Effect of selenium oxidation state on cadmium translocation in chamomile plants

Syntheses and spectral characteristics of cadmium(II) compounds (CdSeO<sub>4</sub>, CdSeO<sub>3</sub>, and Cd(NCSe)<sub>2</sub>(nia)<sub>2</sub>) containing selenium in oxidation states (VI), (IV), and (-II) are described. In Cd(NCSe)<sub>2</sub>(nia)<sub>2</sub>, nicotinamide (nia) and selenocyanate anions are bonded to Cd atom as N-donor monodentate ligands. Nicotinamide is coordinated through the ring nitrogen atom. The effects of these selenium compounds as well as Cd(NCS)<sub>2</sub>(nia)<sub>2</sub> on the growth and Cd accumulation in roots and shoots of hydroponically cultivated chamomile plants (cultivar <i>Lutea</i>) were studied. In the applied concentration range (12–60 <i>μ</i>mol dm<sup>−3</sup>) Cd(NCS)<sub>2</sub>(nia)<sub>2</sub> affected neither the length nor the dry mass of roots and shoots. Other compounds applied at 24 <i>μ</i>mol dm<sup>−3</sup> and 60 <i>μ</i>mol dm<sup>−3</sup> significantly reduced dry mass of roots and shoots. Selenium oxidation state in the cadmium compounds affected Cd accumulation in plant organs as well as Cd translocation within the plants, which was reflected in the values of bioaccumulation (BAF) and translocation factors (S/R). Cd amount accumulated by shoots was lower than that in the roots. The highest BAF values determined for Cd accumulation in shoots were obtained with CdSeO<sub>4</sub>. Substitution of S with Se in the Cd(NCX)<sub>2</sub>(nia)<sub>2</sub> (X = Se or S) caused an increase of Cd translocation into the shoots. Presented at the XVIIIth Slovak Spectroscopic Conference, Spišská Nová Ves, 15–18 October 2006.     

Fitting complex potential energy surfaces to simple model potentials: application of the simplex-annealing method

A stochastic method of optimization, which combines simulated annealing with simplex, is implemented to fit the parameters of a simple model potential. The main characteristic of the method is that it explores the whole space of the parameters of the model potential, and therefore it is very efficient in locating the global minimum of the cost function, in addition to being independent of the initial guess of the parameters. The method is employed to fit the complex intermolecular potential energy surface of the dimer of water, using as a reference the spectroscopic quality anisotropic site-site potential of Feller et al. The simple model potential chosen for its reparameterization is the MCY model potential of Clementi et al. The quality of the fit is assessed by comparing the geometry of the minimum, the harmonic frequencies, and the second virial coefficients of the parameterized potential with the reference one. Finally, to prove more rigorously the robustness of this method, it is compared with standard nonstochastic methods of optimization.     

Über Reaktionen von Nitrosophenolen, 4. Mitt.: Reaktion von Nitrosonaphtholen mit Naphtholen

Zusammenfassung Die Reaktion von 1-Nitroso-2-naphthol mit 1-und 2-Naphthol sowie die Reaktion von 2-Nitroso-1-naphthol mit 2-Naphthol in Äthanol und in Äther bei Anwesenheit von HNO<sub>3</sub> gibt 5<i>H</i>-Dibenzo[<i>a,j</i>]phenoxazon-(5) (I), 5<i>H</i>-Dibenzo[<i>a,j</i>]phenoxazon-(5)-14-oxid (II), 5<i>H</i>-Dibenzo[<i>a,h</i>]phenoxazon-(5) (III) sowie 5<i>H</i>-Dibenzo[<i>a,h</i>]phenoxazon-(5)-14-oxid (IV). Es wurde ein Reaktionsmechanismus vorgeschlagen und die Konstitution der hergestellten Verbindungen spektrophotometrisch und potentiometrisch bestimmt.<hr><blockquote>The reaction of 1-nitroso-2-naphthol with 2-and 2-naphthol and the reaction of 2-nitroso-1-naphthol with 2-naphthol in ethanol or ether in the presence of nitric acid have been studied. The main reaction products isolated were the dibenzophenoxazones I–IV. The reaction mechanism for their formation is proposed.</blockquote><hr><hr><p></p>Mit 4 Abbildungen     

The Binary System BaF2/AlF3

The system BaF<sub>2</sub>/AlF<sub>3</sub> is investigated by X-ray and D.T.A., and the liquid-solid phase diagram is established. Five ternary fluorides are disclosed: trimorphic BaAlF<sub>5</sub>, Ba<sub>3</sub>Al<sub>2</sub>F<sub>12</sub>, Ba<sub>5</sub>AlF<sub>19</sub>, polymorphic Ba<sub>3</sub>AlF<sub>9</sub> and Ba<sub>5</sub>AlF<sub>13</sub>. Neutron thermodiffractometry experiments are performed to specify some parts of the diagram. The cell parameters of the fluorides are given and the results are discussed and compared with those of the previous works.     

Crystal and molecular structure of [9-(2′-tosylaminophenyl)-6-methylthio-3-acetyl-5,7,8-triazanone-3,6,8-thien-2-one]

Institute for Applied Physics, Academy of Sciences of the Moldavian SSR. Institute of Chemistry, Academy of Sciences of the Moldavian SSR. Nat. Research Institute for Physics and Organic Chemistry, Rostov State University. Translated from Zhurnal Strukturnoi Khimii, Vol. 31, No. 2, pp. 199–202, 1990.     

Synthesis, characterization, catalytic, electrochemical and thermal properties of tetradentate Schiff base complexes

In this study, the Schiff base ligands H<sub>2</sub>L<sup>1</sup>–H<sub>2</sub>L<sup>3</sup> and their Cu<sup>II</sup>, Co<sup>II</sup>, Ni<sup>II</sup>, Fe<sup>III</sup> Ru<sup>III</sup> and VO<sup>IV</sup> complexes have been prepared and characterized by spectroscopic and analytical techniques. All the complexes are mononuclear. Keto-enol tautomeric forms of the ligands have been investigated in polar and apolar solvents. The ligands favor the keto-form in the C<sub>7</sub>H<sub>8</sub> and C<sub>6</sub>H<sub>14</sub>. The C–C coupling reaction of the 2,6-di-<i>t</i>-butylphenol has been investigated by the Co<sup>II</sup> and Cu<sup>II</sup> complexes. Thermal properties of the complexes have been assessed using thermal techniques and similar properties were found. In the Fe<sup>III</sup> and Ru<sup>III</sup> complexes, firstly, the coordinated water molecule is lost from the complex; in the second step, the chloride ion leaves the molecule in the 300–350 °C temperature range. Finally, the complexes decompose to the appropriate metal oxide at the higher temperature ranges. The electrochemical properties of the complexes have been studied in the two different solvents (DMF and CH<sub>3</sub>CN).     

On the structure and activity of a Pt/C catalyst subjected to repeated deactivation and regeneration cycles

Electron microscopic studies reveal that repeated air/hydrogen regeneration cycles cause irreversible structural changes of a Pt/C catalyst involving sintering and migration of the platinum over the support. This is reflected by a serious decrease of the catalytic activity. With hydrogen treatment only, these effects are less significant.<hr><blockquote><img src="/content/m036124367665g70/xxlarge1053.gif" alt="Ncy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1072.gif" alt="acy" align="BASELINE" BORDER="0"> <img src="/content/m036124367665g70/xxlarge1086.gif" alt="ocy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1089.gif" alt="scy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1085.gif" alt="ncy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1086.gif" alt="ocy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1074.gif" alt="vcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1077.gif" alt="iecy" align="MIDDLE" BORDER="0"> <img src="/content/m036124367665g70/xxlarge1101.gif" alt="ecy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1083.gif" alt="lcy" align="BASELINE" BORDER="0"><img 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BORDER="0"><img src="/content/m036124367665g70/xxlarge1091.gif" alt="ucy" align="MIDDLE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1078.gif" alt="zhcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1077.gif" alt="iecy" align="MIDDLE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1085.gif" alt="ncy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1086.gif" alt="ocy" align="BASELINE" BORDER="0">, <img src="/content/m036124367665g70/xxlarge1095.gif" alt="chcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1090.gif" alt="tcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1086.gif" alt="ocy" align="BASELINE" BORDER="0"> <img src="/content/m036124367665g70/xxlarge1087.gif" alt="pcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1086.gif" alt="ocy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1074.gif" alt="vcy" 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align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1080.gif" alt="icy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1082.gif" alt="kcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1083.gif" alt="lcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1099.gif" alt="ycy" align="BASELINE" BORDER="0"> <img src="/content/m036124367665g70/xxlarge1074.gif" alt="vcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1086.gif" alt="ocy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1079.gif" alt="zcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1076.gif" alt="dcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1091.gif" alt="ucy" align="MIDDLE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1093.gif" alt="khcy" align="BASELINE" BORDER="0">/<img src="/content/m036124367665g70/xxlarge1074.gif" 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src="/content/m036124367665g70/xxlarge1085.gif" alt="ncy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1080.gif" alt="icy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1103.gif" alt="yacy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1084.gif" alt="mcy" align="BASELINE" BORDER="0"> <img src="/content/m036124367665g70/xxlarge1082.gif" alt="kcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1072.gif" alt="acy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1090.gif" alt="tcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1072.gif" alt="acy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1083.gif" alt="lcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1080.gif" alt="icy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1079.gif" alt="zcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1072.gif" alt="acy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1090.gif" alt="tcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1086.gif" alt="ocy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1088.gif" alt="rcy" align="MIDDLE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1072.gif" alt="acy" align="BASELINE" BORDER="0"> Pt/C, <img src="/content/m036124367665g70/xxlarge1074.gif" alt="vcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1082.gif" alt="kcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1083.gif" alt="lcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1102.gif" alt="yucy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1095.gif" alt="chcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1072.gif" alt="acy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1102.gif" alt="yucy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1097.gif" alt="shchcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1080.gif" alt="icy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1084.gif" alt="mcy" align="BASELINE" BORDER="0"> <img src="/content/m036124367665g70/xxlarge1089.gif" alt="scy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1087.gif" alt="pcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1077.gif" alt="iecy" align="MIDDLE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1082.gif" alt="kcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1072.gif" alt="acy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1085.gif" alt="ncy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1080.gif" alt="icy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1077.gif" alt="iecy" align="MIDDLE" BORDER="0"> <img src="/content/m036124367665g70/xxlarge1080.gif" alt="icy" align="BASELINE" BORDER="0"> <img src="/content/m036124367665g70/xxlarge1084.gif" alt="mcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1080.gif" alt="icy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1075.gif" alt="gcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1088.gif" alt="rcy" align="MIDDLE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1072.gif" alt="acy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1094.gif" alt="tscy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1080.gif" alt="icy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1102.gif" alt="yucy" align="BASELINE" BORDER="0"> <img src="/content/m036124367665g70/xxlarge1087.gif" alt="pcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1083.gif" alt="lcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1072.gif" alt="acy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1090.gif" alt="tcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1080.gif" alt="icy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1085.gif" alt="ncy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1099.gif" alt="ycy" align="BASELINE" BORDER="0"> <img src="/content/m036124367665g70/xxlarge1085.gif" alt="ncy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1072.gif" alt="acy" align="BASELINE" BORDER="0"> <img src="/content/m036124367665g70/xxlarge1085.gif" alt="ncy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1086.gif" alt="ocy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1089.gif" alt="scy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1080.gif" alt="icy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1090.gif" alt="tcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1077.gif" alt="iecy" align="MIDDLE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1083.gif" alt="lcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1077.gif" alt="iecy" align="MIDDLE" BORDER="0">. <img src="/content/m036124367665g70/xxlarge1069.gif" alt="Ecy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1090.gif" alt="tcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1086.gif" alt="ocy" align="BASELINE" BORDER="0"> <img src="/content/m036124367665g70/xxlarge1086.gif" alt="ocy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1090.gif" alt="tcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1088.gif" alt="rcy" align="MIDDLE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1072.gif" alt="acy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1078.gif" alt="zhcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1072.gif" alt="acy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1077.gif" alt="iecy" align="MIDDLE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1090.gif" alt="tcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1089.gif" alt="scy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1103.gif" alt="yacy" align="BASELINE" BORDER="0"> <img src="/content/m036124367665g70/xxlarge1074.gif" alt="vcy" align="BASELINE" BORDER="0"> <img src="/content/m036124367665g70/xxlarge1079.gif" alt="zcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1085.gif" alt="ncy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1072.gif" alt="acy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1095.gif" alt="chcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1080.gif" alt="icy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1090.gif" alt="tcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1077.gif" alt="iecy" align="MIDDLE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1083.gif" alt="lcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1100.gif" alt="softcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1085.gif" alt="ncy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1086.gif" alt="ocy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1084.gif" alt="mcy" align="BASELINE" BORDER="0"> <img src="/content/m036124367665g70/xxlarge1091.gif" alt="ucy" align="MIDDLE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1084.gif" alt="mcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1077.gif" alt="iecy" align="MIDDLE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1085.gif" alt="ncy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1099.gif" alt="ycy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1096.gif" alt="shcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1077.gif" alt="iecy" align="MIDDLE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1085.gif" alt="ncy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1080.gif" alt="icy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1080.gif" alt="icy" align="BASELINE" BORDER="0"> <img src="/content/m036124367665g70/xxlarge1082.gif" alt="kcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1072.gif" alt="acy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1090.gif" alt="tcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1072.gif" alt="acy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1083.gif" alt="lcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1080.gif" alt="icy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1090.gif" alt="tcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1080.gif" alt="icy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1095.gif" alt="chcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1077.gif" alt="iecy" align="MIDDLE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1089.gif" alt="scy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1082.gif" alt="kcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1086.gif" alt="ocy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1081.gif" alt="jcy" align="MIDDLE" BORDER="0"> <img src="/content/m036124367665g70/xxlarge1072.gif" alt="acy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1082.gif" alt="kcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1090.gif" alt="tcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1080.gif" alt="icy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1074.gif" alt="vcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1085.gif" alt="ncy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1086.gif" alt="ocy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1089.gif" alt="scy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1090.gif" alt="tcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1080.gif" alt="icy" align="BASELINE" BORDER="0">. <img src="/content/m036124367665g70/xxlarge1054.gif" alt="Ocy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1076.gif" alt="dcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1085.gif" alt="ncy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1072.gif" alt="acy" align="BASELINE" BORDER="0"> <img src="/content/m036124367665g70/xxlarge1083.gif" alt="lcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1080.gif" alt="icy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1096.gif" alt="shcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1100.gif" alt="softcy" align="BASELINE" BORDER="0"> <img src="/content/m036124367665g70/xxlarge1074.gif" alt="vcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1086.gif" alt="ocy" align="BASELINE" 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BORDER="0"><img src="/content/m036124367665g70/xxlarge1072.gif" alt="acy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1073.gif" alt="bcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1086.gif" alt="ocy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1090.gif" alt="tcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1082.gif" alt="kcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1072.gif" alt="acy" align="BASELINE" BORDER="0"> <img src="/content/m036124367665g70/xxlarge1091.gif" alt="ucy" align="MIDDLE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1084.gif" alt="mcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1077.gif" alt="iecy" align="MIDDLE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1085.gif" alt="ncy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1099.gif" alt="ycy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1096.gif" alt="shcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1072.gif" alt="acy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1077.gif" alt="iecy" align="MIDDLE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1090.gif" alt="tcy" align="BASELINE" BORDER="0"> <img src="/content/m036124367665g70/xxlarge1101.gif" alt="ecy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1090.gif" alt="tcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1080.gif" alt="icy" align="BASELINE" BORDER="0"> <img src="/content/m036124367665g70/xxlarge1101.gif" alt="ecy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1092.gif" alt="fcy" align="MIDDLE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1092.gif" alt="fcy" align="MIDDLE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1077.gif" alt="iecy" align="MIDDLE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1082.gif" alt="kcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1090.gif" alt="tcy" align="BASELINE" BORDER="0"><img src="/content/m036124367665g70/xxlarge1099.gif" alt="ycy" align="BASELINE" BORDER="0">.</blockquote>     

Interaction of tetraphenyl-porphyrin derivatives with DPPC-liposomes: an EPR study

The effect of the symmetry and polarity of the porphyrin molecules on their membrane localization and interaction with membrane lipids were investigated by electron paramagnetic resonance (EPR). For this purpose, two glycoconjugated tetraphenyl porphyrin derivatives were selected, respectively, symmetrically and asymmetrically substituted. Small unilamellar liposomes composed of dipalmitoylphosphatidylcholine (DPPC) and spin labeled stearic acids were prepared. The spin probe was located at the 5th or 7th or 12th or 16th position of the hydrocarbon chain in order to monitor various regions of the lipid bilayer. EPR spectra of porphyrin-free and porphyrin-bound liposomes were recorded at various temperatures below and above the phase transition temperature of DPPC. The effect on membrane fluidity proved to be stronger with the asymmetrical porphyrin derivative than with the symmetrical one. The rigidity increased when the spin label was near lipid head groups. The difference observed between control and porphyrin-treated samples when measured below the main lipid transition temperature disappeared at higher temperature. When the spin label was near the end of the hydrophobic tails, the symmetrical porphyrin derivative caused increase in fluidity, while the asymmetrical one slightly decreased it. To explain this phenomenon we propose that the asymmetrical derivative exerts a stronger ordering effect caused by its fluorophenyl group located at the level of the lipid heads, which is attenuated to the hydrophobic tails. The perturbing effect of the symmetric derivative could not lead to similar extent of ordering at the head groups and looses the hydrocarbon chains deeper in the membrane.     

Cyclic sulfonium salts with S ... O interactions 2. Molecular structures with six-membered rings

1-[2<img src="/content/t048260171306373/xxlarge8242.gif" alt="prime" align="BASELINE" BORDER="0">-(<i>N</i>-methylcarbamoyl)phenyl]-3H-2,1-naphto-(1,8-d,e)-oxathiin-1-ium chloride (2), 1-[2<img src="/content/t048260171306373/xxlarge8242.gif" alt="prime" align="BASELINE" BORDER="0">-(<i>N</i>-methylcarbamoyl)-phenyl]-2-methyl-3-oxo-3H-1, 2-naphto-(1,8-d,e)-thiazin-1-ium chloride (3), 1-[8<img src="/content/t048260171306373/xxlarge8242.gif" alt="prime" align="BASELINE" BORDER="0">-(N-methylcarbamoyl)naphtyl]-2-methyl-3-oxo-3H-1, 2-naphto-(1,8-d,e)-thiazin-1-ium chloride (4) and 1-(8<img src="/content/t048260171306373/xxlarge8242.gif" alt="prime" align="BASELINE" BORDER="0">-carboxylatonaphtyl)-2-methyl-3-oxo-3H-1,2-naphto-(1,8-d,e)-thiazin-1-ium dipolar ion (5) cyclic sulfonium salts were prepared and their chemical properties investigated (spirosulfurane-formation, hydrolysis). The molecular structures obtained from x-ray diffraction can be described with a considerably distorted trigonal bipyramidal arrangement of the ligands about the sulfonium center, with O/N—S ... O=apical angles of 173.9, 164.9, 156.6, and 159.0°, as well as with S—O/N apical bond lengths of 1.648, 1.671, 1.664, and 1.682 Å. The structures exhibit relatively short S ... O close contacts with interatomic distances of 2.253, 2.448, 2.795, and 2.619 Å.