Autoreduction of Pd-Co and Pt-Co cyanogels: exploration of cyanometalate coordination chemistry at elevated temperatures

Cyanogels are coordination polymers made from the reaction of a chlorometalate and a cyanometalate in aqueous solution, which undergo a sol-gel transition to form stable gels. At temperatures above 240 degrees C, the cyanide ligand acts as a reducing agent and reduces the metal centers to lower oxidation states. To understand the mechanism of the autoreduction, the thermal reduction of the Pd-Co cyanogel system formed by the reaction of PdCl4(2-) and Co(CN)6(3-) was studied in an inert atmosphere. It was found that the reduction proceeds through two polymeric cyanide-containing intermediates, CoPd(CN)4 and Pd(CN)2, that form upon reduction of Co(3+) to Co(2+) and involves a significant rearrangement of the coordination structure. The two intermediates upon further heating reduce to metallic products, which by solid-state diffusion form a single Pd/Co alloy product. CoPd(CN)4 was found to have a hydrated form Co(H2O)2Pd(CN)4 x 4 H2O with a layered structure crystallizing in an orthorhombic Pnma space group. The Pt-Co cyanogel was found to autoreduce via a similar route. CoPt(CN)4 was confirmed as an intermediate. Understanding of the mechanism of the cyanogel autoreduction is an important step toward better understanding of opportunities that cyanogels offer in materials chemistry, as well as an expansion of the knowledge of coordination chemistry at elevated temperatures in general.     

Investigations of glycosylation reactions with 2-N-acetyl-2N,3O-oxazolidinone-protected glucosamine donors

NIS/AgOTf-promoted glycosylations with ethyl 2,3-N,O-carbonyl-2-deoxy-1-thio-beta-D-glucopyranoside donors can be performed with either alpha- or beta-selectivity by tuning the reaction conditions. Small amounts of AgOTf (0.1 equiv) and short reaction times give beta-selectivity, whereas 0.4 equiv of AgOTf and prolonged reaction times afford alpha-linked products. NMR-monitored glycosylation and anomerization experiments show initial formation of exclusively the beta-linkage, which anomerizes, through an intramolecular mechanism involving an endocyclic C-O bond cleavage, to the alpha-linkage.     

Multidimensional Persistence and Noise

In this paper, we study multidimensional persistence modules (Carlsson and Zomorodian in Discrete Comput Geom 42(1):71–93, 2009; Lesnick in Found Comput Math 15(3):613–650, 2015) via what we call tame functors and noise systems. A noise system leads to a pseudometric topology on the category of tame functors. We show how this pseudometric can be used to identify persistent features of compact multidimensional persistence modules. To count such features, we introduce the feature counting invariant and prove that assigning this invariant to compact tame functors is a 1-Lipschitz operation. For one-dimensional persistence, we explain how, by choosing an appropriate noise system, the feature counting invariant identifies the same persistent features as the classical barcode construction.     

Two mathematical models for dissolved oxygen in a lake—CMMSE-16

In this paper two mathematical models for handling water pollution are introduced. In the first one we assume that algae and fungi are in competition for resources that come from wastewater, while in the second one we introduce explicitly the equation of nutrients. Both algae and fungi need dissolved oxygen (DO) for their biological process of growth. But there is a difference, indeed algae produce it too and in a higher quantity than the one they use. For the first model it is shown that if the coexistence equilibrium exists, it is stable without additional conditions. If the competition rate between algae and fungi is not high for a chosen set of parameters the stability of the coexistence equilibrium is reached even without an external constant input of DO in the system. For the second model we have found the matching equilibrium points with the ones of the first model, furthermore other two equilibria are found.     

New saccharinate complexes with 3,3′-azobispyridine ligand: synthesis,characterization, and spectroscopic properties

The new metal complexes with saccharinate (sac) and 3,3′-azobispyridine (3,3′-abpy), [Ni(H₂O)₄(3,3′-abpy)₂](sac)₂ (1), [Cu(sac)₂(H₂O)(μ-3,3′-abpy)]_n (2), [Zn(H₂O)₄(3,3′-abpy)₂](sac)₂ (3), [Cd(sac)₂(H₂O)₂(μ-3,3′-abpy)]_n (4), and [Hg₂(μ-sac)₂(sac)₂(μ-3,3′-abpy)(3,3′-abpy)₂]_n (5), were synthesized and characterized by IR spectra, elemental analysis, and single-crystal X-ray diffraction. Spectroscopic (UV–vis and photoluminescence) and thermal properties were also investigated. Single-crystal X-ray analysis reveals that Ni(II) and Zn(II) are coordinated by four aqua ligands and two nitrogens of 3,3′-abpy, while sac is a counter-ion in 1 and 3. In 2, Cu(II) and all ligands are linked by coordination bonds and 3,3′-abpy ligands connect the Cu(II) centers forming a 1-D coordination polymer. In 4, sac N-coordinated to Cd(II) and distorted octahedral geometry of Cd(II) ion is completed by two aqua and bridging 3,3′-abpy ligands. In 5, sac bridges two Hg(II) ions to generate dinuclear [Hg₂(μ-sac)₂] units. These dinuclear units are connected by 3,3′-abpy to form a 1-D coordination polymer. The photoluminescence spectra of 3 and 5 show blue fluorescent emission bands, and these emissions can probably be assigned to intraligand fluorescent emissions. Thermal decompositions of the compounds are also discussed. For all complexes, magnetic susceptibility measurements show expected magnetic behavior.     

Comparison of selected aroma compounds in cultivars of sea buckthorn (<Emphasis Type="Italic">Hippophae rhamnoides</Emphasis> L.)

Thirteen cultivars of sea buckthorn (Hippophae rhamnoides L.) berries: Aromat, Botanicky, Buchlovicky, Hergo, Krasavica, Leicora, Ljubitelna, Pavlovsky, Peterbursky, Sluni?ko, Trofinovsky, Vitaminnaja and Velkoosecky, were tested for the content of volatile aroma compounds using gas chromatography with the solid phase microextraction method during two consequent years (2012–2013). In total, 69 volatile compounds were identified: 26 alcohols, 12 aldehydes, 11 ketones, 9 acids and 11 esters. Based on principal component analysis, 18 most relevant compounds, best representing the variability of the whole system and suitable for the discrimination of the samples, were selected from all compounds identified. These compounds were then compared using the analysis of variance to confirm differences between the samples. Significant (p < 0.05) differences were found in the varieties in both years, Krasavica and Sluni?ko cultivars were found to be quite different from other varieties, being rich in the compounds identified and containing most of the selected compounds. Variability within the cultivars (between picking years) was low or not significant.     

Low-light-induced Violaxanthin De-epoxidation in Shortly Preheated Leaves: Uncoupling from ΔpH-dependent Nonphotochemical Quenching

Plants protect themselves against excessive light by the induction of ΔpH-dependent nonphotochemical quenching (qE) that is associated with de-epoxidation of violaxanthin (V) to zeaxanthin (Z) in thylakoid membranes. In this work, we report that low light (12 μmol photons m⁻² s⁻¹) is sufficient for a marked stimulation of the V to Z conversion in shortly preheated wheat leaves (5 min, 40°C), but without a substantial increase in qE. Re-irradiation of these leaves with high light led to a rapid induction of nonphotochemical quenching, implying a potential photoprotective role of low-light-induced Z in preheated leaves. On the contrary to low light conditions, preheated leaves exposed to high light behaved similar to nonheated leaves with respect to the V to Z conversion and qE induction. The obtained results indicate that low-light-induced lumen acidification in preheated leaves is high enough to activate V de-epoxidation, but not sufficiently high to induce the formation of quenching centers.