Influence of chelating agents in eluent on the separation factor of lithium isotopes

The influence of chelating agents on the separation factor, , of lithium isotopes separation was studied by ion exchange elution chromatography. Eluents contained the chelating agent having different number of coordination sites. The chelating agents used in eluent were Na-glycine (Na–Gly), 2Na-iminodiacetic acid (2Na-IDA), 3Na-nitrilotriacetic acid (3Na-NTA), and 4Na-ethylenediaminetetraacetic acid (4Na-EDTA). The ion exchanger was Dowex 50W-X8, sulfonic acid type, sodium form. As a result,⁶Li was enriched in resin phase, and⁷Li was in solution phase. The separation factor, , was gradually increased with increasing number of coordination site (=1.0022–1.0038) at the same distribution coefficient and with increasing distribution coefficients (=1.0017–1.0026) at the same concentration of chelating agents.     

Simultaneous production of89Zr and90,91m92mNb in α-particle activated yttrium and their subsequent separation by TOA

A study on the separation of lithium isotopes was carried out with an ion exchange resin having 1,7,13-trioxa-4,10,16-triazacyclooctadecane (N₃O₃) as an anchor group. The lighter isotope,⁶Li concentrated in the resin phase, while the heavier isotope,⁷Li is enriched in the fluid phase. Upon column chromatography [0.6 cm (I. D.)×20 cm (height)] using 1.0M ammonium chloride solution as an eluent, single separation factor, , 1.068 (⁶Li/⁷Li)_resin/(⁶Li/⁷Li)_solution was obtained by theGlueckauf method from the elution curve and isotope ratios.     

Lithium isotope separation on a monobenzo-15-crown-5 resin

A study on the separation of Li isotopes was carried out with a resin having monobenzo-15-crown-5 as a functional group, synthesized by substitution reaction of chloromethylated styrene-DVB copolymer with 4-aminobenzo-15-crown-5. Adsorption properties of the resin for Li⁺ were invesgated with batch method in various solvents and counter anions. Upon column chromatography [0.9 cm (I. D.)×25 cm (height)] using 5% (v/v) H₂O in acetonitrile as an eluent, single separation factor, , 1.053 (±0.005), (⁶Li/⁷Li)resin/ (⁶Li/⁷Li) solution was obtained by the GLUECKAUF method from the elution curve and isotope ratios.     

LLX separation of carrier-free,94,95,97,103Ru,93,94,95,96,99mTc and95,96Nb produced in alpha-particle activated molybdenum by TOA

A radiochemical charged particle activation procedure for the simultaneous production of carrier-free radioisotopes of more than one element in a single target and their subsequent separation through LLX has been demonstrated. The carrier free isotopes,^95,96Nb,^{93,94,95,96,99m}Tc and^94,95,97,103Ru formed through Mo(,pxn), Mo(,pxn) and Mo(,xn) nuclear reactions with 40 MeV -particle as detected by nondestructive -ray spectroscopy, have been effectively separated through LLX using TOA as an anionic extractant. Separation of the bulk matrix of molybdenum from the carrier free products has been monitored radiometrically using isotopic^93,99mMo formed through the Mo(,xn) reaction, as radioindicators for the target element. Purity of the separated carrier free radionuclide has been verified by -ray spectrometry.     

Perturbation calculation of oscillator strengths for the isoelectronic series of light atoms

Transition probabilities and oscillator strengths are calculated for the configurations 1s² 2sⁿ¹ and 1s² 2s^n1-1 2pⁿ²⁺¹, which are, respectively, of the form P=a/Z (1+/Z+) andf=/Z (1+/Z+). Numerical values are given fora, ,, and.     

Negativer linearer thermischer Ausdehnungskoeffizient von verstrecktem Polyäthylen

Zusammenfassung Der lineare thermische Ausdehnungskoeffizient von linearem Polyäthylen hoher Dichte wurde im Temperaturbereich –20 °C bis + 40°C bestimmt. Bei isotropen Proben besteht eine lineare Beziehung zwischen Dichte bzw. Kristallisationsgrad _v und. Die gemessenen Koeffizienten liegen fürT ₀ = 20 °C im Bereich = 110 ... 130 · 10^–6 K^–1.Kalt verstreckte Proben mit Verstreckungsgraden = 8 ... 15 haben beiT ₀ = 20 °C in Verstreckrichtung den Koeffizienten _l = –24 · 10^–6 K^–1. Der negative Zahlenwert von _tl ist unabhängig von und weiteren Herstellungsparametern. Seine Ursache ist einerseits die Orientierung derc-Achsen der Kristallite in Verstreckrichtung mit _c = –12 · 10^–6 K^–1 und andererseits der negative Koeffizient _am * –50 · 10^–6 K^–1 der verspannten amorphen Phase, der auf dem gummielastischen Verhalten der tie-molecules beruht.Beim Tempern oberhalb von +40 °C schrumpfen die Proben irreversibel, wobei _| ansteigt und nach dem Aufschmelzen der Proben wieder den Wert des isotropen Materials annimmt. Nach dem Tempern wenig unterhalb der Schmelztemperatur der Kristallite wurden überhöhte Koeffizienten _| gemessen, die eine Rotation der Kristallite um dieb-Achsen erkennen lassen.

---

Summary The linear thermal coefficient of expansion,, of high density linear polyethylene has been determined in the temperature range of –20 ° ... + 40 °C. For isotropic samples a linear relationship between density or crystallinity _v and is valid. Measured values of forT ₀ = 20 °C amount to = 110 ... 130 · 10^–6 K^–1.Cold drawn samples of draw ratios = 8 ... 15 yield _| = –24 · 10^–6 K^–1 atT ₀ = 20 °C parallel to the draw axis. The negative value of _| does not depend on draw ratio or other parameters of sample processing. It is caused byc-axis orientation of the crystallites in draw direction with _c = –12 · 10^–6 K^–1 and by a negative coefficient _am * = –50 · 10^–6 K^–1 of the stressed amorphous phase, which is due to rubber elastic behaviour of the tie molecules.When annealed above 40 °C the samples shrink irreversibly and _| is augmented. After melting the samples the value of isotropic material is restored. Annealing the samples little below the melting temperature of the crystallites leads to superelevated values all which reflect| rotation of the crystallites around theb-axis.

     

Comparative studies of static dipole polarizabilities of ionic crystals on the basis of different self-consistent potentials

The static dipole polarizabilities, ^D , have been studied for the ions O^2–, F^–, Na⁺, Mg²⁺, Cl^–, K⁺ and Ca²⁺ in the crystals NaF, KF, NaCl, KC1, MgO and CaO. The starting zero-order wave functions have been generated using various exchange- and exchange-correlation potentials in order to study the effect of these potentials on ^D . The direct contribution to the dipole polarizability, _o ^D , has been determined by the uncoupled Hartree-Fock method. Self-consistency effects have been included by the geometric approximation. The crystal potential is incorporated using the Watson sphere model. Good agreement between theoretical and experimental results are found for those self-consistent potentials which exclude self-interaction.     

Separation of Cs and Sr using polyoxonium compounds

Extraction separation and concentration of Cs and Sr from aqueous solutions, containing macroconcentrations of competitive ions (Li⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, Al³⁺, Fe³⁺) by the nitrobenzene solutions of bis-1,2-dicarbollylcobaltate in the presence of linear and cyclic polyoxonium compounds (POC) has been investigated. It has been found, that the addition of DB18C6 increases the distribution ratio of cesium (D_cs) but the addition of other crowns and PEG decreases D_Cs value and selectivity of D_Sr and the selectivity of Sr/Ca separation. Separation factors of Sr/Ca increase from (Sr/Ca)2 (found in the absence of POD) to (Sr/Ca)50 (for DB18C6), (Sr/Ca)100 (for 18C6 and DCH18C6) and (Sr/Ca)1000 for 15C5.     

Glycosylation of triterpenoids of the dammarane series I. 20(S),24(R)-epoxydammarane-3α-12β,25-triol 25-O-β-D-glucopyranoside

The glycosylation of 3,12-diacetoxy-20(S),24(R)-epoxydammaran-25-ol with -acetobromoglucose under the conditions of Helferich's modification and with D-glucose tert-butyl orthoacetate under the conditions of the orthoester method gives a high yield (60–64%) of the hexacetate of the -D-glucoside at the tertiary hydroxy group of 20(S),24(R)-epoxydammarane-3,12,25-triol (III) with mp 207–209°C (ethanol), [] _D ²⁰ -20.9 (c 1.0, CHCl₃). Saponification with 10% KOH in methanol gives the free 20(S),24(R)-epoxydammarane-3,12,25-triol 25-O--D-glucoside (V) (yield 90%) with mp 275–279°C (methanol), [] _D ²⁰ +11.4° (c, 1.0, C₅H₅). The results of IR and¹H and¹³C NMR spectroscopy and of elementary analysis are given.Pacific Ocean Institute of Bioorganic Chemistry of the Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 205–208, March–April, 1980.     

Separation of carrier free65Zn and66,67,68Ga, the alpha-particle activation products of copper with HDEHP

A radiochemical charged particle activation procedure has been developed for the production and separation of the carrier free radioisotopes,⁶⁵Zn and^66,67,68Ga. The carrier free radioisotopes produced by the irradiation of a pure copper foil with 50 MeV -particle beam through the nuclear reactions, (, pxn), (,pxn) and (,xn), have been quantitatively separated from the activated copper matrix from an aqueous hydrochloric acid and an alkaline solution using the liquid cation exchanger HDEHP, as an extractant. Detection of different radionuclides in the activated copper target and verification of their purity at different stages of their LLX separation have been performed by -ray spectrometric studies.     

Determination of radioactive nuclides of uranium and thorium series and estimation of α-flux in LSI constituent materials

Gamma-rays of nuclides of uranium and thorium series in silicone resin and ceramics were measured with a Ge(Li) detector. The state of radioactive equilibrium was determined by comparing the concentrations of uranium and thorium with the radioactive concentrations of²¹⁴Pb and²¹²Pb. The radioactive equilibrium was attained in silicone resin but not in ceramics. The -flux was calculated from the concentrations of uranium and thorium and their daughter nuclides. The calculated values of -flux agreed with that of -flux measured.     

Structure and molecular dynamics of solid-state inclusion complexes of cyclodextrin and permethylated cyclodextrin with benzaldehyde studied by high-resolution CP/MAS13C NMR

The structure and molecular dynamics of the benzaldehyde inclusion-complexes with -and-cyclodextrins and permethylated -cyclodextrin in the solid state have been studied by high-resolution cross-polarization/magic angle sample-spinning¹³C NMR spectroscopy. It is shown that the guest benzaldehyde molecule undergoes motion in the host cyclodextrin cavity and the rate of motion depend on the cavity size. In the -cyclodextrin complex, compared to -and permethylated -cyclodextrin complexes, the benzaldehyde motion is severely restricted, but under high-vacuum benzaldehyde is released more easily from the cavity.     

Triterpene glycosides of alfalfa. III. Medicoside I

On the basis of chemical transformations and with the aid of physicochemical results, the structure of glycoside I isolated from the roots of the plantMedicago sativa has been established as hederagin 3-O-[O--L-arabinopyranosyl-(1 2)--D-glucopyranosyl-(1 2)--L-arabinopyranoside] 28-O--D-glucopyranoside. Compound (I), C₅₂H₈₄O₂₂, mp 210–212°C, [] _D ²¹ +38.4° (c 1.48; methanol). Acid hydrolysis of (I) led to hederogenin (II) — C₃₀H₄₈O₄, mp 326–330°C, [] _D ²³ +84.2° (c 0.19; pyridine. The Hakomorimethylation of glycoside (I) yielded the permethylate (IV) — C₆₅H₁₁O₂₂ [] _D ²³ +41.6° (c 1.79; methanol). The GLC analysis of the products of the methanolysis of compound (IV) showed the presence of 3,4,6-tri-O-methyl-D-glucopyranose, 2,3,4,6-tetra-O-methyl-D-glucopyranose, 3,4-di-O-methyl-L-O-arabinopyranose, and 2,3,4-tri-o-methyl-L-arabinopyranose. The alkaline hydrolysis of glycoside I gave compound (III) with mp 230–233°C, [] _D ²¹ +35.2° (c 0.21; methanol), which was identified as medicoside C. Details of the PMR spectrum are given for compound (IV) and of the IR spectrum for compound (I).Institute of the Chemistry of Plant Substances of the Uzbek Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 607–610, September–October, 1986.     

An external standard method for quantification of human cytomegalovirus by PCR

An external standard method for PCR quantification of HCMV was reported. [-³²P]dATP was used as a tracer.³²P-labelled specific amplification product was separated by agarose gel electrophoresis. A gel piece containing the specific product band was excised and counted in a plastic scintillation counter. Distribution of [-³²P]dATP in the electrophoretic gel plate and effect of separation between the³²P-labelled specific product and free [-³²P]dATP were observed. A standard curve for quantification of HCMV by PCR was established and detective results of quality control templets were presented. The external standard method and the electrophoresis separation effect were appraised. The results showed that the method could be used for relative quantification of HCMV.     

Separation of Enantiomers of Non-Protein Amino Acids by High-Performance Liquid Chromatography on a Chiral Ligand-Exchange Column

The HPLC separation of enantiomers of underivatized non-protein amino acids was investigated by using a column packed with octadecylsilanized silica coated with N,S-dioctyl-D-penicillamine as a chiral ligand-exchange phase (Sumichiral OA-5000). Good enantiomeric separations were achieved with a variety of -amino acids carrying aliphatic or aromatic side chains, cyclic imino acids, and -amino acids, together with -methyl--amino acids, by optimizing the amount (0–20%, v/v) of 2-propanol as the organic component and the concentration (1–5 mM) of Cu²⁺ as the complexing metal ion in the aqueous-organic eluent.     

Über die gemeinsame Umsetzung von α-Mercaptoketonen mit Oxoverbindungen und α-Aminocarbonsäureestern

Zusammenfassung Bei der Umsetzung von -Mercaptoketonen mitSchiffschen Basen aus Glykokolläthylester und Oxoverbindungen (Aldehyden, Cyclohexanon) bzw. bei der gemeinsamen Einwirkung derSchiffschen Base-Komponenten Glykokolläthylester und Oxoverbindungen auf -Mercaptoketone entstehen in glatter Reaktion ⁴-Thiazolin-3-yl-essigsäureäthylester.Als cyclische Enamine lassen sich diese ⁴-Thiazoline mit Ameisensäure zu den entsprechenden beständigen Thiazolidinyl-3-essigsäureäthylestern hydrieren.Die ⁴-Thiazolin-3-yl-essigsäureäthylester, die in 2-Stellung monosubstituiert sind, erleiden beim Erhitzen auf etwa 150° Thermolyse, wobei es unter Abspaltung von Essigsäureäthylester zur Bildung von Thiazolen kommt.

---

-Mercapto ketones react with aldehydes (or cyclohexanone) and esters of -amino acids (or their hydrochlorides) or with theSchiff bases formed by these compounds to form esters of ⁴-thiazolin-3-ylacetic acids. These esters can be hydrogenated with formic acid to the corresponding thiazolidines.Esters of ⁴-thiazolinylacetic acids which have a H atom in position 2, can be pyrolysed by heating at about 150° to form the corresponding thiazoles and alkyl acetate. These reactions are illustrated for the case of 2-mercaptopentan-3-on as -mercapto ketone, glycinethylester as amine component and various aldehydes or cyclohexanone as oxo compound.

---

---

60. Mitt.:F. Asinger, W. Schäfer, H. Kersten undA. Saus, Mh. Chem.98, 1841 (1967).

---

Teil der DiplomarbeitC. Dudeck, Techn. Hochschule Aachen, 1967.     

Structure of the X-ray emission CuLα-line in YBa2Cu3O7−δ and CuO based on the SCFXα-SW calculation

Using the SCF X-SW method we have calculated the final states of the X-ray L-transition of the CuO ₄ ^–6 cluster modeling the nearest environment of the copper atom (one of two types) in YBa₂Cu₃O_7- and the nearest environment of copper in CuO. The energies of transitions forming the L-spectrum (with or without many-electron excitations) have been calculated. It has been shown that for interpretation of the main singularities of the X-ray emission L-spectrum, not only should the Coster-Kronig transitions be considered but also the shake-up excitation 2b_1g3b_1g processes and the multiple ionization satellites 3p^–1. An experimental schame has been suggested that allows separation of the effects of different many-electron processes on the L-spectrum.Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 34, No. 4, pp. 3–9, July–August, 1993.Translated by L. Smolina     

Effect of alkali ions (Na+, K+) on the solvent extraction of uranium(VI) with a di-carboxylated calix[4] arene

The solvent extraction of uranium(VI) with a di-carboxylated calix[4]arne (LH₂) in chloroform and 1,2-dichloroethane has been studied in the presence or absence of alkali ions (M=Na⁺,K⁺). For UO ₂ ²⁺ when studied alone, a 12 (metal: ligand) extracted species is evidenced, with a rather low associated extraction equilibrium constant. The efficiency of extraction increases drastically in the presence of alkali ions, due to the formation of heteronuclear complexes. In all cases, the extracted species are found to be both 122 and 112 (UO ₂ ²⁺ MLH₂) mixed complexes, except in chloroform with K⁺, where only the latter is formed. In the case of Na⁺, mass spectrometry spectra confirm the existence of both homo and heteronuclear complexes as determined in the extraction studies.     

<Superscript>1</Superscript>H and <Superscript>13</Superscript>C NMR spectra of some drimanic sesquiterpenoids

One- and two-dimensional homo- and heteronuclear correlation proton, carbon, proton—proton, and proton—carbon NMR spectra of fifteen drimanic sesquiterpenoids: 11,12-dibromodrima-5,8-dien-7-one, drim-8-en-7-one, 11-hydroxydrim-8-en-7-one, 11,12-dihydroxydrim-8-en-7-one, 11-hydroxy-11,12-epoxydrim-8-en-7-one, 11-hydroxy-11,12-epoxydrim-8-en-7-one, 8,9-epoxydriman-7-one, 8,9-epoxydriman-7-ol, 11,12-diacetoxydrim-8-en-7-ol, drimane-7,8,11-triol, 7,8-isopropylidenedioxydriman-11-al, 9, 11-dihydroxydrim-7-en-6-one, drimane-7,8,9-triol, drimane-7,8,11-triol, and drim-8-ene-7,11,12-triol were studied. The proton and carbon chemical shifts were assigned.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2589–2594, December, 2004.     

The identification of small amounts of sugars by means of X-ray diffraction patterns

Summary The identification of small amounts of sugars by their X-ray powder diagrams is suggested as a most simple and practical method in routine analysis.It is especially valuable in working with minute amounts of material, and has proved very useful for the final identification of chromatographically-separated sugars.The characteristics of the powder diagrams of a number of monosaccharides of special interest to the physiological chemist are reported in detail. The substances thus investigated are- and-D-glucose and-glucose monohydrate,- and-D-galactose,- and-D-mannose,D-fructose,D-glucuronolactone,- and-D-glucosamine hydrochloride,- and-D-galactosamine (chondrosamine) hydrochloride,-L-fucose, andD-ribose. For various reasons arabinose, lyxose, and xylose have also been included.It is clear from the powder diagrams of the galactoses that the crystalstructure earlier ascribed to-galactose is that of-galactose.A single-crystal study of-glucosamine hydrochloride was carried out by theWeissenberg technique. The crystal-dimensions obtained agree with those earlier found byCox et al^{5, 7}.The optical rotation of chondrosamine hydrochloride was found to be [] _D ^20° = - 135° - 93° - 39°, the first value being considerably higher than that given for the-form byLevene. A method for the preparation of-mannose is described.

---

Zusammenfassung Die Identifizierung kleiner Mengen verschiedener Zuckerarten mit Hilfe ihrer Röntgen-Pulverdiagramme wird als einfache und praktische Routinemethode vorgeschlagen.Diese Methode ist besonders wertvoll, wenn nur kleine Substanzmengen zur Verfügung stehen, und hat sich für die endgültige Identifizierung von chromatographisch getrennten Zuckern als sehr geeignet erwiesen.Die Einzelheiten der Pulverdiagramme folgender physiologisch-chemisch bedeutungsvoller Monosaccharide werden mitgeteilt:- und-D-Glukose und Glukosehydrat,- und-D-Galaktose,- und-D-Mannose,D-Fruktose,D-Glukuronolakton,- und-D-Glukosaminhydrochlorid,- und-D-Galaktosamin-(Chondrosamin)-hydrochlorid,-L-Fukose, dieD-Pentosen Arabinose, Lyxose, Ribose und Xylose.Aus den Pulverdiagrammen der Galaktosen geht deutlich hervor, daß die Krystallstruktur, die früher der-Galaktose zugeschrieben wurde, tatsächlich diejenige der-Form ist.Die Untersuchung eines Einzelkristalles von-Glukosaminhydrochlorid wurde nach derWeissenberg-Technik ausgeführt. Die erhaltenen Werte stimmen mit den früher vonCox und Mitarbeitern gefundenen überein.Die optische Drehung des Chondrosaminhydrochlorids wurde zu [] _D ^20° = + 135° + 93° + 39° gefunden. Der erstgenannte Wert ist größer als der entsprechende, vonLevene angegebene Drehungswert.Eine Methode zur Darstellung von-Mannose wird beschrieben.

---

Résumé On propose une méthode de routine simple et pratique pour l'identification de petites quantités de divers sucres au moyen de leur diagramme de poudres aux rayons X. Cette méthode est particulièrement précieuse quand on n'a que de petites quantités de matière à sa disposition et elle s'est montrée très convenable pour l'identification finale de sucres séparés par chromatographie. Des particularités des diagrammes de poudres des monosaccharides suivants intéressent le chimiste physiologiste: et-D-glucose et hydrate de glucose, et-D-galactose, et-D-mannose, D-fructose,D-glucuronolactone, chlorhydrate d' et-D-glucosamine, chlorhydrate d' et-D-galactosamine (chondrosamine), l'-L-fucose, lesD-pentoses, l'arabinose, le lyxose, le ribose, le xylose. Des diagrammes de poudres des galactoses découle clairement le fait que la structure cristalline qui fut attribuée précédemment à l'-galactose est celle de la forme. L'expérience sur un cristal unique de chlorhydrate d'-glucosamine a été effectuée d'après la technique deWeissenberg. Les valeurs obtenues concordent avec celles trouvées précédemment parCox et ses collaborateurs. Le pouvoir rotatoire du chlorhydrate de chondrosamine a été trouvé égal à _D ²⁰ = + 135° + 93° + 39°. La première valeur est plus grande que celle donnée parLevene. On décrit une préparation de l'-mannose.

---

---

With 3 figures.