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Analysis involving long-term outcomes of pathogenetic treatment of Helicobacter pylori-associated gastroduodenopathies caused by nonsteroidal anti-inflammatory medications throughout sufferers with osteo arthritis.
A detailed study for the synthesis of dinickel(II)-thiolate and dinickel(II)-hydrosulfide complexes and the complete characterization of the relevant intermediates involved in the C-S bond cleavage of thiolates are presented. Hydrated Ni(II) salts mediate the hydrolytic C-S bond cleavage of thiolates (NaSR/RSH; R = Me, Et, n Bu, t Bu), albeit inefficiently, to yield a mixture of a dinickel(II)-hydrosulfide complex, [Ni2(BPMP)(μ-SH)(DMF)2]2+ (1), and the corresponding dinickel(II)-thiolate complexes, such as [Ni2(BPMP)(μ-SEt)(ClO4)]1+ (2) (HBPMP is 2,6-bis[[bis(2-pyridylmethyl)amino]methyl]-4-methylphenol). A systematic study for the reactivity of thiolates with Ni(II) was therefore pursued which finally yielded 1 as a pure product which has been characterized in comparison with the dinickel(II)-dichloride complex, [Ni2(BPMP)(Cl)2(MeOH)2]1+ (3). While the reaction of thiolates with anhydrous Ni(OTf)2 in dry conditions could only yield [Ni2(BPMP)(OTf)2]1+ (5) instead of the expected dinickel(II)-thiolate compound, the C-S bond cleavage could be suppressed by the use of a chelating thiol, such as PhCOSH, to yield [Ni2(BPMP)(SCOPh)2]1+ (6). Finally, with the suitable choice of a monodentate thiol, a dinickel(II)-monothiolate complex, [Ni2(BPMP)(SPh)(DMF)(MeOH)(H2O)]2+ (7), was isolated as a pure product within 1 h of reaction, which after a longer time of reaction yielded 1 and PhOH. Complex 7 may thus be regarded as the intermediate that precedes the C-S bond cleavage and is generated by the reaction of a thiolate with an initially formed dinickel(II)-solvento complex, [Ni2(BPMP)(MeOH)2(H2O)2]3+(4). Selected dinickel(II) complexes were explored further for the scope of substitution reactions, and the results include the isolation of a dinickel(II)-bis(thiolate) complex, [Ni2(BPMP)(μ-SPh)2]1+ (8).A series of new phosphasalalen pro-ligands, analogues of salalen but with an iminophosphorane replacing the imine functionality, and their corresponding rare-earth alkoxide and siloxide complexes were synthesized. The multinuclear NMR spectra and X-ray diffraction analyses revealed that, for the tert-butoxide and ethoxide complexes, the resulting phosphasalalen rare-earth product was composed of a mononuclear alkoxide and a binuclear complex containing bridged alkoxo and hydroxo groups, while an analogous binuclear complex was isolated as the sole product for the siloxide complex. All the complexes could catalyze the heteroselective ring-opening polymerization (ROP) of rac-lactide (Pr up to 0.77) with high catalytic activities and a controlled polydispersity. Remarkably, the yttrium and lutetium phosphasalalen complexes could also efficiently catalyze the ROP of rac-β-butyrolactone to produce syndiotactic polymers (Pr up to 0.73) while their salalen analogues were inert, revealing the special effects of the iminophosphorane moiety. Detailed end-group analyses and kinetic investigations suggested that the alkoxo-hydroxo-bridged complexes maintained their binuclear structures in the polymerization.A polyoxovanadate-based nickel-organic framework, [Ni(bib)2]V2O6(V6-MOF, bib = 1,4-bis(1H-imidazoly-1-yl)benzene), was facilely prepared under gentle hydrothermal conditions and structurally characterized. Single-crystal X-ray diffraction analysis indicates that the V6 cluster in the V6-MOF is constructed of two VO5 tetragonal pyramids and four VO4 tetrahedrons via the apex sharing of O atoms, presenting a hollow Linqvist-like structure, which is different from these reported hexanuclear vanadium clusters. Proteasome inhibitor The V6-MOF not only expands the structure of polyoxovanadates (POVs) but also catalyzes the rapid detoxification of mustard gas simulant (2-chloroethyl ethyl sulfide, CEES) at 25 °C. The catalytic results were determined by means of GC, GC-MS, and 1H NMR. Using V6-MOF as a heterogeneous catalyst, CEES underwent catalyzed oxidation to only nontoxic product 2-chloroethyl ethyl sulfoxide (CEESO) within 40 min, and the conversion and selectivity were almost 100%. In addition, V6-MOF exhibits high sustainability, and no obvious reductions in conversion and selectivity are observed after five runs.The crown-ether coordination compounds ZnX2(18-crown-6), EuX2(18-crown-6) (X Cl, Br, I), MnI2(18-crown-6), Mn3Cl6(18-crown-6)2, Mn3I6(18-crown-6)2, and Mn2I4(18-crown-6) are obtained by ionic-liquid-based synthesis. Whereas MX2(18-crown-6) (M Zn, Eu) show conventional structural motives, Mn3Cl6(18-crown-6)2, Mn3I6(18-crown-6)2, and Mn2I4(18-crown-6) exhibit unusual single MnX4 tetrahedra coordinated to the crown-ether complex. Surprisingly, some compounds show outstanding photoluminescence. Thus, rare Zn2+-based luminescence is observed and unexpectedly efficient for ZnI2(18-crown-6) with a quantum yield of 54%. Unprecedented quantum yields are also observed for Mn3I6(18-crown-6)2, EuBr2(18-crown-6), and EuI2(18-crown-6) with values of 98, 72, and 82%, respectively, which can be rationalized based on the specific structural features. Most remarkable, however, is Mn2I4(18-crown-6). Its specific structural features with finite sensitizer-activator couples result in an extremely strong emission with an outstanding quantum yield of 100%. Consistent with its structural features, moreover, anisotropic angle-dependent emission under polarized light and nonlinear optical (NLO) effects occur, including second-harmonic generation (SHG). The title compounds and their optical properties are characterized by single-crystal structure analysis, X-ray powder diffraction, chemical analysis, density functional theory (DFT) calculations, and advanced spectroscopic methods.Interaction of copper ions with Aβ peptides alters the redox activity of the metal ion and can be associated with neurodegeneration. Many studies deal with the characterization of the copper binding mode responsible for the reactivity. Oxidation experiments of dopamine and related catechols by copper(II) complexes with the N-terminal amyloid-β peptides Aβ16 and Aβ9, and the Aβ16[H6A] and Aβ16[H13A] mutant forms, both in their free amine and N-acetylated forms show that efficient reactivity requires the oxygenation of a CuI-bis(imidazole) complex with a bound substrate. Therefore, the active intermediate for catechol oxidation differs from the proposed "in-between state" for the catalytic oxidation of ascorbate. During the catechol oxidation process, hydrogen peroxide and superoxide anion are formed but give only a minor contribution to the reaction.
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