Rheological analysis of the structural properties effecting the percutaneous absorption and stability in pharmaceutical organogels

This study presents the organogels of glyceryl monostearate emulsifiers and coconut oil as an alternative for developing the traditional organogels. We investigated how the emulsifier type affects the semisolid consistency and the drug release. In these aspects we compared glyceryl monostearate organogels (GMSO) to commercially available references, while studying the effect of the individual constituents on the structural and functional properties.Rheology provided indirect information on the structure, relevant from an application point of view. We observed that glyceryl monostearate as an organogelator results in a network with elastic nature and moderate crosslink energy. The products had low viscosity and low yield value which means practically an easily spreadable pharmaceutical dosage form with soft consistency.Modelling the percutaneous absorption in vitro, we observed that the diffusion of the piroxicam incorporated was significantly affected by the thermodynamical potency of piroxicam, which was favoured by the emulsifier. The glyceryl monostearate enhanced the partition of the suspended drug, resulting in higher drug release.This paper was presented at the first Annual European Rheology Conference (AERC) held in Guimarães, Portugal, September 11-13, 2003.     

HPLC analysis of metabolically produced formaldehyde

Radiolabelled (-)-deprenyl is orally administered to rats, and urinary elimination of radiolabelled formaldehyde is detected. The separation is performed using high-performance liquid chromatography on octadecyl-silica stationary phase. Both the radioactivity and the UV absorbance of the dinitrophenylhydrazine formaldehyde peak are determined. Formaldehyde generation takes place by N-demethylation. Low levels of formaldehyde may have a beneficial role in counterbalancing the oxidative stress of the everyday person's life.     

Thermal Behavior and Primary Degradation Mechanism of Some Aromatic Polyethers with Semi-flexible Chain

The present paper describes a thermogravimetric study combined with mass spectrometry of some aromatic polyethers and copolyethers in order to obtain information on the degradation mechanism. The investigated polymers were synthesized starting from 3,3-bis(chloromethyl) oxetane and various bisphenols: 4,4'-dihydroxyazobenzene, 4,4'-dihydroxydiphenyl, bisphenol A and 4,4'-dihydroxydiphenylether. The presence of an oxetanic spacer in the structure, permitting the opening of the cycle, induces more complications in the characterization procedure. But, due to the possibilities relative to the modification of polymers or cross-linking reactions, the presence of the oxetanic moiety may offer some advantages. Out of all the investigated polymers, those containing azobenzenic moieties have the lower thermostability. If the chain flexibility is augmented, the degradation mechanism is based on chain transfer reactions. All polymers present higher thermostability in an argon atmosphere. Based on mass spectra, a degradation mechanism sustained with the assumption that the oxetanic unit is the most labile was proposed. The opening of the oxetanic cycle begins with the most tensioned bond (-C-CH₂-) and generates across-linking process, which is more evident if the polymer melts below 200°C. This revised version was published online in July 2006 with corrections to the Cover Date.     

Kinetik und Mechanismus der Substitutionsreaktionen von Komplexverbindungen, 22. Mitt.: Neue Derivate der Bis-dimethylglyoximato-diselenocyanato-kobalt(III)-säure und die Kinetik der Aquotisierung des Komplexes

Zusammenfassung Es wurden 29 neue Komplexsalze der Säure: H[CoDim ₂ ^**(NCSe)₂] erhalten. Spektrophotometrische Messungen wurden im UV- und IR-Bereiche durchgeführt. Die Kinetik der Aquotisierung der [CoDim ₂(NCSe)₂]^–-Ionen wurde untersucht. Die Ergebnisse wurden mit den kinetischen Parametern der Aquotisierung der analogen [Co_{Dim 2} X ₂]^–-Ionen (mitX=Cl, Br, J, NCS) verglichen.

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Kinetics and mechanism of substitution reactions in complex compounds, XXII.: New derivatives of hydrogen bis-(dimethyl-glyoximatodiselenocyanato)-cobaltiatic(III) acid and kinetics of the hydrolysis of the [CoDim₂(NCSE)₂]^– ion

A series of 29 novel complex salts of the acid H[CoDim ₂(NCSe)₂] has been prepared and characterized. UV, Vis. and IR spectra were recorded and the aquation kinetics of the [CoDim ₂(NCSe)₂]^– ions studied. Results were compared with kinetic parameters of the aquation of the analogous [CoDim ₂ X ₂]^– ions, whereX=Cl, Br, J, SCN.

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Mit 2 Abbildungen

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Aquotisierung = Austausch eines Komplexliganden gegen Wasser.     

Uniform catalytic site in Sn-beta-zeolite determined using X-ray absorption fine structure

The Sn silicate zeolite, Sn-beta, has been shown to be an efficient, selective heterogeneous catalyst for Baeyer-Villiger oxidations. Using primarily a multishell fit to extended X-ray absorption fine structure (EXAFS) data, we show that the Sn does not randomly insert into the beta-zeolite structure but rather occupies identical, specific, crystallographic sites. These sites are the T5/T6 sites in the six-membered rings. Moreover, the Sn is substituted in pairs on opposite sides of these six-membered rings. We believe that it is the specific, uniform crystallographic location of the Sn in the beta crystal structure that leads to sites with uniform catalytic activity, and consequently to the high chemical selectivity demonstrated for this catalyst. This manifests itself in the almost enzyme-like selectivity of this catalyst in Baeyer-Villiger oxidations. This uniform site distribution of the Sn suggests that there is likely a symbiotic relationship between the structure-directing agent in the zeolite synthesis and the Sn heteroatoms during the framework formation.     

The role of the solvation shell decomposition of alkali metal ions in their selective complexation by resorcinarene and its cavitand

2-Methylresorcinarene and its methylene-bridged cavitand derivative as host compounds were investigated in selective complexation of alkali metal ions as guests in methanol media by photoluminescence measurements. These host molecules possess either flexible (2-methylresorcinarene) or rigid (cavitand) molecular skeleton. The Benesi–Hildebrand method and the van't Hoff theory have been applied to determine the stability constants and the thermodynamic parameters, respectively. Considerable interactions between 2-methylresorcinarene and Li⁺ or Na⁺ ions have been observed while the rigid cavitand derivative can interact only with K⁺ or Cs⁺ ions. Neither the complexes of 2-methylresorcinarene with K⁺ or Cs⁺ nor those of the cavitand derivative with Li⁺ or Na⁺ ions are stable at room temperature in methanol media. Quantum-chemical investigations justified that only solvated Li⁺ and Na⁺ ions can form stable complexes with 2-methylresorcinarene while unsolvated K⁺ and Cs⁺ ions form stable complexes with the methylene-bridged cavitand. These results highlight that the stability of the guest solvation shell and its size could play a key role in the selectivity behaviour of host molecules.