Intereferences from uranium fission in neutron-activation analysis in an Argonaut-type Low Flux Reactor

The interferences by uranium fission on the determination by neutron activation analysis of Zr, Mo, Ru, La, Ce, Nd and Sm are investigated for the Argonaut-type Low Flux Reactor at ECN, Petten, The Netherlands. In addition, the spectral interference of the determination of Sm by²³⁹Np is considered. The experimental values for fission yields are found to be in good agreement with calculated values based on recent cross-section compilations.     

The fluorination of Butane over cobalt trifluoride

The fluorination of butane over cobalt trifluoride has given a complex mixture of partially fluorinated compounds: 51 of these have been identified, comprising over 99% of the products. Most were polyfluorobutanes but 1-2% were polyfluoro-2-methylpropanes. The reaction has no synthetic utility. There was some selectivity in the fluorination: secondary C-H was converted into C-F more easily then primary, and the ease of replacement of a particular H was reduced by geminal and vicinal fluorines. A computer of the fluorination was only partially successful, perhaps because the fluorination proceeded in part by simple F for H replacement and in part via alkenes: the model only allowed for the former.     

Regio- and diastereoselective synthesis of 2-alkylidenetetrahydrofurans by domino SN/SN' and SN/SN reactions of 1,3-dicarbonyl dianions

The domino C,O-cyclodialkylation reaction of dilithiated 1,3-dicarbonyl compounds with 1,4-dibromo-2-butene resulted in regio- and diastereoselective formation of 2-alkylidene-5-vinyltetrahydrofurans. The cyclization of 1,3-dicarbonyl dianions with 1-bromo-2-chloroethane regio- and diastereoselectively afforded 2-alkylidenetetrahydrofurans under thermodynamic reaction control.     

Determination of trace elements in soil and plants in the Orontes basin of Syria by using instrumental neutron activation analysis

Instrumental neutron activation analysis (INAA) have been used for the determination of some major, minor and trace elements (As, Cr, Co, Ni, Zn, Sb, Sc, Ce, Ti, Fe, Mn and V) in various plant leaves together with their soil. The accuracy of the measurements have been evaluated by analyzing a number of plant and soil reference materials, precision have been estimated by triplicate analysis of the sample as well as that of the reference material. The obtained accurate and reliable data of some trace elements on microgram level for plants and soil will serve as baseline values and will be helpful to monitor the changes in the trace element content of soil and plant leaves.The authors are thankful to Prof. I. Othman General Director of AECS for his encouragement and his support.     

Acid-base equilibria of some pyridinol derivatives in binary water/organic solvent systems

Summary pK _a values of 2-hydroxy 3-pyridinol (HHP), 2-mercapto 3-pyridinol (MHP), and 2-carboxy-3-pyridinol (CHP) were determined by potentiometric titration in water/organic solvent mixtures containing 20 mole% of organic solvent at 25±0.1 °C and 0.1M ionic strength (KNO₃) applying an empiricalpH correction for mixed aqueous solvents. The influence of the organic solvents on the dissociation constants and tautomeric equilibria of the pyridinol derivatives is discussed. The effect of the molecular structure of the compounds onpK _a is also explained. Titrations of a mixture of two weak diprotic acids (HHP andCHP) in a water/dimethylsulphoxide medium containing 20 mole% organic solvent at constant ionic strength were evaluated using theGran method.

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Säure-Basen-Gleichgewichte einiger Pyridinolderivate in binären Systemen aus Wasser und organischen Lösungsmitteln

Zusammenfassung DiepK _a-Werte von 2-Hydroxy-3-pyridinol (HHP), 2-Mercapto-3-pyriodinol (MHP) und 2-Carboxy-3-pyridinol (CHP) wurden durch potentiometrische Titration in wäßrigen Systemen mit 20 mol% organischem Lösungsmittelanteil bei 25±0.1 °C und einer lonenstärke von 0.1M KNO₃ unter Anwendung einer empirischenpH-Korrektur für Lösungsmittelgemische bestimmt. Der Einfluß der organischen Lösungsmittel auf die Dissoziationskonstanten und die tautomeren Gleichgewichte der untersuchten Verbindungen und der Einfluß der molekularen Strukturen auf diepK _a-Werte werden diskutiert. Die Titration eines Gemisches von zwei schwachen zweibasigen Säuren (HHP undCHP) in Wasser/Dimethylsulfoxid bei konstanter Ionenstärke wurde mit Hilfe derGranschen Methode ausgewertet.

     

Biphenylenes-xxxi: Condensation of benzocyclobutene-1,2-dione with aliphatic and heterocyclic 1,2-diamines and the synthesis of cis-2-cyano-3-(2'-cyanovinyl)-1,4-diaz

As possible routes to 1,4-diazabiphenylene and its 2,3-disubstituted derivatives we have studied the condensation of benzocyclobutene-1,2-dione (BBD) with various 1,2-diamines. Instead of giving the 1,4-diazabiphenylene ring system, BBD reacted with ethylenediamine, diaminomaleonitrile, 4,5-diaminopyrimidine, 2-aminopyridine, also 2,3- and 3,4-diaminopyridine to give, respectively, 2-o-carboxyphenylimidazolidinium acetate 4, 3,4-dicyano-2,5-dihydro[2,5]benzodiazocine-1,6-dione 10, 4-amino-5a,9b-dihydro-5-,9b-dihydroxybenzo [3',4']cyclobuta[1',2'-4,5]imidazo[1,2-c]pyrimidine 14, 5a,9b-dihydro-5a,9b-dihydroxybenzo[3',4']cyclobuta[1',2'-4,5] imidazo[1,2-a]pyridine 17, the 4-amino derivative 16 of the latter, and the zwitter ion 18 of 4-amino-3(2-carboxy-benzylideneamino) However, BBD reacted with 4,5-diaminobenzotriazole to give the expected 1,2,3,6,11-penta-aza-1-H-indeno [4,5-b]biphenylene 20, which, on amination followed by oxidation, gave a very low yield of cis-2-cyano-3-(2'-cyanovinyl)-1,4-diazabiphenylene 3. In model experiments, 7,8-diphenylfurazano [3,4-f]quinox-aline 28 was reduced to 2,3-diamino-5,6-diphenyl quinoxaline 29, which on oxidation, gave a mixture of cis- and trans-2-cyano-3-(2'-cyanovinyl)5,6-diphenylpyrazine, 30 and 31. The pentacyclic compounds, 1,3,6,II-tetra-aza-2-oxa-2H-indeno [4,5-b]biphenylene 23 and 1,3,5,10-tetra-aza-1-H-indeno[5,6-b] biphenylene 25, were formed from BBD and the appropriate 1,2-diamines but the 5-membered heterocyclic rings could not be cleaved by reduction and hydrolysis respectively) to give tetracyclic diamines which might have undergone oxidation to give derivatives of 1,4-diazabiphenylene. Compounds 14, 16, 20, 23, 25 and 28 are derivatives of new heterocyclic systems.     

TheK-shell conversion coefficient of the 135.5 keVM4 transition in193mPt decay

TheK conversion coefficient of the 135.5 keVM4 transition in^193m pt has been determined by the XPG method. The result is _K =135.2±10.5 and the value exhibits a deviation 3.4% below the theoretical prediction of Hager and Seltzer. Similar deviations have been systematically observed in precision values ofE3 andM4 conversion coefficients reported in the literature.     

Polyvinyl chloride-based membranes for flow injection analysis of quinine in beverages

Potentiometric response characteristics were evaluated for quinine selective sensors based on a lipophilic ion-exchanger potassium tetrakis[3,5-bis(trifluoromethylphenyl)]borate (PTFB) immobilized together with plasticizing solvents in polyvinyl chloride membranes. The use of dioctyl phthalate (DOP), 2-nitrophenyl phenyl ether (NPPE), and bis(2-ethylhexyl)adipate (BEHA) plasticizers produced good quality quinine sensors that were sensitive and fast responding, and exhibited near Nernstian responses when used as batch-sensors. These membranes were further tested in a wall-jet flow-through potentiometric flow injection analysis (FIA) detector. Quinine sensors containing BEHA were the most suitable membrane, with no noticeable differences in sensitivity even after 5 h of continuous exposure to solutions. Interference by foreign species such as alkali, alkaline earth metal ions, sugars, and sodium benzoate was minimal in either the batch-mode (log selectivity coefficients <-2.60) or as FIA detector. When the FIA method was used, recoveries averaged 99.70% from mineral water samples spiked with 16.22 and 162.20 ppm quinine. Results for determination of quinine in other drinks such as carbonated (64.88 and 71.37 ppm) and bitter lemon drinks (55.15 ppm) agreed with those of the manufacturer's claimed values of <68, <81, and 51 ppm, respectively. With a sample throughput of 50 samples/h under optimized flow conditions, the method can be routinely used to monitor quinine in such samples.     

Sensitive detection and semiquantitative determination of mercury(II) and lead(II) in aqueous media using polyurethane foam immobilized 1,5-di-(2-fluorophenyl)-3-mercaptoformazan

1,5-Di-(2-fluorophenyl)-3-mercaptoformazan (F(2)H(2)Dz) immobilized and plasticized with tri-n-butylphosphate (TBP) polyurethane foam (PUF) were found suitable for the detection of mercury(II) and lead(II) in extremely dilute aqueous solutions. In batch mode of extraction with immobilized F(2)H(2)Dz-foam as low as 0.05 and 0.15 mug ml(-1) of mercury(II) and lead(II), respectively were detected and the colored chelates were found more stable over 72 h. Lower concentrations of these metal ions (相似文献   

XRF induced by PIXE: Comparison with PIXE

Two different modes of sample excitation have been used for elemental analysis of thin standard reference materials and of chemical standards with known composition. PIXE /2.5 MeV protons/ and XRF induced by PIXE, will be called XRF-PIXE /2.5 MeV protons on Mo primary target/. The same samples were alternatively exposed to protons and X-ray beams. The sensitivities under standard running conditions are determined for both an XRF-PIXE and a PIXE analysis system. It is shown that the sensitivity of the PIXE spectrometer depends strongly on the sample matrix, whereas the XRF-PIXE sensitivity is rather constant with respect to different kinds of samples. In addition, the advantages of one mode of excitation on the other are discussed. It is shown that XRF-PIXE can be a useful complement to PIXE analysis.