On line ion exchange separation of short-lived Zr, Hf, Mo, Ta and W isotopes as homologs of transactinide elements

The short-lived isotopes of W and their descendants have been separated from nuclear reaction products arising in the bombardment of samarium target with²⁴Mg ions at the U-400 cyclotron of JINR-Dubna. Chemical separations were performed using previously elaborated fast and continuous ion exchange. In similar way products of²³⁵U fission, obtained at the microtron MT-25 during irradiation of²³⁵U target with photoneutrons were separated.     

Oliveridepsidones A–D,antioxidant depsidones from Garcinia oliveri

Four new prenylated depsidones, oliveridepsidones A–D, were isolated from the bark of Garcinia oliveri collected in Vietnam. Their structures were elucidated using mainly NMR techniques (¹H and ¹³C NMR, HMQC, HMBC and NOE experiments). Copyright © 2012 John Wiley & Sons, Ltd.     

Enhanced stabilization and deposition of Pt nanocrystals on carbon by dumbbell-like polyethyleniminated poly(oxypropylene)diamine

Pseudo-dendritic polyethyleniminated poly(oxypropylene)diamine (D400(EI)(20)) was used as a stabilizer and promoter to prepare Pt nanoparticles in aqueous solution, which was then deposited on carbon surface followed by calcination. After being deposited on carbon surface, no Pt(0) could be detected in the solution phase. In all steps, the increasing molar ratio of the amino groups of D400(EI)(20) to H(2)PtCl(6) ([N]/[Pt]) drastically reduced the size and the polydispersity and kept a constant low value after [N]/[Pt] = 20. Under a [N]/[Pt] ratio of 20, the particle sizes obtained from transmission electron microscopy (TEM) were very small in solution (2.7-2.4 nm) and remained the same after being deposited on carbon surface (2.7-2.4 nm), and were only slightly increased to 3.6-3.0 nm after calcination. The stabilizing ability of D400(EI)(20) to Pt on carbon surface before and after calcination can be interpreted by the existence of binding energy between Pt and amine nitrogen. The X-ray diffraction (XRD) pattern together with the TEM image reveals that the obtained Pt nanoparticles exist in single-crystal form. The results of photoelectron spectroscopy (XPS) evidence that the metallic Pt(0) rather than the oxidized Pt is the predominant species in the Pt/C catalysts. The electrochemical active surface (EAS) area of the Pt/C catalyst is only slightly higher than that of the E-TEK Pt/C catalyst, but the utilization factor (93.4%) is remarkably higher than the latter (62.8%). The increasing time of thermal treatment increases the crystallinity of Pt(0) on carbon, accompanied by the increasing EAS areas, which corresponds to its enhanced electrocatalytic performance to methanol oxidation.     

Uncovering the Stoichiometry of Pyrococcus furiosus RNase P,a Multi‐Subunit Catalytic Ribonucleoprotein Complex,by Surface‐Induced Dissociation and Ion Mobility Mass Spectrometry

We demonstrate that surface‐induced dissociation (SID) coupled with ion mobility mass spectrometry (IM‐MS) is a powerful tool for determining the stoichiometry of a multi‐subunit ribonucleoprotein (RNP) complex assembled in a solution containing Mg²⁺. We investigated Pyrococcus furiosus (Pfu) RNase P, an archaeal RNP that catalyzes tRNA 5′ maturation. Previous step‐wise, Mg²⁺‐dependent reconstitutions of Pfu RNase P with its catalytic RNA subunit and two interacting protein cofactor pairs (RPP21⋅RPP29 and POP5⋅RPP30) revealed functional RNP intermediates en route to the RNase P enzyme, but provided no information on subunit stoichiometry. Our native MS studies with the proteins showed RPP21⋅RPP29 and (POP5⋅RPP30)₂ complexes, but indicated a 1:1 composition for all subunits when either one or both protein complexes bind the cognate RNA. These results highlight the utility of SID and IM‐MS in resolving conformational heterogeneity and yielding insights on RNP assembly.     

Chemical isolation of element 106 from aqueous solutions according to model experiments with short-lived tungsten isotopes

The short-lived isotopes of W and their descendants have been isolated from the products of the bombardment of¹⁴⁴Sm with²⁴Mg by a fast continuous ion-exchange method, using HF solution media. The feasibility of this method for isolation of element 106 is discussed.     

Labelless impedance immunosensor based on polypyrrole-pyrolecarboxylic acid copolymer for hCG detection

In this work, a sensitive label-free impedimetric hCG-immunosensor was constructed by using a commercial screen-printing carbon ink electrode (namely disposable electrochemical printed chip) as the basis. The carbon ink electrode of DEP chip is modified first by deposition of polypyrrole-pyrole-2-carboxylic acid copolymer and thence hCG antibody immobilization via the COOH groups of pyrrole-2-carboxylic acid, which can serve as a linker for covalent biomolecular immobilization. The experimental results exposed that the designed immunosensor is more sensitive than other previously reported immunosensors, in the case of detection limit and linear range for antigen detection. With optimal fabrication parameters, the detection limit for α-hCG was 2.3 pg/mL in 10 mM phosphate buffer saline (PBS) solution containing 1% bovine serum albumine (BSA). Moreover, the use of inexpensive DEP chip as a basis for these immunosensors will allow for simple instrumentation, disposable and portable at low cost. This work also demonstrates a new approach to develop a sensitive and label-free impedimetric immunosensor based on screen-printed electrode for applications in clinical diagnosis.     

Anion-selective exhaustive injection-sweeping microemulsion electrokinetic chromatography

In this study, anion-selective exhaustive injection-sweeping (ASEI-sweeping) technique, which is a selective on-line sample concentration technique, was first proposed in microemulsion electrokinetic chromatography (MEEKC) for analyses of eight acidic phenolic compounds. In contrast to a capillary that is typically filled with nonmicellar background solution in conventional ASEI-sweeping MEKC method, in the proposed ASEI-sweeping MEEKC method, a capillary is filled with a low pH microemulsion solution (pH 2.0), and then with a short acid plug (pH 2.0, 1.9 cm) before field-amplified sample injection. This proposed design has two functions. First, the microemulsion solution that is present at the front of capillary column is able to avoid phase separation of microemulsion solution during MEEKC separation. Second, the presence of the short acid plug would effectively limit the partition behavior of acid analytes with the oil droplets in the microemulsion during field-amplified sample injection; otherwise, the stacking effect of acid analytes would be markedly reduced. This optimal ASEI-sweeping MEEKC method afforded about 96,000-fold to 238,000-fold increases in detection sensitivity in terms of peak areas without any separation efficiency loss when compared to normal MEEKC separation. Furthermore, trace levels (about 3 ng/g) of gallic acid and catechin in foods were also detected successfully by the proposed ASEI-sweeping MEEKC technique.     

Uncovering the Stoichiometry of Pyrococcus furiosus RNase P,a Multi‐Subunit Catalytic Ribonucleoprotein Complex,by Surface‐Induced Dissociation and Ion Mobility Mass Spectrometry

We demonstrate that surface‐induced dissociation (SID) coupled with ion mobility mass spectrometry (IM‐MS) is a powerful tool for determining the stoichiometry of a multi‐subunit ribonucleoprotein (RNP) complex assembled in a solution containing Mg²⁺. We investigated Pyrococcus furiosus (Pfu) RNase P, an archaeal RNP that catalyzes tRNA 5′ maturation. Previous step‐wise, Mg²⁺‐dependent reconstitutions of Pfu RNase P with its catalytic RNA subunit and two interacting protein cofactor pairs (RPP21?RPP29 and POP5?RPP30) revealed functional RNP intermediates en route to the RNase P enzyme, but provided no information on subunit stoichiometry. Our native MS studies with the proteins showed RPP21?RPP29 and (POP5?RPP30)₂ complexes, but indicated a 1:1 composition for all subunits when either one or both protein complexes bind the cognate RNA. These results highlight the utility of SID and IM‐MS in resolving conformational heterogeneity and yielding insights on RNP assembly.     

Fast and continuous chemical isolation of short-lived isotopes of Hf,Ta and W as homologs of elements 104, 105 and 106

Some short-lived isotopes of Hf, Ta and W, synthesized at the U-400 cyclotron of JINR-Dubna, have been isolated using a previously elaborated fast continuous method of chemical isolation of element 104 from nuclear reaction products. The products were transported by a NaCl aerosol jet, from the irradiated targets to a separation device in which Hf, Ta and W were isolated by using three coupled ion-exchange columns.     

Fast and continuous isolation of short-lived mercury isotopes from diluted sulphuric acid solution

The seconds living mercury isotopes have been isolated from nuclear reaction products arising in the bombardment of ¹⁴⁷Sm target with ⁴⁰Ar ions at the U-400 cyclotron of JINR-Dubna.