Coordinatively Unsaturated Polynuclear Mixed-Valent Sn<Superscript>II</Superscript>–Sn<Superscript>IV</Superscript> and Cu<Superscript>II</Superscript>–Sn<Superscript>IV</Superscript> Oxo-Centered Carboxylates

The tetranuclear mixed-valent oxo-cluster [Sn^IISn^IVO(O₂CCF₃)₄]₂ (1) has been prepared by reacting SnCl₂ with AgO₂CCF₃ in a sealed ampoule at 90 °C. Alternatively, 1 was obtained by acidolysis of Ph₃SnSnPh₃ with trifluoroacetic acid in solution. The X-ray diffraction study of 1 revealed the presence of a Sn^IIOSn₂^IVOSn^II core comprised of the penta-coordinated divalent and six-coordinated tetravalent tin atoms. The ¹¹⁹Sn NMR studies confirmed the stability of the cluster in solution and the presence of two different oxidation states of tin. An acidolysis of Ph₃SnSnPh₃ in the presence of [Cu₂^II(O₂CCF₃)₄] followed by sublimation of the resulting product at 90 °C afforded the first trinuclear mixed metal Sn–Cu cluster [(C₆H₅)₂Sn₂^IVCu^IIO(O₂CCF₃)₆] (2). The X-ray diffraction analysis of 2 revealed the presence of two phenyl groups attached to the six-coordinated tin(IV) atoms and the tetragonal pyramidal environment of the copper(II) atom. Both complexes have been obtained free of exogenous ligands.     

<Superscript>13</Superscript>C-labeled bilirubin: synthesis of 3<Superscript>1</Superscript>(3<Superscript>2</Superscript>),17<Superscript>1</Superscript>(17<Superscript>2</Superscript>)-di-[<Superscript>13</Superscript>C]-mesobilirubin-XIIIα

Abstract  The title compound, labeled with ¹³C in the ethyl groups was synthesized from K¹³CN and low-molecular-weight components. The synthetic relay compound was 3¹(3²)[¹³C]-xanthobilirubinic acid methyl ester in a synthetic route that leads to a label in the ethyl β-substituent of a dipyrrinone model for bilirubin. This labeled dipyrrinone was oxidatively coupled to the dimethyl ester of mesobiliverdin-XIIIα, thereby providing a route to a ¹³C-labeled mesobiliverdin and mesobilirubin, with one carbon of each ethyl being 98% ¹³C-enriched. Graphical Abstract        

Extractive separation of Cu<Superscript>2+</Superscript>–Co<Superscript>2+</Superscript> and Ni<Superscript>2+</Superscript>–Co<Superscript>2+</Superscript> mixtures using <Emphasis Type="Italic">N</Emphasis>-salicylideneaniline

A study on the extraction of copper(II), cobalt(II), and nickel(II) from solutions containing ions of both metals with N-salicylideneaniline(SAN) in chloroform has been realized. Distribution of the metal ions in wide range of pH has been studied. Extraction of copper(II) was always favored over that of cobalt(II). Extraction of copper(II) from binary metal solution is selective and it can be quantitatively separated from cobalt(II). The equilibrium constant of the extraction of cobalt and nickel from an aqueous solution containing both metals using SAN were evaluated. The separation factors for cobalt and nickel were expressed as a function of the distribution of nickel and cobalt. From these results, salicylideneaniline is an adequate extractant for extractive separation of such mixtures.     

A simple and quick method for the preparation of radionuclide <Superscript>87</Superscript>Y/<Superscript>87m</Superscript>Sr generator using the <Superscript>nat</Superscript>Rb(α,xn)<Superscript>87</Superscript>Y reaction

A rapid method for the preparation of ⁸⁷Y/^87mSr radionuclide generator from a rubidium chloride target irradiated with 35 MeV α-particles is described. A simple two-step procedure is used to obtain a carrier-free ^87mSr isotope with a high enough radiochemical yield and high purity in the final aqueous fraction.     

Cyclotron production of <Superscript>211</Superscript>At/<Superscript>211g</Superscript>Po by <Superscript>209</Superscript>Bi(α,2n) reaction

Astatine-211 (T _1/2 = 7.214 h) is an α-emitter at secular equilibrium by EC with its ultra-short-lived α-emitting daughter, polonium-211g (T _1/2 = 0.516 s), with a high Linear Energy Transfer (LET — 130 eV·nm⁻¹) and a half-life suitable for metabolic radiotherapy; the overall α branching of the ²¹¹At/^211gPo system is 100%. The direct production of ²⁰⁹Bi(α,2n)²¹¹At/^211gPo seems the most satisfactory method; Bi targets were irradiated at JRC-Ispra Cyclotron of European Commission, EC, using α-energy higher than 28.61 MeV in order to produce, via ²⁰⁹Bi(α,3n) reaction, small amounts of the γ-emitter ²¹⁰At (used as internal spike).     

Preparation of <Superscript>235m</Superscript>U targets for <Superscript>235</Superscript>U(n,n′)<Superscript>235m</Superscript>U cross section measurements

This paper describes the preparation of samples for an experiment to measure the cross-section for ²³⁵U(n,n′)^235mU in a fast fission spectrum of neutrons provided by a fast pulsed reactor/critical assembly. Samples of ^235mU have been prepared for the calibration of the internal conversion electron detector that is used for the ^235mU measurement. Two methods are described for the preparation of ^235mU. The first method used a U-Pu chemical separation based on anion-exchange chromatography and the second method used an alpha recoil collection method. Thin, uniform samples of ^235mU+²³⁵U were prepared for the experiment using electrodeposition.     

Validation of <Superscript>239,240</Superscript>Pu, <Superscript>238</Superscript>Pu separation method using molecular recognition product AnaLig<Superscript>®</Superscript> Pu02 gel and extraction chromatography TRU<Superscript>®</Superscript> resin

Two separation techniques for plutonium determination using AnaLig^® Pu02 molecular recognition technology product (MRT) and extraction chromatography TRU^® resin were tested. The methods performance was investigated by analysis of National Physical Laboratory (NPL-Alpha-Beta High, ABH 2003, 2005) intercomparison test samples. The results obtained for both procedures were compared in terms of activities and recoveries. Data analysis showed good agreement with the reference values. The AnaLig^® Pu02 separation method for ^239,240Pu, ²³⁸Pu determination was successfully validated with the same performance as the TRU^® resin method.     

Relativistic coupled cluster calculations of the electronic structure of KrH<Superscript>+</Superscript>, XeH<Superscript>+</Superscript> and RnH<Superscript>+</Superscript>

Potential energy curves of NgH⁺ cations (Ng = Kr, Xe, Rn) were obtained by using four-component relativistic CCSD(T) coupled cluster calculations. Dissociation energies, equilibrium bond lengths, electronic properties, such as dipole moments and electric field gradients at the nuclei, and the related spectroscopic parameters of the electronic ground state have been determined. The results obtained for KrH⁺ and XeH⁺ are in good agreement with available experimental data, while those for RnH⁺ have been determined for the first time at this level of theory.     

Crystallinity of Dynasan<Superscript>®</Superscript>114 and Dynasan<Superscript>®</Superscript>118 matrices for the production of stable Miglyol<Superscript>®</Superscript>-loaded nanoparticles

This study focuses on the physicochemical characterization of lipid materials useful for the production of the so-called solid lipid nanoparticles (SLN) and nanostructured lipid carriers (NLC). The chosen lipids were Dynasan^®114 (glyceril trimyristate) and Dynasan^®118 (glyceril tristearate) as solid lipids (SL), melting temperature above 80 °C, and Miglyol^®812 (caprylic/capric triglyceride) and Miglyol^®840 (propylene glycol dicaprylate/dicaprate) as liquid lipids (LL), crystallizing below ?15 °C. Raw lipids (pure or SL:LL mixtures) were analyzed by differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD), and Polarized Light Microscopy (PLM), before and after tempering at 80 °C for 1 h. The selected SL:LL combination was 70% (Dynasan^®114 and 118) and 30% (Miglyol^®812 and 840) for the production of SLN and NLC by high-pressure homogenization (HPH), respectively. Particles with a mean size of 200 nm (polydispersity index <0.329) and zeta potential of ?15 mV were obtained, and their long-term stability was confirmed for 3 months of storage at 7 °C.     

Cis→Trans Isomerization of Pro<Superscript>7</Superscript> in Oxytocin Regulates Zn<Superscript>2+</Superscript> Binding

Ion mobility/mass spectrometry techniques are employed to investigate the binding of Zn²⁺ to the nine-residue peptide hormone oxytocin (OT, Cys¹-Tyr²-Ile³-Gln⁴-Asn⁵-Cys⁶-Pro⁷-Leu⁸-Gly⁹-NH₂, having a disulfide bond between Cys¹ and Cys⁶ residues). Zn²⁺ binding to OT is known to increase the affinity of OT for its receptor [Pearlmutter, A. F., Soloff, M. S.: Characterization of the metal ion requirement for oxytocin-receptor interaction in rat mammary gland membranes. J. Biol. Chem. 254, 3899–3906 (1979)]. In the absence of Zn²⁺, we find evidence for two primary OT conformations, which arise because the Cys⁶–Pro⁷ peptide bond exists in both the trans- and cis-configurations. Upon addition of Zn²⁺, we determine binding constants in water of K_A = 1.43 ± 0.24 and 0.42 ± 0.12 μM^?1, for the trans- and cis-configured populations, respectively. The Zn²⁺ bound form of OT, having a cross section of Ω = 235 Ų, has Pro⁷ in the trans-configuration, which agrees with a prior report [Wyttenbach, T., Liu, D., Bowers, M. T.: Interactions of the hormone oxytocin with divalent metal ions. J. Am. Chem. Soc. 130, 5993–6000 (2008)], in which it was proposed that Zn²⁺ binds to the peptide ring and is further coordinated by interaction of the C-terminal, Pro⁷-Leu⁸-Gly⁹-NH₂, tail. The present work shows that the cis-configuration of OT isomerizes to the trans-configuration upon binding Zn²⁺. In this way, the proline residue regulates Zn²⁺ binding to OT and, hence, is important in receptor binding.

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Graphical Abstract ?

     

Near-infrared DC approach by Bi<Superscript>3+</Superscript>–Yb<Superscript>3+</Superscript> co-doped YAG phosphor

Bi³⁺–Yb³⁺ ion pair co-doped YAG phosphors were successfully synthesized using conventional solid state reaction method varying the concentration of Yb³⁺ ions from 0.5 to 10 mol%. The optimum phosphors were characterized by powder X-ray diffraction (XRD), and surface morphology was studied with a scanning electronic microscope (SEM). The photoluminescence (PL) properties were studied with a spectrophotometers in near infrared (NIR) and ultraviolet visible (UV-Vis) regions. The synthesized phosphors can convert a photon of UV region (330 nm) into photons of NIR region (979 and 992 nm). The co-operative energy transfer (CET) was studied using a time decay curve and PL spectra. The theoretical value of quantum efficiency (QE) was calculated from steady time decay measurement, and the maximum efficiency approached up to 166.91 %. Hence, this phosphor could be used as a downconversion (DC) luminescent convertor in front of crystalline silicon solar cell (c-Si) panels to reduce heat loss due to spectral mismatch of the solar cells.     

Complexation of 4′-Nitrobenzo-15-crown-5 with Zn<Superscript>2+</Superscript>, Mn<Superscript>2+</Superscript>, Cr<Superscript>3+</Superscript> and Sn<Superscript>4+</Superscript> Cations in Acetonitrile–Ethanol Binary Mixtures

The complexation reactions of 4′-nitrobenzo-15-crown-5 (4′NB15C5) with Zn²⁺, Mn²⁺, Cr³⁺ and Sn⁴⁺ cations were studied in acetonitrile–ethanol (AN–EtOH) binary solvent mixtures at different temperatures by the electrical conductometry method. The stability constants of the resulting 1:1 complexes were determined from computer fitting of the conductance versus mole ratio data. The results show that the selectivity order of 4′NB15C5 for the metal cations in the AN–EtOH (mol-%AN=76) binary solvent at 298.15 K is: Cr³⁺>Mn²⁺≈Zn²⁺>Sn⁴⁺, but the selectivity order changes with the composition of the mixed solvents. A nonlinear relationship was observed between the stability constants (log ₁₀ K _f) of these complexes and the composition of the AN–EtOH binary solvents. The corresponding thermodynamic parameters (DH_c^o, DS_c^o)(\Delta H_{\mathrm{c}}^{\mathrm{o}}, \Delta S_{\mathrm{c}}^{\mathrm{o}}) were obtained from the temperature dependence of the stability constants using van’t Hoff plots. The results show that the values and also the sign of these parameters are influenced by the nature and composition of the mixed solvents.     

Production possibility of <Superscript>186</Superscript>Re via the <Superscript>192</Superscript>Os(p,α3n)<Superscript>186</Superscript>Re nuclear reaction

Experimentally measured cross-sections are presented for the first time for the ¹⁹²Os(p,α3n)¹⁸⁶Re nuclear reaction up to 67 MeV. Highly enriched thin ¹⁹²Os targets (15 pcs), prepared by electro-deposition onto Cu backings, were irradiated with an external proton beam delivered by the SSC cyclotron of iThemba LABS. The excitation function curve of the ¹⁹²Os(p,α3n)¹⁸⁶Re reaction shows a maximum cross-section of ~82 mb at about 24 MeV. According to the yield calculations based on the present results, the available cumulative no-carrier-added ¹⁸⁶Re yield is 7.76 MBq/μAh (0.21 mCi/μAh) over the energy region 13.4 → 27.3 MeV.     

Complexation of 4′-nitrobenzo-15-crown-5 with Mg<Superscript>2+</Superscript>, Ca<Superscript>2+</Superscript>, Sr<Superscript>2+</Superscript> and Ba<Superscript>2+</Superscript> metal cations in acetonitrile-methanol binary solutions

The complex formation reactions between Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺ metal cations with macrocyclic ligand, 4′-nitrobenzo-15C5, were studied in acetonitrile (AN)-methanol (MeOH) binary mixtures at different temperatures using conductometric method. The results show that 4′-nitrobenzo-15C5 forms 1:1 [ML] complexes with Mg²⁺, Ca²⁺ and Sr²⁺ metal cations in solutions. But in the case of Ba²⁺ cation a 1:2 [ML₂] complex is formed in these solvent systems. The stability of the complexes is sensitive to the solvent composition and a non-linear behavior was observed for variation of logK _f of the complexes versus the composition of the binary mixed solvents. The stability constants of complexes decrease suddenly with increasing the concentration of methanol in this binary system. The values of thermodynamic parameters (ΔH _c^° and ΔS _c^°) for formation of (4′-nitrobenzo-15C5.Mg)²⁺, (4′-nitrobenzo-15C5.Ca)²⁺ and (4′-nitrobenzo-15C5.Sr)²⁺ complexes were obtained from temperature dependence of the stability constants and the results show that these parameters are affected by the nature and composition of the mixed solvents. A non-linear behavior is observed between the ΔS _c^° and the composition of the mixed solvents.     

Quantum chemical study of formation of Cu<Superscript>II</Superscript>–Y<Superscript>III</Superscript> metallamacrocyclic complexes based on glycinehydroximate ligands

The process of solution-phase formation of the Cu^II–Y^III 15-metallacrown-5 complexes bearing the glycinehydroximate ligands has been for the first time investigated by methods of quantum chemistry. The DFT modeling at the B3LYP/DGDZVP (PCM) level was carried out for mono-, bi-, and tri-nuclear copper(II) complexes and also for heteronuclear Cu^II–Y^III derivatives as the metallamacrocycle precursors. The dependence of relative stability of these complexes on the Cu^II and Y^III coordination surroundings and also on the mutual positions of ligands was found. The structural (variations of interatomic distances and valence angles), electronic (changes in the atomic charges and electron density), and thermodynamical (enthalpies and Gibbs free energies) regularities of 15-metallacrown-5 formation were revealed. The key role of Y^III cation was established for the process of formation of the polynuclear metallamacrocyclic compound (15-metallacrown-5).     

Mössbauer effect at <Superscript>119</Superscript>Sn<Superscript>4+</Superscript> nuclei in fine crystalline MnO

The hyperfine structure of the low-temperature Mössbauer spectra of dopant ¹¹⁹Sn⁴⁺ ions (0.4 at. %) in a fine crystalline MnO sample, characterized by X-ray diffraction and magnetic measurements, has been studied. The ¹¹⁹Sn spectra show that tin is distributed over positions with an inhomogeneous cationic environment. The appearance of such positions is explained by the local compensation for the excess charge of Sn⁴⁺ by manganese vacancies V _Mn and segregation of defects resulting in precipitation of MnSnO₃ clusters. The non-uniform distribution of Sn⁴⁺ and the related dependence of the number of broken magnetic bonds on the local tin concentration are responsible for the fluctuation of the T _N values, which is “perceived” by ¹¹⁹Sn in different MnO crystallites. The ¹¹⁹Sn spectra exclude the possibility that tin enters into the composition of superpara-magnetic particles.     

Interactions between AuCl<Subscript>4</Subscript><Superscript>−</Superscript> and CTA<Superscript>+</Superscript> ions in water

The solubility of hexadecyltrimethylammonium tetrachloroaurate (CTA·AuCl₄) in water was measured at different temperatures of 288.2, 293.2, 298.2, 303.2, and 308.2 K. The enthalpy change associated with the formation of the CTA·AuCl₄ precipitate was estimated on the basis of the van’t Hoff equation and was found to be −42.5 ± 2.8 kJ mol⁻¹ at 298.2 K. The calorimetric enthalpy change for the CTA·AuCl₄ precipitate formation was directly determined by isothermal titration calorimetry performed at 298.2 K and was found to agree well with that estimated from the van’t Hoff equation.     

Identification of Anionic Supramolecular Complexes of Sulfonamide Receptors with Cl<Superscript>−</Superscript>, NO<Stack><Subscript>3</Subscript><Superscript>−</Superscript></Stack>, Br<Superscript>−</Superscript>, and I<Superscript>−</Superscript> by APCI-MS

As part of a mass spectrometric investigation of the binding properties of sulfonamide anion receptors, an atmospheric pressure chemical ionization mass spectrometric (APCI-MS) method involving direct infusion followed by thermal desorption was employed for identification of anionic supramolecular complexes in dichloromethane (CH₂Cl₂). Specifically, the dansylamide derivative of tris(2-aminoethyl)amine (tren) (1), the chiral 1,3-benzenesulfonamide derivatives of (1R,2S)-(+)-cis-1-amino-2-indanol (2), and (R)-(+)-bornylamine, (3), were shown to bind halide and nitrate ions in the presence of (n−Bu)₄N⁺X⁻ (X⁻ = Cl⁻, NO₃⁻, Br⁻, I⁻). Solutions of receptors and anions in CH₂Cl₂ were combined to form the anionic supramolecular complexes, which were subsequently introduced into the mass spectrometer via direct infusion followed by thermal desorption. The anionic supramolecular complexes [M+X]⁻, (M=1–3, X⁻=Cl⁻, NO₃⁻, Br⁻, I⁻) were observed in negative mode APCI-MS along with the deprotonated receptors [M−H]⁻. Full ionization energy of the APCI corona pin (4.5 kV) was necessary for obtaining mass spectra with the best signal-to-noise ratios.     

Nucleation of water vapor on Na<Superscript>+</Superscript>Cl<Superscript>−</Superscript> ion pairs: Computer simulation

The Monte Carlo method is used to calculate the free energy, entropy, and work of water cluster formation in the field of Na⁺Cl⁻ ion pairs. A detailed model is used that allows for polarization and covalent many-particle interactions, as well as the effects of ion charge reversal. The model is matched to the experimental data on the free energy of ion hydration and the results of the quantum-chemical calculations of stable configurations. The hydration leads to the cleavage of an ion pair in a molecular cluster after approximately ten water molecules are captured. As vapor molecules are added, the stable interion distance monotonically elongates. The low free energy barrier separating the dissociated and nondissociated states of the ion pair in an equilibrium cluster does not hinders the reversible spontaneous transitions between the states, which are responsible for strong fluctuations and the instability of the system. Unlike hydroxonium-containing ion pairs, the formation of long-lived metastable states of hydrated Na⁺Cl⁻ pairs is impossible.     

Triboluminescence of zirconium η<Superscript>5</Superscript>-complexes

This work describes a comparative study of tribo- and photoluminescence of metallocenes (Cp₂HfCl₂, Cp₂TiCl₂, Cp₂ZrCl₂, (CpMe)₂ZrCl₂, rac-Me₂C(3-Bu^t-Cp)₂ZrCl₂, Ind*₂ZrCl₂). Occurring under mechanodestruction of polycrystals, triboluminescence of zirconium bis-cyclopentadienyl complexes, Cp₂ZrCl₂, (CpMe)₂ZrCl₂, and rac-Me₂C(3-Bu^t-Cp)₂ZrCl₂ has been revealed for the first time. The triboluminescence spectrum in air is similar to the photoluminescence spectrum of zirconocene polycrystals. The triboluminescence spectrum does not show *N₂ luminescence. Ne and Ar lines are observed in the triboluminescence spectrum in the atmosphere of these gases. An increase in the number of substituents in zirconocene ligands leads to a bathochromic shift of the emission band maximum in triboluminescence spectra of the complexes. Possible mechanisms of zirconocene triboluminescence excitation are discussed.