Design and synthesis of intramolecular hydrogen bonding systems. Their application in metal cation sensing based on excited-state proton transfer reaction

We reported the design and synthesis of a new type of metal-cation probes, 3-hydroxy-4-(1,4,7,10-tetraoxa-13-azacyclopentadec-13-ylmethyl)naphthalene-2-carbaldehyde (1a) and its single hydrogen-bond analogue 1-(1,4,7,10-tetraoxa-13-azacylopentadec-13-ylmethyl)-2-naphthol (2a), in which 1-aza-15-crown-5 ether in combination with the naphthol oxygen acts as a receptor, while the mechanism of excited-state intramolecular proton transfer (ESIPT) is exploited as a signal transducer. The association constant of (2.5±0.5)×10⁴, (3.8±0.4)×10⁴, (5.5±0.5)×10³ and (1.2±0.3)×10⁴ M⁻¹ for the formation of 1a/Na⁺, 1a/Ca²⁺, 2a/Na⁺ and 2a/Ca²⁺ complexes, respectively, in CH₃CN plus drastic fluorescence changes due to the fine-tuning of ESIPT reaction upon complexation, lead 1a and 2a to be highly sensitive fluorescent sensors. The results add a new class into the category of metal-cation probes, with the perspective of designing ESIPT systems capable of sensing bio-analytes.     

Improving the high variable bioavailability of griseofulvin by SEDDS

To enhance the dissolution and oral absorption of poorly water-soluble griseofulvin (GF), self-emulsifying drug delivery system (SEDDS) composed of oil, surfactant and cosurfactant for oral administration of griseofulvin was formulated, and its physicochemical properties and pharmacokinetic parameters were evaluated. The solubility of griseofulvin was further improved by the addition of hydrochloric acid. Droplet size of griseofulvin emulsion was kept constant both in simulated gastric fluid without pepsin and simulated intestinal fluid throughout 12 weeks incubation period. Griseofulvin in the SEDDS rapidly dissolved in different dissolution media. This was not the case for the commercial GRIS-PEG tablets. In different fed diet groups, AUC 0-->24 h, Cp max, and T max of griseofulvin after oral administration of SEDDS in rats were comparable to those after oral dose of GRIS-PEG tablet. Although, in fed lipidic diet group, the mean AUC and Cp max after oral administration of GRIS-PEG in rats were 1.28 and 1.15 fold higher, respectively, compared with those of SEDDS, these have not shown to be significantly different. These results demonstrate that the SEDDS of griseofulvin composed of Capmul GMO-50, Poloxamer and Myvacet 9-45 greatly enhanced the dissolution of griseofulvin (without ultramicronisation). However, food intake effect on the bioavailability of griseofulvin has remained. Thus, this system may provide a useful dosage form for oral water-insoluble drugs which have problems in their dissolution.     

Forward dynamic utility functions: A new model and new results

A major obstacle in the existing models of forward dynamic utilities and investment performance evaluation is to establish the existence and uniqueness of the optimal solutions. Consequently, we present a new model of forward dynamic utilities. In doing so, we establish the existence and uniqueness of the solutions for a general (smooth) utility function, and we show that the assumptions needed for such solutions are similar to those under the backward formulation. Moreover, we provide unique viscosity solutions. We also provide discontinuous viscosity solutions. In addition, we introduce Hausdorff-continuous viscosity solutions to the portfolio model.     

8-(1,4,7,10-Tetraoxa-13-azacyclopentadec-13-ylmethyl)quinolin-7-ol: synthesis and application as a highly sensitive metal cation probe

A new metal ion probe 8-(1,4,7,10-tetraoxa-13-azacyclopentadec-13-ylmethyl)quinolin-7-ol (1a) was synthesized via a modified Mannich reaction, in which the mechanism of recognition incorporates excited-state proton transfer reactions. The remarkable differentiation in spectral properties upon metal complexation makes 1a a highly sensitive fluorescence probe.     

Colloidal silver nanoparticles stabilized by a water-soluble triosmium cluster

Silver nanoparticles stabilized by the water soluble triosmium cluster Os₃(μ-H)(CO)₁₀S(CH₂)₁₀COO]Na were prepared by both photochemical and chemical reduction of silver nitrate. The silver nanoparticles were characterized by UV-Vis spectroscopy and high resolution TEM. The particles obtained by chemical reduction showed remarkable stability.     

Luminescent silver nanoparticles stabilised by a crown ether capped with an organometallic cluster

Monolayer-protected clusters of silver have been synthesised by the NaBH₄ reduction of a mixture of silver nitrate and the crown ether (6-mercaptohexyloxy)methyl-15-crown-5, or the triosmium cluster derivative Os₃(μ-H)(CO)₁₀[(6-mercaptohexyloxy)methyl-15-crown-5]. The nanoparticles showed good stability, are soluble in a wide range of organic solvents, and are luminescent.     

A new stochastic factor model: General explicit solutions

We present a new stochastic factor model. In doing so, we provide general, explicit solutions to the portfolio optimization problem.