Chemical separation and inductively coupled plasma–atomic emission spectrometric determination of seventeen trace metals in thorium oxide matrix using a novel extractant – Cyanex-923

Comprehensive studies have been carried out on the extraction behaviour of thorium matrix vis-a-vis 17 trace metallic elements using a novel extractant viz. Cyanex-923. The near total extraction of thorium and quantitative separation of these metals has been established using inductively coupled argon plasma–atomic emission spectrometry (ICP–AES). The recovery of few representative elements has been confirmed by radio-active tracer studies. The studies carried out here have enabled determination of μg/l amounts of all analyte elements with a precision of better than 1% RSD with prior chemical separation from as low as 1 g thorium sample in just five chemical extractions.     

A mass spectrometric study of the pyrolysis of gibberellic acid

The behaviour of gibberellic acid (GA₃) under electron impact and chemical ionization conditions has been examined. The tendency of GA₃ to undergo pyrolysis by the loss of the elements of water and carbon dioxide has been identified. Two methods of sample introduction can be used to minimize the occurrence of this pyrolysis. Accurate mass measurement allows the composition of the pyrolysis product to be determined and metastable techniques confirm the structure of this product to be epi-allogibberic acid rather than its isomer allogibberic acid. This result corrects a misconception in the literature and illustrates the advantage of metastable methods compared with accurate mass measurements, for the determination of small structural differences within a molecule.     

Alpha decay studies of neutron-deficient radium isotopes

Neutron-deficient isotopes of radium have been produced in the reactions³⁵Cl+¹⁷⁵Lu,⁴⁰Ar+^170,171Yb, and³⁶Ar+^170,171Yb and separated in-flight with a gas-filled recoil separator. The activities have been identified on the basis of correlated alpha decay chains. The alpha particle energy E_α and the half-life T_1/2 of an isomeric state of the new isotope,^203m Ra, have been determined to be (7615±20) keV and (33 _?10 ⁺²² ) ms, respectively. An assignment of another decay with E_α = (7577±20) keV and T_1/2=(1.1 _?0.5 ^+5.0 ) ms to^203g Ra is made on the basis of one observed three-decay chain. Tentative evidence for the production of the new isotope²⁰²Ra is also given. The values E_α = (7860±60) keV and T_1/2=(0.7 _?0.3 ^+3.3 ) ms were measured. Improved decay data have been obtained for²⁰⁴Ra. The results are E_α = (7484±10) keV and T_1/2=(59 _?9 ⁺¹² ) ms. Earlier findings concerning the decay of two states in²⁰⁵Ra and an isomer in²⁰⁷Ra have been confirmed. Approximate values for cross sections have been determined for²⁰²Ra, produced using the³⁶Ar+¹⁷⁰Yb reaction and for²⁰³Ra,²⁰⁴Ra, and²⁰⁵Ra using the³⁵Cl+¹⁷⁵Lu reaction. The results are 2 nb (²⁰²Ra), 4 nb (²⁰³Ra), 40 nb (²⁰⁴Ra), and 800 nb (²⁰⁵Ra).     

Acyl vs sulfonyl transfer in N-acyl beta-sultams and 3-oxo-beta-sultams

[reaction: see text] N-Acylsulfonamides usually react with nucleophiles by acyl transfer and C-N bond fission. However, the hydrolysis of N-acyl beta-sultams is a sulfonyl transfer reaction that occurs with S-N fission and opening of the four-membered ring. Similar to other beta-sultams, the N-acyl derivatives are at least 10(6)-fold more reactive than N-acyl sulfonamides. 3-Oxo-beta-sultams are both beta-lactams and beta-sultams but also hydrolyze with preferential S-N bond fission.     

Synthesis of the methanesulfonates of α-(4-chlorophenyl)-α-[1-(2-chlorophenyl)emenyl]-1H-1,2,4-triazole-1-ethanol and α-[1-(2-chlorophenyl)ethenyl]-α-(2,4-difluorophenyl)-1H-1,2,4-triazole-1-ethanol,alpha styryl carbinol antifungal agents

The methanesulfonates of (α-(4-chlorophenyl)-α-[1-(2-chlorophenyl)ethenyl]-1H-1,2,4-triazole-1-ethanol and α-[1-(2-chlorophenyl)ethenyl]-α-(2,4-difluorophenyl)-1H-1,2,4-triazole-1-ethanol ( 1a, b ) are orally effective α-styryl carbinol derivatives developed for the treatment and prevention of systemic fungal infections. Practical new processes amenable for the large-scale production of these compounds are described. Of note is the selection of dichlorostyrene as a convenient precursor of the styryl portion, modification of a sensitive Grignard addition into a realistic preparative reaction and the use of 1,2,4-triazole simultaneously as a base transfer agent and nucleophile.     

Variable low-mass filtering using an electrodynamic ion funnel

An adjustable low-mass filter has been developed for an electrospray ionization (ESI) source to block ions associated with unwanted background species from entering the mass spectrometer. The low-mass filter is made by using an adjustable potential energy barrier from the conductance-limiting plate of an electrodynamic ion funnel, which prohibits species with higher ion mobilities from exiting the ESI source. We show that this arrangement provides a linear voltage adjustment for low-mass filtering from m/z 0 to 500. Mass filtering above m/z 500 is also performed; however, higher-mass species are attenuated. The mass filter was tested with a liquid chromatography/mass spectrometry (LC/MS) analysis of a bovine serum albumin (BSA) tryptic digest and resulted in the ability to block low-mass, background species, which accounted for 40-70% of the total ion current immediately behind the ESI source during peak elution and detection.