Treatment of Malignant Melanoma by High-Peak-Power 1064 nm Irradiation Followed by Photodynamic Therapy

Irradiation of B16 pigmented melanoma subcutaneously transplanted in C57 mice with a single 650 mj pulse (10 ns) of 1064 nm light from a Q-switched Nd: YAG laser caused instantaneous bleaching of the pigmented tissue. Visual and histological examination of the resulting gray-colored tumor revealed the breakdown of melanosomes with no detectable alteration of the normal and tumor-overlying skin. Histological examination of the irradiated tumor showed some degree of vascular damage; the depth of the photodamage was not affected by the successive delivery of three consecutive light pulses. The bleached tumor grew at a modestly slower rate but the high-peak-power (HPP) laser treatment did not affect the tumor concentration of a photodynamic sensitizer Si(IV)-naphthalocyanine (isoBO-SiNc) intravenously injected 24 h before Nd : YAG irradiation. Treatment of the B16 pigmented melanoma by photodynamic therapy (PDT: 1 mg/kg isoBO-SiNc, 300 mW/cm², 520 J/cm²) from a 774 nm diode laser immediately after the 1064 nm irradiation resulted in a 16 day delay of tumor regrowth, which was markedly longer than the delay (ca 6 days) obtained after PDT under identical conditions without the preirradia-tion. Thus, pretreatment of pigmented tumors with HPP 1064 nm light appears to enhance their susceptibility to conventional PDT. The tumor response was further enhanced by repeating the combined HPP/PDT treatment at an interval of 10 days (regrowth delay: 27 days), as well as by applying hyperthermia immediately after HPP/PDT (regrowth delay: ca 34 days).     

The class reconstruction number of maximal planar graphs

The reconstruction numberrn(G) of a graphG was introduced by Harary and Plantholt as the smallest number of vertex-deleted subgraphsG _i =G – v _i in the deck ofG which do not all appear in the deck of any other graph. For any graph theoretic propertyP, Harary defined theP-reconstruction number of a graph G P as the smallest number of theG _i in the deck ofG, which do not all appear in the deck of any other graph inP We now study the maximal planar graph reconstruction numberrn(G), proving that its value is either 1 or 2 and characterizing those with value 1.     

Synthesis and anion binding properties of 2,5-diamidothiophene polypyrrole Schiff base macrocycles

[reaction: see text] Two easy-to-synthesize polypyrrolic 2,5-diamidothiophene Schiff base macrocycles are reported, along with their anion binding properties as determined via UV-vis spectroscopic titrations carried out in dichloroethane. There is a striking difference between the interactions with anions of the two macrocycles, a finding ascribed to differences in their rigidity. For example, the more flexible dipyrromethane-derived macrocycle displays a 1.2:1 hydrogen sulfate versus nitrate selectivity, while its more rigid bipyrrole-derived congener shows a 7.4:1 selectivity in favor to hydrogen sulfate.     

Synthesis, structure, and nonlinear optical properties of cross-conjugated perphenylated iso-polydiacetylenes

Monodisperse, cross-conjugated perphenylated iso-polydiacetylene (iso-PDA) oligomers, ranging from monomer 15 to pentadecamer 25, have been synthesized by using a palladium-catalyzed cross-coupling protocol. Structural characteristics elucidated by X-ray crystallographic analysis demonstrate a non-planar backbone conformation for the oligomers due to the steric interactions between alkylidene phenyl groups. The electronic absorption spectra of the oligomers show a slight red-shift of the maximum absorption wavelength as the chain length increases from dimer 17 b to pentadecamer 25, a trend that has saturated by the stage of nonamer 22. Fluorescence spectroscopy confirms that the pendent phenyl groups present on the oligomer framework enhance emission, and the relative emission intensity consistently increases as a function of chain length n. The molecular third-order nonlinearities, gamma, for this oligomer series have been measured via differential optical Kerr effect (DOKE) detection and show a superlinear increase as a function of the oligomer chain length n. Molecular modeling and spectroscopic studies suggest that iso-PDA oligomers (n>7) adopt a coiled, helical conformation in solution.     

Development of a perfusion reversed-phase HPLC method for the separation of soybean and cereal (wheat, corn, and rice) proteins in binary mixtures. Application to the detection of soybean proteins in commercial bakery products

A perfusion reversed-phase HPLC method enabling the simultaneous separation of soybean and cereal (wheat, corn, and rice) proteins in commercial bakery products has been proposed for the first time. The method utilises an acetonitrile-water gradient containing an ion-pairing agent. Different ion-pairing agents were tried, 0.3% (v/v) acetic acid being observed to enable the separation of soybean from wheat, rice, and corn proteins while with 0.1% (v/v) trifluoroacetic acid only the separation of soybean and corn proteins was possible. Optimisation of the solubilisation conditions for proteins was achieved by testing different acetonitrile concentrations for the simultaneous extraction of soybean and cereal proteins: best recoveries were found with 25% (v/v) acetonitrile + 0.3% (v/v) acetic acid and with 40% (v/v) acetonitrile + 0.1% (v/v) trifluoroacetic acid. Chromatographic conditions such as gradient, temperature, and wavelength detection were also optimised. The method enabled the separation of soybean and cereal proteins in binary mixtures (soybean and wheat, soybean and corn, or soybean and rice proteins) in less than 5 minutes in a total analysis time of 20 min.     

The aza-xylylene Diels-Alder approach for the synthesis of naturally occurring 2-alkyl tetrahydroquinolines

The recently discovered intramolecular aza-xylylene Diels-Alder reaction, based on a 1,4-dehydrohalogenation reaction, was extended in terms of substrates and leaving groups allowing the assembly of tetrahydroquinolines in two synthetic steps. Intramolecular cleavage of a thiocarbamate using triphenylphosphine and tetrachloromethane (Appel conditions) to give chloromethyl phenylisocyanate has been presented for the first time. The synthetic feasibility of this process was demonstrated in the first total syntheses of the alkaloids rac-Angustureine and 1-methyl-2-propyltetrahydroquinoline.