Determination of petitgrain oils landmark parameters by using gas chromatography–combustion–isotope ratio mass spectrometry and enantioselective multidimensional gas chromatography

Gas chromatography–combustion–isotope mass spectrometry was employed for the assessment of the Carbon isotope ratios of volatiles in Italian mandarin and lemon petitgrain oils. In addition, the composition of the whole oil and the enantiomeric distribution of selected chiral compounds were determined for all the samples by using gas chromatography and by multidimensional and conventional enantioselective gas chromatography. The composition of the oils was compared with previous studies. The enantiomeric distribution of lemon petitgrain oils is here reported for the first time. On the composition of mandarin petitgrain oil, the information available in literature, to date, is relative only to one sample from Egypt. Carbon isotope ratio of several terpene hydrocarbons and of their oxygenated derivatives contained in petitgrains was compared with the δ ¹³C_VPDB values of the same compounds present in the corresponding genuine Italian Citrus peel oil. The results prove that the isotopic values obtained for lemon and mandarin petitgrain oils are very close to those relative to the corresponding peel oils determined in previous studies.     

Intra-Galactic Thin Shell Wormhole and Its Stability

In this paper, we construct an intra-galactic thin shell wormhole joining two copies of identical galactic space times described by the Mannheim–Kazanas–de Sitter solution in conformal gravity and study its stability under spherical perturbations. We assume the thin shell material as a Chaplygin gas and discuss in detail the values of the relevant parameters under which the wormhole is stable. We study the stability following the method by Eiroa and we also qualitatively analyze the dynamics through the method of Weierstrass. We find that the wormhole is generally unstable but there is a small interval in radius for which the wormhole is stable.     

Ionic complexes of 1,1′‐dimethyltitanocene(IV) dichloride with simple α‐amino acids: synthesis,structural characterisation and investigation on hydrolytic stability in aqueous solution

Five cationic complexes of the general formula [Cp′₂Ti(A)₂]²⁺ [Cl^?]₂ [Cp′ = η⁵‐(CH₃)C₅H₄ and A = glycine, 1 ; 2‐methylalanine, 2 ; N‐methylglycine, 3 ; L ‐alanine, 4 ; and D ‐alanine 5 ] were prepared by the reaction of Cp′₂TiCl₂ and the appropriate α‐amino acid in 1:2 molar ratio from methanol–water solution in high yield. Air‐stable crystalline solids, highly soluble in water, were characterized by means of elemental analysis, IR, Raman, ¹H, ¹³C and ¹⁴N NMR spectroscopy. The structure of compound 3 was determined by single crystal X‐ray crystallography: orthorhombic Pbca No. 61, a = 9.5310(3), b = 18.2980(5), c = 26.6350(5) Å, V = 4654 ų, Z = 8. Hydrolytic stability of all compounds in D₂O was investigated using ¹H NMR spectroscopy within the pD interval of 2.9–6.5. All compounds slowly decomposed during 24 h at pD = 2.94, forming a mixture of hydrolytic products [Cp′₂Ti(A)(D₂O)]²⁺, [Cp′₂Ti(D₂O)₂]²⁺ and respective α‐amino acids. By elevating pD to 4.0 and up to 6.5, a yellowish precipitate was formed, which indicates decomposition of the complexes. These compounds were characterized using elemental analyses, IR and Raman spectroscopy and attributed to oligomeric and/or polymeric structures described empirically by the formula Ti(Cp′)_xO_y(OH)_z (x = 0.65; y = 0.3, z = 1.9). Copyright © 2005 John Wiley & Sons, Ltd.     

Crystallographic report: The [bis(η5‐methylcyclopentadienyl)titanium(IV)‐bis(N‐methylglycine)] dichloride

The crystal network of [Cp′₂Ti(N?CH₃? Gly)₂]²⁺[Cl^?]₂ (Cp′ = (CH₃)C₅H₄) complex, which crystallizes as a solvate with CH₃OH, is built up with discrete cationic units connected through intermolecular H· · ·Cl bonds. The α‐amino acid ligands are attached through an intramolecular H· · ·O bond within one cationic unit. Copyright © 2004 John Wiley & Sons, Ltd.     

Control over Electrochemical Water Oxidation Catalysis by Preorganization of Molecular Ruthenium Catalysts in Self‐Assembled Nanospheres

Oxygen formation through water oxidation catalysis is a key reaction in the context of fuel generation from renewable energies. The number of homogeneous catalysts that catalyze water oxidation at high rate with low overpotential is limited. Ruthenium complexes can be particularly active, especially if they facilitate a dinuclear pathway for oxygen bond formation step. A supramolecular encapsulation strategy is reported that involves preorganization of dilute solutions (10^?5 m ) of ruthenium complexes to yield high local catalyst concentrations (up to 0.54 m ). The preorganization strategy enhances the water oxidation rate by two‐orders of magnitude to 125 s^?1, as it facilitates the diffusion‐controlled rate‐limiting dinuclear coupling step. Moreover, it modulates reaction rates, enabling comprehensive elucidation of electrocatalytic reaction mechanisms.     

Simple and efficient access to pyrazine-2,5- and -2,6-dicarbaldehydes

Efficient two-step synthesis of pyrazine-2,5- and -2,6-dicarbaldehydes is presented that consists of transformation of easily available corresponding dimethylpyrazines to distyryl derivatives and oxidation of the latter with the tandem system of osmium tetroxide/periodate ions. The proper choice of dehydration agent in the first reaction step and the good efficiency of the subsequent low-temperature oxidation are the key points of the developed protocol. Other examined synthesis routes were much less successful, but one of them leads to new powerful routes to methyl (5-hydroxymethyl)pyrazine-2-carboxylate and dimethyl 3,4-dihydropyrazine-2,6-dicarboxylate. Previously unknown characteristics of the title compounds are reported.     

Sorption properties of sheep wool irradiated by accelerated electron beam

Electron beam (EB) irradiated wool was examined for sorption of chromic ions. Sorption increased with the adsorbed dose non-monotonously, which is a result of the generation of S-oxidized groups, secondary structure variation, and the breaking of the keratin backbone. For a dose of 400 kGy, an increase by 120 % was observed at the cystine dioxide and cysteine acid amounts. Examining sorption of unexposed wool and that irradiated with doses of 25 kGy and 40 kGy for basic, methylene blue (MB), or acidic, pyrogallol red (PR) dyes revealed that such low doses have no effect on the carboxylic or amino groups of keratin. Sorption of MB is independent of the EB treatment and is identical for both samples due to the interaction of MB amino groups with the carboxylic groups of wool; however, the sorption capacity for PR is a function of the EB treatment. The sample irradiated with the dose of 25 kGy showed higher PR sorption than that with the EB dose of 40 kGy, which was equal to that of unexposed wool. While the 25 kGy sample provided more active sites for PR interaction compared with the unexposed one, the 40 kGy sample contained already enough active sites to generate intra- and intermolecular interactions inside wool. Thus, PR adherence to the 40 kGy sample was restricted and comparable to the level of unexposed wool.     

A node-based layered graph approach for the Steiner tree problem with revenues,budget and hop-constraints

The Steiner tree problem with revenues, budget and hop-constraints (STPRBH) is a variant of the classical Steiner tree problem. The goal is to find a tree maximizing the collected revenue, which is associated with nodes, subject to a given budget for the edge cost of the tree and a hop-limit for the distance between the given root node and any other node in that tree. In this work, we introduce a novel generic way to model hop-constrained tree problems as integer linear programs and apply it to the STPRBH. Our approach is based on the concept of layered graphs that gained widespread attention in the recent years, due to their computational advantage when compared to previous formulations for modeling hop-constraints. Contrary to previous MIP formulations based on layered graphs (that are arc-based models), our model is node-based. Thus it contains much less variables and allows to tackle large-scale instances and/or instances with large hop-limits, for which the size of arc-based layered graph models may become prohibitive. The aim of our model is to provide a good compromise between quality of root relaxation bounds and the size of the underlying MIP formulation. We implemented a branch-and-cut algorithm for the STPRBH based on our new model. Most of the instances available for the DIMACS challenge, including 78 (out of 86) previously unsolved ones, can be solved to proven optimality within a time limit of 1000 s, most of them being solved within a few seconds only. These instances contain up to 500 nodes and 12,500 edges, with hop-limit up to 25.