Characterization and properties of the copper(II/I) complexes of macrocyclic hexathiaether ligand [21]aneS6

The copper(II/I) complexes of hexathiaether macrocyclic ligand, 1,4,8,11,15,18-hexathiacyclohenicosane ([21]aneS₆), were synthesized, and characterized by electrochemical and spectroscopic techniques. Cyclic voltammetric studies indicate that Cu([21]aneS₆)^2+/+ forms a reversible one-electron redox couple. The electrochemical potential obtained for Cu([21]aneS₆)^2+/+ (E^f = 0.89 V, against SHE) was found to be the highest potential reported to date for a Cu^2+/+ macrocyclic system in aqueous solution. By employing the Nernst equation, we can infer that the practical upper limit for formal potential of Cu(II/I)L systems maybe close to this high value. Stability constant data obtained for these complexes indicate that Cu([21]aneS₆)⁺is 12 orders of magnitude greater in stability than that of Cu([21]aneS₆)²⁺ indicating the favorable nature of this large macrocyclic ligand towards formation of Cu(I) complexes over Cu(II) complexes. Crystal structure of Cu([21]aneS₆)⁺ ( Fig. 2) shows that four sulfurs adjacent to one another are coordinated to Cu⁺ ion in this complex. Bond angles and distances calculated for the crystal indicate that it is a distorted tetrahedron, a geometry commonly encountered by Cu(I) complexes. This is the first report of synthesis and characterization of a metal coordinated [21]aneS₆ complex.     

Simultaneous preparation of tritiated uracil and uridine

Summary Tritiated uracil and uridine have been prepared simultaneously from a mixture of their respective halogenated analogues (5-bromouracil and5-bromouridine) by halogen-tritium exchange in a one pot preparation, followed by purification. The tritiated products thus obtained have specific activities of 0.962 TBq/mmol and 1.036 TBq/mmol, respectively.     

Synthesis,ABTS-Radical Scavenging Activity,and Antiproliferative and Molecular Docking Studies of Novel Pyrrolo[1,2-a]quinoline Derivatives

A new 2,2′-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS)-radical scavenging and antiproliferative agents of pyrrolo[1,2-a]quinoline derivatives have been synthesized. An efficient method for the synthesis of 14 novel diversified pyrrolo[1,2-a]quinoline derivatives has been described using 4-(1,3-dioxolan-2-yl)quinoline and different phenacyl bromides in acetone and followed by reacting with different acetylenes in dimethylformamide/K₂CO₃. The structure of the newly synthesized compounds was determined by infrared, ¹H NMR, ¹³C NMR, mass spectrometry, and elemental analysis. The in vitro antioxidant activity revealed that among all the tested compounds 5n exhibited maximum scavenging activity with ABTS. Compound 5b has showed good antiproliferative activity as an inhibitor of epidermal growth factor receptor (EGFR) tyrosine kinase.     

Preparation of tritiated fluorenone and fluorenol

Summary Tritiated fluorenone 2 was prepared from 2-iodofluorenone 1 by halogen-tritium exchange. The product had specific activity of 17 Ci/mmol. The product 2(after dilution with unlabeled congener) on reduction with NaBH₄gave the corresponding tritiated fluorenol 3.     

Ion association and hydration in aqueous solutions of copper(II) sulfate from 5 to 65 degrees C by dielectric spectroscopy

Aqueous solutions of copper(II) sulfate have been studied by dielectric relaxation spectroscopy (DRS) over a wide range of frequencies (0.2 less, similar nu/GHz < or = 89), concentrations (0.02 < or = m/mol kg(-1) less, similar 1.4), and temperatures (5 < or = t/ degrees C < or = 65). The spectra show clear evidence for the simultaneous existence of double-solvent-separated, solvent-shared, and contact ion pairs at all temperatures, with increasing formation especially of contact ion pairs with increasing temperature. The overall ion association constant corresponding to the equilibrium: Cu2+(aq) + SO4(2-)(aq) right harpoon over left harpoon CuSO4(0)(aq) was found to be in excellent agreement with literature data over the investigated temperature range. However, the precision of the spectra and other difficulties did not allow a thermodynamic analysis of the formation of the individual ion-pair types. Effective hydration numbers derived from the DRS spectra were high but consistent with simulation and diffraction data from the literature. They indicate that both ions influence solvent water molecules beyond the first hydration sphere. The implications of the present findings for previous observations on copper sulfate solutions are briefly discussed.     

High resolution 1H NMR structural studies of sucrose octaacetate in supercritical carbon dioxide

High pressure (HP), high resolution (HR), proton nuclear magnetic resonance (1H NMR) spectroscopy has been utilized for the first time to investigate the solution structure of a carbohydrate based system, sucrose octaacetate (SOA), in supercritical CO2. The studies indicate that the average solution state conformation of the alpha-D-Glucopyranosyl ring of SOA in scCO2 medium is consistent with the 4C1 chair form, while the beta-D-fructofuranosyl ring adopts an envelope conformation. The investigations also suggest that scCO2 is a promising medium to study the solution structure and conformation of acetylated sugar systems. Spectral manifestations of a specific interaction between the acetate methyl protons and CO2 molecules are also presented.     

Effect of biotic and abiotic stresses on volatile emission of Achillea collina Becker ex Rchb

This study describes the application of headspace solid-phase microextraction (HS-SPME)–gas chromatography/mass spectrometry (GC/MS) to characterise the volatile fingerprint changes of Achillea collina, induced by aphids' infestation, mechanical damage and jasmonic acid (JA) treatment. The volatile organic compound profiles of A. collina, Prunus persica and Pisum sativum infested by Myzus persicae were also compared. Several changes were observed between control, infested, mechanically damaged and JA-treated plants, and new inducible volatile organic compounds (IVOCs) were emitted in response to biotic or abiotic stresses. Some of these were in common for all stresses and other compounds were in common only for two types of stress. Conversely some IVOCs were emitted only in response to the specific stimuli. The results suggested that there were species-specific and common IVOCs emitted by A. collina, P. persica and P. sativum in response to M. persicae infestation. In conclusion, HS-SPME–GC/MS seems to be a reliable analytical approach to study in vivo plant reaction to external stimuli.     

Development of an algorithm for automatic detection and rating of squeak and rattle events

A new algorithm for automatic detection and rating of squeak and rattle (S&R) events was developed. The algorithm utilizes the perceived transient loudness (PTL) that approximates the human perception of a transient noise. At first, instantaneous specific loudness time histories are calculated over 1-24 bark range by applying the analytic wavelet transform and Zwicker loudness transform to the recorded noise. Transient specific loudness time histories are then obtained by removing estimated contributions of the background noise from instantaneous specific loudness time histories. These transient specific loudness time histories are summed to obtain the transient loudness time history. Finally, the PTL time history is obtained by applying Glasberg and Moore temporal integration to the transient loudness time history. Detection of S&R events utilizes the PTL time history obtained by summing only 18-24 barks components to take advantage of high signal-to-noise ratio in the high frequency range. A S&R event is identified when the value of the PTL time history exceeds the detection threshold pre-determined by a jury test. The maximum value of the PTL time history is used for rating of S&R events. Another jury test showed that the method performs much better if the PTL time history obtained by summing all frequency components is used. Therefore, rating of S&R events utilizes this modified PTL time history. Two additional jury tests were conducted to validate the developed detection and rating methods. The algorithm developed in this work will enable automatic detection and rating of S&R events with good accuracy and minimum possibility of false alarm.     

Bremsstrahlung shielding parameters in polymer concretes

Concretes are used for shielding in nuclear power plants. Beta radiation is emitted during the nuclear reactions. This beta radiation interacts with the concrete and results in secondary radiation such as bremsstrahlung. Shielding parameters of beta-induced bremsstrahlung in concretes are important in the field of radiation protection. We have evaluated the cross section, yield, intensity and dose rate of beta-induced bremsstrahlung by pure beta nuclides of end point energy ranges from 0.4 to 5?MeV in some polymer-based concretes such as sulfur polymer concrete, barium polymer concrete, calcium polymer concrete, fluorine polymer concrete, chlorine polymer concrete and germanium polymer concrete. We have compared the shielding properties among the studied polymer concretes. The efficiency, intensity and dose rate of bremsstrahlung increases with a maximum energy of beta nuclide and modified atomic number of the concrete. From the detailed study, it is clear that the barium polymer concrete is having large bremsstrahlung dose rate and specific bremsstrahlung constant values than the other studied polymer concretes. This means barium polymer concrete is a good absorber of bremsstrahlung radiation than the other studied polymer concretes.     

Determination of bromide and nitrite by indirect redox titration using phenyl iodosoacetate

Bromide has been determined by its oxidation with an excess of phenyl iodosoacetate in the presence of acetanilide to give bromine which subsequently reacts with acetanilide to form 4-bromoacetanilide. The residual amount of phenyl iodosoacetate was evaluated iodometrically. Thus, for every mol of bromide one mol of phenyl iodosoacetate was consumed. For the determination of bromine in organic compounds, the test substance was decomposed by fusion with alkali peroxide to liberate bromide which was then evaluated by the phenyl iodosoacetate method. For its determination, nitrite has been reacted with an excess of isoniazid in acid medium to form isonicotinyl azide (which does not react with phenyl iodosoacetate) and the residual amount of isoniazid was titrated with phenyl iodosoacetate in the presence of acidified bromide and methyl red indicator (when isoniazid and phenyl iodosoacetate react in a 12 molar ratio). Each mol of nitrite is equivalent to 2 mol of phenyl iodosoacetate.