SYNTHESIS OF POSITIVELY CHARGED PHTHALOCYANINES and THEIR ACTIVITY IN THE PHOTODYNAMIC THERAPY OF CANCER CELLS

Positively charged zinc containing or metal free phthalocyanines 6a-c and 7a-c were prepared via a three step procedure starting from 4-nitrophthalonitrile. The phthalocyanines contain alkyl chains of different length in order to influence the hydrophilic vs lipophilic character of the compounds. The partition between a hydrophilic (water) and lipophilic (octanol-1) phase was determined, and the photoredox activities were investigated. Initial results on the photodynamic activity of these compounds were compared with those of Dougherty's Photofrin II on different malignant and non-malignant cell lines (XP 29MAmal, CX1, HeLa, S180 and NO17). Positively charged phthalocyanines in vitro showed a higher photodynamic activity than Photofrin II.     

Theoretical and experimental study of the adsorption on radioactive gases on continuous flow columns

A bimolecular reaction model was used to describe the adsorption process in continuous flow columns filled with solid adsorbents. The analytical solution of the model for low gas concentrations and a cascade-type numerical method for higher gas concentrations were developed. An air flow apparatus using activated carbon as adsorbent and methyl-iodide labelled with¹²⁵I as adsorbate was constructed for measuring breakthrough- and accumulation curves.     

Über das Nicotellin und die Synthese eines neuen Terpyridyls

Zusammenfassung Das Nicotellin enthält wahrscheinlich nicht, wie die meisten anderen Tabakalkaloide, 2 N-Atome in der Molekel, sondern hat die Formel C₁₅H₁₁N₃. Es werden gewichtige Gründe dafür beigebracht, es als 3,2;6,3-Terpyridyl (I) aufzufassen. Diese Hypothese wird durch Synthese des damit isomeren 3,2;4,3-Terpyridyls (V) und Vergleich der Infrarotspektren der beiden Terpyridyle mit denen von 4 bekannten Bipyridylen gestützt. Betrachtungen über eine mögliche Synthese des Nicotellins in der Pflanze führen zu Versuchen, diese Synthese in vitro nachzuahmen; diese Versuche geben aber eine andere Verbindung, wahrscheinlich das 1,5-Di--pyridyl-pentadien-(1,4)-on-(3).Herrn Prof. Dr.L. Ebert zum 60. Geburtstage in aufrichtiger Verehrung gewidment.     

Vierring-synthesen durch [3 + 1]-cycloaddition . Synthese von 3-imino-azetidinen aus azomethin-yliden und isonitrilen

Azomethine ylide 3 , generated by thermolysis of 3,4-diphenyl-Δ¹-1,2,3-triazoline-5,5-dimethyldicarboxylate 1 , can be trapped by isonitriles to give 3-imino-1,4-diphenylazetidine-2,2-dimethyldicarboxylates 5 . The IR, ¹H-NMR, ¹³C-NMR and mass spectral data of the new compounds are discussed.     

Reversible storage of molecular hydrogen by sorption into multilayered TiO2 nanotubes

The sorption of hydrogen between the layers of the multilayered wall of nanotubular TiO2 was studied in the temperature range of -195 to 200 degrees C and at pressures of 0 to 6 bar. Hydrogen can intercalate between layers in the walls of TiO2 nanotubes forming host-guest compounds TiO2 x xH2, where x < or = 1.5 and decreases at higher temperatures. The rate of hydrogen incorporation increases with temperature and the characteristic time for hydrogen sorption in TiO2 nanotubes is several hours at 100 degrees C. The rate of intercalate formation is limited by the diffusion of molecular hydrogen inside the multilayered walls of the TiO2 nanotube. 1H NMR-MAS and XRD data confirm the incorporation of hydrogen between the layers in the walls of TiO2 nanotubes. The nature and possible applications of the observed intercalates are considered.     

Electronic communication through the ureylene bridge: spectroscopy, structure and electrochemistry of dimethyl 1,1-ureylenedi(1-ferrocenecarboxylate)

Dimethyl 1^′,1^′-ureylenedi(1-ferrocenecarboxylate) (1) formed during the synthesis of 1-amino, 1^′-ferrocenecarboxylic acid shows virtual molecular centrosymmetry. Electronic coupling between the two Fc groups through the ureylene bridge results in both Fc groups being individually oxidizable (ΔE_1/2?0.14 V). The possible existence of intermolecular electronic communication has discussed. The oxidation was followed by spectroelectrochemistry. The separation between the two halfwave potentials ΔE_1/2=137±5 mV and the comproportionation constant K_c=207.     

Glutamate receptor incorporated in a mixed hybrid bilayer lipid membrane array, as a sensing element of a biosensor working under flowing conditions

The realization of a reliable receptor biosensor requires stable, long-lasting, reconstituted biomembranes able to supply a suitable biomimetic environment where the receptor can properly work after incorporation. To this end, we developed a new method for preparing stable biological membranes that couple the biomimetic properties of BLMs (bilayer lipid membranes) with the high stability of HBMs (hybrid bilayer membranes); this gives rise to an innovative assembly, named MHBLM (mixed hybrid bilayer lipid membrane). The present work deals with the characterization of biosensors achieved by embedding an ionotropic glutamate receptor (GluR) on MHBLM. Thanks to signal (transmembrane current) amplification, which is typical of natural receptors, the biosensor here produced detects glutamate at a level of nmol L(-1). The transmembrane current changes linearly vs glutamate up to 100 nmol L(-1), while the limit of detection is 1 nmol L(-1). In addition, the biosensor response can be modulated both by receptor agonists (glycine) and antagonists (Mg(2+)) as well, and by exploiting the biosensor response, the distribution of different kinds of ionotropic GluR present in the purified sample, and embedded in MHBLM, was also evaluated. Finally, one of the most important aspects of this investigation is represented by the high stability of the biomimetic system, which allows the use of biosensor under flowing conditions, where the solutions flow on both biomembrane faces.     

Configurationally and conformationally homogeneous cyclicN-aryl sulfimides. II.13C-and1H NMR spectra

The configuration and (in case of mobile ring systems) the preferred conformation in a series of thiane- and ofcis-andtrans-1-thiadecalin-1-N-4-chlorophenyl imides were assigned by means of¹³C- and¹H nmr spectroscopy.¹H nmr criteria known to be valid for determination of the stereochemistry of cyclic sulfoxides may be applied (with limitations) to cyclicN-aryl sulfimides, if both isomers (S–N bond equatorial and axial, respectively) are known. The assignments are easier, and unambiguous for single isomers, by comparison of¹³C nmr chemical shifts of ring carbon atoms of sulfimides and sulfides. The influence of equatorially and axially oriented sulfimide groups on the chemical shifts of neighbouring protons, and on the carbon atoms of the heterocyclic rings are discussed in detail.

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Konfigurativ und konformationell einheitliche cyclische N-Aryl-sulfimide. II.¹³C- und¹H-NMR-Spektroskopie

Zusammenfassung Die Konfiguration und (bei beweglichen Ringsystemen) die bevorzugte Konformation einer Reihe von Thian- und voncis- undtrans-1-Thiadekalin-1-N-4-chlorophenylimiden wurde durch¹³C- und¹H-NMR-Spektroskopie bestimmt. Bekannte¹H-NMR-Kriterien zur Festlegung der Stereochemie cyclischer Sulfoxide sind (mit Einschränkungen) auch bei cyclischenN-Arylsulfimiden anwendbar, wenn beide Isomere (S–N-Bindung äquatorial bzw. axial) bekannt sind. Leichter, und auch bei Vorliegen von nur einem Isomeren eindeutig, gelingt die Zuordnung durch Vergleich der¹³C-NMR-Verschiebungen der Ringkohlenstoffatome von Sulfimiden und Sulfiden. Die Einflüsse äquatorial oder axial orientierter Sulfimidgruppen auf die chemischen Verschiebungen benachbarter Wasserstoffe und der Kohlenstoffe des Heterorings werden diskutiert.

     

Electron spin resonance g tensors for complexes of Ne and Ar with AlO: theoretical studies related to the large matrix effect observed for AlO

For Ne(n)-AlO (n=2, 4, 6, 8, 10) and Ar(n)-AlO clusters (n=2, 4, 6, 8), the perpendicular (relative to AlO) component of the g tensor was calculated by second-order perturbation theory, using multireference configuration-interaction wave functions. The rare-gas (Rg) atoms were placed axially and/or off axially (one or two rings of four Rg atoms each), and the distance of the Rg atoms from the Al and O atoms, or from the AlO axis, was varied from 4 to 12 bohrs. Rg atoms placed axially mostly increase g(perpendicular), whereas off-axially placed ones lower it below the gas-phase value of AlO. The largest deviations from g(perpendicular) of isolated AlO occur at Ne-Al,O distances of 5-6 bohrs, and Ar-Al,O distances of 6-9 bohrs, with maximal lowerings of about 1600 ppm for Ne and about 2200 ppm (estimated) for Ar in the case of two axial and eight off-axial Rg atoms. Electron spin resonance studies by Knight and Weltner found large matrix effects for AlO, with downshifts of g(perpendicular) observed to be about 450 and 1150 ppm in Ne and Ar matrices, respectively.     

Freie Mischungsenthalpie der Mischung von 1,2-Dichloräthan mit Cyclohexan

Zusammenfassung Totaldampfdrucke des Systems 1,2-Dichloräthan + Cyclohexan wurden bei 13°, 20° und 32° C über den gesamten Konzentrationsbereich gemessen. Für Cyclohexan-reiche Mischungen des Systems wurde ferner die Schmelzkurve bestimmt. Aus diesen Meßgrößen wurde die zusätzliche freie Mischungsenthalpie G ^E des Systems für verschiedene Temperaturen berechnet. Bei 20°C beträgt G ^E für die äquimolare Mischung 773 J/mol. Ein Vergleich mit Literaturangaben über die Mischungswärme (H=1611 J/mol für äquimolare Mischung bei 20°C) ergibt, daß die zusätzliche Mischungsentropie S ^E des Systems stark positiv ist. Eine Interpretation der Ergebnisse wird in einer anderen Arbeit gegeben, wo auch Ergebnisse an anderen Dihalogenäthan + Kohlenwassersoff-Systemen berücksichtigt werden.

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Free enthalpy of mixing for the system 1,2-dichloroethne-cyclohexane

Total vapour pressures of the system 1,2-dichloroethane + cyclohexane were measured at 13°, 20° and 32°C over the total concentration interval. For mixtures rich in cyclohexane the

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Mit 5 Abbildungen