Magnesium isotope separation by ion exchange using hydrous manganese(IV) oxide

The magnesium isotope effects were investigated by chemical ion exchange with a hydrous manganese(IV) oxide. The capacity of manganese(IV) oxide was 0.5 meq g(-1). The distribution coefficient of magnesium ions on the MnO(2) was determined by a batch method. The heavier isotopes of magnesium were enriched in the solution phase, while the lighter isotopes were enriched in the hydrous MnO(2) phase. The separation factor was determined according to the method of Glueckauf from the elution curve and isotopic assays. The separation factors of (24)Mg(2+)-(25)Mg(2+), (24)Mg(2+)-(26)Mg(2+), and (25)Mg(2+)-(26)Mg(2+) isotope pair fractionations were 1.011, 1.021, and 1.011, respectively.     

Adsorption and isotope effects by ion exchange with aqueous-2-aminomethyl-18-crown-6 bonded merrifield resin

Magnesium isotopes effects were investigated by chemical ion exchange using synthesized 2-aminomethyl-18-crown-6 (AM18C6) bonded Merrifield peptide resin. It was found that separation factors larger those reported previously were obtained, and the hydration and isotope mass effects are more significant than that of the complexation. The capacity of the crown ion exchanger was 2.3 meq/g dry resin. The adsorption capacity of the resin for magnesium ion was 26.8 mg/g dry resin at pH 7. The heavier isotopes of magnesium were enriched in the solution phase, while the lighter isotopes were enriched in the resin phase. The separation factors of (24)Mg-(25)Mg, (24)Mg-(26)Mg, and (25)Mg-(26)Mg were 1.0085, 1.0162, and 1.0081, respectively.     

Separation of magnesium isotopes by a 2'-aminomethyl-18-crown-6 bonded Merrifield peptide resin

Separation of magnesium isotopes was investigated by chemical ion exchangewith synthesized 2'-aminomethyl-18-crown-6 (AM18C6) bonded Merrifieldpeptide resin using an elution chromatographic technique. The capacity ofthe novel crown ion exchanger was found to be 2.3 meq/g dry resin. The heavierisotopes of magnesium were enriched in the solution phase, while the lighterisotopes were enriched in the resin phase. The single stage separation factorwas determined according to the method of GLUECKAUF from the elution curveand isotopic assays. The separation factors of ²⁴Mg–²⁵ Mg, ²⁵ Mg–²⁶ Mg, and ²⁴ Mg–²⁶ Mg isotope pair fractionations were 1.012, 1.005, and 1.022, respectively.     

Syntheses and separating properties of triazacrown and AM18C6 bonded Merrifield peptide resins

Separation of lithium and magnesium isotopes by cation exchange elution chromatography was carried out with a synthesized 1,13,16-trioxa-4,7,10-triazacyclooctadecane (N₃O₃)-4,7,10-trimerrifield peptide resin and with a 2^′-aminomethyl-18-crown-6 (AM18C6) bonded Merrifield peptide resin. The resins have a capacity of 0.1 and 2.3 meq/g dry resin. A single stage separation factor of lithium isotopes, 1.018 was obtained by the Glueckauf theory from the elution curve and isotopic assays. The heavier isotope, ⁷Li was concentrated in the resin phase, while the lighter isotope, ⁶Li concentrated in the solution phase. On the other hand, the heavier isotopes of magnesium were concentrated in the solution phase, while the lighter isotopes were concentrated in the resin phase. The separation factors of ²⁴Mg-²⁵Mg, ²⁴Mg-²⁶Mg, and ²⁵Mg-²⁶Mg isotope pair fractionations were 1.012, 1.022, and 1.012, respectively.     

Enrichment of Magnesium Isotopes by N3O2 Azacrown Ion Exchange Resin

The elution chromatographic separation of magnesium isotopes was investigated by chemical ion exchange with the synthesized 1,7-dioxa-4,10,13-triazacyclopentadecane-4,10,13-trimerrifield peptide resin [N₃O₂·3M]. The capacity of novel N₃O₂ azacrown ion exchanger was 0.21 meq/g dry resin. The heavier isotopes of magnesium concentrated in the resin phase, while the lighter isotopes are enriched in the solution phase. The glass ion exchange column used in our experiment was 30 cm long with inner diameter of 0.2 cm, and the 2.0M NH₄Cl solution was used as an eluent. The separation factors of ²⁴Mg-²⁵Mg, ²⁵Mg-²⁶Mg, and ²⁴Mg-²⁶Mg were 1.030, 1.009, and 1.027, respectively.     

Enrichment of Magnesium Isotopes by 2′-Aminomethyl-15-Crown-5 Bonded Merrifield Peptide Resin

Magnesium isotope enrichment was investigated by chemical ion exchange with a synthesized 2-aminomethyl-15-crown-5 bonded Merrifield peptide resin using elution chromatography. The capacity of the novel crown ion exchanger was found to be 2.25 meq/g dry resin. The heavier isotopes of magnesium were enriched in the solution phase, while the lighter isotopes were enriched in the resin phase. The separation factor was determined according to the method of GLUECKAUF from the elution curve and isotopic assays. The separation factors of ²⁴Mg²⁺–²⁵Mg²⁺, ²⁴Mg²⁺–²⁶Mg²⁺, and ²⁵Mg²⁺–²⁶Mg²⁺ isotope pair fractionations were 1.00095, 1.00857, and 1.00014, respectively.     

Separation of magnesium isotopes by N4S2 azacrown ion exchanger

The chromatographic separation of magnesium isotopes was investigated by chemical ion exchange with 1,16-dithia-4,7,10,13-tetraazacyclooctadecane-4,7,10,13-tetramerrifield peptide resin[N₄S₂·4M] synthesized recently. The capacity of novel N₄S₂ azacrown ion exchanger was 0.34 meq/g dry resin. The heavier isotopes of magnesium concentrated in the resin phase, while the lighter isotopes are enriched in the solution phase. The glass ion exchange column used was 30 cm long with inner diameter of 0.2 cm, and the 1.0M NH₄Cl solution was used as an eluent. The separation factors of²⁴Mg−²⁵Mg,²⁵Mg−²⁶Mg, and²⁴Mg−²⁶Mg were 1.047, 1007, and 1.008, respectively.     

Separation of magnesium isotopes by NTOE bonded merrifield peptide resin

Separation of magnesium isotopes was investigated by chemical ion exchange with synthesyzed 1,12-diaza-3,4:9,10-dibenzo-5,8-dioxacyclo pentadecane(NTOE) bonded merrifield peptide resin using elution chromatographic technique. The capacity of novel diazacrown ion exchanger was 0.29 meq/g dry resin. The heavier isotopes of magnesium were concentrated in the solution phase, while the lighter isotopes were enriched in the resin phase. The glass ion exchange column used in our experiment was 32 cm long with inner diameter of 0.2 cm, and 0.5M NH₄Cl solution was used as an eluent. The single stage separation factor was determined according to the method of GLUECKAUF from the elution curve and isotopic assays. The separation factors of ²⁴Mg²⁺–²⁵Mg²⁺, ²⁴Mg²⁺–²⁶Mg²⁺, and ²⁵Mg²⁺–₂₆Mg²⁺ were 1.063, 1.080, and 1.021, respectively.     

镁同位素分析技术应用于葡萄酒辨别的探索研究

建立了阳离子树脂富集镁的方法.以1 mol/L HNO3为淋洗液、AG W50-X8阳离子树脂富集镁.方法回收率为(101.6±1.2)％.以H2 (2.1 mL/min)、He(7.0 mL/min)混合碰撞气消除12C12 C+,12C21H+等干扰的MC-ICP-MS分析方法.分析了40种葡萄酒中镁同位素组成,结果表明:不同产地葡萄酒中镁同位素组成差异明显;而且,来自同一产区不同葡萄园的葡萄酒中镁同位素组成也有显著差异.这表明镁同位素具有区分不同产地葡萄酒的能力,而且地理分辨率较高.对于部分镁同位素组成差异不明显的样品,结合元素分析手段,可以准确区分.     

Separation of magnesium isotopes by chemical exchange with a polymer-bound azacrown compound

The chromatographic separation of magnesium isotopes was investigated by chemical exchange with the recently synthesized 1-oxa-4,7,10,13-tetraazacyclopentadecane-4,7,10,13-tetramerrifield peptide resin [N₄O·4M]. The capacity of the novel N₄O-4 Merrifield ion exchanger was 1.0 meq/g dry resin. The heavier isotope²⁶Mg concentrated in the resin phase, while the lighter isotopes²⁴Mg, and²⁵Mg are enriched in the fluid phase. The maximum separation factors , for²⁵Mg–²⁶Mg and²⁴Mg–²⁶Mg were found to be 1.048 and 1.022, respectively, at 20.0±0.02 °C with 2.0 M ammonium chloride solution as an eluent.     

Magnesium isotope effects in enzymatic phosphorylation

Recent discovery of magnesium isotope effect in the rate of enzymatic synthesis of adenosine triphosphate (ATP) offers a new insight into the mechanochemistry of enzymes as the molecular machines. The activity of phosphorylating enzymes (ATP-synthase, phosphocreatine, and phosphoglycerate kinases) in which Mg(2+) ion has a magnetic isotopic nucleus 25Mg was found to be 2-3 times higher than that of enzymes in which Mg(2+) ion has spinless, nonmagnetic isotopic nuclei 24Mg or 26Mg. This isotope effect demonstrates unambiguously that the ATP synthesis is a spin-dependent ion-radical process. The reaction schemes, suggested to explain the effect, imply a reversible electron transfer from the terminal phosphate anion of ADP to Mg(2+) ion as a first step, generating ion-radical pair with singlet and triplet spin states. The yields of ATP along the singlet and triplet channels are controlled by hyperfine coupling of unpaired electron in 25Mg+ ion with magnetic nucleus 25Mg. There is no difference in the ATP yield for enzymes with 24Mg and 26Mg; it gives evidence that in this reaction magnetic isotope effect (MIE) operates rather than classical, mass-dependent one. Similar effects have been also found for the pyruvate kinase. Magnetic field dependence of enzymatic phosphorylation is in agreement with suggested ion-radical mechanism.     

Nuclear spin catalysis in living nature

Experiments with cells enriched in stable magnesium isotopes, magnetic ²⁵Mg or nonmagnetic ²⁴Mg and ²⁶Mg, are carried out. It is revealed that adaptation of bacteria E. coli to the growth media enriched in magnetic ²⁵Mg proceeds faster as compared to the growth media enriched in nonmagnetic magnesium isotopes. In experiments with another commonly accepted cell model, S. cerevisiae yeast, it is revealed that the rate constant of postradiation recovery of the cells after UV irradiation is two times higher for cells enriched in ²⁵Mg than for cells enriched in the nonmagnetic isotope. In collaboration with Ukrainian colleagues from the Palladin Institute of Biochemistry, the effects of different isotopes of magnesium on ATPase activity of myosin isolated from myometrium are studied. It is found that the rate of the enzymatic hydrolysis of ATP for ²⁵Mg is 2.0–2.5 times higher as compared to nonmagnetic isotopes ²⁴Mg and ²⁶Mg. Some possible mechanisms of magnetic isotope effects (nuclear spin catalysis) in biological objects are discussed.     

The Influence of Electric Parameters on the Dynamics of the Electrokinetic Decontamination of Soils

Elution chromatographic separation of lithium isotopes was carried out with aminobenzo-15-crown-5 bonded merrifield resin. This resin have a capacity of 0.24 meq/g dry resin. By column chromatography using 1.0M NH₄Cl solution as an eluent, a single separation factor 1.026 was obtained from the elution curve and isotope ratios according to the Glucckauf theory. The heavier isotope, ⁷Li was concentrated in the resin phase, while the lighter isotope, ⁶Li enriched in the solution phase.     

Separation of lithium isotopes by NTOE-bonded Merrifield peptide resin

A study of the elution chromatographic separation of lithium isotopes was carried out with NTOE-bonded Merrifield peptide resin. This resin had a capacity of 0.29 meq/g dry resin. Upon column chromatography [0.2 cm(I.D)×32 cm (height)] using 1.0M NH₄Cl solution as an eluent, a single separation factor of 1.026 was obtained by the Glueckauf theory. The heavier isotope, ⁷Li was concentrated in the resin phase, while the lighter isotope, ⁶Li was enriched in the solution phase.     

Separation of lithium isotopes with the N3O2 trimerrifield peptide resin

A study on the separation of lithium isotopes was carried out with 1,13-dioxa-4,7,10-triazacyclopentadecane-4,7,10-trimerrifield peptide resin [N₃O₂3M]. The resin having N₃O₂ as an anchor group has a capacity of 0.2 meq/g dry resin. Upon column chromatography [0.1 cm (I.D)×30 cm (height)] using 1.0M NH₄Cl solution as an eluent, a single separation factor of 1.00104 was obtained from the elution curve and isotope ratios based on theGlueckauf theory. The heavier isotope,⁷Li concentrated in the resin phase, while the lighter isotope,⁶Li enriched in the solution phase.     

Enrichment of lithium isotopes by a triazacrown trimerrifield peptide resin

A study on the elution chromatographic separation of lithium isotopes was carried out with a triazacrown trimerrifield peptide resin. The capacity of the triazacrown trimerrifield peptide resin has a value of 0.08 meq/g. Upon column chromatography [0.2 cm (I.D)×35 cm (height)] using 4.0M NH₄Cl solution as an eluent, the single stage separation factor of 1.028 was obtained by the Glueckauf theory. The heavier isotope, ⁷Li, was concentrated in the resin phase, while the lighter isotope, ⁶Li, was enriched in the solution phase.     

Separation of lithium isotopes by N4S2 azacrown ion exchanger

The novel N₄S₂ azacrown ion exchange resin was prepared. The ion exchange capacity of N₄S₂ ion exchanger was 0.34 meq/g dry resin. A study on the separation of lithium isotopes was carried out with N₄S₂ azacrown ion exchange resin. The lighter isotope,⁶Li is concentrated in the resin phase, while the heavier isotope,⁷Li is enriched in the solution phase. With column chromatography [0.1 cm (I.D.)×32 cm (height)] using 2.0M NH₄Cl as an eluent, separation factor, a=1.034 was obtained.     

Separation of lithium isotopes by NDOE bonded Merrifield peptide resin

The novel NDOE (1,12,15-triaza-3,4:9,10-dibenzo-5,8-dioxacycloheptadecane) ion exchange resin was prepared. The ion exchange capacity of NDOE azacrown ion exchanger was 0.2 meq/g dry resin. A study on the separation of lithium isotopes was carried out with NDOE novel azacrown ion exchange resin. The lighter isotope,⁶Li concentrated in the solution phase, while the heavier isotope,⁷Li is enriched in the resin phase. By column chromatography (0.1 cm I.D.×32 cm height) using 2.0M NH₄Cl as an eluent, a separation factor,a=1.0201 was obtained.     

Chromatographic separation of magnesium isotopes by monoazacrown bonded Merrifield peptide resins

Magnesium isotope separation was investigated by chemical ion exchange with the 1-aza-12-crown-4 (I) and the 1-aza-18-crown-6 (II) bonded Merrifield peptide resin using an elution chromatographic technique. The capacities of each novel monoazacrown ion exchanger were 1.0 meq/g for (I) and 2.3 meq/g for (II) bonded Merrifield peptide resins, respectively. The single stage separation factor was determined according to the method of Glueckauf from the elution curves and isotopic assays. The separation factors of magnesium isotope pairs, ²⁴Mg²⁺–²⁵Mg²⁺, ²⁴Mg²⁺–²⁶Mg²⁺ and ²⁵Mg²⁺–²⁶Mg²⁺ were 1.015, 1.029, and 1.014 for (I) and 1.012, 1.024, and 1.009 for (II) bonded Merrifield peptide resins, respectively.     

Nuclear spin catalysis in biochemical physics

Magnetic isotope effects have been recently discovered in living nature. They were observed for the first time in experiments on cells enriched with various magnesium isotopes, magnetic ²⁵Mg or non-magnetic ones. A catalytic effect of the magnetic isotope of magnesium was discovered in experiments with myosin, the most important biomolecular motor utilizing the energy of ATP to perform mechanical work. The rate of ATP hydrolysis with the magnetic ²⁵Mg isotope is 2.0–2.5 times higher than that obtained with nonmagnetic ²⁴Mg or ²⁶Mg. A similar effect of the nuclear spin catalysis was experimentally observed for zinc isotopes. The rate of ATP hydrolysis in the case of magnetic ⁶⁷Zn increased by 40–50% as compared to that observed experimentally for nonmagnetic isotopes (⁶⁴Zn or ⁶⁸Zn). Catalytic effects of the magnetic isotope of magnesium were also experimentally found for H⁺-ATPase isolated from yeast mitochondria and ATPase of the plasma membrane of the myometrium. The magnetic isotope effect indicates unambiguously that the chemomechanical processes involve a limiting step catalyzed by biomolecular motors, which depends on the electronic spin state, and that this step is accelerated in the presence of nuclear spin of the magnetic isotope.