<Superscript>103</Superscript>Rh, <Superscript>17</Superscript>O,and <Superscript>31</Superscript>P NMR study of Rh(III) complex formation in acidic sulfate-phosphate media

Rhodium(III) complex formation with phosphoric acid in strong acidic solutions has been studied by ¹⁰³Rh, ¹⁷O, and ³¹P NMR. Phosphoric acid is mainly coordinated to rhodium as a monodentate terminal HPO₄²⁻ ion, while the coordinated phosphate ion accounts for no more than 7%.     

Quantitative analysis of hydrogen peroxide by <Superscript>1</Superscript>H NMR spectroscopy

A technique utilizing ¹H NMR spectroscopy has been developed to measure the concentration of hydrogen peroxide from 10^–3 to 10 M. Hydrogen peroxide produces a peak at around 10–11 ppm, depending upon the interaction between solvent molecules and hydrogen peroxide molecules. The intensity of this peak can be monitored once every 30 s, enabling the measurement of changes in hydrogen peroxide concentration as a function of time. ¹H NMR has several advantages over other techniques: (1) applicability to a broad range of solvents, (2) ability to quantify hydrogen peroxide rapidly, and (3) ability to follow reactions forming and/or consuming hydrogen peroxide as a function of time. As an example, this analytical technique has been used to measure the concentration of hydrogen peroxide as a function of time in a study of hydrogen peroxide decomposition catalyzed by iron(III) tetrakispentafluorophenyl porphyrin.Electronic Supplementary Material Supplementary material is available for this article at     

Thermodynamic behavior of complexation of 18-crown-6 with Tl<Superscript>+</Superscript>, Pb<Superscript>2+</Superscript>, Hg<Superscript>2+</Superscript>, and Zn<Superscript>2+</Superscript> metal cations in methanol-water binary media

The equilibrium constants and thermodynamic parameters for complex formation of 18-Crown-6 (18C6) with Tl⁺, Pb²⁺, Hg²⁺, and Zn²⁺ metal cations have been determined by conductivity measurements in methanol (MeOH)-water (H₂O) binary solutions. 18-Crown-6 forms 1:1 complexes with Hg²⁺ and Zn²⁺ cations, but in the case of Tl⁺ and Pb²⁺ cations, in addition to 1:1 stoichiometry, 1:2 (ML₂) complexes are formed in some binary solvents. The thermodynamic parameters (ΔH _c⁰ and ΔS _c⁰), which were obtained from the temperature dependences of equilibrium constants, show that in most cases the complexes are enthalpy destabilized but entropy stabilized. Non-linear behavior is observed between the equilibrium constants (log K _f ) of complexes and the composition of the mixed solvent. The selectivity of the ligand for these metal cations is sensitive to the solvent composition, and, in some cases, the selectivity order is reversed in certain compositions of the mixed solvent. The results also show that the mechanism of complexation reactions and the stoichiometry of complexes of some metal cations change with the nature and even with the composition of the mixed solvent. The article was submitted by the authors in English.     

On the characterization of some [bmim][X]/co-solvent binary mixtures: a multidisciplinary approach by using kinetic, spectrophotometric and conductometric investigations

In order to study the intrinsic characteristics and to evaluate the structural variations determined by the addition of a co-solvent to 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF₄]) we examined the behaviour of some probes in [bmim][BF₄]/co-solvent binary mixtures. The rate constants of the piperidino-catalyzed rearrangement of the Z-phenylhydrazone of the 3-benzoyl-5-phenyl-1,2,4-oxadiazole into the relevant 4-benzoylamino-2,5-diphenyl-1,2,3-triazole as well as the spectrometric properties of pyrene and Nile Red were evaluated. With the same purpose also ¹H NMR and conductivity measurements were carried out. By comparison the behaviour of 1-butyl-3-methylimidazolium bis-(trifluoromethylsulfonylimide)/1,4-dioxane mixtures has been analyzed. The whole of data confirms the presence of weak interactions that determine a partially preorganized structure for [bmim][X]. This is perturbed at some degrees by quantity and nature of guest molecules. For example conductivity measurements support the idea that different charged aggregates are present in the [bmim][X]/co-solvent binary mixtures.     

<Superscript>29</Superscript>Si NMR Spectroscopy Investigation of Alcoholic Phenyltrimethyl Ammonium Silicate Solutions

²⁹Si NMR spectroscopy is a powerful tool for studies of the silicate species existing in both aqueous and non-aqueous solutions. In this report ²⁹Si NMR spectroscopy was used to characterize species present in alkaline alcoholic silicate solutions. Phenyltrimethylammonium (PTMA) hydroxide was used as a base. The effects of polymerization/depolymerization of silicate anions in alcoholic alkaline solutions were investigated with different alcohols by ²⁹Si NMR spectroscopy. The esterification of monomeric silicate, Si(OH)₄, in the presence of different alcohols was also studied. Esterification depends on the alkyl chain as well as number of hydroxyl groups in the alcohol.     

The solvation dynamics of Na<Superscript>+</Superscript> and K<Superscript>+</Superscript> ions in liquid methanol

The structure of the solvation shell of Na⁺ and K⁺ in fully deuterated liquid methanol has been studied by ab initio Car-Parrinello molecular dynamics simulations. The solvent cage has been found relatively stable and this property has been explained by means of charge transfer and electrostatic interactions as was previously done for Li⁺ in the same solvent. The differences with Li⁺ such as the increase of the coordination number going from Li⁺ to K⁺ and the reduced stability of the cage have been ascribed to the increase in the ionic radius.     

Long-range <Superscript>19</Superscript>F-<Superscript>1</Superscript>H spin-spin coupling as an indication of conformational equilibrium of fluoro-substituted aryl vinyl sulfides

Long-range ¹⁹F-¹H spin-spin coupling with participation of vinyl group protons, observed in the ¹H NMR spectra of fluoro-substituted aryl vinyl sulfides, indicates that these compounds exist as equilibrium mixtures of s-cis and s-trans rotational isomers.     

Thermodynamic study of complexation reactions between 1,7,10,16 Tetra oxa 4,13 diaza cyclo octa decane (Kryptofix22) and Ni<Superscript>2+</Superscript>, Cd<Superscript>2+</Superscript> and Ag<Superscript>+</Superscript> metal cations in some pure and binary mixed non-aqueous solvents using conductometry

The complexation reactions between Ni²⁺, Cd²⁺ and Ag⁺ metal cations with the macrocyclic ligand Kryptofix22 (K22), in pure acetonitrile (AN), ethylacetate (EtOAc), methanol (MeOH) and their binary mixtures have been studied at different temperatures using conductometric method. The obtained results show that in most solvent systems, the stoichiometry of the complexes formed between the macrocyclic ligand and the metal cations is 1: 1 [ML], but in some of the solvent systems, a 1: 2 [ML₂] complex and also [M₂L], [M₂L₂] and [M₂L₃] complexes are formed in solutions. The stability constans of the 1: 1 complexes were obtained using a computer program GENPLOT. A non-liner behavior was observed for changes of logK_f of the 1: 1 complexes versus the composition of AN–EtOAc binary solutions. The stability order of the 1: 1 complexes at 25°C in the binary solvent solution of AN–EtOAc (mol % AN = 50) was found to be: (K22.Ag)⁺ > (K22.Ni)²⁺ > (K22.Cd)²⁺. The obtained values of thermodynamic quantities (ΔH_c⁰,ΔS_c⁰) show that in most of the AN–EtOAc binary solvent solutions, the 1:1 complexation reactions are enthropy stabilized, but from the enthalpy view point, depending on the nature and composition of mixed solvents they are exothermic or athermic.     

Determination of <Superscript>241</Superscript>Am/<Superscript>243</Superscript>Am ratios

Determination of ²⁴¹Am/²⁴³Am ratios is required for vanous purposes including assay of Am by isotope dilution techniques. Alpha-spectrometry on electrodeposited sources is a preferred technique for this determination. However, there is an inherent problem of tail contribution which necessitates the use of suitable algorithms to account for the same. Recently, in the frame of a Coordinated Research Program (CRP) of the International Atomic Energy Agency (IAEA), WinALPHA software has been developed which is a combination of an asymmetrical Gaussian for the main part of the peak and a low energy function. Therefore, it was of interest to compare the use of this algorithm with the routinely used method, in our laboratory, based on geometric progression (G. P.) decrease. Since, there are no reference materials available commercially for ²⁴¹Am/²⁴³Am ratios, synthetic mixtures covening a wide range (0.3 to 2.0) of ²⁴¹Am/²⁴³Am α-activity ratios were used and un-ignited electrodeposited sources were prepared for α-spectrometry. The α-spectra obtained using PIPS detector, were evaluated using the two algonthms The ²⁴¹Am/²⁴³Am α-activity ratios obtained were also compared with those determined by thermal ionization mass spectrometry (TIMS). An agreement of about 1% was obtained in the ²⁴¹Am/²⁴³Am ratios determined by the two methods and also by using the two algorithms for α-spectrum evaluation.     

IR and <Superscript>31</Superscript>P NMR spectroscopic study of complexation of carbamoyl methyl phosphinates with U<Superscript>VI</Superscript> and Th<Superscript>IV</Superscript> in nitric acid solutions

The composition of complexes formed upon the extraction of U^VI and Th^IV nitrates with O-n-nonyl(N,N-dibutylcarbamoylmethyl) methyl phosphinate (L) from solutions of nitric acid without additional solvent was determined by ³¹P NMR spectroscopy. The structures of the complexes formed were studied by IR spectroscopy. Uranium(VI) is extracted from 3 and 5 M solutions of HNO₃ as the [UO₂(L)₂(NO₃)₂] complex, while thorium(IV) is extracted from 5 M HNO₃ as the [Th(L)₃(NO₃)₃]⁺·NO ₃ ⁻ complex. In both cases, ligand L has bidentate coordination. Ligand L contacts with 3 and 5 M nitric acid to form adducts L·HNO₃ and L· (HNO₃)₂, respectively. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2460–2464, November, 2005.     

Aluminum Solvate Complexes Forming in Acidic Methanol-Acetone Mixtures Studied by <Superscript>27</Superscript>Al NMR Spectroscopy

²⁷Al NMR spectroscopy is a powerful tool for the study of coordination and solvation in both aqueous and nonaqueous solutions. In this study, the complexes coexisting upon dissolution of AlCl₃ in acidic acetone + methanol solutions are shown to consist essentially of mixed hexacoordinated species of the general formula [Al(CH₃OH)_6−n (CH₃COCH₃) _n ]³⁺ (n=1,2 and 3), all exhibiting distinctly different ²⁷Al shielding effects. The relative populations of the various mixed species are found to be highly dependent upon the acetone:methanol mole ratio that in the more acetone-rich mixtures with aluminum become appreciably coordinated by acetone. The results demonstrate that the key factor for the formation of acetone-containing species in acidic methanolic solutions is having the CH₃COCH₃:CH₃OH mole ratio at 3:1.     

Determination of the molecular weight of polyoxypropylenepolyols by <Superscript>1</Superscript>H NMR spectroscopy

Commercial and laboratory samples of polyoxypropylenepolyols were studied by ¹H NMR spectroscopy at operating frequencies of 100 and 500 MHz. Various methods depending on the solvent used were suggested for determining the equivalent weight (molecular weight of the polyether per terminal hydroxy group). The ¹H NMR data are compared to the data obtained by chemical methods and gel permeation chromatography.     

Study of Complex Formation between Kryptofix 21 with La<Superscript>3+</Superscript>, Y<Superscript>3+</Superscript> and Ce<Superscript>3+</Superscript> Cations in Some Binary Mixed Non-Aqueous Solvents Using the Conductometric Method

The complexation reactions between La³⁺, Y³⁺ and Ce³⁺ cations with the macrocyclic ligand, kryptofix 21, were studied in methanol-acetonitrile (MeOH-AN) and methanol-methylacetate (MeOHMeOAc) binary mixed solvent solutions at different temperatures using the conductometric method. The conductance data show that in most solvent systems, the kryptofix 21 forms a 1: 1 [M: L] complex with La³⁺, Y³⁺ and Ce³⁺ metal cations, but in the case of Y³⁺ cation in pure methylacetate, in addition of formation of a 1: 1 [ML] complex, 1: 2 [ML₂] and 1: 3 [ML₃] complexes are formed in solution. In the case of Ce³⁺cation, a 1: 1 [ML] and also a 1: 2 [ML₂] complexes are formed in this solvent system at all studied temperatures. The electrical conductance data in acetonitrile, show that a 1: 1 [ML] and also a 1: 2 [ML₂] complexes are formed between the ligand and La³⁺ and Ce³⁺ metal cations at different temperatures. The stability constants of the 1: 1 [ML] complexes were determined using the conductometric data and a computer program, GENPLOT. A non-monotonic relationship was observed between log_{K f} of the 1: 1 complexes with the composition of the binary solvent solutions which was discussed in term of solvent-solvent interactions and also preferential solvation of the metal cations and the ligand in solutions. The selectivity order of the ligand for the metal cations in MeOH–AN and MeOH–MeOAc binary solvent solutions, at 25°C was found to be: Y³⁺ > La³⁺ > Ce³⁺ and La³⁺ > Y³⁺ > Ce³⁺, respectively. The values of the standard thermodynamic quantities (ΔH _c ^° and ΔS _c ^° ) for formation of the 1: 1 complexes were obtained from temperature dependence of the stability constans of the complexes and the results show that the thermodynamics of the complexation reactions between kryptofix 21 and La³⁺, Y³⁺ and Ce³⁺ cations, is affected by the nature and composition of the mixed solvents systems.     

NMR Spectra of Cyclic Nitrones. 7. The Influence of Substituents and a Hydrogen Bond on <Superscript>14</Superscript>N and <Superscript>17</Superscript>O Chemical Shifts in Derivatives of 3-Imidoazoline 3-Oxide

Derivatives of 3-imidazoline 3-oxide have been studied by ¹⁴N and ¹⁷O NMR methods. Regularities of the influence of substituents and of a hydrogen bond on chemical shifts have been made apparent. The range of changes of the chemical shifts of the nitrogen and oxygen nuclei of the nitrone group has been determined. Both in the ¹⁷O and in the ¹⁴N NMR spectra the signals of the amino derivatives are the highest field signals for the nitrone group, and the lowest field signals are the signals of the cyano derivatives in the series of derivatives investigated. Depending on the substituent (from amino to cyano group) the ¹⁷O chemical shifts varied over a range ∼155 ppm, but the interval of change of the ¹⁴N chemical shifts for the same substituents was ∼110 ppm. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1336–1341. September, 2005.     

Structure of binuclear platinum(III) acetamidate complexes in solutions as probed by <Superscript>195</Superscript>Pt, <Superscript>13</Superscript>C,and <Superscript>1</Superscript>H NMR spectroscopy

¹⁹⁵Pt, ¹H, and ¹³C NMR spectroscopy was used to study the structure of binuclear platinum(III) acetamidate complexes with 1,10-phenanthroline and 2,2′-bipyridine ligands [Pt₂(phen)₂(acam)₄](NO₃)₂ (1) and [Pt₂(bipy)₂(acam)₄](NO₃)₂ (2) in aqueous solutions. The ¹⁹⁵Pt NMR spectra of solutions of complexes 1 and 2 in D₂O exhibit two signals with satellites due to the ¹⁹⁵Pt–¹⁹⁵Pt spin-spin coupling (¹ J(Pt–Pt) ≈ 6345 Hz), whereas their ¹H and ¹³C NMR spectra contain four sets of signals for the protons and the carbon atoms of the heterocyclic and acetamidate ligands. The signals were assigned using the COSY, NOESY, and HSQC/ HMBC experiments and comparing the coordination shifts of the signals for the protons of heterocycles. These data allowed us to draw a conclusion that binuclear complexes 1 and 2 in solution have a head-to-head structure with nonequivalent platinum(III) atoms (coordination cores PtN₅ and PtN₃O₂), the axial-equatorial coordination of the bidentate heterocyclic molecules, and two bridging and two terminal acetamidate ligands.     

Through space spin-spin coupling <Superscript>19</Superscript>F-<Superscript>1</Superscript>H as the base for comparative analysis of conformational equilibrium in fluorine-substituted aryl vinyl selenides and sulfides

The analysis of long-range spin-spin coupling ¹⁹F-¹H and the other conformation-dependent parameters of ¹H NMR spectra shows that aryl vinyl selenides like aryl vinyl sulfides exist as mixtures of s-cis and s-trans rotational isomers. The combined data of ¹H and ¹³C NMR spectra reveal the increase in the torsional angle ϑ at the bond X-CH=CH₂ (X = S, Se) in selenides compared to sulfides due to diminished interaction energy of the unshared electron pairs of selenium with the π*-orbitals of the double bond as compared to analogous interaction in sulfides.     

Sequential separation of <Superscript>99</Superscript>Tc, <Superscript>94</Superscript>Nb, <Superscript>55</Superscript>Fe, <Superscript>90</Superscript>Sr and <Superscript>59/63</Superscript>Ni from radioactive wastes

A sequential separation procedure has been developed for the determination of ⁹⁹Tc, ⁹⁴Nb, ⁵⁵Fe, ⁹⁰Sr and ^59/63Ni in various radioactive wastes generated from nuclear power plants. Ion exchange and extraction chromatography were adopted for individual separation of the radionuclides. Precipitation was supplementarily utilized for both purification of the individual radionuclides and preparation of the radionuclide sources for use in a radioactivity measurement. The chromatographic separation behavior of the radionuclides both from the sample matrix metals and from one another was investigated using stable metals, Re (as a surrogate of ⁹⁹Tc), Nb, Fe, Sr and Ni. The validity of the procedure for reliability and applicability was evaluated by measuring the recovery of the metal carriers added to synthetic radioactive waste solutions. The recoveries by the chromatographic separation were in the range of 84.8 to 102.2% with 2s of less than 8.6%, the recoveries by the precipitation being in the range of 84.3 to 97.3% with 2s of less than 10.9%.     

First-principles simulations of the <Superscript>27</Superscript>Al and <Superscript>17</Superscript>O solid-state NMR spectra of the CaAl<Subscript>2</Subscript>Si<Subscript>3</Subscript>O<Subscript>10</Subscript> glass

The local and medium-range structure of the 20CaO·20Al₂O₃·60SiO₂ glass generated by classical molecular dynamics simulations has been compared to NMR experiments by computing the ²⁷Al and ¹⁷O NMR parameters and NMR spectra from first-principles simulations. The calculation of the NMR parameters (chemical shielding and quadrupolar parameters), which are then used to simulate solid-state MAS and 3QMAS NMR spectra, is achieved by the gauge including projector augmented-wave and the projector augmented-wave methods on the DFT-PBE relaxed structure. The NMR spectra calculated with the present approach are found to be in excellent agreement with the experimental data, providing an unambiguous view of the local and medium-range structure of aluminosilicate glasses.     

Conversion factors for carbohydrate analysis by hydrolysis and <Superscript>1</Superscript>H-NMR spectroscopy

Conversion factor to calibrate the lower xylan content in carbohydrate compositional analysis in wood by ¹H-NMR spectroscopy was investigated. During acid hydrolysis, xylan monomer was dehydrated as furfural, and that furfural was further degraded or condensed in acidic reaction condition. Anomeric hydrogen peaks integration in ¹H-NMR spectroscopic method excluded xylose reacted products (such as furfural and their condensed or degraded products). Only 52% of xylose was counted in anomeric hydrogen integration and 62% of xylose was counted in integration of furfural peak and anomeric hydrogen. For accurate carbohydrate compositional analysis by NMR spectroscopic method, furfural and their reacted products should be counted as xylose. Conversion factor for xylose content analysis was introduced from the acid hydrolysis of several different combinations of standard cellulose and xylan. In this study xylan conversion factor 0.66 was obtained based on compared NMR data from the prepared cellulose and xylan mixtures acid hydrolyzed with the same condition for woodmeal and pulps. With corrected xylan content calculation, NMR spectroscopic method gave rather closer carbohydrate composition compared to the other analytical methods.     

The state of Al(III) in alcohol solutions of aluminum alkoxide as probed by <Superscript>27</Superscript>Al and <Superscript>13</Superscript>C NMR and small-angle X-ray scattering

Solutions of aluminum alkoxides obtained by interaction of aluminum metal with methyl, ethyl, and isopropyl alcohols were studied by ²⁷Al and ¹³C NMR and small-angle X-ray scattering. Alkoxides with a tetrahedral environment of aluminum prevail in methanol solutions, and those with an octahedral environment of aluminum predominate in ethanol solutions. In isopropyl alcohol at 293 K, polynuclear alkoxides with tetrahedral, octahedral, and pentacoordinated aluminum environments coexist. The structure of polynuclear complexes was refined by comparison of their calculated dimensions with small-angle X-ray scattering data.