Solid-state thermal degradation behaviour of 1-D coordination polymers of Ni(II) and Cu(II) bridged by conjugated ligand

Monometallic complexes [Cudadb·yH₂O]_n (2) and [Nidadb·yH₂O]_n (3) and heterobimetallic complex [Cu_0.5Ni_0.5dadb·yH₂O]_n (4) {where dadbH₂ = 2,5-Diamino-3,6-dichloro-1,4-benzoquinone (1); y = 2–4; n = degree of polymerization} were characterized by elemental analysis, atomic absorption spectroscopy, infrared spectroscopy (FTIR) and powder X-ray diffraction. The thermal behaviour of the complexes was studied by thermal analysis (TG/DTA) under air as well as under helium atmospheres. The released gaseous products were investigated by evolved gas analysis performed by an online coupled mass spectrometer (TG/DTA-MS). Thermal degradation of 2 under helium atmosphere is distributed over five steps, whereas 3 and 4 exhibited only four degradation steps due to overlap of second and third degradation steps of into one major step. All the complexes exhibit three steps degradation under air. The complex 2 loses NH group in the second and HCl/Cl₂, CO groups simultaneously in third steps of decomposition under helium, whereas it loses NH and CO groups simultaneously in low temperature region of second step of degradation under air atmosphere as the loss of CO group is facilitated by air. EGA-MS under air and helium atmospheres shows that HCl, CO/CO₂ and (CN)₂ fragments are lost simultaneously at multiple steps, and not successively as predicted earlier. Rate of evolution of most evolved gases exhibits several maxima as a consequence of degradation followed by recombination reactions. Final residues under air and helium atmospheres correspond to the metal oxides and metals along with some carbonaceous matter.     

Positive bases in spaces of polynomials

For a nonempty compact set we determine the maximal possible dimension of a subspace of polynomial functions over Ω with degree at most m which possesses a positive basis. The exact value of this maximum depends on topological features of Ω, and we will see that in many of the cases m can be achieved. Whereas only for low m or finite sets Ω it is possible that we have a subspace X with positive basis and with dim X = m + 1. Hence there is no Ω for which a positive basis exists in for all . This work was accomplished during the 2^nd author’s stay in Paris under his Marie Curie fellowship, contract # MEIF-CT-2005-022927.     

Determination of Coccidiostats in Milk Products by LC–MS and Its Application to a Fermentation Experiment

A liquid chromatographic tandem mass spectrometric (LC–MS–MS) method for the determination of five chemical coccidiostats (decoquinate, diclazuril, halofuginone, nicarbazin, and robenidine) and five ionophore coccidiostats (maduramicin, monensin, narasin, salinomycin, and semduramicin) in yoghurt, kefir, and sour cream is presented. Lasalocid, the sixth ionophore listed in 124/2009/EC was not included because of its extremely dissimilar behavior during sample preparation. Main steps of the method include extraction with acetonitrile, centrifugation, clean-up on Oasis HLB solid phase extraction cartridge, evaporation under nitrogen stream, and LC–MS–MS determination. Selectivity, linearity, sensitivity, accuracy, repeatability, within-laboratory reproducibility, limit of determination, and limit of quantitation were determined during the validation procedure. The method proved to be applicable for both qualitative and quantitative determination of the ten above-mentioned target compounds. In our in-house fermentation experiments, milk fortified with coccidiostats was fermented to get yoghurt, kefir, and sour cream. Our results show that the coccidiostat content did not change significantly during fermentation for any of the target compounds.     

Co-crystal of (R,R)-1,2-cyclohexanediol with (R,R)-tartaric acid,a key structure in resolution of the (±)-trans-diol by supercritical extraction,and the related ternary phase system

A novel co-crystal of trans-(R,R)-1,2-cyclohexanediol and (R,R)-tartaric acid (with 1:1 molar ratio, 1) has been found to be a key crystalline compound in the improved resolution of (±)-trans-1,2-cyclohexanediol by supercritical fluid extraction. The molecular and crystal structure of this co-crystal, which crystallizes in orthorhombic crystal system (space group P2₁2₁2₁, a = 6.7033(13) Å, b = 7.2643(16), c = 24.863(5), Z = 4), has been solved by single crystal X-ray diffraction (R = 0.064). The packing arrangement consists of two dimensional layers of sandwich-like sheets, where the inner part is constructed by double layers of tartaric acids which hydrophilicity is “covered” on both upper and bottom side by cyclohexanediols with the hydrophobic cyclohexane rings pointing outward. Thus, a rather complex hydrogen bonding pattern is constructed. The relatively high melting point (133 °C) observed by both simultaneous TG/DTA and DSC, and the main features of FTIR-spectrum of 1 are explained by the increased stability of this crystal structure. DSC studies on binary mixtures of co-crystal 1 with (R,R)-1,2-cyclohexanediol or (R,R)-tartaric acid, revealed eutectic temperatures of T_eu = 100 or 131 °C, respectively. Between (S,S)-1,2-cyclohexanediol and (R,R)-tartaric acid a eutectic temperature of T_eu = 85 °C have also been observed. The phase relations have been confirmed by powder X-ray diffraction, as well.     

Monotone operators and first category sets

In this paper we show that the local monotonicity in the sense of Minty and Browder on some residual sets assure the global monotonicity and, according to an earlier result, the convexity of the inverse images. We pay some special attention to the residual sets arising as complements of some special first Baire category sets, namely the $\sigma $ -affine sets, the $\sigma $ -compact sets and the $\sigma $ -algebraic varieties. We achieve this goal gradually by showing, at first, that the continuous real valued functions of one real variable, which are locally nondecreasing on sets whose complements have no nonempty perfect subsets, are globally nondecreasing. The convexity of the inverse images combined with their discreteness, in the case of local injective operators, ensure the global injectivity. Note that the global monotonicity and the local injectivity of regular enough operators is guaranteed by the positive definiteness of the symmetric part of their Gateaux differentials on the involved residual sets. We close this work with a short subsection on the global convexity which is obtained out of its local counterpart on some residual sets.     

About the Maximal Monotonicity of the Generalized Sum of Two Maximal Monotone Operators

We give several regularity conditions, both closedness and interior point type, that ensure the maximal monotonicity of the generalized sum of two strongly-representable monotone operators, and we extend some recent results concerning on the same problem.     

Review on the recent progress in the preparation and stability of graphene-based nanofluids

Journal of Thermal Analysis and Calorimetry - Graphene has attracted much attention from the science world because of its mechanical, thermal, and physical properties. Graphene nanofluid is well...