Organic Geochemistry and Petrology of Oil Source Rocks, Carpathian Overthrust Region, Southeastern Poland — Implications for Petroleum Generation

The organic matter rich Oligocene Menilite black shales and mudstones are widely distributed in the Carpathian Overthrust region of southeastern Poland and have excellent hydrocarbon generation potential, according to TOC, Rock-Eval, and petrographic data. Extractable organic matter was characterized by an equable distribution of steranes by carbon number, by varying amounts of 28,30-dinor-hopane, 18α(H)-oleanane and by a distinctive group of C24 ring-A degraded triterpanes. The Menilite samples ranged in maturity from pre-generative to mid-oil window levels, with the most mature in the southeastern portion of the study area. Carpathian petroleum samples from Campanian-Oligocene sandstone reservoirs were similar in biomarker composition to the Menilite rock extracts. Similarities in aliphatic and aromatic hydrocarbon distributions between petroleum asphaltene and source rock pyrolyzates provided further evidence genetically linking Menilite kerogens with Carpathian oils

Organic Geochemistry of Permian Organic-rich Sediments from the Sudetes Area, SW Poland

Lacustrine and marine sediments from the Permian rift-basins of southwestern Poland were analysed using GC-MS and petrographic techniques. High Pr/Ph ratios, gamma- and beta-carotanes and gammacerane in the lacustrine sediments indicate deposition under elevated water salinities. The primary organic matter is represented by bacterial and algal lipids with variable terrestrial input. Marine algal lipids with minor bacterial and cyanobacterial lipids are the primary source of organic matter in the marine sediments. Extended hopanes, n-alkanes with even-odd predominance and low Ts/Tm ratios are consistent with deposition in a closed, evaporitic basin with substantial carbonate sedimentation

Di‐ and Tetracyano‐Substituted Pyrene‐Fused Pyrazaacenes: Aggregation in the Solid State

Means to stream: Five di- and tetracyano-substituted pyrene-fused pyrazaacenes were synthesized and studied as potential electron acceptors in the solid state. Single crystals of all compounds were grown, and the crystal packing was studied by XRD and DFT calculations of transfer integrals and reorganization energies with a view to their possible use as n-type semiconductors. Five di- and tetracyano-substituted pyrene-fused pyrazaacenes were synthesized and studied as potential electron acceptors in the solid state. Single crystals of all compounds were grown and the crystal packing studied by DFT calculations (transfer integrals and reorganization energies) to get insight into possible use for semiconducting charge transport

Host‐Guest Chemistry of Truncated Tetrahedral Imine Cages with Ammonium Ions

Three shape-persistent [4+4] imine cages with truncated tetrahedral geometry with different window sizes were studied as hosts for the encapsulation of tetra-n-alkylammonium salts of various bulkiness. In various solvents the cages behave differently. For instance, in dichloromethane the cage with smallest window size takes up NEt$_{4}$t$^{+}$ but not NMe$_{4}$t$^{+}$, which is in contrast to the two cages with larger windows hosting both ions. To find out the reason for this, kinetic experiments were carried out to determine the velocity of uptake but also to deduce the activation barriers for these processes. To support the experimental results, calculations for the guest uptakes have been performed by molecular mechanics’ simulations. Finally, the complexation of pharmaceutical interested compounds, such as acetylcholine, muscarine or denatonium have been determined by NMR experiments

Quinoxalinophenanthrophenazine Based Cruciforms

Quinoxalinophenanthrophenazines (QPPs) and related structures are an emerging class of stable fused N-heteropolycyclic aromatics. By vertical attachment of aromatic substituents at the pyrene core, cruciform QPPs are accessible, which open new opportunities to adjust HOMO and LUMO levels of the QPPs nearly independent from each other. A series of cruciform aryl-substituted quinoxalinophenanthrophenazine derivatives (QPPs) was synthesized through Suzuki-Miyaura cross-coupling of a 2,7-diborylated pyrene tetraketal building block. The QPPs were analyzed for their optoelectronic properties by absorption and emission spectroscopy, cyclic voltammetry and quantum-chemical calculations. The solid-state packing was investigated as well and evaluated for its charge transport properties by calculated charge transfer integrals

Triptycene End‐Capped Benzothienobenzothiophene and Naphthothienobenzothiophene

Previously it was demonstrated that triptycene end‐capping can be used as a crystal engineering strategy to direct the packing of quinoxalinophenanthrophenazines (QPPs) towards cofacially stacked π dimers with large molecular overlap resulting in high charge transfer integrals. Remarkably, this packing motif was formed under different crystallization conditions and with a variety of derivatives bearing additional functional groups or aromatic substituents. Benzothienobenzothiophene (BTBT) and its derivatives are known as some of the best performing compounds for organic field‐effect transistors. Here, the triptycene end‐capping concept is introduced to this class of compounds and polymorphic crystal structures are investigated to evaluate the potential of triptycene end‐caps as synthons for crystal engineering

Two Dimensional Triptycene End‐Capping and Its Influence on the Self‐Assembly of Quinoxalinophenanthrophenazines †

In this report we investigated two-dimensionally triptycene end-capped QPPs in terms of their solution and solid-state behavior. For this purpose, a triphenylene based ortho-diamine decorated with two triptycenyl units as well as a phenylene diamine with two non-annulated triptycene units have been synthesized. Sequences of condensation reactions with a pyrene-based tetraketone and ortho-diamines yielded a series of QPPs and UV/Vis investigations of the corresponding compounds led to the conclusion, that the QPPs form dimers in solution, which was further supported by MALDI-TIMS-TOF-MS. Single-crystal X-ray analysis of the triply and quadruply triptycene end-capped QPPs furthermore showed short π-π-distances of 3.3—3.4 Å and a perfect shape match during the dimerization of the triply triptycenyl end-capped QPP making it possible synthon fo

Environmental Forensic Characterization of Former Rail Yard Soils Located Adjacent to the Statue of Liberty in the New York/New Jersey Harbor

Identifying inorganic and organic soil contaminants in urban brownfields can give insights into the adverse effects of industrial activities on soil function, ecological health, and environmental quality. Liberty State Park in Jersey City (N.J., USA) once supported a major rail yard that had dock facilities for both cargo and passenger service; a portion remains closed to the public, and a forest developed and spread in this area. The objectives of this study were to: 1) characterize the organic and inorganic compounds in Liberty State Park soils and compare the findings to an uncontaminated reference site (Hutcheson Memorial Forest); and 2) identify differences between the barren low-functioning areas and the forested high-functioning areas of the brownfield. Soil samples were solvent-extracted, fractionated, and analyzed by gas chromatography–mass spectrometry and subjected to loss-on-ignition, pyrolysis-gas chromatography–mass spectrometry, inductively-coupled-plasma mass spectrometry, and optical microscopy analyses. Compared to soil from the reference site, the forested soils in Liberty State Park contained elevated percentages of organic matter (30–45%) and more contaminants, such as fossil-fuel-derived hydrocarbons and coal particles. Microscopy revealed bituminous and anthracite coal, coke, tar/pitch, and ash particles. Barren and low-functioning site 25R had a similar organic contaminant profile but contained a higher metal load than other Liberty State Park sites and also lacked higher plant indicators. These can obscure the signatures of contaminants, and data from adjacent barren and vegetated sites are valuable references for soils studies. A deeper understanding of the chemistry, biochemistry, and ecology of barren soils can be leveraged to prevent land degradation and to restore dysfunctional and phytotoxic soils