An efficient synthesis of 3-aminoisothiazolo[5,4-b] -quinoline from quinoline

Treatment of readily available 3-formylquinoline-2-thiol ( 1 ) with ammoniacal sodium hypochlorite directly afforded isothiazolo[5,4-b]quinoline ( 3 ) in high yield, probably via 3-formylquinoline-2-sulfenamide ( 2 ). Facile conversion of 3 to the corresponding 3-amino derivative ( 7 ) was accomplished by the following sequence: base induced opening of the isothiazole ring to 3-cyanoquinoline-2-thiol ( 5 ), oxidation of 5 to the corresponding stable sulfenamide ( 6 ) and sodium ethoxide catalysed reclosure of the isothiazole ring which provided 3-aminoisothiazolo[5,4-b]quinoline ( 7 ).     

Electrolytic determination of nanomolar concentrations of silver in solution with a piezoelectric quartz crystal

Silver in solution is determined in situ by the frequency change of a piezoelectric quartz crystal on electrodeposition on the electrode of the crystal. The electrolyte solution flows through a cell containing the platinum-plated electrode (cathode) of the quartz crystal, a coiled platinum-wire anode and a silver—silver(I) chloride reference electrode, and is electrolyzed at —0.2 V vs. $\text{Ag}\text{AgCl}$. The frequency change is proportional to the silver concentration in the range 10^-5–5 × 10^-7 M after electrodeposition for 5 min, and in the range 10^-8–10^-9 M by recycling 20 ml of the solution over the electrodes for 3 h.     

The ring-opening reactions of propylene oxide with chloroacetic acids

The association constants, k_d, of dichloroacetic acid (DCA) with ethers (tetrahydrofuran, tetrahydropyran, dibutyl ether, 1,4-dioxane) were measured in CCl₄ from 20°–40° using near IR spectra. A linear relationship between log₁₀K_D and log₁₀K_p was found, where K_p was the association constant of phenol with ethers. On the basis of their relationship the association constants of DCA with propylene oxide (PO) were estimated from those of phenol with PO. Furthermore, the ring-openings of PO with chloroacetic acids (trichloroacetic acid (TCA) or DCA) were studied kinetically in toluene. It was found that the PO-TCA reactions obeyed the second-order kinetics dependent on the first order both in the PO concn and in the TCA concn, and that the PO-DCA reactions obeyed the third-order kinetics on the first order in the PO concn and on the second order in the DCA concn. The elementary reaction rate constants were estimated on the basis of measured rate constants and estimated equilibrium constants and activation enthalpies were obtained from their temp dependence to be 13.5 $\text{kcal}\text{mol}$ in the PO-TCA reaction and 19.7 $\text{kcal}\text{mol}$ in the PO-DCA reaction. The mechanism was based on the activation enthalpy of elementary reaction and it was concluded that the main factor governing the reaction was the extent of activation of the protonated oxirane (the extent of polarization of the C-O bond in the oxirane ring).     

Exact determination of phagocytic activity of alveolar macrophages toward polymer microspheres by elimination of those attached to the macrophage membrane

A method for exact determination of phagocytic activity of alveolar macrophage (M) cells toward synthetic microspheres (MS) by optical microscopy was developed. We examined the effectiveness of the treatment of M samples with trypsin, acid or xylene to remove the polystyrene latex microspheres (PSL MS) attached to M cell membranes during their phagocytosis by M cells. We found that centrifugation, which was employed to collect M samples after incubation with MS, affected significantly the efficiency of the various treatments. Of the three treatments, xylene treatment without centrifugation was the most effective to determine the phagocytic activity of M cells, as xylene dissolved the PSL MS on the cell surface almost completely. This treatment was also effective in the case of poly(lactic-co-glycolic acid) MS (PLGA MS), which have been commonly used as an efficient vehicle for drug delivery system.     

Synthesis of dimethyl gloiosiphone a by way of palladium-catalyzed domino cyclization

The synthesis of a spiro[4.4]nonane skeleton by the palladium-catalyzed domino cyclization of a linear 7-methylene-2,10-undecadienyl acetate is described. The pi-allylpalladium intermediate underwent intramolecular alkene insertion with high intraannular diastereoselectivity, followed by intramolecular Heck-type cyclization, leading to a spiro[4.4]nonane system. Oxidation of the allylic ether moiety and transformation of the vinyl group to an exo-methylene unit provided 3, which is the known synthetic intermediate of dimethyl gloiosiphone A (2).     

Catalysis of 3‐Carboxy‐1,2‐benzisoxazole Decarboxylation by Hydrophobic Antibody Binding Pockets

Monoclonal antibodies were generated against a 3‐phenyl‐1,2‐benzisoxazole derivative and shown to catalyze the solvent‐sensitive decarboxylation of 3‐carboxy‐1,2‐benzisoxazoles. In addition to rate accelerations up to 2300‐fold over background, the antibodies exhibit distinctive selectivities for substrates bearing 5‐ or 6‐NO₂ substituents, with preferential decarboxylation of the less reactive substrate in one case. These effects are the likely consequence of substrate destabilization, achieved by forcing the carboxylate group into a relatively apolar binding pocket and stabilization of the charge‐delocalized transition state through dispersive interactions. Comparison with a more active antibody decarboxylase previously raised against 2‐acetamido‐naphthalene‐1,5‐disulfonate suggests, however, that a judicious mix of polar and apolar interactions may ultimately be more effective for achieving high decarboxylase activity.     

Photoluminescence and population analysis of single-walled carbon nanotubes produced by CVD and pulsed-laser vaporization methods

Band gap photoluminescence (PL) behaviors of single-walled carbon nanotubes (SWNTs) grown by the methods of chemical vapor deposition and pulsed-laser vaporization are investigated over the wide diameter range (≈0.8–1.4 nm). The peak intensity of the PL signals strongly depends on chirality and the ‘(2n + m) family type’ of SWNTs. Based on the PL results, a population analysis of these SWNTs is conducted by combining the calculated PL yields for each (n, m) tube. The results are directly compared with the histograms of diameter distributions estimated by the transmission electron microscope (TEM) observations to check the validity of the analysis.     

Microstructures and Optical Properties of Scales of Butterfly Wings

This paper describes the mechanism generating the beautiful wing colors of various male butterflies and the relationship between the wing material and the color appearance. The microstructure of the scales covering the upper surface of the wings was analyzed with the aid of a scanning electron microscope. The basic mechanism of color generation of structurally colored scales is determined for the first time in accordance with the theory of optical interference in thin film layers using a model of wing scales. Optical properties were found in relation to the three-dimensional spectral reflectance of the samples, and differences were observed between the brightness perceived in subjective evaluations and calculated values based on the reflective spectra of the structurally colored wings. The results of this study suggest that the microroughness of the upper wing surface may influence the perceived gloss of structurally colored wings.