Kinetics of adsorption of the cobalt ions on the "electrolytic solution/gamma-alumina" interface

In the present work we studied, for the first time, the kinetics of adsorption of the Co(H(2)O)(6)(2+) species on the "electrolytic solution/gamma-Al(2)O(3)" interface at pH = 7 and 25 degrees C for a very broad range of Co(II) surface concentrations ranged from 0.03 to 6 theoretical Co(H(2)O)(6)(2+) surface layers. Moreover, we studied the surface dissolution of gamma-alumina in the presence of the Co(H(2)O)(6)(2+) ions in the impregnating solution, the contribution of the Co(II) desorption on the whole deposition process and the deposition isotherm. It was found that under the conditions where the deposition has taken place, the dissolution of the gamma-alumina surface is negligible even in the presence of the Co(H(2)O)(6)(2+) species in the impregnating solution. It was, moreover, inferred that the Co(II) desorption does not participate significantly to the whole deposition process. It was found that the deposition kinetics may be described by the following kinetic expression r(Co,bulk) = k'C(Co,bulk)(2), which relates the rate of disappearance of the Co(H(2)O)(6)(2+) ions from the impregnating solution, r(Co,bulk,) with their concentration C(Co,bulk). This kinetic expression may be derived assuming the following deposition scheme: nS + 2[Co(H(2)O)(6)(2+)] --> S(n) - [Co(H(2)O)(x,x)(<)(6)(2+)](2), where S represents the surface reception sites. The above expressions indicated that two Co(H(2)O)(6)(2+) ions are involved, from the side of the interface, in the reaction with the reception sites. It seems probable that the deposition step involves the simultaneous adsorption and dimerization of the two interfacial Co(H(2)O)(6)(2+) ions through (hydr)oxobridges. On the other hand, the sigmoidal form of the deposition isotherm and the dependence of the apparent rate constant, k', on the interfacial Co(II) concentration suggested that the already deposited Co(II) species may be involved in the reception sites, S, promoting the adsorption and resulting to the formation of multinuclear complexes and Co(II) surface precipitates. Finally, reasonable interface potential values for oxides were determined for the first time using kinetic results.     

Antioxidant activity of novel indole derivatives and protection of the myocardial damage in rabbits

Novel indole derivatives containing a triazole moiety (1a-d, 2a-c) were synthesized as lead compounds with interesting pharmacological profiles. Their antioxidant activity was investigated on in vitro non-enzymatic rat hepatic microsomal lipid peroxidation. All compounds showed significant effect in the above assay. The effect depended mainly on the attachment position of the triazole moiety on the indole nucleus. The most potent antioxidant derivatives la, 1c and 1d were tested for their protective ability against the oxidative damage of the myocardium after ischemia-reperfusion, in male rabbits which were subjected to 30 min regional ischemia followed by reperfusion. The tested antioxidant compounds 1a, 1c and 1d were continuously infused for 30 min starting at 10th min of ischemia and lasted at 10th min of reperfusion. The concentration of malondialdehyde (MDA, a marker of lipid peroxidation) and hemodynamic parameters (blood pressure and heart rate) were measured in the baseline, at 20th min of the sustained ischemia, 1st and 20th min of reperfusion. It was found that the examined compounds la, 1c and 1d reduced significantly the level of MDA in rabbits under ischemia-reperfusion and proved to be promising substances for further evaluation of anti-ischemic properties.     

Nucleation and growth of copper on glassy carbon: Studies in extended overpotential interval

The nucleation and growth of copper crystals on a glassy carbon electrode are investigated at different constant overpotentials. Current transients are recorded and the number of copper nuclei is microscopically registered. The experimental data for the growth current are interpreted according to the theories of progressive and instantaneous nucleation and information is obtained on the stationary nucleation rate, the saturation nucleus number density and the exchange current density at the crystals–solution interface boundary.     

CsMBi(3)Te(6) and CsM(2)Bi(3)Te(7) (M = Pb, Sn): new thermoelectric compounds with low-dimensional structures

The new materials CsPbBi(3)Te(6) and CsPb(2)Bi(3)Te(7) were discovered through reactions of CsBi(4)Te(6) with PbTe, whereas the isostructural materials CsSnBi(3)Te(6) and CsSn(2)Bi(3)Te(7) were discovered through corresponding reactions with SnTe. The compounds can also be prepared from stoichiometric mixtures of Cs(2)Te, Pb (Sn), Bi, and Te. The crystal structures show a layered architecture of NaCl-type slabs alternating with layers of Cs atoms. This group of compounds offers a new quaternary system, Cs-M-Bi-Te (M = Pb and Sn), available for thermoelectric investigations, including fine-tuning of compositions and doping.     

Energy of scattering solitons in the Ward model

We present the results derived in our paper [Proc. Royal. Soc. Lond. A 461 (2005) 1965], where we have shown that the energy density of a scattering-soliton solution in Ward's integrable chiral model is the same as the energy density of a static multi-lump solution of the ℂP ³ sigma model. This explains the quantization of the total energy in the Ward model. Presented at the International Colloquium “Integrable Systems and Quantum Symmetries”, Prague, 16–18 June 2005.     

Controlled synthesis of homopolymers and block copolymers based on 2-(acetoacetoxy)ethyl methacrylate via RAFT radical polymerisation

Reversible addition-fragmentation chain transfer (RAFT) radical polymerisation enables to synthesise well-defined homopolymers and block copolymers based on 2-(acetoacetoxy)ethyl methacrylate, which are capable to strongly coordinate to metals and metal ions.     

Synthesis of asymmetric 3,5-diaryl-4H-1,2,6-thiadiazin-4-ones via Suzuki–Miyaura and Stille coupling reactions

Asymmetric 3,5-diaryl substituted 4H-1,2,6-thiadiazin-4-ones can be prepared from 3,5-dichloro-4H-1,2,6-thiadiazin-4-one (1) via a multi-step protocol: selective nucleophilic mono-chloro substitution gives either the mono-methoxy or benzyloxy substituted mono-chlorothiadiazinones that can be phenylated via Suzuki–Miyaura coupling. Subsequent BBr₃ mediated dealkylation gives 3-hydroxy-5-phenyl-4H-1,2,6-thiadiazin-4-one (9) that can be activated by a modified Finkelstein halodehydroxylation via the triflate, enabling further arylation reactions using Suzuki–Miyaura or Stille coupling chemistry.     

<Superscript>7</Superscript>Be in the lower atmosphere at a mid-latitude (40°N) during the year 2009 of a particular minimum of solar activity

⁷Be activity concentrations were measured in the lower atmosphere at Thessaloniki, Northern Greece (40°38′N, 22°58′E) over the year 2009, a year of a particular minimum of solar activity. The mean annual activity concentration of ⁷Be at that year was 6.01 mBq m⁻³. The variability of ⁷Be surface concentrations related to the solar cycle appeared to be deviated about 40% between the maximum and the minimum values. A positive correlation (R = 0.97) was revealed between the activity concentrations of ⁷Be and the temperature, confirming that the increased rates of vertical transport within the troposphere, especially during the warmer months, resulted in carrying down to the surface layer air masses enriched in ⁷Be. Relatively high values of ⁷Be activity concentrations were observed by increasing of the tropopause height. A negative correlation (R = −0.65) between the ⁷Be activity concentrations and the relative humidity was due to the condensation process in the lower atmosphere which resulted in increased aerosol particle sizes with higher scavenging rates of aerosols and low activity concentrations of ⁷Be in the atmosphere. Influence of precipitation on the changes of ⁷Be activity concentrations was also observed.     

Radon concentrations and absorbed dose measurements in a Pleistocenic cave

Radon concentration measurements were carried out using solid-state nuclear track-etch detectors (SSNTDs) type CA 80-15 cellulose nitrate films, in a Pleistocenic cave at Petralona, in Halkidiki, Northern Greece, at 55 km from the city of Thessaloniki. Radon levels as high as 88 kBq^.m^-3 (2.38 nCi^.l^-1) have been recorded inside the cave equivalent to 11.90 WL in terms of occupational exposure to radon and its decay products. Absorbed dose rates were performed using TL dosimeters, type TLD-200 (CaF₂-Dy) in a continuous monitoring program (integrated measurements). Dose rate levels as high as 110 nGy^.h^-1 were recorded inside the cave. In interpreting the high levels of radiation doses, radioactivity measurements regarding the naturally occurring ²³⁸U, ²³²Th and ⁴⁰K radionuclides were carried out in various speleothems found at different sites in the cave.     

Silver-mediated palladium-catalyzed direct C-H arylation of 3-bromoisothiazole-4-carbonitrile

Silver(I) fluoride-mediated Pd-catalyzed C-H direct arylation/heteroarylation of 3-bromoisothiazole-4-carbonitrile (1a) gives twenty-four 5-aryl/heteroaryl-3-bromoisothiazole-4-carbonitriles. The reaction was partially optimized with respect to catalyst, ligand, and base. During this study 3,3'-dibromo-5,5'-biisothiazole-4,4'-dicarbonitrile (3a) was isolated as a byproduct and subsequently prepared via the silver-mediated Pd-catalyzed oxidative dimerization of 3-bromoisothiazole-4-carbonitrile in 67% yield. The analogous phenylation and oxidative dimerization of 3-chloroisothiazole-4-carbonitrile (1b) gave 3-chloro-5-phenylisothiazole-4-carbonitrile (4) and 3,3'-dichloro-5,5'-biisothiazole-4,4'-dicarbonitrile (3b) in 96% and 69% yields, respectively.