Condensed cyclic and bridged-ring systems. VII. Acid-catalysed cyclisation of methyl substituted benzylcyclohexanols. Factors influencing the nature of cyclisation products

The gross structures of the cyclised products from the acid-catalysed cyclisations of 2-benzyl-1, 3-dimethylcyclohexanol (6) and 1-benzyl-3, 5-dimethylcyclohexanol (11) revealing the influence of the structure of the benzylcyclohexanol derivative, and of the cyclisation reagent, have been evaluated. Polyphosphoric acid and aluminium chloride catalysed cyclisations of (6) result in the formation of predominantly 1, 4a-dimethyl-1, 2, 3, 4, 4a, 9a-hexahydrofluorene (7) and 4, 9-dimethyl-7, 8-benzobicyclo [3.3.1] non-7-ene (9) respectively. Under the same conditions, (11) produced cyclised products consisting mostly the benzobicyclo [3.3.1] non-7-ene derivative (12), characterised through 1,3-dimethyl-7,8-benzobicyclo [3.3.1] non-6-oxo-7-ene (14) by oxidation with chromium trioxide. Phosphorus pentoxide induced cyclisation of (6), followed by oxidation gave a mixture of the bridged-ring ketone (10) and the 9-oxohydrofluorene (8) in a ratio ofca. 3 : 2, whereas 2-benzyl-5-methylcyclohexanol (19) resulted in mostly 2-methyl-7,8-benzobicyclo [3.3.1] non-6-oxo-7-ene (19).     

CONFORMATIONAL CHANGES OF BOVINE LENS CRYSTALLINS IN A PHOTODYNAMIC SYSTEM

Abstract— Conformational changes of bovine lens crystallins in a photodynamic system generating singlet oxygen, have been investigated. The formation of intersubunit crosslinks was observed in all three classes (α-, β and γ-) of crystallins by irradiation in the presence of the photosensitizer methylene blue. Near-UV circular dichroism (CD) spectra of the crystallins were significantly altered by irradiation under these conditions, indicating changes in tertiary structure but the far-UV CD remained unchanged suggesting that the secondary structure ((β-sheet conformation) remains unchanged. Significant changes in the absorption and fluorescence spectra were also observed. Measurement of total sulfhydryl content showed a decrease of 27%, 50% and 37% for α-, β- and γ-crystallins respectively, after irradiation. Fluorescence lifetime measurements of N-iodoacetyl-N'-(5-sulfo-l-naphthyl)ethylenediamine-labeled crystallins showed a significant decrease of the lifetime of the major decay components of the label bound to sulfhydryl groups of α- and γ-crystallins, but showed no change in the microenvironment of the sulfhydryl groups of β-crystallin. The results are consistent with the microenvironments of the tryptophan and sulfhydryl groups predicted from sequence studies.     

Synthesis, characterisation and evaluation of polydithiocarbamate resin supported on macroreticular styrene-divinylbenzene copolymer for the removal of trace and heavy metal ions

A new chelating resin was synthesised by the modification of styrene-divinylbenzene (2%) copolymer and incorporation of dithiocarbamate groups. The polydithiocarbamate resin was characterised by elemental analysis, thermal studies and IR studies. The analytical characteristics of the sorbent were established and optimum sorption conditions for Cu, Ni, Pb, Fe, As and Mn determined. The total sorption capacity of the resin was 37 mg g⁻¹ for Ni(II), 35 mg g⁻¹ for Cu(II), 29 mg g⁻¹ for Fe(III) and 23 mg g⁻¹ for Pb(II). The optimum pH for the removal of metal ions was 3-5 for Ni(II), 5 for Cu(II), 4 for Fe(III) and 4-5 for Pb(II). High sorption capacity was observed when compared with other conventional chelating polymers. The sorption kinetics was fairly rapid, as apparent from the loading half time t_1/2 values, indicating a better accessibility of the chelating sites.     

Spectrophotometric determination of uranium(VI) using a synergic mixture of ethyl acetoacetate and pyridine

A method is proposed for the extractive spectrophotometric determination of uranium(VI) using the synergic combination of ethyl acetoacetate (EAA) and pyridine (Py) as extractants. The optimum conditions have been evaluated by varying pH and ethyl acetoacetate and pyridine concentration. The nature of the extracted species has been determined by 1g D-1g C plots and the extracted species was found to be UO₂(EAA)₂.Py. The method has been applied for the separation and determination of uranium(VI) from synthetic mixtures.     

The effect of pressure on the dissociation constant of hydrofluoric acid and the association constant of the NaF ion pair at 25°C

The effect of pressure on the dissociation constant of hydrofluoric acid was determined by using the indicator technique at 25°C at an ionic strength of 0.1m over a pressure range of 1 to 2000 atm. A value of 3.14 for pK _a ^* at I =0 was obtained by extrapolation to zero ionic strength at 1 atm. The pressure dependence yielded a partial molar volume change of –9.6 cm³-mol^–1 and a compressibility change of — 35×10^–3 cm³-mol^–1 –atm^–1 for the dissociation. The dependence of ionic strength on the association constant K _A ^* of NaF was studied at 25°C and 1 atm. Extrapolation to I=0 yielded a pK _A ^* of –0.78. The pressure dependence of K _A ^* gave a change of volume of 3.26 cm³-mol^–1 and a change in compressibility of 6×10^–3 cm³-mol^–1-atm^–1 for the formation of the ion pair.     

Extraction and separation of scandium salicylate with triphenylphosphine oxide

Scandium can be extracted from 5.0 × 10^–2 mol/l sodium salicylate solution, adjusted to pH 4.0–5.0 with 0.5% triphenylphosphine oxide dissolved in toluene as an extractant. After stripping from the organic phase with 0.5 mol/l HCl it can be subsequently determined spectrophotometrically with Alizarin Red S. The method permits a separation of Sc(III) from Ti(IV), V(V), Cr(VI), Fe(III), Y(III), La(III), Ce(III), Nd(III) and Sm(III) in synthetic mixtures. The method is fast, simple and selective. Received: 6 May 1996 / Revised: 21 July 1996 / Accepted: 25 July 1996     

Performance of immobilized Saccharomyces cerevisiae in the removal of long lived radionuclides from aqueous nitrate solutions

The efficiency of tailor made immobilized Saccharomyces cerevisiae(biomatrix) for the sorption of radionuclides ²³³U, ²³⁹Pu, ²⁴¹Am, ¹³⁷Ce, ¹⁴⁴Cs, ^103,106Ru and ⁹⁰Sr from aqueous nitrate solutions at different pH was studied. Effect of ionic strength, anionic components, initial metal concentration and particle size of the biomatrix on the sorption of metal ions were investigated. At pH in the range of 1 to 2 more than 95% sorption of U, Pu, Am and Ce could be accomplished, while that of Ru was 65%. Sorption of Cs and Sr were negligible under similar conditions. The metal ion-biomatrix system for Pu, Am and Ce reached equilibrium within 60 minutes. In the case of U, equilibrium attained in 100 minutes. The presence of anionic components, Cl^-, C₂O₄ ^2-, CH₃COO^-, NO₃ ^- and SO₄ ^2- (up to 0.5 mol^.dm^-3 of their individual concentration) in the aqueous solutions has no effect on the sorption of Pu by the biomatrix. Sorption of U, Pu, Am were observed in the presence of several cationic impurities such as Al, Be, Cd, Cr, Fe, Mn, Pb, Ce, Dy, Eu, Gd and Sm. Metal sorbed on the biomatrix could be leached out using 5 mol^.dm^-3 nitric acid. The I.R spectra of U bearing biomatrix suggest chemical interaction of uranyl ion with the biomatrix.     

Extraction study of uranium(VI) and thorium(IV) salicylates with triphenylarsine oxide

Triphenylarsine oxide is proposed as an extractant for the solvent extraction of uranium and thorium salicylates. The optimum extraction conditions are established by studying the various parameters such as pH, sodium salicylate concentration, triphenylarsine oxide concentration, diluents and shaking time. The probable extracted species as ascertained by logD-logC plots are UO₂(Hsal)₂·2TPAsO and Th(Hsal)₄·2TPAsO. The method is simple, fast, precise and permits the determination of uranium and thorium in monazite sand samples.     

THE EFFECTS OF NEAR-UV RADIATION ON HUMAN LENS β-CRYSTALLINS: PROTEIN STRUCTURAL CHANGES and THE PRODUCTION OF O2_ and H2O2

beta-Crystallins (beta 1-, beta 2- and beta 3-crystallin) comprise nearly half the protein of the human lens. The effect of near-UV radiation, which is one of the possible risk factors in cataract formation, on the beta-crystallins is investigated in this study. Protein intersubunit crosslinking, change in charge of the protein subunits to more acidic species and changes in protein tertiary structure (conformation) by 300 nm irradiation are reported. The fluorescence yield of protein tryptophan residues decreases by 300 nm irradiation. There is an increase in nontryptophan fluorescence (lambda cx 340 nm, lambda cm 400-600 nm), and in protein absorption at 340 nm, due to the formation of tryptophan photooxidation products. Both tryptophan and its oxidation products can be photoexcited by 300 nm irradiation and the latter are known to be good photosensitizers. The results provide evidence for the generation of H2O2 in the irradiated human beta-crystallin solutions by the Type I photosensitizing action of the chromophores absorbing at 300 nm. The H2O2 is generated via the intermediate production of O2 anion; the latter spontaneously dismutates to H2O2, presumably via O2- protein interactions. The amount of H2O2 generated per absorbed photon is compared for various solutions of beta 1-, beta 2- and beta 3-crystallins from human lenses of different age.     

Condensed cyclic and bridged-ring systems : part 12: A novel synthetic route to 4-p-methoxyphenyl-bicyclo[ 2.2.2 ]octan-2-ones and some bicyclo [ 3.2.1 ] octane derivatives by acid-catalyzed intramolecula

The efficacy of a new acid-catalyzed intramolecular C-alkylation has been demonstrated by the synthesis of 1-methyl-4-$\text{p}$-methoxyphenylbicyclo [2.2.2] octan-2-one ($\text{5}$) and 4-$\text{p}$-methoxyphenylbicyclo [2.2.2] octan-2-one ($\text{6}$) from easily accessible starting materials. The carbinol $\text{20}$, derived from $\text{5}$, undergoes facile rearrangement leading to 1-$\text{p}$-methoxyphenyl-4-methyl bicyclo [3.2.1] oct-3-ene ($\text{22}$), which has been transformed to $\text{endo}$-1-$\text{p}$-methoxyphenyl-4-methylbicyclo [3.2.1] octan-3-one ($\text{25}$).