New discotic liquid crystals based on large polycyclic aromatic hydrocarbons as materials for molecular electronics

A series of new columnar discotic liquid crystalline materials based on the superphenalene (C96) core has been synthesized by oxidative cyclodehydrogenation with iron(III) chloride of suitable three-dimensional oligophenylene precursors. These compounds were investigated by means of differential scanning calorimetry (DSC), polarized optical microscopy (POM) and wide angle X-ray scattering (WAXS), and showed highly ordered supramolecular arrays and mesophase behavior over a broad temperature range. Good solubility, through the introduction of long alkyl chains, and the fact that these new superphenalene derivatives were found to be liquid crystalline at room temperature enabled the formation of highly ordered films (using the zone-casting technique), a requirement for application in organic electronic devices. The one-dimensional, intracolumnar charge carrier mobilities of superphenalene derivatives were determined using the pulse-radiolysis time-resolved microwave conductivity technique (PR-TRMC). Electrical properties of different C96-C12 architectures on mica surfaces were examined by using Electrostatic Force Microscopy (EFM) and Kelvin Probe Force Microscopy (KPFM). Hexa-peri-hexabenzocoronene (C42) derivatives substituted at the periphery with six branched alkyl ether chains were also synthesized. It was found that the introduction of ether groups within the side chains enhances the affinity of the discotic molecules towards polar surfaces, resulting in homeotropic self-assembly (as shown by POM and 2D-WAXS) when the compounds are processed from the isotropic state between two surfaces. A new, insoluble, superphenalene building block bearing six reactive sites was prepared, and was further used for the preparation of dendronized superphenalenes with bulky dendritic substituents around the core. UV/Vis and fluorescence experiments suggest reduced π-π stacking of the superphenalene cores as a result of steric hindrance between the peripheral dendritic units. A new family of graphitic molecules with partial ”zig-zag” periphery has been established. The incorporation of ”zig-zag” edges was shown to have a strong influence on the electronic properties of the new molecules (as studied by solution and solid-state UV/Vis, and fluorescence spectroscopy), leading to a significant bathochromic shift with respect to the parent PAHs (C42 and C96). The reactivity of the additional double bonds was examined. The attachment of long alkyl chains to a ”zig-zag” superphenalene core afforded a new, processable, liquid crystalline material.

Synthetical engineering of supramolecular properties of large polycyclic aromatic hydrocarbons

An important property for devices is the charge-carrier mobility values for discotic organic materials like hexa-peri-hexabenzocoronenes. A close relation exists between the degree of their columnar self-arrangement of the molecules and their mobilities. Within this first step an induction of a higher order via hydrogen-bonding was considered, which mainly pointed towards the improvement of the intracolumnar stacking of the materials. For the analytics a broad range of methods was used including differential scanning calorimetry (DSC), wide-angle X-ray diffractometry (WAXS), solid-state NMR spectroscopy and scanning tunneling microscopy (STM). Indeed, a specific influence of the hydrogen-bonds could be identified, although in several cases by the cost of a severe reduction of solubility and processability. This effect was dampened by the addition of a long alkyl chain next to the hydrogen-bond exerting functional group, which resulted in an improved columnar arrangement by retention of processability. In contrast to the before mentioned example of inducing a higher intracolumnar order by hydrogen-bonding, the focus was also be set upon larger aromatic systems. The charge-carrier mobility is also in close relation to the size of the aromatic core and larger π-areas are expected to lead to improved mobilities. For photovoltaic applications a high extinction coefficient over a broad range of the spectrum is favorable, which can also be achieved by enlarging the aromatic core component. In addition the stronger π-interactions between the aromatic core components should yield an improved columnar stability and order. However the strengthening of the π-interactions between the aromatic core components led to a reduction of the solubility and the processability due to the stronger aggregation of the molecules. This required the introduction of efficiently solubilizing features in terms of long alkyl chains in the corona of the aromatic entity, in combination of a distortion of the aromatic core moiety by bulky tert-butyl groups. By this approach not only the processing and cleaning of the materials with standard laboratory techniques became possible, but moreover the first structure-rich UV/vis and a resolved 1H-NMR spectra for an aromatic system two times larger than hexa-peri-hexabenzocoronene were recorded. The bulk properties in an extruded fiber as well as on the surface showed a columnar self-assembly including a phase in which a homeotropic alignment on a substrate was observed, which turns the material into an interesting candidate for future applications in electronic devices.

From pyrene to large polycyclic aromatic hydrocarbons

Studies of polycyclic aromatic hydrocarbons have shown that the overall size, periphery, and functionalization of PAHs are crucial parameters which significantly alter their electronic structure and chemical reactivity. Therefore, the major direction of this thesis is the synthesis and characterization of extended PAHs: (i) with different functional groups improving their processability, (ii) with different periphery changing their chemical reactivity, (iii) with inclusions of different metal ions, which influence their physical properties. • The cyclodehydrogenation reaction has been proposed for to synthesise polyphenylene ribbons with preplanarized (dibenzo[e,l]pyrene) moieties in the aromatic core with up to 10 nm linear size. The synthetic strategy employed is discussed in Chapter 2 and is based on stoichiometrically controlled DIELS-ALDER cycloaddition. All molecules possessed very good solubility in common organic solvents allowing their characterization by standard analytical techniques. • A new concept was developed to extend PAH’s core. Here the introduction of “zigzag” sites, discussed in Chpater 3 was shown to lower the HOMO-LUMO gap and to result in higher chemical reactivities. This allowed, in Chapters 3, 4 and 5, further functionalization of PAH and enlargement of their aromatic cores up to 224 atoms. Despite the size of these novel molecules, extraordinary solubilities in common organic solvents were obtained due to distortions from planarity of the aromatic cores by bulky tert-butyl groups, which hampered the usually very pronounced aggregation tendency of extended π-systems. All extended PAHs posses the small HOMO-LUMO gap together with good electron affinities making them potential candidates for application in organic FETs. • Another alternative synthetic route has been proposed to obtain extended the metal-PAH complexes. Using the quinoxaline methodology in Chapter 5 three new phenanthroline ligands (up to 60 skeletal atoms) have been synthesized and characterized. Four different (Ru(II), Cu(II) and Pt(II)) complexes were synthesized, allowing to construct a range of large metal complexes by varying the metal as well as the number and nature of ligands.

Electron spectroscopy of novel charge transfer systems based on polycyclic aromatic hydrocarbons

Organische Ladungstransfersysteme weisen eine Vielfalt von konkurrierenden Wechselwirkungen zwischen Ladungs-, Spin- und Gitterfreiheitsgraden auf. Dies führt zu interessanten physikalischen Eigenschaften, wie metallische Leitfähigkeit, Supraleitung und Magnetismus. Diese Dissertation beschäftigt sich mit der elektronischen Struktur von organischen Ladungstransfersalzen aus drei Material-Familien. Dabei kamen unterschiedliche Photoemissions- und Röntgenspektroskopietechniken zum Einsatz. Die untersuchten Moleküle wurden z.T. im MPI für Polymerforschung synthetisiert. Sie stammen aus der Familie der Coronene (Donor Hexamethoxycoronen HMC und Akzeptor Coronen-hexaon COHON) und Pyrene (Donor Tetra- und Hexamethoxypyren TMP und HMP) im Komplex mit dem klassischen starken Akzeptor Tetracyanoquinodimethan (TCNQ). Als dritte Familie wurden Ladungstransfersalze der k-(BEDT-TTF)2X Familie (X ist ein monovalentes Anion) untersucht. Diese Materialien liegen nahe bei einem Bandbreite-kontrollierten Mottübergang im Phasendiagramm.rnFür Untersuchungen mittels Ultraviolett-Photoelektronenspektroskopie (UPS) wurden UHV-deponierte dünne Filme erzeugt. Dabei kam ein neuer Doppelverdampfer zum Einsatz, welcher speziell für Milligramm-Materialmengen entwickelt wurde. Diese Methode wies im Ladungstransferkomplex im Vergleich mit der reinen Donor- und Akzeptorspezies energetische Verschiebungen von Valenzzuständen im Bereich weniger 100meV nach. Ein wichtiger Aspekt der UPS-Messungen lag im direkten Vergleich mit ab-initio Rechnungen.rnDas Problem der unvermeidbaren Oberflächenverunreinigungen von lösungsgezüchteten 3D-Kristallen wurde durch die Methode Hard-X-ray Photoelectron Spectroscopy (HAXPES) bei Photonenenergien um 6 keV (am Elektronenspeicherring PETRA III in Hamburg) überwunden. Die große mittlere freie Weglänge der Photoelektronen im Bereich von 15 nm resultiert in echter Volumensensitivität. Die ersten HAXPES Experimente an Ladungstransferkomplexen weltweit zeigten große chemische Verschiebungen (mehrere eV). In der Verbindung HMPx-TCNQy ist die N1s-Linie ein Fingerabdruck der Cyanogruppe im TCNQ und zeigt eine Aufspaltung und einen Shift zu höheren Bindungsenergien von bis zu 6 eV mit zunehmendem HMP-Gehalt. Umgekehrt ist die O1s-Linie ein Fingerabdruck der Methoxygruppe in HMP und zeigt eine markante Aufspaltung und eine Verschiebung zu geringeren Bindungsenergien (bis zu etwa 2,5eV chemischer Verschiebung), d.h. eine Größenordnung größer als die im Valenzbereich.rnAls weitere synchrotronstrahlungsbasierte Technik wurde Near-Edge-X-ray-Absorption Fine Structure (NEXAFS) Spektroskopie am Speicherring ANKA Karlsruhe intensiv genutzt. Die mittlere freie Weglänge der niederenergetischen Sekundärelektronen (um 5 nm). Starke Intensitätsvariationen von bestimmten Vorkanten-Resonanzen (als Signatur der unbesetzte Zustandsdichte) zeigen unmittelbar die Änderung der Besetzungszahlen der beteiligten Orbitale in der unmittelbaren Umgebung des angeregten Atoms. Damit war es möglich, präzise die Beteiligung spezifischer Orbitale im Ladungstransfermechanismus nachzuweisen. Im genannten Komplex wird Ladung von den Methoxy-Orbitalen 2e(Pi*) und 6a1(σ*) zu den Cyano-Orbitalen b3g und au(Pi*) und – in geringerem Maße – zum b1g und b2u(σ*) der Cyanogruppe transferiert. Zusätzlich treten kleine energetische Shifts mit unterschiedlichem Vorzeichen für die Donor- und Akzeptor-Resonanzen auf, vergleichbar mit den in UPS beobachteten Shifts.rn

Inhalant deaths in South Australia: a 20-year retrospective autopsy study

A 20-year retrospective study of inhalant deaths in South Australia, autopsied at Forensic Science SA, was undertaken from January 1983 to December 2002. Thirty-nine cases were identified from an autopsy pool of 18,880 cases, with a male to female ratio of 12:1. Sixty-four percent of the victims (N = 25) died during voluntary inhalation of volatile substances and 28% (N = 11) committed suicide utilizing a volatile substance or gas. The remaining 3 cases involved a workplace accident (N = 1) and 2 cases of autoerotic death where inhalants were being used to augment solitary sexual activity. The mean age of the 28 victims of accidental inhalant death of 21 years (range, 13-45 years) was considerably less than that of the 11 suicide victims of 31.5 years (range, 17-48 years). No homicides were found. Approximately one quarter of the victims were Aboriginal (N = 11), 10 of whom had died as a result of gasoline inhalation ("petrol sniffing"). Other common substances of abuse were aliphatic hydrocarbons such as butane. The study has shown that those most at risk for accidental or suicidal inhalant deaths were young males, with 92% of victims overall being male, and with 77% of victims being under 31 years of age. Gasoline inhalation remains a significant problem in Aboriginal communities in South Australia.

Parametric combustion modeling for ethanol-gasoline fuelled spark ignition engines

Ethanol-gasoline fuel blends are increasingly being used in spark ignition (SI) engines due to continued growth in renewable fuels as part of a growing renewable portfolio standard (RPS). This leads to the need for a simple and accurate ethanol-gasoline blends combustion model that is applicable to one-dimensional engine simulation. A parametric combustion model has been developed, integrated into an engine simulation tool, and validated using SI engine experimental data. The parametric combustion model was built inside a user compound in GT-Power. In this model, selected burn durations were computed using correlations as functions of physically based non-dimensional groups that have been developed using the experimental engine database over a wide range of ethanol-gasoline blends, engine geometries, and operating conditions. A coefficient of variance (COV) of gross indicated mean effective pressure (IMEP) correlation was also added to the parametric combustion model. This correlation enables the cycle combustion variation modeling as a function of engine geometry and operating conditions. The computed burn durations were then used to fit single and double Wiebe functions. The single-Wiebe parametric combustion compound used the least squares method to compute the single-Wiebe parameters, while the double-Wiebe parametric combustion compound used an analytical solution to compute the double-Wiebe parameters. These compounds were then integrated into the engine model in GT-Power through the multi-Wiebe combustion template in which the values of Wiebe parameters (single-Wiebe or double-Wiebe) were sensed via RLT-dependence. The parametric combustion models were validated by overlaying the simulated pressure trace from GT-Power on to experimentally measured pressure traces. A thermodynamic engine model was also developed to study the effect of fuel blends, engine geometries and operating conditions on both the burn durations and COV of gross IMEP simulation results.

LIFE CYCLE ASSESSMENTS (LCAs) OF PYROLYSIS-BASED GASOLINE AND DIESEL FROM DIFFERENT REGIONAL FEEDSTOCKS: CORN STOVER, SWITCHGRASS, SUGAR CANE BAGASSE, WASTE WOOD, GUINEA GRASS, ALGAE, AND ALBIZIA

Renewable hydrocarbon biofuels are being investigated as possible alternatives to conventional liquid transportation fossil fuels like gasoline, kerosene (aviation fuel), and diesel. A diverse range of biomass feedstocks such as corn stover, sugarcane bagasse, switchgrass, waste wood, and algae, are being evaluated as candidates for pyrolysis and catalytic upgrading to produce drop-in hydrocarbon fuels. This research has developed preliminary life cycle assessments (LCA) for each feedstock-specific pathway and compared the greenhouse gas (GHG) emissions of the hydrocarbon biofuels to current fossil fuels. As a comprehensive study, this analysis attempts to account for all of the GHG emissions associated with each feedstock pathway through the entire life cycle. Emissions from all stages including feedstock production, land use change, pyrolysis, stabilizing the pyrolysis oil for transport and storage, and upgrading the stabilized pyrolysis oil to a hydrocarbon fuel are included. In addition to GHG emissions, the energy requirements and water use have been evaluated over the entire life cycle. The goal of this research is to help understand the relative advantages and disadvantages of the feedstocks and the resultant hydrocarbon biofuels based on three environmental indicators; GHG emissions, energy demand, and water utilization. Results indicate that liquid hydrocarbon biofuels produced through this pyrolysis-based pathway can achieve greenhouse gas emission savings of greater than 50% compared to petroleum fuels, thus potentially qualifying these biofuels under the US EPA RFS2 program. GHG emissions from biofuels ranged from 10.7-74.3 g/MJ from biofuels derived from sugarcane bagasse and wild algae at the extremes of this range, respectively. The cumulative energy demand (CED) shows that energy in every biofuel process is primarily from renewable biomass and the remaining energy demand is mostly from fossil fuels. The CED for biofuel range from 1.25-3.25 MJ/MJ from biofuels derived from sugarcane bagasse to wild algae respectively, while the other feedstock-derived biofuels are around 2 MJ/MJ. Water utilization is primarily from cooling water use during the pyrolysis stage if irrigation is not used during the feedstock production stage. Water use ranges from 1.7 - 17.2 gallons of water per kg of biofuel from sugarcane bagasse to open pond algae, respectively.

Oxygenated polycyclic aromatic hydrocarbons and azaarenes in urban soils: A comparison of a tropical city (Bangkok) with two temperate cities (Bratislava and Gothenburg)

Environmental conditions in the tropics favor the formation of polar polycyclic aromatic compound (polar PACs, such as oxygenated PAHs [OPAHs] and azaarenes [AZAs]), but little is known about these hazardous compounds in tropical soils. The objectives of this work were to determine (i) the level of contamination of soils (0–5 and 5–10 cm layers) from the tropical metropolis of Bangkok (Thailand) with OPAHs and AZAs and (ii) the influence of urban emission sources and soil properties on the distribution of PACs. We hypothesized that the higher solar insolation and microbial activity in the tropics than in the temperate zone will lead to enhanced secondary formation of OPAHs. Hence, OPAH to related parent-PAH ratios will be higher in the tropical soils of Bangkok than in temperate soils of Bratislava and Gothenburg. The concentrations of ∑15OPAHs (range: 12–269 ng g−1) and ∑4AZAs (0.1–31 ng g−1) measured in soils of Bangkok were lower than those in several cities of the industrialized temperate zone. The ∑15OPAHs (r = 0.86, p < 0.01) and ∑4AZAs (r = 0.67, p < 0.01) correlated significantly with those of ∑20PAHs highlighting similar sources and related fate. The octanol–water partition coefficient did not explain the transport to the subsoil, indicating soil mixing as the reason for the polar PAC load of the lower soil layer. Data on PAC concentrations in soils of Bratislava and Gothenburg were taken from published literature. The individual OPAH to parent-PAH ratios in soils of Bangkok were mostly higher than those of Bratislava and Gothenburg (e.g. 9-fluorenone/fluorene concentration ratio was 12.2 ± 6.7, 5.6 ± 2.4, and 0.7 ± 02 in Bangkok, Bratislava and Gothenburg soils, respectively) supporting the view that tropical environmental conditions and higher microbial activity likely lead to higher OPAH to parent-PAH ratios in tropical than in temperate soils.

Organic petrography and extractable hydrocarbons of sediments at DSDP Leg 58 Holes

The quantity, type, and maturity of organic matter of Quaternary and Tertiary sediments from the Philippine Sea (DSDP Leg 58; Sites 442-446) were determined. Hydrocarbons in lipid extracts were analyzed by capillary-column gas chromatography. Kerogen concentrates were investigated by microscopy for vitrinite reflectance values and maceral composition. In the Shikoku Basin sediments (Sites 442, 443, and 444), organic carbon values range between 0.03 and 0.44 per cent. The higher values in the younger sediments are interpreted as an indication of increasing deposition of eroded organic particles during the past 4 m.y. Microscopic analyses revealed a dominance of reworked organic matter. Primary material could not be distinguished readily; thus, no maturation trend could be established. Extract yields were low. TV-alkane distributions mostly show maxima at n-C29 and n-C31 and high odd-over-even predominances, typical of material which originated in terrigenous higher plants. The organic-carbon values of sediments of the Daito Ridge and Basin region (Sites 444 and 445) range from less than 0.01 to 0.05 per cent. TV-alkanes exhibit varying marine and terrigenous influences. Some carbonate-rich samples show a pronounced even-over-odd predominance. At least the older sediments contained less recycled organic matter than the Shikoku Basin samples. The maturity, where measurable, was low. None of the Philippine Sea samples indicates a significant hydrocarbon-generation potential.

Low-molecular-weight hydrocarbons in sediments at DSDP Sites 89-585 and 89-586

C2-C8 hydrocarbon concentrations (about 35 compounds identified, including saturated, aromatic, and olefinic compounds) from 38 shipboard sealed, deep-frozen core samples of Deep Sea Drilling Project Sites 585 (East Mariana Basin) and 586 (Ontong-Java Plateau) were determined by a gas stripping-thermovaporization method. Total concentrations, which represent the hydrocarbons dissolved in the pore water and adsorbed on the mineral surfaces of the sediment, vary from 20 to 630 ng/g of rock at Site 585 (sub-bottom depth range 332-868 m). Likewise, organic-carbon normalized yields range from 3*10**4 to 9*10**5 ng/g Corg, indicating that the organic matter is still in the initial, diagenetic evolutionary stage. The highest value (based on both rock weight and organic carbon) is measured in an extremely organic-carbon-poor sample of Lithologic Subunit VB (Core 585-30). In this unit (504-550 m) several samples with elevated organic-carbon contents and favorable kerogen quality including two thin "black-shale" layers deposited at the Cenomanian/Turonian boundary (not sampled for this study) were encountered. We conclude from a detailed comparison of light hydrocarbon compositions that the Core 585-30 sample is enriched in hydrocarbons of the C2-C8 molecular range, particularly in gas compounds, which probably migrated from nearby black-shale source layers. C2-C8 hydrocarbon yields in Site 586 samples (sub-bottom depth range 27-298 m) did not exceed 118 ng/g of dry sediment weight (average 56 ng/g), indicating the immaturity of these samples.

Hydrocarbons, sterols and alkenones at time series station KERFIX

Hydrocarbons, sterols and alkenones were analyzed in samples collected from a 10 month sediment trap time series deployed in the Indian Ocean sector of the Southern Ocean. Fluxes and within-class distributions varied seasonally. During higher mass and organic carbon (OC) flux periods, which occurred in austral summer and fall, fresh marine inputs were predominant. Vertical fluxes were most intense in January, but limited to one week in duration. They were, however, low compared with other oceanic regions. In contrast, low mass and OC flux periods were characterized by a strong unresolved complex mixture (UCM) in the hydrocarbon fraction and a high proportion of stanols as a result of zooplanktonic grazing. Terrigenous inputs were not detectable. The alkenone compositions were consistent with previous data on suspended particles from Antarctic waters. However, UK'37 values diverged from the linear and exponential fits established by Sikes et al. (1997, doi:10.1016/S0016-7037(97)00017-3) in the low temperature range. The seasonal pattern of alkenone production implied that IPT (integrated production temperature) is likely to be strongly imprinted by austral summer and fall SST (sea surface temperature).

The Identification of Best Management Practices in a Materials Recovery Facility to Increase Solid Waste Diversion in the Department of Defense (DoD) Installations along the Front Range of Colorado to Satisfy the DoD Solid Waste Diversion Goal of 40 Percent

The five installations operated by the Department of Defense (DoD) in the Front Range region of Colorado do not meet the DoD non-hazardous solid waste diversion goal of 40 percent, further impacting landfills and generating greenhouse gases. This applied capstone project identifies and evaluates best management practices of a Materials Recovery Facility (MRF), qualitatively and quantitatively, to increase solid waste diversion at a DoD MRF. An environmental benefits model quantified the externalities of increasing solid waste diversion at the installations. By implementing best management practices at a MRF, the DoD would divert an additional 1,400 tons of solid waste per year, resulting in the equivalent of 1,502,567 gallons of gasoline being saved, among many benefits presented in this capstone.

Abatement of hydrocarbons by acid ZSM-5 and BETA zeolites under cold-start conditions

Simulated cold-start tests have been carried out to evaluate the performance of H-ZSM-5 and H-BETA zeolites as hydrocarbon traps under simulated gasoline car exhaust gases, paying special attention to the effect of water on their behaviour. It is concluded that the hydrothermal treatment of the zeolites in the acidic form contributes to the better performance of these materials as hydrocarbon traps since the stabilization of the zeolites takes place. Moreover, the decrease of the surface acidity of the zeolites results in an increase of the Si/Al ratio, which contributes to the decrease of the water affinity for adsorption sites. Thus, the competition with hydrocarbon molecules in the exhaust for the adsorption sites is reduced which increases their trap efficiency. The stabilized H-ZSM-5 is the zeolite that showed the best performance with a propene offset temperature of 240 °C, which should be high enough for the three-way catalyst to carry out its role as catalytic converter.