Interfacial solubilization of model amphiphilic molecules in block copolymer micelles

We investigate the solubilization of 2-nitrodiphenylamine, a hydrophobic but polar dye molecule, in aqueous solutions of polystyrene(310)-b-poly(acrylic acid)(47) micelles. The solubilization capacity of the micelles, which consist of a polystyrene core and poly(acrylic acid) corona, and the micelle-water partition coefficient are evaluated as a function of the solubilizate concentration. The solubilization isotherm shows a nonlinear behavior, and the partition coefficient, instead of being constant, is strongly dependent on the dye concentration. These results are explained by treating solubilization as a binding process, and by fitting the data to a Langmuir adsorption model. In addition, we examine the locus of solubilization of 2-nitrodiphenylamine using its solvatochromic properties and solubility in model solvents, and we identify the micellar interface as the solubilization site. Confirmatory studies, including the dependence of solubilization on the interfacial area of the aggregates, the role of the poly(acrylic acid) corona chains in stabilizing the solubilized molecules, and the effect of the solubilizate structure on the extent of incorporation, were also conducted. The results, consistent with surface localization, show that solubilization is dependent on the interfacial area of the aggregates, and on the affinity of the solubilizate for the micellar interface.     

Aquation kinetics of chloro- and bromo-pentamminecobalt(III) ions in water-acetone mixtures

Summary The aquation kinetics of [Co(NH₃)₅Cl]²⁺ and [Co(NH₃)₅Br]²⁺ ions in acetone-water have been investigated over a wide range of solvent compositions and temperatures. The variation of thermodynamic properties of the activated complex with the mole fraction of acetone reveals the existence of specific solvation. The correlation of the rate constant with dielectric constant of the medium is examined and discussed. A reaction mechanism which describes the solvent effect on reaction rate is proposed.     

Solvent effects on the dissociation reactions of tartaric, maleic and phthalic acids; comparative study and analysis of thermodynamic functions

The first and second dissociation constants of tartaric, maleic and phthalic acids have been determined using EMF method in water-ethanol mixed solvents, over a wide range of solvent composition (0-60 wt% ethanol) at six different temperatures (ranging from 30 to 55 degrees C at intervals of 5 degrees C). The thermodynamic parameters (DeltaG degrees , DeltaH degrees and DeltaS degrees ) for the first and the second ionization reactions were calculated from the well known equations. The results have been discussed in terms of the solute-solvent interactions and were compared with those of malic, malonic and succinic acids in the same mixed solvents.     

Crystal structure of some niobium and tantalum oxides. IV. The structure of KTa5O13 and its relationship to the α-PbO2 structure

KTa₅O₁₃ crystallizes in the orthorhombic system with unit-cell dimensions a = 5.653(3), b = 10.708(5), and c = 16.799(7) Å with space group Pbcm, z = 4. The structure was solved by conventional methods; of 1445 unique reflections measured by counter methods, 982 that obeyed the condition I ? 3σ(I) were used in the refinement of the model to a conventional R of 0.053 (R_w = 0.052). The structure consists of edge-and corner-shared tantalum-oxygen octahedra joined such that tunnels are formed in which the potassium ions are located. Slabs of octahedra are of the α-PbO₂ type and are related to one another by a mirror plane (in which the potassium ions are located) producing a structure that may be considered as a “chemical twin” of the α-PbO₂ structure.     

Substituted 5-Antipyrinylazo-4-phenyl-2-aminothiazoles as Disperse Dyes for Dyeing Polyester Fabrics

Summary. A series of some new substituted 5-antipyrinylazo-4-phenyl-2-aminothiazole disperse dyes was synthesized by diazocoupling of 4-antipyrinyldiazonium chloride with aminothiazole derivatives. The synthesized dyes were characterized by UV-Vis absorption, IR, ¹H NMR, and MS spectroscopy. The dyes gave orange to reddish-violet shades with very good depth and levelness when applied to polyester fabrics as disperse dyes and their fastness properties were evaluated on polyester fibers. Also the position of color in CIELAB coordinates (L^*, a^*, b^*, H^*, and C^*) was assessed.     

Sinularectin, a new diterpenoid from the soft coral Sinularia erecta

A new norcembrane, designated sinularectin 3, was isolated from the Kenyan soft coral Sinularia erecta. Sinularectin is a chlorinated highly oxygenated norcembrane with an unprecedented functionalisation of the cembrane isopropyl group. The structure of sinularectin was elucidated by interpretation of the HRESMS results as well as 1D and 2D NMR spectra.     

Triterpene glycosides and glucosyl esters, and a triterpene from the leaves of Schefflera actinophylla

From the EtOAc and 1-BuOH fractions, three new ursane-type and four new lupane-type triterpenes, along with nine known glycosides and glycosyl esters of lupane-type were isolated from the leaves of Schefflera actinophylla. All the isolated compounds were obtained for the first time from this plant. The structures of the new triterpenes were determined through a combination of spectroscopic and chemical analyses.     

A methoxylated quercetin glycoside harnesses HCC tumor progression in a TP53/miR-15/miR-16 dependent manner

Abstract

This study focused on studying the impact of flavonoids isolated from Cleome droserifolia on HCC cell lines and to further unveil their possible impact on TP53 and its downstream tumor suppressor miRNAs. Three flavonol glycosides were isolated from C. droserifolia namely, Isorhamnetin-3-O-β-D-glucoside (1), Quercetin-3`-methoxy-3-O-(4``-acetylrhamnoside)-7-O-α-rhamnoside (2), and Kaempferol-4`-methoxy-3,7-O-dirhamnoside (3). They showed a concentration and time dependent reduction in cellular viability and anchorage-independent growth of HCC cells. Moreover, they exhibited a decrease in the migrating capacity of HepG2 cells in a pattern similar to positive control cells. (2) Showed the most potent effects in halting HCC tumorigenic activity (IC₅₀=36?±?1.70?µM) and a repression of the cellular proliferation rate of HepG2 cells. Restoration of TP53 and its downstream tumor suppressor miRNAs; miR-15a, miR-16, miR-34a by (2) was observed. Moreover, attenuation of (2) mediated actions was shown upon using anti-miR-15a and anti-miR-16. To conclude, this study crystallizes a novel role of C. droserifolia in harnessing HCC progression in-vitro with a possible contribution of TP53/miR-15a/miR-16.     

Pairing of propellers: dimerization of octahedral ruthenium(II) and osmium(II) complexes of eilatin via pi-pi stacking featuring heterochiral recognition

Five octahedral eilatin complexes of the type [M(L-L)(2)(eilatin)](2+) (M = Ru, Os; L-L = bipyridyl-type ligands) were synthesized, and their dimerization via pi-pi stacking was studied by crystallography and (1)H NMR techniques. The X-ray structures of these racemic complexes were solved and revealed that the eilatin complexes are organized as discrete dimers in which the eilatin residues of each complex are stacked in centrosymmetric packing. Chemical shift dependence on concentration in the (1)H NMR spectra support fast dimer-monomer equilibrium, and the structures of the dimers in acetonitrile solution are proposed to be analogous to their solid-state structures. Dimerization constants in acetonitrile were measured for the five racemic eilatin complexes that exhibit different structural parameters, as well as for the two enantiomeric forms of one of these complexes. They were found to be independent of the metal (Ru vs Os), strongly dependent on the steric effects introduced by the L-L ligands (2,2'-bipyridine, 1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, and 2,2'-biquinoline), and dependent on the optical purity of the complexes. A clear preference for heterochiral over homochiral dimer formation was demonstrated. This is the first report of chiral recognition in solution, exhibited by simple chemical systems held solely by pi-stacking interactions.     

Aquation kinetics of chloropentamminecobalt (III) perchlorate in dicarboxylate media containing 10% (v/v) acetone

The aquation kinetics of [Co(NH₃)₅Cl]²⁺ in dicarboxylate media containing 10% (v/v) acetone is measured in the temperature range of 35–60°C. A new empirical correlation between the rate coefficient, k_obs, and the stoichiometric concentration of the dicarboxylate ligand (C_L) has been established and a reaction mechanism is proposed. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 311–316, 1997.