Cavitands bearing four fluorophores

The synthesis of novel cavitands containing four fluorophores [tert-butoxycarbonyl protected 2,2′-bis(furyl)benzidine (t-BOC FurylBz) or 5,5′-bis(4-aminophenyl)-2,2′-bifuryl (t-BOC PFDA)] and ionophoric functional groups on the upper rim is reported. The cavitands bearing the four fluorophores emit blue light photoluminescence. In particular, the cavitand containing PFDA moieties exhibits a high photoluminescence quantum yield.     

Synthesis, structure and heterogeneous catalytic activities of Cu-containing polymeric compounds: anion effect and comparison of homogeneous vs. heterogeneous catalytic activity

The structures of new polymeric compounds containing Cu(II) ions and btp (2,6-bis(N'-1,2,4-triazolyl)pyridine) ligands have been determined. The btp ligands bridge Cu(II) ions to form double zigzag chains, [Cu(ClO4)2(btp)2] 3 with perchlorate anions, and form single zigzag chains, [Cu(btp)(H2O)4](SO4).2H2O 4 with sulfate anions. The polymeric compound 3 was found to effectively catalyze the epoxide ring-opening reaction with methanol, while polymeric compound 4 was almost inactive with epoxides under the same conditions. The polymeric compound 3 showed an efficient catalytic activity and regioselective reactivity in the ring opening of epoxides and allowed reuse without a significant loss of activity through three runs with epoxides.     

[Rb2(H2O)2][Re3(μ-Cl)3Br7(H2O)2]2 · H2O,ein gemischtes Halogenid-Hydrat mit anionischen Dimeren {[Re3(μ-Cl)3Br7(H2O)2]2 · H2O}2−

[Rb₂(H₂O)₂][Re₃(μ-Cl)₃Br₇(H₂O)₂]₂ · H₂O, a Mixed Halide-Hydrate with the Anionic Dimer {[Re₃(μ-Cl)₃Br₇(H₂O)₂]₂ · H₂O}^2? [Rb₂(H₂O)₂][Re₃(μ-Cl)₃Br₇(H₂O)₂]₂ · H₂O crystallizes as dark redbrown single crystals from an hydrobromic-acid solution of ReCl₃ and RbBr at 0°C. An important feature of the crystal structure (monoclinic, C2/c; a = 1494.61(8); b = 835.71(4); c = 3079.96(19) pm; β = 97.801(4)°; V_m = 573.9(4) cm³mol^?1; R = 0.060; R_w = 0.038) is the connection of two anions [Re₃(μ-Cl)₃Br₇(H₂O)₂]^? via a water molecule to dimers, {[Re₃(μ-Cl)₃Br₇(H₂O)₂]₂ · H₂O}^2?. These dimeric units are contained in slabs that are stacked in the [001] direction and held together by Rb⁺ cations and crystal water.     

Bisbakuchiols A and B, novel dimeric meroterpenoids from Psoralea corylifolia

Two novel dimeric meroterpenoids, bisbakuchiols A and B, along with (S)-bakuchiol were isolated from the seeds of Psoralea corylifolia L. (Fabaceae). Bisbakuchiols A and B contain an unprecedented dimeric meroterpenoid skeleton in which two meroterpenes are linked through a dioxane bridge. All compounds were evaluated for their potential to inhibit hypoxia-inducible factor-1 (HIF-1) activation induced by hypoxia in a HIF-1-mediated reporter gene assay in AGS human gastric cancer cells. (S)-Bakuchiol inhibited hypoxic activation of HIF-1 with an IC₅₀ value of 6.1 μM.     

Bis induces growth inhibition and differentiation of HL-60 cells via up-regulation of p27

Bis (Bag-3, CAIR), a Bcl-2-interacting protein, promotes the anti-apoptotic activity of Bcl-2 and increased levels of Bis have been observed in several disease models. The involvement of Bcl-2 and some Bcl-2-binding proteins in differentiation has recently been reported. However, the relevance of Bis to cellular differentiation remains unknown. The findings herein show that Bis expression is up-regulated during the differentiation of HL-60 cells. To investigate the effect of Bis expression on differentiation, we established Bis-overexpressing HL-60 cells (HL-60-bis). HL-60-bis cells have a low nuclear: cytoplasmic ratio and indented nucleus in Wright- Giemsa staining, and an increased expression of CD11b in immunofluorescence study, indicating the promotion of differentiation. The overexpression of Bis also resulted in a retarded cell growth rate, accompanied by the accumulation of HL-60 cells at the G0/G1 phase of the cell cycle, which was sustained during the differentiation process. Western blot analysis revealed that the expression of p27, a representative inducer of cell cycle arrest at the G1 phase, was increased 2.5-fold in HL-60-bis cells compared to HL-60-neo cells. These results suggest that the Bis induced growth inhibition of HL-60 cells promotes G0/G1 phase arrest via up-regulation of p27, which seems to be a prerequisite for differentiation. Further studies will be required to define the exact roles of Bis on cellular differentiation more precisely.     

The predictive accuracy for estimating infinite dilution activity coefficients by γ∞-based UNIFAC

The predictive accuracy for estimating infinite dilution activity coefficients by a modification of the UNIFAC method wherein the group interaction parameters were based on only data (referred to as -based UNIFAC) has been studied. Estimates and measured values were compared for six prototypical solutes in a series of homologous n-alkanes, l-alcohols and alkanenitrile solvents. Despite the fact that the interaction parameters were derived using only data, this approach still gave serious errors due to several inherent problems in the original UNIFAC model. Its performance is sometimes even poorer than that of the original UNIFAC method. For example for nitromethane in alcohols and p-dioxane in nitriles values predicted by the -based UNIFAC are essentially zero. The large errors for these systems are most likely due to inaccurate interaction parameters in the -based UNIFAC method.     

Quantitative analyses of shape-selective intercalation of isomeric mixtures of muconates into [LiAl2(OH)6]Cl.yH2O layered double hydroxide

Quantitative investigation of the shape selectivity for the competitive intercalation reaction of isomeric mixtures in the interlayer of LDH was achieved by analyzing the solid phases synthesized by the reaction of [LiAl(2)(OH)(6)]Cl.yH(2)O with various compositional mixtures of (E,E)- and (Z,Z)-muconates. The apparent partition constant K' for the anion-exchange reaction between (E,E)- and (Z,Z)-muconates was quite dependent on the mole fraction of muconates in solution. The only single phase saturated with [LiAl(2)(OH)(6)](2)[(E,E)-C(6)H(4)O(4)].zH(2)O could be obtained in the range of the initial mole fraction of (E,E)-muconate larger than 0.6 in the starting solution, while mixed phases intercalated with (E,E)- and (Z,Z)-muconates could be obtained at lower mole fractions of (E,E)-muconate. The shape selectivity for the competitive reaction of two muconates on the [LiAl(2)(OH)(6)](+) lattice could be ascribed to thermodynamic processes, and the conditions under which that pure (E,E)-muconate was efficiently separated from isomeric mixtures of two muconates were successfully evaluated.     

Fluoride-facilitated deuterium exchange from DMSO-d6 to polyamide-based cryptands

Multiple deuterium exchange between DMSO-d6 and amide hydrogens in two hexaamido cryptand fluoride receptors has been verified by 19F and 2H NMR and FAB mass spectral studies. Structural results for one of the complexes indicate a tricapped trigonal prism hydrogen bond coordination geometry around an encapsulated fluoride, with hydrogen bonds from fluoride to six amide and three phenyl hydrogens.     

Cytotoxic Constituents from the Stem Bark of Zanthoxylum Pistaciiflorum

Two new esters, methyl 4‐(prenyloxy)dihydrocinnamate and methyl 4‐(geranyloxy)dihydrocinnamate, together with fourteen known compounds have been isolated from the stem bark of Zanthoxylum pistaciiflorum. The structures of two new compounds were determined through spectral analyses. Among the isolates, four compounds exhibited effective cytotoxicities against P‐388 and HT‐29 cell lines in vitro.     

An improved method for constructing a full-length enriched cDNA library using small amounts of total RNA as a starting material

We have developed an improved method for constructing a full-length cDNA library using small quantity of material by modifying the original oligo-capping method. In our devised method, total RNAs are used in sequential oligo-capping steps directly without preliminary mRNA purification. Using this method, we constructed full- length cDNA libraries from 100 mg of total RNA. These libraries contained 8x10(5) to 8x10(6) independent clones with average insert sizes of 2.0 kb. Moreover, the number of full-length cDNAs containing the translation initiation codon ATG in the constructed libraries was estimated to 60-70%. In addition, 54% of the known cDNAs had a longer 5' end than the corresponding genes in the public database. Our results show that the method can be effectively used to construct full-length enriched cDNA libraries, especially, if starting material is limited.