Adsorption and structure formation of the weak polyelectrolytic diblock copolymer,PVP-<Emphasis Type="Italic">b</Emphasis>-PDMAEMA

This paper reports on the pH-dependent adsorption of weak the polyelectrolytic diblock copolymer poly(2-vinylpyridine)-block-poly(dimethylaminoethyl methacrylate), (PVP-b-PDMAEMA). Aqueous PVP-b-PDMAEMA solutions have been adsorbed on alkaline pretreated silicon substrates. Altogether two copolymers differing in block ratio and molecular weight were used for the investigations. While the electrical charge of both samples in solution was investigated by electrophoretic measurements, the adsorbed polymer layers were studied with ellipsometry and atomic force microscopy (AFM). Depending on pH the electrical charge of both blocks of the diblock copolymer varied. Three different regimes have been identified. Under acidic conditions at pH<5, both blocks are mainly positively charged. At medium pH between 5 and 8, only the PDMAEMA block is positively charged. At pH>8, both blocks are nearly uncharged and a polymer precipitation occurred in solution. Each of these pH regimes was characterized by a specific adsorption behaviour leading to two adsorption maxima at acidic and alkaline pH values, while at medium pH a plateau in the adsorbed amount was observed. Moreover, the structures of the polyelectrolytes formed on the substrate after adsorption were specific to each of the three pH regimes.     

Binuclear and mononuclear cobalt(II), nickel(II) and copper(II) complexes of 4,4′-bis(alkylaminoisonitrosoacetyl)diphenyl-methane derivatives

4,4-Bis(chloroacetyl)diphenylmethane has been prepared from ClCH₂COCl and Ph₂CH₂. 4,4-Methylenebis(phenylglyoxylohydroximoyl chloride has also been obtained. Four new substituted 4,4-bis(alkylaminoisonitrosoacetyl)diphenylmethanes (ligands) have been prepared from 4,4-methylenebis(phenylglyoxylohydroximoyl chloride) and the corresponding amines. The Ni^II, Cu^II and Co^II complexes of these ligands were prepared and their structures were identified using AAS, i.r., ¹H-n.m.r. spectral data, elemental analyses and magnetic susceptibility measurements.     

Determination of in vitro antioxidant and radical scavenging activities of propofol

Propofol (2,6-diisopropylphenol) is a hypnotic intravenous agent with in vivo antioxidant properties. This study was undertaken to examine the in vitro antioxidant activity of propofol using different antioxidant tests including by 1,1-diphenyl-2-picryl-hydrazil (DPPH.) radical scavenging, metal chelating, hydrogen peroxide scavenging, superoxide anion radical scavenging, reducing power and total antioxidant activities. At the concentrations of 25, 50, and 75 microg/ml, propofol exhibited 97.7, 98.6 and 100% inhibition on peroxidation of linoleic acid emulsion, respectively. On the other hand, at the 75 microg/ml concentration of standard antioxidants such as butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT) and alpha-tocopherol exhibited 88.7, 94.5, and 70.4% inhibition on peroxidation of linoleic acid emulsion, respectively. In addition, at same concentrations, propofol was shown that it had effective reducing power, DPPH. free radical scavenging, superoxide anion radical scavenging, hydrogen peroxide scavenging and metal chelating activities. These various antioxidant activities were compared to standard antioxidants such as BHA, BHT and alpha-tocopherol. These results indicate that propofol prevents lipid peroxidation and radicalic chain reactions. At the same time, propofol revealed more effective antioxidant capacity than BHA, BHT and alpha-tocopherol.     

Molecular-level control of the photoluminescence from PPV nanostructured films

The fabrication of varied molecular architectures in layer-by-layer (LbL) films is exploited to control the photoluminescence (PL) of poly(p-phenylene vinylene) (PPV) in an unprecedented way. This was achieved by controlling the F?rster energy transfer between PPV layers (donors) and layers of a commercial azodye, Brilliant Yellow (BY) (acceptors). Energy transfer was controlled by inserting spacer layers of inert polymers between PPV and BY layers and by photoaligning the BY molecules via trans-cis-trans isomerization. The PPV/BY LbL films displayed polarized PL whose intensity could be varied almost continuously by changing the time of photoalignment, which was carried out by impinging a linearly polarized laser light simultaneously to the PL experiments. For PPV/BY films with no spacer layers, PL was completely quenched, but its intensity increased with the number of spacing layers. Further increase in PL was obtained by photoaligning the BY molecules perpendicularly to the PPV molecules. This minimizes energy transfer, since F?rster processes are directional, dipole-dependent resonant transfers. Energy transfer is also controlled by imparting a preferential orientation of the PPV chains on PPV/BY LbL films deposited onto flexible Teflon substrates that may be stretched.     

Solubility of Triethylamine in Tetraethylammonium Chloride Aqueous Solutions from 20 to 35°C

Solubilities of triethylamine in aqueous tetraethylammonium chloride solutions were measured at 20, 25, and 35°C. The molalities in Et₄NCl of the aqueous solvents ranged from 0.03 to 1 mol-kg^–1. The data were evaluated from density measurements using a vibrating-tube densimeter. At each temperature, least-squares method was used to fit experimental density data points to double polynomial equations of various degrees. Triethylamine molalities of the saturated aqueous phases were estimated by extrapolation from those equations. Experimental data were interpreted in terms of hydrophobic and electrostatic perturbed domains in the hydration shells of the noneleceory and of the cation of the salt, as a function of temperature and salt concentration. The conclusions obtained are consistent with previous volumetric studies.     

The Legacy of Raimond Castaing

 In April 1998 Raimond Castaing left the world of electrons, of ions and others particles, his wife and his family, his numerous students, for the world of stars. Raimond Castaing (Fig. 1) had a very strong personality. No one will forget their first meeting with him and all his students remember how brilliant he was as a teacher. A lot of anecdotes about his famous hot temper are still circulating among his friends and his former students. But in this paper, we would like to evoke Castaing’s memory through his achievements in Instrumental Physics, from the time of his doctoral thesis to later developments with his students, which were all centred on the imaging of the microstructures of materials and their quantitative chemical analysis.     

Studies on the subcellular localization of the porphycene CPO

This study was designed to provide more detailed information on the subcellular sites of binding of the porphycene, termed 9-capronyloxytetrakis (methoxyethyl) porphycene (CPO), with a fluorescence resonance energy transfer (FRET) technique. The proximity of CPO to two fluorescent probes was determined: nonyl acridine orange (NAO), a dye with specific affinity for the mitochondrial lipid cardiolipin, and dihexa-oxacarbocyanine iodide (DiOC6), an agent that labels the endoplasmic reticulum (ER). FRET spectra indicated energy transfer between DiOC6 and CPO but no significant transfer between NAO and CPO. These results confirm data obtained by fluorescence microscopy, suggesting a similar pattern of subcellular localization by CPO and DiOC6 but not by CPO and NAO. However, when cells containing CPO were irradiated and then loaded with NAO, FRET between the two fluorophores was observed. Hence, a relocalization of CPO can occur during irradiation. These data provide an explanation for recent studies on CPO-catalyzed photodamage to both ER and mitochondrial Bcl-2.     

Validation of UV spectrophotometric and nonaqueous titration methods for the determination of carvedilol in pharmaceutical formulations

Ultraviolet (UV) spectrophotometric and nonaqueous volumetric methods are described for the determination of carvedilol in pharmaceutical formulations. Linearity, precision, and accuracy were evaluated according to the validation guidelines of the International Conference on Harmonization and the United States Pharmacopeia for both methods. The UV spectrophotometric procedure was performed in ethanol at 244 nm. Good linearity was obtained between 2 and 7 microg/mL with a correlation coefficient of 0.9999. The intra- and interday precision values were <2% for all samples analyzed. The accuracy, determined from recovery studies, was between 97.5 and 102.2%. The other procedure was based on the volumetric quantitation of carvedilol in a nonaqueous medium with 0.01 M perchloric acid and 1% violet crystal as the indicator. The validation of the volumetric method yielded good results that included linearity (r of > 0.999), precision (relative standard deviations of <2% for intra- and interday precision), and accuracy (96.4-102.4%). The methods were applied to tablets and compounded capsules. Statistical analysis by analysis of variance showed no significant difference between the results obtained by the proposed methods.