Tracer packet: A new conception for the production of tracers

The concept of tracer packet, which can be defined as a group of carrier-free radioactive isotopes of few elements, which have been produced together with an objective to study some particular physical, chemical or biological systems has been introduced in this paper. The tracer packet can be produced with low projectile energy (5-7 MeV/u) contrary to the multitracer technique. A thick cobalt foil has been irradiated consecutively with ¹⁶O, ⁷Li and ¹²C beams to produce the tracer packet containing carrier free radiotracers of Mn, Cu, Zn, Ga, Ge, As and Se which after removal of bulk cobalt can be used for further studies of essential micro nutrient elements.     

Electrochemical Behavior of Epinephrine at a Penicillamine Self-Assembled Gold Electrode,and its Analytical Application

The fabrication and electrochemical characteristics of a penicillamine (PCA) self-assembled monolayer modified gold electrode were investigated. The self-assembled electrode shows obvious electrocatalytic activity for the oxidation of epinephrine (EP). In phosphate buffer (pH 7.73), a sensitive oxidation peak was observed at 0.190V with the PCA modified Au electrode. The peak current is proportional to the concentration of EP in the range of 2.0×10^–56.0×10^–4molL^–1 and 5.0×10^–6 2.0×10^–4molL^–1 for cyclic voltammetry (CV) and differential pulse voltammetry (DPV) with the detection limits of 1.8×10^–7 and 1.3×10^–7molL^–1, respectively. The possible reaction mechanism is also discussed. The PCA self-assembled monolayer modified gold electrode is highly stable and can be applied to the determination of EP in practical injection samples. Application is simple, rapid and produces accurate results.     

Application of tracer packet technique to the study of the bio-sorption of heavy and toxic metal radionuclides by algae

The bio-sorption of heavy and toxic radionuclides by three genera of algae from different taxonomic groups was studied employing the recently developed 'Tracer Packet' technique. The tracer packet of heavy and toxic metals' contained ¹⁹⁷Hg, ^{198,199,200,201}Tl, ^199,200,201Pb, ²⁰⁴Bi and ^204,205Po radionuclides in carrier-free state and was produced by irradiating a gold metal foil with medium energy ⁷Li and ¹²C beams successively in a 12 MV Pelletron. Three genera, Spirulina from Cyanophyceae, Oedogonium from Chlorophyceae and Catenella from Rhodophyceae were cultured in laboratory condition and were used in the experiment. The radionuclide accumulation varied according to different genera at different pH levels. At basic pH Spirulina showed a maximum radionuclide accumulation in comparison to other genera.     

Flame Atomic Absorption Spectrometric Determination of Gold and Palladium Using Microcolumn On-line Preconcentration and Separation

A microcolumn on-line preconcentration and separation system was developed for the flame atomic absorption spectrometric (FAAS) determination of trace levels of gold and palladium. The analytes were selectively adsorbed onto the microcolumn packed with 2-mercaptothiazole immobilized silica gel (MBTSG) in an acidity range of 0.1 to 6.0M HCl at a sampling flow rate of 4.0mLmin^–1. The analytes adsorbed could be desorbed by a thiourea solution with a flow rate of 2.0mLmin^–1. Most of the common coexisting metal ions at a concentration of 25.0mgmL^–1 and anions at a concentration of 50.0mgmL^–1 did not interfere with the preconcentration and determination of Au and Pd. The limits of detection (LOD), defined as three times the standard deviation of the blank (3), of Au and Pd are 10ngmL^–1 and 26ngmL^–1, respectively, with a preconcentration time of 60s. The relative standard deviation (RSD) is about 2.0% for 0.20µgmL^–1 Au and 0.30µgmL^–1 Pd. With a sample loading time of 30min, 6.7ngmL^–1 Au and 10ngmL^–1 Pd can be preconcentrated quantitatively. A geological sample, an anode slime and a secondary nickel alloy were successfully determined with the proposed method, and the results obtained showed good agreement with the certified values.Received December 23, 2002; accepted May 14, 2003 Published online August 8, 2003     

Determination of Heavy Metal Ions in Chinese Herbal Medicine by Microwave Digestion and RP-HPLC with UV-Vis Detection

A new method for the simultaneous determination of heavy metal ions in Chinese herbal medicine by microwave digestion and reversed-phase high-performance liquid chromatography (RP-HPLC) has been developed. The Chinese herbal medicine samples were digested by microwave digestion. Lead, cadmium, mercury, nickel, copper, zinc, and tin ions in the digested samples were pre-column derivatized with tetra-(4-chlorophenyl)-porphyrin (T₄-CPP) to form the colored chelates which were then enriched by solid phase extraction with C₁₈ cartridge and eluted from the cartridge with tetrahydrofuran (THF). The chelates were separated on a Waters Xterra RP₁₈ column by gradient elution with methanol (containing 0.05molL^–1 pyrrolidine-acetic acid buffer salt, pH=10.0) and THF (containing 0.05molL^–1 pyrrolidine-acetic acid buffer salt, pH=10.0) as mobile phase at a flow rate of 0.5mLmin^–1 and detected with a photodiode array detector in the range of 350–600nm. In the original samples the detection limits of lead, cadmium, mercury, nickel, copper, zinc and tin are 4ngL^–1, 3ngL^–1, 6ngL^–1, 5ngL^–1, 2ngL^–1, 6ngL^–1, and 4ngL^–1, respectively. This method was applied to the determination of lead, cadmium, mercury, nickel, copper, zinc and tin in Chinese herbal medicine samples with good results.     

Energy Transfer Electrogenerated Chemiluminescence for the Determination of Sulfite

A simple and novel electrogenerated chemiluminescence (ECL) method for the determination of sulfite has been developed based on the energy transfer ECL process. It was found that a weak ECL signal of sulfite was electrochemically generated on a platinum electrode in neutral aqueous solution. The signal was strongly enhanced by rhodamine B as an energy receptor and further enhanced by the neutral surfactant Tween 80. In 0.10M phosphate buffer solution (pH=7.5) containing 2.0×10^–6gmL^–1 rhodamine B and 0.4% (v/v) Tween 80, the ECL response to the concentration of sulfite at a potential of 0.82V was linear over a range of 1.0×10^–7gmL^–1 to 8.0×10^–6gmL^–1, and the detection limit was 5×10^–8gmL^–1. The relative standard deviation (n=11, 1.0×10^–6gmL^–1) was 3.8%. The proposed method has been successfully applied to the determination of sulfite in pharmaceutical injections and white sugar samples.     

Reaction of methylmagnesium iodide with steroid keto oxides

Summary The reaction of the 3-acetate of the 20-ketal of 16,17-oxido-⁵-pregnenol-3-one-20 with methylmagnesium iodide and subsequent hydrolysis of the reaction product yielded 16-methyl-⁵-pregnenediol-3 –17-one –20. 18-Nor-17-methyl-17-iso-^5.11-pregnadienediol-3,16-one-20 was formed as a by-product.     

The effect of outer sphere cations on the thermal stability of nitritocuprates(II)

Thermal analyses by Derivatograph were made for salts of the general formula M ₂ ^I M^II[Cu(NO₂)₆] where M^I=K⁺, Rb⁺ or Cs⁺; and M^II=Ca²⁺, Sr²⁺, Ba²⁺ or Pb²⁺. From the results and the chemical and diffractometric analysis of sinters of chosen salts, the mechanism of thermal decomposition was established. Some conclusions concerning the effects of outer sphere cations on the thermal stabilities of these salts are also drawn.

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Zusammenfassung Es wurden thermische Analysen mit einem Derivatographen für die Salze der allgemeinen Formel M₂ ^IM^II [Cu(NO₂)₆] durchgeführt [M^I=K⁺, Rb⁺, Cs⁺; M^II=Ca²⁺, Sr²⁺, Ba²⁺, Pb²⁺]. Aus den Ergebnissen dieser sowie der chemischen und diffraktometrischen Analysen der Sinterprodukte der jeweiligen Salze wurde der Mechanismus ihrer chemischen Zersetzung ermittelt. Einige Folgerungen bezüglich der Wirkung von Kationen der äusseren Sphäre auf die thermische Stabilität konnten ebenfalls gemacht werden.

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Résumé Le mécanisme de la décomposition thermique des sels de formule générale M₂ ^IM^II [Cu(NO₂)₆] où M^I=K⁺, Rb⁺, Cs⁺ et M^II=Ca²⁺, Sr²⁺, Ba²⁺, Pb²⁺ a été établi à partir des données thermiques obtenues à l'aide d'un Derivatograph, ainsi que par des analyses thermiques et diffractométriques sur les produits frittés. L'effet des cations de la couche externe sur la stabilité thermique de ces sels est discuté.

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M ₂ ^I M^II[Cu(NO₂)₆], M^I=K⁺, Rb⁺, Cs⁺; M^II=Ca²⁺, Sr²⁺, Ba²⁺, b²⁺. , , . , .

     

Studies of the reactions of Br(2P3/2) and Br(2P1/2) with SiH4

Photobromination of SiH₄ under uv-irradiation at various wavelengths has been studied. Rate constants for the elementary reactions Br(²P_3/2)+SiH₄HBr+SiH₃ (k=3.2×10^–11 exp(–21.8±2.5)/RT, cm³/s) and Br^* (²P_1/2)+SiH₄HBr+SiH₃ (k^*=(3±1)×10^–13 cm³/s) have been determined in the temperature range from 300 to 415 K.

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- . Br(²P_3/2)+SiH₄HBr+SiH₃, k=3,2×10^–11 exp (–21,8±2,5)/RT ³/ Br^*(²P_1/2)+SiH₄HBr+SiH₃, k^*=(3±1)×10^{–13 3}/ 300–415 K.

     

Mechanism of the liquid-phase oxidation of diethyl sulfide catalyzed by heteropoly acids

It has been established that in the oxidation of diethyl sulfide by¹⁸O₂ in CH₃C¹⁶O₂H–H₂ ¹⁶O solution at 369 K catalyzed by heteropoly acids, sulfoxide and sulfone with 44–54%¹⁸O enrichment are formed. The process is accompanied by isotope exchange of molecular oxygen.

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, ¹⁸O₂ CH₃C¹⁶O₂H–H₂ ¹⁶O 369 ¹⁸O 44–54%, .

     

Kinetic parameters of the thermal decompositions of nitritonickelates(II)

Kinetic parameters of thermal decomposition of compounds of general formulaM ₂ ^I M ^II[Ni(NO₂)₆], whereM ^I= K⁺, Rb⁺ or Cs⁺ andM ^II= Ca²⁺, Sr²⁺ or Ba²⁺, were investigated on the basis of the respective thermal curves. Calculations of the reaction order and activation energy carried out by the Coats-Redfern method and by Doyle's method (modified by Zsakó) gave similar results, The reaction order is 2 for all the compounds investigated. In the group of potassium salts the activation energy increases fromM ^II=Ca²⁺ toM ^II=Ba²⁺. In the groups of rubidium and caesium salts, the lowest activation energy is observed whenM ^II=Sr²⁺. Such behaviour of the nitritonickelates is explained in terms of structures and the principle of maximum density.

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Zusammenfassung Die kinetischen Parameter der thermischen Zersetzung von Verbindungen der allgemeinen FormelM ₂ ^I M ^II [Ni(NO₂)₆] (M ^I= K⁺, Rb⁺ oder Cs⁺ und M^II = =Ca²⁺, Sr²⁺ oder Ba²⁺) wurden auf Grund der entsprechenden thermischen Kurven untersucht. Die an Hand der Coats-Redfern Methode und der durch Zsakó modifizierten Doyleschen Methode durchgeführten Berechnungen der Reaktionsordnung und der Aktivierungsenergie ergaben ähnliche Resultate. Die Reaktionsordnung ist 2 für sämtliche untersuchten Verbindungen. In der Gruppe der Kaliumsalze steigt die Aktivierungsenergie vonM ^II=Ca²⁺ in RichtungM ^II=Ba²⁺ an. In der Gruppe der Rubidium- und Caesiumsalze wird die niedrigste Aktivierungsenergie beiM ^II=Sr²⁺ beobachtet. Dieses Verhalten der Nitritonickelate wird durch die Strukturen und das Prinzip der maximalen Dichte erklärt.

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₁ ^{2 II}[Ni(NO₂)₆], ^I= ⁺, Rb⁺Cs⁺,a ^II= ²⁺,8r²⁺²⁺. , - ( ), . 2. ^{+ 2+}. ^II=S²⁺. .

     

Kinetics of the acid-catalyzed equilibration of methylenecyclohexane and 1-methylcyclohexene

The rates of isomerization of methylenecyclohexane and 1-methylcyclohexene have been measured in acetic acid, usingp-toluenesulfonic acid as a catalyst, at temperatures of 20.30, 24.07, 30.00, 32.30, 39.85 and 40.21 °C. The overall forward and reverse rate constants can be expressed as k ₁ ⁰ =4.41×10⁸ exp (–17.6×10³/RT) s^–1 and k ₂ ⁰ =0.64×10⁸ exp ((–19.5×10³/RT) s^–1. From the difference in the activation energies the heat of isomerization is estimated as 7.9 kJ mol^–1.

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1- , - 20,30, 24,07, 30,00, 32,30, 39,85 40,21 °C. k ₁ ⁰ =4.41×10⁸ exp (–17.6×10³/RT) ^–1 k ₂ ⁰ =0.64×10⁸ exp (–19.5×10³/RT) ^–1. 7,9 /.

     

Determination of Attogram Quantities of Silver via Quenching of the Solid Substrate Room-Temperature Phosphorescence of Rhodamine B Based on the Catalysis of its Oxidation by Potassium Persulfate

A new method of SS-RTP for the determination of trace silver has been established. This method is based on the fact that Ag⁺, when activated by ,-bipyridyl (bipy) in a media of HAc–NaAc (pH=4.9), can catalyze the reaction of Rhodamine B (RhoB) oxidized by K₂S₂O₈, thus causing the Solid Substrate Room-Temperature Phosphorescence (SS-RTP) of RhoB to be quenched. The activating efficiency of bipy is 6.7 times higher than that of o-phenanthroline (phen). The reduction of the phosphorescence intensity (I_p) of RhoB is directly proportional to the concentration of Ag⁺ ions in the range of 1.6016.0agspot^–1 (0.40µLspot^–1). The regression equation of the working curve can be expressed as I_p=18.78+5.100m_Ag+ (agspot^–1) (r=0.9994, n=6), the detection limit is 0.28agspot^–1. This rapid, accurate and sensitive method has been successfully applied to the determination of trace silver in tea and human hair samples, and the results agree well with the Atomic Absorption Spectroscopy (AAS) method. The mechanism of the catalyzing reaction is also discussed.     

Competitive uptake of Cs+, Ba2+, and Zn2+ ions from binary aqueous mixtures by zeolite-13X

The preferential exchange uptake of the cations Cs⁺, Ba²⁺ and Zn²⁺ from pure solutions by zeolite-13X follows the order Q [Cs⁺]>Q [Ba²⁺]>Q [Zn²⁺], while in case of binary mixtures the order is Q [Ba²⁺(Zn²⁺)]>Q [Ba²⁺(Cs⁺)]>Q [Cs⁺(Zn²⁺)]>Q [Cs⁺(Ba²⁺)]>Q [Zn²⁺(Cs⁺)]>Q [Zn²⁺(Ba²⁺)]. Ba²⁺ uptake from mixtures shows the least suppression effect.

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Cs⁺, Ba⁺² Zn⁺² -13 Q[Cs⁺]>Q[Ba⁺²]>Q[Zn⁺²] Q[Ba⁺²(mix Zn⁺²)]>Q[Ba⁺²(mix Cs⁺)]>Q[Cs⁺(mix Zn⁺²)]>Q[Cs⁺(mix Ba⁺²)]>Q[Zn⁺²(mix Cs⁺)]>Q[Zn⁺²(mix Ba⁺²)]. Ba⁺² .

     

α,β-Butenolides

,-Dibromo--('-carbethoxyacetony)-^,-butenolide (I) reacts with amines in diethyl ether solution to give -bromo-amino--('-carbethoxyacetony)-^,-butenolides. Compounds n are converted to -bromo-amino--('-carbethoxyacetony)-^,-butenolides on reaction with amines. The corresponding arylhydrazones (VI and VII) are obtained by the reaction of I and II with p-nitro- and 2,4-dinitrophenylhydrazines. Compound I reacts with phenylhydrazine to give furopyridazine VIII.See [1] for communication IV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 867–871, July, 1972.     

The Electrochemical Behavior of p-Aminophenol at a ω-Mercaptopropionic Acid Self-Assembled Gold Electrode

A -mercaptopropionic acid (MPA) self-assembled monolayer modified electrode (MPA/SAM/Au) on a gold electrode has been fabricated. The characterization of the MPA/SAM/Au was investigated using attenuated total reflection-fourier transform infrared (ATR-FTIR) and A.C. impedance. The electrochemical behaviors of p-aminophenol (p-AP) were studied at the MPA/SAM/Au by cyclic voltammetry and semi-derivative voltammetry (SDV) in BR buffer solution. The modified electrode shows excellent electrocatalytic activity for the redox of p-AP and accelerates the electron transfer rate. The diffusion coefficient (D) is 4.55×10^–6cm²s^–1. The oxidative peak current increases linearly with the concentration of p-AP in the range of 4.0×10^–88×10^–6molL^–1 and 1.0×10^–52×10^–4molL^–1 by square wave voltammetry response, respectively. The detection limit (three times the signal blank/slope) is up to 1.2×10^–8molL^–1. The modified electrode is able to eliminate the interference of p-benzenediol, o-benzenediol and o-AP at a 40-, 90- or 70-fold concentration of p-AP, and it has been satisfactorily used for the determination of the real sample.     

Liquid-liquid extraction of α-activation products of iron with HDEHP

The carrier-free radiotracers,^52,56Mn,^55,56,58Co and^56,57Ni were produced simultaneously by accelerated -particle activation of iron. They were subsequently studied through LLX using the liquid cation exchanger, HDEHP, as an extractant. A considerable enrichment of individual carrier free radionuclides of manganese, cobalt and nickel was achieved. Production and verification of purity of the carrier-free radiotracers at different stages of their extraction were carried out by -ray spectroscopic studies.     

Heat capacity of indium from 300 to 1000 K

The heat capacity of high-purity indium has been determined by adiabatic-shield calorimetry in the range 300 to 1000 K. Values of thermodynamic functions have been calculated andC _p (1000 K), [H° (1000 K)–H° (298.15 K)], and [S° (1000 K)–S° (298.15 K)] are (27.11±0.15) J K^–1 mole^–1, (22873±70) J mole^–1, and (41.567 ±0.125) J K^–1 mole^–1, respectively. The enthalpy of fusion is (3283±7) J mole^–1 and the melting temperature (429.77±0.01) K. The premelting heat capacity is compatible with the presence of a mole fractionx 1·10^–6 of a liquid-soluble/solidinsoluble impurity in the sample.

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Zusammenfassung Die Wärmekapazität von hochreinem Indium wurde im Bereich von 300 bis 1000 K durch adiabatische Schildkalorimetrie bestimmt. Die Berechnungen der thermodynamischen Funktionen:C _p (1000 K), [H° (1000 K)–H° (298.15 K)] und [S° (1000 K–S° (298.15 K)] ergab 27.11±0.15 J K^–1 Mol^–1, (22 875±70) J Mol^–1, bzw. (41.567±0.125) J K^–1 Mol^–1. Die Schmelzenthalpie beträgt (3283±7) J Mol^–1 und die Schmelztemperatur (429.77±0.01) K. Die Vorschmelz-Wärmekapazität ist mit der Gegenwart einer Molfraktionx1×10^–6 einer flüssig-löslich/fest-unlöslichen Verunreinigung in der Probe vereinbar.

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Résumé La chaleur spécifique de l'indium de haute pureté a été déterminée entre 300 et 1000 K par calorimétrie adiabatique. Les valeurs des fonctions thermodynamiques suivantes ont été calculées:C _p (1000 K)=(27.11±0.15) J K^–1mol^–1, [H° (1000 K)–H° (298.15 K)]= (22 875±70) J mol^–1 et [S° (1000 K)–S° (298.15 K)]=(41.567±0.125) J K^–1 mol^–1. L'enthalpie de fusion est (3283±7) J mol^–1 et la température de fusion (429.77±0.01) K. La chaleur spécifique de pré-fusion est compatible avec la présence d'une fraction molairex1×10^–6 d'une impureté dans l'échantillon, soluble dans le liquide, insoluble dans le solide.

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C - 300 1000 . : _p(1000 ), [ (1000 ) — H (298,15 )] [S (1000 ) — S (298.15 )], : 27.11±0.15 . ^–1. ^–1, 2 2875±70 . ^–1 41.567±0.125 . ^{– 1–1}. 3283±7 .^–1, – 429.77±0,01 . - / 1.10^–6.

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The assistance of Bjørn Lyng Nielsen with the experimental work is recognized with thanks.     

Ab initio investigation of the electron structure in bis-Cu+ acetylene and vinylidene complexes

[Cu(-C₂H₂)₂]⁺, [Cu(-CCH₂)₂]⁺ and [Cu(-C₂H₂) (-CCH₂]⁺ complexes have been studied by the ab initio double-zeta basis set method. It has been established that all calculated compounds are stable to decomposition into two C₂H₂ molecules and Cu⁺ cation and into one C₂H₂ molecules and the respective monocomplex. Calculation results suggest the possibility of intramolecular acetylene-vinylidene rearrangement in the coordination sphere of Cu⁺.

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ab initio : [Cu(-C₂H₂)₂]⁺, [Cu(-CCH₂)₂]⁺, [Cu(-C₂H₂) (-CCH₂)]⁺. C₂H₂ Cu⁺ C₂H₂ . - Cu⁺.