Glucosylated sesquiterpene alcohols from Fraxinus griffithii

Phytochemical investigation of the leaves of Fraxinus griffithii has led to the isolation of two new glucosylated acyclic sesquiterpene alcohols, griffithosides D (1) and E (2), along with iridoid and secoiridoid glycosides. The molecular structures of these compounds were elucidated using NMR, MS and other spectroscopic techniques, as well as comparison with literature data. The isolated compounds were tested for radical-scavenging activity and cytotoxicity against A549 human lung adenocarcinoma cells and Leishmania major parasites.     

Control of the size and characteristic features of fluorine-containing aromatic polyamide particles

Nano-sized aromatic polyamide particles with trifluoromethyl groups were prepared via a precipitation polymerization method from 4,4′-diphenyldicarbonyl chloride and 2,2-bis(4-aminophenyl)hexafluoropropane in a dioxane solution containing pyridine. The average diameter of the particles decreased from ca. 500 to 150 nm as the pyridine content increased. The particles were spherical with narrow size distributions. Also, the inherent viscosity and yield of the particles decreased gradually as the pyridine content increased. For all the particles, the degrees of crystallinity were low, and the thermal decomposition temperatures were above 457 °C. The addition of pyridine significantly influenced not only the polymerization but also the affinity between the product and the reaction solution, resulting in a difference in the diameters and characteristic features of the particles. Furthermore, these characteristic features were found to be determined predominantly during precipitation from the reaction solution. Meanwhile, trifluoromethyl groups in the particles had significant influence on the morphology and characteristic features of the particles.     

Effect of freezing rate on physical stability of lyophilized cationic liposomes

Factors affecting the storage stability of lyophilized cationic liposomes were investigated using liposomes prepared with various excipients and by different freezing rates, either quick freezing (freezing by immersion into liquid nitrogen) or slow freezing (cooling to -50 degrees C at a rate of -10 degrees C/h). Increases in the particle size of cationic liposomes observed during freeze-drying were inhibited by the addition of sucrose, trehalose and sucrose-dextran mixtures (1 : 1 and 2 : 1 by weight). The storage instability of the formulations, as indicated by changes in particle size, was affected by their glass transition temperature (T(g)). Addition of high-T(g) excipients resulted in smaller increases in the particle size, indicating improvement of storage stability. The storage stability of cationic liposome formulations was also affected by freezing rate. Formulations prepared by slow freezing exhibited better stability. Longer shear relaxation times were observed for formulations prepared by slow freezing compared with those prepared by quick freezing. This indicates that formulations prepared by slow freezing have a lower matrix mobility, which may result in better storage stability. T(g) or (1)H-NMR relaxation measurements could not detect differences in matrix mobility between formulations prepared by different freezing rates. Shear relaxation measurements seem to be a useful method for evaluating the storage stability of cationic liposome formulations.     

Complexation Constants of Lanthanide Ions with Poly(Methacrylic Acid) and its Copolymers

Complexation of some lanthanide ions with poly(methacrylic acid) and its copolymers was studied by potentiometric titration. Poly [methacrylic acid-co-oligo(ethylene oxide)methacrylate] and poly(methacrylic acid-co-acrylamide) formed tris-carboxylate coordinate lanthanide complexes with large overall complexation constants, while poly-(methacrylic acid)s and copolymer with higher content of the methacrylic acid residue formed bis-coordinate ones. It was concluded that the comonomer residues in the copolymer chains decreased the steric hindrance for the complexation and/or acted as co-coordinating groups of the carboxylic group to lanthanide ions. Very large positive and favorable entropy changes were observed for the complexation with poly(methacrylic acid) and its copolymers. This contribution of thermodynamic parameters to the complexation was contrary to that for the analogous monomeric methacrylic acid complex and is assumed to be induced by dehydration of the polymers through the lanthanide ion complexation.     

Di(triptycyl)carbene: a fairly persistent triplet dialkylcarbene

The title carbene was generated and characterized by matrix spectroscopy (ESR and UV/vis) and laser flash photolysis along with theoretical calculations, which revealed interesting effects of triptycyl groups on structure and reactivities of carbenes.     

Artificial model for cystathionine β-synthase: efficient β-replacement reaction with thiols employing a novel pyridoxal model compound having an imidazole function

As a second-generation pyridoxal model compound for cystathionine β-synthase, we designed a novel model compound having an ionophore function and an imidazole function, application of which to the β-replacement reaction with various thiols smoothly took place to give S-substituted cysteines. Peptides having a serine-O-carbonate residue at the N-terminal position were also converted to the corresponding peptides having an S-substituted cysteine residue under the catalytic conditions of the novel pyridoxal model compound.     

Polymerization and photoinitiation behavior in the light-cured dental composite resins

The polymerization behavior and photoinitiation process in the visible light-cured dental composite resins were studied using ESR and IR spectroscopies. The concentration of methacryl propagating radical corresponded to the transmittance of irradiated light. While the radical was stable and long-lived in the cured resin, its concentration quickly decreased in the oral cavity due to the ventilation of atmospheric oxygen accompanied by respiration. Camphorquinone radical in the presence of tertiary amine easily initiated the radical polymerization. A decrease in monomer consumption was explained by the inhibition effect of oxygen in the photoinitiation process. Post-curing by the residual radical proceeded effectively in the deeper part of the resin.