Application of Tri-n-octylamine for the substoichiometric separation of chromium(VI) in activation analysis

A method has been developed for the substoichiometric separation of Cr(VI) by extraction with tri-n-octylamine solution in benzene from 0.1M H₂SO₄ solution. The method has been applied to the determination of chromium in silicon and aluminium by the neutron activation method.     

The place of sioh groups in the absolute acidity scale from ab initio calculations

The deprotonation energy of a (H₃Si)O-H group as a simplified structural element of silica gel and aluminosilicates is estimated from ab initio calculations on H₂O, CH₃0H and SiH₃0H to be near 1475 kJ/mol. Results of the effect of Lewis acids on the Brønsted acidity of SiOH are given.     

The Photophysics of β-Tyrosine and Its Simple Derivatives

Synthesis and photophysical studies of (O-methyl)--tyrosine (-tyrosine; an analogue of tyrosine, in which the amino group is moved from the - to the -carbon, closer to the phenol ring) and its derivatives with a blocked amino and/or carboxyl group were performed to explain the nature of the fluorescence of tyrosine derived analogues. All -tyrosine derivatives, except Ac-Tyr(Me), displayed the monoexponential fluorescence decay. The biexponential fluorescence decay observed for Ac-Tyr(Me) is assumed to be the result of the presence of two low-energy conformations (extended and with an intramolecular hydrogen bond). Higher quenching of the fluorescence of -tyrosine derivatives by the N-acetyl group than by the N-methylamide group moved farther was found, contrary to the data found for the respective derivatives of natural tyrosine. The obtained photophysical data are discussed with theoretical calculations (AMBER, AM1) on the basis of the rotamer model.     

Thermal decomposition of vesuvianite

The thermal decomposition of vesuvianite was studied by means of thermal, FTIR and X-ray methods. It was found that two structural forms of vesuvianite, a high-temperature (disordered) and a low-temperature (ordered) one, differ distinctly in the mechanism of their decomposition (dehydroxylation). Dehydroxylation of low vesuvianites begins at lower temperatures (ca. 900°C), and the strong endothermic peak with maximum at ca. 1020°C is usually followed by an exothermic peak. Dehydroxylation of high vesuvianites begins at ca. 1000°C, and the OTA curve usually displays two endothermic peaks not followed by an exothermic effect. The crystallization products of vesuvianite are grossular, gehlenite and anorthite. Vesuvianite melts in the temperature range 1100–1200°C.The authors thank Mr. A. Gawel for kindly recording the X-ray powder diffractograms. This study was supported by KBN grant No 6 P201 018 04.     

Pharmacological Characterization of µ-Opioid Receptor Agonists with Biased G Protein or β-Arrestin Signaling,and Computational Study of Conformational Changes during Receptor Activation

In recent years, G protein vs. β-arrestin biased agonism at opioid receptors has been proposed as an opportunity to produce antinociception with reduced adverse effects. However, at present this approach is highly debated, a reason why more information about biased ligands is required. While the practical relevance of bias in the case of µ-opioid receptors (MOP) still needs to be validated, it remains important to understand the basis of this bias of MOP (and other GPCRs). Recently, we reported two cyclopeptides with high affinity for MOP, the G protein biased Dmt-c[d-Lys-Phe-pCF₃-Phe-Asp]NH₂ (F-81), and the β-arrestin 2 biased Dmt-c[d-Lys-Phe-Asp]NH₂ (C-33), as determined by calcium mobilization assay and bioluminescence resonance energy transfer-based assay. The biased character of F-81 and C-33 has been further analyzed in the [³⁵S]GTPγS binding assay in human MOP-expressing cells, and the PathHunter enzyme complementation assay, used to measure β-arrestin 2 recruitment. To investigate the structural features of peptide-MOP complexes, we performed conformational analysis by NMR spectroscopy, molecular docking, and molecular dynamics simulation. These studies predicted that the two ligands form alternative complexes with MOP, engaging specific ligand–receptor contacts. This would induce different displays of the cytosolic side of the seven-helices bundle, in particular by stabilizing different angulations of helix 6, that could favor intracellular coupling to either G protein or β-arrestin.     

Structure and magnetic properties of a copper(II) compound with syn–anti carboxylato- and linear Cu–Cl–Cu chloro-bridges

The copper(II) polymer Cu(2-qic)Cl (2-qic = quinoline-2-carboxylate) was synthesized and then characterized by X-ray crystal structure determination, spectroscopic and magnetic studies. The crystal structure consists of copper(II) ions with two different chromophores: four-coordinated in a square-planar geometry and five-coordinated in an environment between square-pyramidal and trigonal-bipyramidal. The copper ions are bridged sequentially through the carboxylate groups in a syn–anti conformation, forming an infinite one-dimensional zigzag chain with two alternating non-equivalent copper(II) chromophores. The chloride atom acts as a single chloro-bridge link to adjacent chains, forming a ribbon type structure (1D). The variable-temperature (1.8–300 K) magnetic susceptibility data of the complex were interpreted with the dimer law using the molecular field approximation. The results obtained indicate a very weak ferromagnetic (J₂ = 0.37 cm⁻¹) interchain interaction through the syn–anti carboxylate bridge. A relatively strong antiferromagnetic interaction, transmitted through the chloro-bridge with an exchange coupling of J₁ = −57.0 cm⁻¹, dominates the magnetic properties of this complex. The magnitude and the nature of the exchange coupling are explained on the basis of the structural results.     

Solvation of bivalent transition metalcations. II. Heats of transfer of metal perchlorates between water and several amides

Heats of solution of acetonitrile, solvated or hydrated perchlorates, Mn(ClO₄)₂·6AN, Co(ClO₄)₂·6AN, Ni(ClO₄)₂·6AN, Cu(ClO₄)₂·4AN, Cu(ClO₄)₂·6H₂O, Zn(ClO₄)₂·6AN, and Zn(ClO₄)₂·6H₂O have been determined in NMF, DMF, DMA, and water. Complete or almost complete exchange of AN and water molecules in amides is inferred from the visible spectra determinations. The heats of transfer of perchlorate anion from water to DMA and NMF have been obtained from separately determined heats of solution of NaBPh₄, AsPH₄Cl·H₂O, NaClO₄, NaCl, and SiPh₄ in the respective solvents. The heats of transfer of cations from water to amides have been determined from the above data and the heats of solvation of cations using literature data for the heats of hydration.     

Both nucleophile and substrate bind to the catalytic Fe(II)-center in the type-II methionyl aminopeptidase from Pyrococcus furiosus

Metalloproteases utilize their active site divalent metal ions to generate a nucleophilic water/hydroxide. For methionine aminopeptidases (MetAPs), the exact location of this nucleophile, as well as of the substrate, with respect to the active site metal ion is unknown. In order to address this issue, we have examined the catalytically competent Fe(II)-loaded form of PfMetAP-II ([Fe(PfMetAP-II)]) in the absence and presence of both nitric oxide (NO) and the substrate-analogue inhibitor butaneboronic acid (BuBA) by kinetic and spectroscopic (EPR, UV-vis) methods. NO binds to [Fe(PfMetAP-II)] with a Kd of 200 microM forming an {FeNO}7 complex. UV-vis spectra of the resulting [Fe(PfMetAP-II)]-NO complex indicate that the Fe(II) ion is six coordinate. These data suggest that NO binding occurs without displacing the bound aquo/hydroxo moiety in [Fe(PfMetAP-II)]. On the basis of EPR spectra, the resulting Fe-NO complex is best described as NO- (S = 1) antiferromagnetically coupled to a high-spin Fe(III) ion (S = 5/2). The addition of BuBA to [Fe(PfMetAP-II)]-NO displaces the coordinated water molecule forming a six-coordinate adduct. EPR data also indicate that an interaction between the bound NO- and BuBA occurs forming a complex that mimics an intermediate step between the Michaelis complex and the tetrahedral transition-state.     

Thermal studies of zinc and cadmium halide complexes with N-tert-alkylacrylamides

The thermal properties of complexes of N-tert-butylacrylamide and N-tert-amylacrylamide with ZnCl₂, ZnBr₂, CdCl₂ and CdBr₂ have been studied in air and in argon by TG and DTA. The decomposition proceeds in two steps with evolution of simple, low molecular weight gaseous products. The use of various heating rates revealed an additional exothermic DTA peak for complexes with zinc and cadmium chlorides corresponding to a solid state polymerization reaction which was confirmed by IR spectral analysis. This effect was not observed for corresponding complexes of zinc and cadmium bromides, which show much lower thermal stability.

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Zusammenfassung Die thermischen Eigenschaften der Komplexe von N-Tertbutylacrylamid und N-Tertamylacrylamid mit ZnCl₂, ZnBr₂, CdCl₂ und CdBr₂ wurden in Luft und in Argon durch TG und DTA studiert. Die Zersetzung verläuft in zwei Stufen unter Entwicklung einfacher gasförmiger Produkte niedriges Molekulargewichts. Der Einsatz verschiedener Aufheizgeschwindigkeiten zeigte für Komplexe mit Zink- und Cadmiumchloriden einen zusätzlichen DTA Peak, der Festphasen-Polymerisationsreaktion entsprechend, welche durch IR-Spektralanalyse bestätigt wurde. Dieser Effekt wurde bei den entsprechenden Komplexen der Zink- und Cadmiumbromide, welche eine viel geringere Thermostabilität besitzen, nicht beobachtet.

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Résumé On a étudié, par TG et ATD, dans l'air et l'argon, les propriétés thermiques des complexes du N-tertbutyl-acrylamide et du N-tétramylacrylamide avec ZnCl₂, ZnBr₂, CdCl₂ et CdBr₂. La décomposition s'effectue en deux étapes, avec dégagement de produits gazeux simples de faible poids moléculaire. L'application de différentes vitesses de chauffage a révélé, pour les complexes des chlorures de zinc et de cadmium, un pic exothermique additionnel en ATD qui correspond à la réaction de polymérisation dans l'état solide et qui a été confirmé par spectrométrie infrarouge. On n'a pas observé cet effet dans le cas des complexes correspondants des bromures de zinc et cadmium dont la stabilité thermique est bien plus faible.

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N- - N- ZnCl₂, ZnBr₂, CdCl₂ CdBr₂. , . . , . , .

     

UV-spectroscopic study of the influence of traces of water on the protolytic equilibria of substituted pyridine N-oxides in aprotic solvents

Using a UV-spectrophotometric method, an attempt has been made to estimate quantitatively the influence of traces of water in aprotic solvents on the acidic-basic equilibria involving heterocyclic N-oxides. The N-oxides under study were pyridine N-oxide (PyO), 4-methoxy-pyridine N-oxide (4-MeOPyO), and 2-, 3-, and 4-picoline N-oxide (2-, 3-, and 4-PicO). For particular N-oxide the UV-spectra of acetonitrile solutions containing the free base and/or its simple or semiperchlorate have been recorded. To carry out the calculations various equilibrium models which include the protolytic equilibrium with water and basic species present in the solvent have been tested using the program STOICHIO which is based on non-linear regression analysis. It turned out that apart from the acidic-basic dissociation of a protonated N-oxide and cationic homoconjugation (the equilibria which are usually considered in such systems) it is absolutely necessary to take into account the protolytic equilibrium between the cationic acid and water present as impurity. Implications concerning investigations of other equilibrium systems in aprotic solvents and, in particular, the quality of the acidity constants for the calibration agents used in potentiometry are discussed.