Mössbauer and infrared spectroscopic studies of novel mixed valence states in cobaltous ferrocyanides and ferricyanides

Novel mixed valence states have been obtained by the treatment of cobaltous ferrocyanides (Co⁺²Fe^II) and ferricyanides (Co⁺²Fe^III) in an ozone flow. The CN stretching bands occur at 2085 cm^–1 for Co⁺²Fe^II and at 2160 cm^–1 for Co⁺²Fe^III. After the ozonization process of Co⁺²Fe^II, an intense band approximately at 2125 cm^–1 is detected. This intermediate band must correspond to a mixed valence state of the type: Fe^II–CN–Co²⁺–NC–Fe^III Mössbauer spectra recorded in situ during the ozonization of Co⁺²Fe^II show the presence of two components: a doublet with isomer shift and quadrupole splitting values close to the cobalti ferricyanide and a very broad line for the mixed valence state. From the Mössbauer and infrared spectra of the aged samples of the Co⁺²Fe^II after ozonization, a relaxation process to the initial state of the samples is observed but the mixed valence state is stable.     

Elucidating Factors Manipulated the Formation of Multiply Charged Protein Homomultimeric Complexes by Electrospray Ionization

Native non‐covalently bonded protein‐protein and protein‐substrate complexes are of great interest and have been extensively studied by electrospray ionization mass spectrometry (ESI‐MS). Multiply charged protein homomultimeric complexes are shown to form by ESI‐MS. This study addresses factors that can artificially induce the formation of multiply charged protein homomultimeric complexes. Cytochrome c (Cyt c) and ubiquitin, which are monomers in solution, were found to generate (Cyt c)_mⁿ⁺ by electrospray ionization (ESI). The homomultimeric complexes were not limited to dimeric complexes but include also multiply charged trimers, tetramers, and pentamers. The observation of these homomultimeric complexes has never been revealed from a Cyt c solution at the concentration as low as 10 μM. Increasing the concentration of Cyt c enhanced the formation of (Cyt c)_mⁿ⁺ as expected; however, the protein concentration does not affect the relative intensities of monomeric and dimeric complexes. Additionally the enrichment of NH₄OH also promotes the formation of (Cyt c)_mⁿ⁺. Notably, source collision‐induced dissociations (source‐CID) of (Cyt c)_mⁿ⁺ alter the charge state distribution (CSD) and may lead to an incorrect interpretation of Cyt c conformations. Hence, extra care should be taken when using CSD to interpret the conformation of a protein derived from ESI‐MS.     

Theoretical and experimental investigation of the effect of proton transfer on the (27)al MAS NMR line shapes of zeolite-adsorbate complexes: an independent measure of solid Acid strength

Assessing the degree of proton transfer from a Br?nsted acid site to one or more adsorbed bases is central to arguments regarding the strength of zeolites and other solid acids. In this regard certain solid-state NMR measurements have been fruitful; for example, some (13)C, (15)N, or (31)P resonances of adsorbed bases are sensitive to protonation, and the (1)H chemical shift of the Br?nsted site itself reflects hydrogen bonding. We modeled theoretically the structures of adsorption complexes of several bases on zeolite HZSM-5, calculated the quadrupole coupling constants (Q(cc)) and asymmetry parameters (eta) for aluminum in these complexes and then in turn simulated the central transitions of their (27)Al MAS NMR spectra. The theoretical line width decreased monotonically with the degree of proton transfer, reflecting structural relaxation around aluminum as the proton was transferred to a base. We verified this experimentally for a series of adsorbed bases by way of single-pulse MAS and triple quantum MQMAS (27)Al NMR. The combined theoretical and experimental approach described here provides a strategy by which (27)Al data can be applied to resolve disputed interpretations of proton transfer based on other evidence.     

Synthesis and Cytotoxicity Evaluation of Metal‐Chelator‐Bearing Flavone,Carbazole, Dibenzofuran,Xanthone, and Anthraquinone

2‐(Aryloxymethyl)‐5‐benzyloxy‐1‐methyl‐1H‐pyridin‐4‐ones 8a – 8g , 2‐(aryloxymethyl)‐5‐hydroxy‐4H‐pyran‐4‐ones 9a – 9g , and 2‐(aryloxymethyl)‐5‐hydroxy‐1‐methyl‐1H‐pyridin‐4‐ones 10a – 10g were prepared from the known 5‐benzyloxy‐2‐(hydroxymethyl)pyran‐4‐one ( 3 ) in a good overall yield. These compounds were evaluated in vitro against a three‐cell lines panel consisting of MCF7 (breast), NCI‐H460 (lung), and SF‐268 (CNS), and the active compounds passed on for evaluation in the full panel of 60 human tumor cell lines derived from nine cancer cell types. The results indicated that 5‐hydroxy derivatives are more favorable than their corresponding 5‐benzyloxy precursors ( 10a – 10g vs. 8a – 8g ), and 1‐methyl‐1H‐pyridin‐4‐ones are more favorable than their corresponding pyran‐4(1H)‐ones ( 10a – 10g vs. 9a – 9g ). Among these three types of compounds, 2‐(aryloxymethyl)‐5‐hydroxy‐1‐methyl‐1H‐pyridin‐4‐ones 10a – 10g were the most cytotoxic; they inhibited the growth of almost all the cancer cells tested. On the contrary, compound 8a (a mean GI₅₀=27.8 μM ), 8b (38.5), 8d (11.0), and 8e (30.5) are especially active against the growth of SK‐MEL‐5 (a melanoma cancer cell) with a GI₅₀ of <0.01, 5.65, 0.55, and 0.03 μM , respectively (cf. Table 2).     

Expanding the Synthesis Field of High-Silica Zeolites

Aluminosilicate zeolites are synthesized under hydrothermal conditions in a basic/alkaline medium in the pH range between 9 and 14. The synthesis of MFI-type zeolite in an acidic medium is presented. The critical parameter determining the zeolite formation in an acidic medium was found to be the isoelectric point (IEP) of gel particles. MFI-type zeolite was synthesized above the isoelectric point of the employed silica source, where the silica species exhibit a negative charge and the paradigm of zeolite formation based on the electrostatic interaction with the positively charged template is retained. No zeolite formation is observed below the isoelectric point of silica. The impact of aluminum on the zeolite formation is also studied. The results of this study will serve to extend the synthesis field of high silica zeolites to the acidic medium and thus open new opportunities to control the zeolite properties.