Silver selective electrodes based on thioether functionalized calix[4]arenes as ionophores

Silver selective electrodes based on thioether functionalized calix[4]arenes 1 and 2 as ionophores were investigated. For both ionophores the selectivity coefficients (log kAg,M) were lower than −2.2 for Hg(II) and lower than −4.6 for other cations tested. The best results were obtained with membranes containing dithioether functionalized calix[4]arene (ionophore 2), potassium tetrakis(4-chlorophenyl) borate (KTpCIPB) and bis(1-butylpentyl)adipate (BBPA) as a plasticizer. The Ag(I)-response functions exhibited almost theoretical Nernstian slopes in the activity range 10−6–10−1M of silver ions.\ud \u

Chemically modified field effect transistors: the effect of ion-pair association on the membrane potentials

A theoretical model has been developed which relates physically accessible parameters to the formation of a membrane potential. The description is an extension of a theoretical description presented previously by our group, now including divalent cations and ion-pair association. Simulations of the overall membrane potential reveal several factors that may lead to non-Nernstian response curves. For monovalent and divalent cations a reduction in the slope of the response curve (sub-Nernstian response) should virtually always be expected when ion-pair association takes place in the membrane. Ion-pair association of divalent cations and sample anions can lead to a super-Nernstian response. A diffusion potential generally reduces the Nernstian slope of the response curve. In addition, several experimental results are described which illustrate and confirm our theoretical model

Covalent binding studies on the 14C-labeled antitumour compound 2,5-bis(1-aziridinyl)-1,4-benzoquinone. Involvement of semiquinone radical in binding to DNA, and binding to proteins and bacterial macromolecules in situ

2,5-Bis(1-aziridinyl)-1,4-benzoquinone (BABQ) is a compound from which several antitumour drugs are derived, such as Trenimone, Carboquone and Diaziquone (AZQ). The mechanism of DNA binding of BABQ was studied using 14C-labeled BABQ and is in agreement with reduction of the quinone moiety and protonation of the aziridine ring, followed by ring opening and alkylation. The one-electron reduced (semiquinone) form of BABQ alkylates DNA more efficiently than two-electron reduced or non reduced BABQ. Covalent binding to polynucleotides did not unambiguously reveal preference for binding to specific DNA bases. Attempts to elucidate further the molecular structure of DNA adducts by isolation of modified nucleosides from enzymatic digests of reacted DNA failed because of instability of the DNA adducts. The mechanism of covalent binding to protein (bovine serum albumin, BSA) appeared to be completely different from that of covalent binding to DNA. Binding of BABQ to BSA was not enhanced by reduction of the compound and was pH dependent in a way that is opposite to that of DNA alkylation. Glutathione inhibits binding of BABQ to BSA and forms adducts with BABQ in a similar pH dependence as the protein binding. The aziridine group therefore does not seem to be involved in the alkylation of BSA. Incubation of intact E. coli cells, which endogenously reduce BABQ, resulted in binding to both DNA and RNA, but also appreciable protein binding was observed

First Report on the Complexation of Actinides and Lanthanides Using 2,2′,2′′-(((1,4,7-Triazonane-1,4,7-triyl)tris(2-oxoethane-2,1-diyl)) tris(oxy)) tris(N, N-dioctylacetamide):Synthesis, Extraction, Luminescence, EXAFS, and DFT Studies

A novel tripodal diglycolamide ligand containing a triazamacrocycle center (2,2′,2′′-(((1,4,7-triazonane-1,4,7-triyl)tris(2-oxoethane-2,1-diyl)) tris(oxy)) tris(N,N-dioctylacetamide), abbreviated as T9C3ODGA) was synthesized and characterized by conventional techniques. The ligand resulted in efficient extraction of actinide/lanthanide ions yielding the trend: Eu3+ &gt; Pu4+ &gt; Am3+ &gt; NpO2 2+ &gt; UO2 2+ &gt; Sr2+ &gt; Cs+. Similar to most of the other diglycolamide (DGA) ligands, Eu3+ was preferentially extracted as compared to Am3+ the separation factor (DEu/DAm) value at 3 M HNO3 was ca. 4.2. In contrast, separation from UO2 2+ ion was less effective as compared to that of other tripodal DGA ligands studied earlier. Solvent extraction studies indicated extraction of species of the ML2 (where L is T9C3ODGA) stoichiometry. The formation of an inclusion complex with no inner-sphere water molecule was confirmed from luminescence spectral studies. DFT computations predicted the presence of an inner-sphere nitrate ion in the most preferred complex, which was also supplemented by EXAFS and luminescence studies. The selectivity of T9C3ODGA could be explained on the basis of its more favorable interactions with Eu3+ as compared to those with Am3+ both in the gas and the solution phases.</p