/²³⁸U ratio was achieved by a correction factor of 0.22% amu as a function of ion-beam intensity with sample loads of around 250?ng of U. The resulting reproducibility for standards and soil samples was better than 0.2% at two standard deviations (SD). Uranium isotopic compositions have been determined in several reference soil samples such as Buffalo river sediment, NIST 2704, river sediment SRM 4350b and ocean sediment NIST-4357 and a Chernobyl soil sample. There was a significant deviation from the natural uranium in comparison with Chernobyl soil samples.