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- Bravo, L, et al.
(author)
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- 2021
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swepub:Mat__t
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- Tabiri, S, et al.
(author)
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- 2021
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swepub:Mat__t
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- Ivanov, Alexander V., et al.
(author)
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Chemisorption Synthesis of the Ion-Polymeric Heteronuclear Gold(III)-Bismuth(III) Complex ([Au{S2CN(C3H7)2}2]3[Bi2Cl9])n Based on [Bi2{S2CN(C3H7)2}6]: 13C MAS NMR, Supramolecular Structure, and Thermal Behavior
- 2018
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In: Russian journal of coordination chemistry. - : Springer. - 1070-3284 .- 1608-3318. ; 44:8, s. 518-531
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Journal article (peer-reviewed)abstract
- Chemisorption synthesis on the basis of the binuclear compound [Bi2{S2CN(C3H7)2}6] (I) and preparative isolation of the ion-polymeric heteronuclear gold(III)-bismuth(III) complex ([Au{S2CN(C3H7)2}2]3[Bi2Cl9])n (II) are carried out. Compounds I and II are characterized in comparison by IR spectroscopy and 13C CP-MAS NMR. According to the X-ray diffraction analysis data (CIF file CCDC no. 1407705), the cationic moiety of compound II exhibits an unusually complicated supramolecular structure including six isomeric noncentrosymmetric complex cations [Au{S2CN(C3H7)2}2]+ (hereinafter A-F) and two binuclear anions [Bi2Cl9]3- as conformers. The isomeric gold(III) cations perform various structural functions. Owing to pair secondary interactions Au···S, cations B, C, E, and F form centrosymmetric ([E···E], [F···F]) and noncentrosymmetric ([B···C]) binuclear aggregates [Au2{S2CN(C3H7)2}4]2+, whereas cations A and D are not involved in dimerization. The strongest secondary Au···S bonds are formed between the binuclear and mononuclear cations, resulting in the formation of supramolecular cation-cationic polymer chains of two types: (⋅⋅⋅A⋅⋅⋅[B⋅⋅⋅C]⋅⋅⋅A⋅⋅⋅[B⋅⋅⋅C]⋅⋅⋅)n and (D⋅⋅⋅[E⋅⋅⋅E]⋅⋅⋅D⋅⋅⋅[F⋅⋅⋅F]⋅⋅⋅])n. In both chains, the gold atoms of the binuclear cations are characterized by a distorted octahedral coordination [S6], whereas in the mononuclear cations the gold atoms retain the square environment [S4]. The cation-anionic interactions are provided by secondary bonds Cl⋅⋅⋅S involving the terminal chlorine atoms of isomeric [Bi2Cl9]3- and the sulfur atoms of the binuclear cations [Au2{S2CN(C3H7)2}4]2+. The character of the thermal behavior of compounds I and II is studied by simultaneous thermal analysis with the identification of intermediate and final products of the thermal transformations. The thermolysis of compound I at 193-320°C is accompanied by the formation of Bi2S3 with an impurity of reduced metallic bismuth particles. The final products of the thermal transformations of compound II are reduced elemental gold and Bi2O3, and the thermal transformation intermediates are BiCl3 and Bi2S3.
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- Korneeva, E.V., et al.
(author)
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Crystalline nickel(II) di-i-amyl dithiophosphate, [Ni{S2P(O-i-C5H11)2}2] : Preparation, structure, heteronuclear (13C, 31P) CP/MAS NMR spectra, and thermal behavior
- 2017
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In: Russian journal of coordination chemistry. - : Springer. - 1070-3284 .- 1608-3318. ; 43:4, s. 223-231
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Journal article (peer-reviewed)abstract
- The crystalline nickel(II) di-i-amyl) dithiophosphate (Dtph), [Ni{S2P(O-i-C5H11)2}2] (I) was isolated on a preparative scale and characterized by 13C, 31P MAS NMR, and X-ray diffraction (CIF file CCDC no. 1469369). The χ2-statistic diagrams were constructed from full 31P CP/MAS NMR spectra for calculating the 31P chemical shift anisotropy: δaniso = δzz–δiso and the asymmetry parameter η = (δyy–δxx)/(δzz–δiso). The key structural unit of I is the centrosymmetric [Ni{S2P(O-i-C5H11)2}2] molecule in which the nickel atom coordinates two Dtph ligands in the isobidentate fashion. In molecule I, each carbon, oxygen, and sulfur atom is statistically disordered over two sites with equal occupancies. However, the disorder does not affect nickel and phosphorus. These results were interpreted as the presence in I of two [Ni{S2P(O-i-C5H11)2}2] molecules rotated through 21.0(1)° (the angle between the [NiS4] chromophore planes) relative to each other around the bisecting P–Ni–P axis passing through both four-membered [NiS2P] rings. The two molecules occupy crystal lattice sites with equal probabilities. The thermal behavior of I was studied by simultaneous thermal analysis under argon. The course of the thermal destruction of the complex was established, nickel pyrophosphate (Ni2P2O7) was identified as the final product of thermal transformations.
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- Zaborowski, AM, et al.
(author)
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Microsatellite instability in young patients with rectal cancer: molecular findings and treatment response
- 2022
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In: The British journal of surgery. - : Oxford University Press (OUP). - 1365-2168 .- 0007-1323. ; 109:3, s. 251-255
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Journal article (peer-reviewed)abstract
- In this study of 400 patients with early-onset rectal cancer, 12.5 per cent demonstrated microsatellite instability (MSI). MSI was associated with a reduced likelihood of nodal positivity, an increased rate of pathological complete response, and improved disease-specific survival.
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