Sulfur isotope fractionation during incorporation of sulfur nucleophiles into organic compounds

34S enrichment is shown to occur during sulfurization reactions and for the first time conclusively attributed to an isotope equilibrium effect rather than selective addition of 34S enriched nucleophiles

Thermal alteration of organic matter in recent marine sediments. 1: Pigments

Sediment from Tanner Basin, the outer continental shelf off Southern California, was analyzed for photosynthetic pigments and their derivatives, namely carotenes and chlorins. Samples of the sediment were also exposed to raised temperatures (65, 100, 150 C) for various periods of time (1 week, 1 month, 2 months). Analysis of the heat-treated sediment revealed the presence of alpha-ionene and 2,6-dimethylnapthalene, thermal degradation products of Betacarotente. Chlorins were converted to nickel porphyrins of both DPEP and etio series. Possible mechanisms of these transformations are presented

Колаборативний підхід до управління з використанням тристоронньої моделі менеджменту

Due to the current economic instability, environmental and social change the problem of collaborative governance is very urgent for Ukraine, as well as other developing countries. The purpose of this scientific article is to examine theoretical and practical applications of the collaborative approach to the governing of the state, using a tripartite management model. In particular, the paper investigates the tripartite model (triad) as an integrative framework that includes three sectorssocial, political and financial. The political sector is represented in government, financial one in for-profit organizations, and social sector in any chosen NGO or NPO, which will act as a mediator between the public and government. Moreover, the author suggests that only though collaboration between those three sectors the effectiveness of the state governance could be achieved, also ensuring the sustainable development. The article presents a compelling argument against establishing sole power in the hands of a single institutional entity, instead outlining the possible benefits of sharing power and responsibility among all citizens. Using the example of Ukraine, it delineates a potential scenario where state adopts the triad to undertake a path to sustainable development. Therefore, while the article limitations might be in that it carries mostly theoretical implication of the tripartite management model, it nevertheless builds a successful ground for adoption of this model in the future by any developing country.Через економічну нестабільність, екологічні та соціальні зміни проблема колаборативного управління є надзвичайно актуальною як для України, так і для інших країн, що розвиваються. Метою цієї статті є обґрунтування теоретичних положень та особливостей практичного застосування колаборативного підходу до управління державою з використанням тристоронньої моделі управління. Досліджено тристоронню модель (тріаду) як інтегративну структуру, яка містить три сектори: соціальний, політичний та фінансовий. Політичний сектор представлений в уряді, фінансовий – у комерційних організаціях, а соціальний – у будь-яких недержавних організаціях, які виступають посередниками між громадськістю та урядом. Крім того, автори припускають, що лише завдяки співпраці між цими трьома секторами може бути досягнута ефективність управління державою, що також може забезпечити сталий розвиток. У статті викладено переконливий аргумент проти встановлення єдиної влади в руках одного інституційного утворення, натомість окреслено можливі переваги розподілу влади та відповідальності між усіма громадянами. На прикладі України окреслюється потенційний сценарій, коли держава приймає тріаду задля проходження шляху до сталого розвитку. Хоча обмеження статті і можуть полягати в тому, що в основному увага приділена теоретичному обґрунтуванню тристоронньої моделі управління, проте саме воно створює успішний ґрунт для практичного застосування цієї моделі в майбутньому

Synthesis of macrocyclic receptors with intrinsic fluorescence featuring quinizarin moieties

An unprecedented class of macrocycles with intrinsic fluorescence consisting of phenolic trimers and quinizarin is developed. Though they are lacking strong hydrogen bonds as observed in calixarenes, the two examples introduced here each adopt a vase-like conformation with all four aromatic units pointing in one direction (syn orientation). This “cone” conformation has been confirmed by NMR spectroscopy, molecular modeling, and X-ray crystallography. The laminar, electron-rich fluorophore as part of the macrocycle allows additional contacts to enclosed guest molecules

A Mississippian black shale record of redox oscillation in the Craven Basin, UK

Early diagenetic redox oscillation processes have been rarely recognised in the ancient rock record but potentially exert an important control on mineral authigenesis, hydrocarbon prospectivity and supply of metals and/or reduced S as part of associated mineral systems. The upper unit of the Mississippian Bowland Shale Formation is a candidate record of diagenetic redox oscillation processes because it was deposited under a relatively high sediment accumulation rate linked to a large delta system, and under dominantly anoxic and intermittently sulphidic bottom-water conditions. In order to characterise the syngenetic and early diagenetic processes, sedimentological and geochemical data were integrated through the Upper Bowland Shale at three sites in the Craven Basin (Lancashire, UK). Organic matter (OM) comprises a mixture of Type II, II-S, II/III and III OM. ‘Redox zones’ are defined by patterns of Fe-speciation and redox-sensitive trace element enrichment and split into two groups. ‘Sulphidic’ zones (EUX, AN-III, AN-I and AN-IT) represent sediments deposited under conditions of at least intermittently active sulphate-reduction in bottom-waters. ‘Non-sulphidic’ zones (OX-RX, OX-F and OX) represent sediments deposited under non-sulphidic (oxic to ferruginous anoxic) bottom-waters. Operation of a shelf-to-basin ‘reactive Fe’ (FeHR) shuttle, moderated by sea level fluctuation and delta proximity, controlled the position and stability of redoxclines between zones of Fe and sulphate reduction, and methanogenesis. Early diagenetic redoxclines were capable of migration through the shallow sediment column relatively quickly, in response to sea level fluctuation. Preservation of syngenetic and early diagenetic geochemical signals shows redoxclines between Fe and sulphate reduction, and the upper boundary of sulphate-methane transition zone, were positioned within decimetres (i.e., 10 s cm) of seabed. Falling sea level and increasing FeHR supply is recognised as a switch from zones EUX (high sea level), AN-III and ultimately AN-I and AN-IT (low sea level). Zone AN-I defines the operation of ‘redox oscillation’, between zones of Fe and sulphate reduction in shallow porewaters, associated with enhanced degradation of OM and complete dissolution of primary carbonate. Preservation of OM and carbonate, in this system, was a function of changing bottom and pore water redox processes. Redox oscillation operated in a siliciclastic, prodeltaic environment associated with a relatively high sediment accumulation rate and high loadings of labile organic matter and metal oxides. These findings are important for understanding Late Palaeozoic black shales in the context of hydrocarbon and mineral systems