Titanocene(III) chloride mediated radical-induced one-pot synthesis of α-methylene-γ-butyrolactones

A simple and efficient methodology has been developed for the one-pot preparation of α-methylene-γ-butyrolactones by free-radical induced Barbier-type reaction of methyl 2-(bromomethyl)acrylate and aldehydes followed by in situ lactonization. The radical initiator titanocene(III) chloride (Cp₂TiCl) was easily generated in situ from commercially available Cp₂TiCl₂ and activated zinc dust in THF. Ketones remained unaffected under the reaction conditions.     

Titanocene(III) chloride mediated radical-induced addition to Baylis-Hillman adducts: synthesis of (E)- and (Z)-trisubstituted alkenes and alpha-methylene/arylidene delta-lactones

Baylis-Hillman adduct underwent smooth radical-induced condensation with activated bromo compounds and epoxides using titanocene(III) chloride (Cp2TiCl) as the radical generator. The reactions of activated bromo compounds with 3-acetoxy-2-methylene alkanoates provided (E)-alkenes exclusively, whereas similar reactions with 3-acetoxy-2-methylenealkanenitriles led to (Z)-alkenes as the major product. The reactions of epoxides with Baylis-Hillman adduct furnished alpha-methylene/arylidene-delta-lactones in good yield via addition followed by in situ lactonization.     

Nuclear and chemical data for life sciences

Use of reactor produced radionuclides is popular in life sciences. However, cyclotron production of proton rich radionuclides are being more focused in recent times. These radionuclides have already gained attention in various fields, including life sciences, provided they are obtained in pure form. This article is a representative brief of our contributions in generating nuclear data for the production of proton rich radionuclides of terbium, astatine, technetium, ruthenium, cadmium, niobium, zirconium, rhenium, etc., which may have application in clinical, biological, agriculture studies or in basic research. The chemical data required to separate the product isotopes from the corresponding target matrix have been presented along with a few propositions of radiopharmaceuticals. It also emphasizes on the development of simple empirical technique, based on the nuclear reaction model analysis, to generate reliable nuclear data for the estimation of yield and angular distribution of emitted neutrons and light charged particles from light as well as heavy ion induced reactions on thick stopping targets. These data bear utmost important in radiation dosimetry.     

Separation of no-carrier-added <Superscript>149</Superscript>Gd from <Superscript>12</Superscript>C activated natural praseodymium matrix

¹⁴⁹Gd was produced from the ¹²C induced reaction on natural praseodymium target. No-carrier-added (nca) ¹⁴⁹Gd was separated from the bulk target matrix by liquid–liquid extraction (LLX) using cation exchanger di-(2-ethylhexyl)phosphoric acid (HDEHP) dissolved in cyclohexane. High separation factor of 2,450 was achieved at the optimal experimental condition when 1% HDEHP and 0.1 M HCl were used as organic and aqueous phases respectively. The result was also compared with the previous reports.     

Use of an automated capillary DNA sequencer to investigate the interaction of cisplatin with telomeric DNA sequences

The determination of the sequence selectivity of DNA-damaging agents is very important in elucidating the mechanism of action of anti-tumour drugs. The development of automated capillary DNA sequencers with fluorescent labelling has enabled a more precise method for DNA sequence specificity analysis. In this work we utilized the ABI 3730 capillary sequencer with laser-induced fluorescence to examine the sequence selectivity of cisplatin with purified DNA sequences. The use of this automated machine enabled a higher degree of precision of both position and intensity of cisplatin-DNA adducts than previously possible with manual and automated slab gel procedures. A problem with artefact bands was overcome by ethanol precipitation. It was found that cisplatin strongly formed adducts with telomeric DNA sequences.     

Separation of no-carrier-added <Superscript>90</Superscript>Nb from proton induced natural zirconium target

Amongst various radionuclides of molybdenum, ⁹⁰Mo and ⁹⁹Mo have suitable β energy for clinical uses. In this paper we report separation of ⁹⁹Mo from ⁹⁹Mo-^99mTc equilibrium mixture. The liquid–liquid extraction technique has been employed using trioctylamine (TOA) diluted in cyclohexane as organic phase and HCl as aqueous phase. At 10⁻⁵ M HCl and 0.5 M TOA concentration ^99mTc quantitatively transferred to the organic phase leaving ⁹⁹Mo in the aqueous phase. The developed separation method is efficient and provides very high separation factor.