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72. Elucidation of Donor:Acceptor Phase Separation in Nonfullerene Organic Solar Cells and Its Implications on Device Performance and Charge Carrier MobilitySebastian F. Hoefler, Georg Haberfehlner, Thomas Rath, Andreas Keilbach, Mathias Hobisch, Alexander Dixon, Egon Pavlica, Gvido Bratina, Gerald Kothleitner, Ferdinand Hofer, Gregor Trimmel, 2019, original scientific article Abstract: In bulk-heterojunction solar cells, the device performance strongly depends on the donor and acceptor properties, the phase separation in the absorber layer, and the formation of a bicontinuous network. While this phase separation is well explored for polymer:fullerene solar cells, only little is known for polymer:nonfullerene acceptor solar cells. The main hurdle in this regard is often the chemical similarity of the conjugated polymer donor and the organic nonfullerene acceptor (NFA), which makes the analysis of the phase separation via atomic force microscopic (AFM) phase images or conventional transmission electron microscopy difficult. In this work, we use the donor polymer PTB7-Th and the small molecule acceptor O-IDTBR as the model system and visualized the phase separation in PTB7-Th:O-IDTBR bulk-heterojunctions with different donor:acceptor ratios via scanning transmission electron microscopy (STEM) high-angle annular dark-field (HAADF) images and electron energy loss spectroscopy (EELS) based elemental mapping, which resulted in a good contrast between the donor and the acceptor despite very low differences in the chemical composition. AFM as well as grazing-incidence wide-angle X-ray scattering (GIWAXS) investigations support the electron microscopic data. Furthermore, we elucidate the implications of the phase separation on the device performance as well as charge carrier mobilities in the bulk-heterojunction layers, and a high performance of the solar cells was found over a relatively broad range of polymer domain sizes. This can be related to the larger domain sizes of the acceptor phase with higher amounts of O-IDTBR in the blend, while the polymer donor phase still forms continuous pathways to the electrode, which keeps the hole mobility at a relatively constant level.
Keywords: nanomorphology bulk-heterojunction scanning transmission electron microscopy organic photovoltaics charge carrier mobility
Published in RUNG: 15.01.2020; Views: 2962; Downloads: 85
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73. The role of charge transfer at reduced graphene oxide/organic semiconductor interface on the charge transport propertiesGvido Bratina, Egon Pavlica, 2019, original scientific article Abstract: The effect of 1-pyrenesulfonicacid sodium salt (1-PSA), tetracyanoethylene (TCNE) and tetrafluoro- tetracyanoquinodimethane (F4-TCNQ) on charge transport properties of reduced graphene oxide (RGO) is examined by measuring the transfer characteristics of field-effect transistors and co-planar time-of-flight photocurrent technique. Evidence of p-type doping and a reduction of mobility of electrons in RGO upon deposition of these materials is observed. Time-resolved photocurrent measurements show a reduction in elec- tron mobility even at submonolayer coverage of these materials. The variation of transit time with different coverages reveals that electron mobility decreases with increasing the surface coverage of 1-PSA, TCNE and F4- TCNQ to a certain extent, while at higher coverage the electron mobility is slightly recovered. All three molecules show the same trend in charge carrier mobility variation with coverage, but with different magnitude. Among all three molecules, 1-PSA acts as weak electron acceptor compared to TCNE and F4-TCNQ. The additional fluorine moieties in F4-TCNQ provides excellent electron withdrawing capability compared to TCNE. The experimental results are consistent with the density functional theory calculations.
Keywords: organic semiconductors, reduced graphene oxide, time-resolved photocurrent measurements, organic thin film transistors
Published in RUNG: 28.10.2019; Views: 3547; Downloads: 1
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74. Uranium bearing dissolved organic matter in the porewaters of uranium contaminated lake sedimentsBreda Novotnik, Wei Chen, R. Douglas Evans, 2018, original scientific article Abstract: Uranium (U) mobility in the environment strongly depends on its oxidation state and the presence of complexing
agents such as inorganic carbon, phosphates, and dissolved organic matter (DOM). Despite the importance of
DOM in U mobility, the exact mechanism is still poorly understood. Therefore, the aim of our investigation was
to characterise sediment porewater DOM in two lakes in Ontario, Canada (Bow and Bentley Lakes) that were
historically contaminated with U and propose possible composition of UO2-bearing DOM. Depth profiles of U
concentrations in porewaters and total sediment digests reveal U levels of up to 1.3 mg L−1 in porewater and up
to 0.8 mg−1 g in sediment. Depth profiles of U did not correlate with Fe, Mn, SO4
2−, or Eh profiles. Therefore,
porewater DOM was analysed and taken into consideration as the primary source of U mobility. Porewater DOM
in each sediment section (1 cm sections, 20 cm core length) was analysed by high-resolution electrospray ionisation
mass spectrometry. PCA analyses of porewater DOM mass spectra showed grouping and clear separation
of DOM in sediment sections with elevated U concentrations in comparison to sections with background U
concentrations. Several criteria were set to characterise UO2-bearing DOM and more than 70 different molecules
were found. The vast majority of these UO2-DOM compounds fell in the category of carboxyl-containing aliphatic
molecules (H/C between 0.85 and 1.2 and O/C≤0.4) and had a mean value of m/z about 720.
Keywords: Uranium
Lake sediments
Porewater
Disolved organic matter
High resolution mass spectrometry
Published in RUNG: 09.10.2019; Views: 3153; Downloads: 0
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75. Real-time multi-marker measurement of organic compounds in human breath: Towards fingerprinting breathIain R. White, Kerry A Willis, Christopher Whyte, Rebecca Cordell, Robert S Blake, Andrew J Wardlaw, 2013, original scientific article Abstract: The prospects for exploiting proton transfer reaction-time of flight-mass spectrometry (PTR-ToF-MS) in medical diagnostics are illustrated through a series of case studies. Measurements of acetone levels in the breath of 68 healthy people are presented along with a longitudinal study of a single person over a period of 1 month. The median acetone concentration across the population was 484 ppbV with a geometric standard deviation (GSD) of 1.6, whilst the average GSD during the single subject longtitudinal study was 1.5. An additional case study is presented which highlights the potential of PTR-ToF-MS in pharmacokinetic studies, based upon the analysis of online breath samples of a person following the consumption of ethanol. PTR-ToF-MS comes into its own when information across a wide mass range is required, particularly when such information must be gathered in a short time during a breathing cycle. To illustrate this property, multicomponent breath analysis in a small study of cystic fibrosis patients is detailed, which provides tentative evidence that online PTR-ToF-MS analysis of tidal breath can distinguish between active infection and non-infected patients.
Keywords: Volatile Organic Compounds, breath, proton transfer reaction mass spectrometry, Cystic Fibrosis
Published in RUNG: 22.07.2019; Views: 3281; Downloads: 0
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76. Increased sensitivity in proton transfer reaction mass spectrometry by incorporation of a radio frequency ion funnelShane Barber, Robert S Blake, Iain R. White, Paul S Monks, Fraser Reich, Stephen Mullock, Andrew M Ellis, 2012, original scientific article Abstract: A drift tube capable of simultaneously functioning as an ion funnel is demonstrated in proton transfer reaction mass spectrometry (PTR-MS) for the first time. The ion funnel enables a much higher proportion of ions to exit the drift tube and enter the mass spectrometer than would otherwise be the case. An increase in the detection sensitivity for volatile organic compounds of between 1 and 2 orders of magnitude is delivered, as demonstrated using several compounds. Other aspects of analytical performance explored in this study include the effective E/N (ratio of electric field to number density of the gas) and dynamic range over which the drift tube is operated. The dual-purpose drift tube/ion funnel can be coupled to various types of mass spectrometers to increase the detection sensitivity and may therefore offer considerable benefits in PTR-MS work.
Keywords: Analytical performance, Detection sensitivity, Drift tube, Dynamic range, Ion funnels, Proton-transfer reaction mass spectrometry, Volatile organic compounds
Published in RUNG: 18.07.2019; Views: 2822; Downloads: 0
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77. Development of an adaptable headspace sampling method for metabolic profiling of the fungal volatomeWaqar M Ahmed, Pavlos Geranios, Iain R. White, Oluwasola Lawal, Tamara M Nijsen, Michael J Bromley, Royston Goodacre, Nicholas D Read, Stephen J Fowler, 2018, original scientific article Abstract: Pulmonary aspergillosis can cause serious complications in people with a suppressed immune system. Volatile metabolites emitted by Aspergillus spp. have shown promise for early detection of pathogenicity. However, volatile profiles require further research, as effective headspace analysis methods are required for extended chemical coverage of the volatome; in terms of both very volatile and semi-volatile compounds. In this study, we describe a novel adaptable sampling method in which fungal headspace samples can be sampled continuously throughout a defined time period using both active (pumped) and passive (diffusive) methods, with the capability for samples to be stored for later off-line analysis. For this method we utilise thermal desorption-gas chromatography-mass spectrometry to generate volatile metabolic profiles using Aspergillus fumigatus as the model organism. Several known fungal-specific volatiles associated with secondary metabolite biosynthesis (including α-pinene, camphene, limonene, and several sesquiterpenes) were identified. A comparison between the wild-type A. fumigatus with a phosphopantetheinyl transferase null mutant strain (ΔpptA) that is compromised in secondary metabolite synthesis, revealed reduced production of sesquiterpenes. We also showed the lack of terpene compounds production during the early growth phase, whilst pyrazines were identified in both early and late growth phases. We have demonstrated that the fungal volatome is dynamic and it is therefore critically necessary to sample the headspace across several time periods using a combination of active and passive sampling techniques to analyse and understand this dynamism.
Keywords: Volatile Organic Compounds, Fungi, Mycelial growth
Published in RUNG: 18.07.2019; Views: 2904; Downloads: 0
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78. TD/GC–MS analysis of volatile markers emitted from mono- and co-cultures of Enterobacter cloacae and Pseudomonas aeruginosa in artificial sputumIain R. White, Oluwasola Lawal, Hugo Knobel, Weda Hans, Tamara M E Nijsen, Royston Goodacre, Stephen J Fowler, Waqar M Ahmed, Antonio Artigas, Jonathan Barnard-Smith, Lieuwe D Bos, Marta Camprubi, Luis Coelho, Paul Dark, Alan Davie, Emili Diaz, Gemma Goma, Timothy Felton, Jan H Leopold, Pouline M P van Oort, Pedro Póvoa, Craig Portsmouth, 2018, original scientific article Abstract: Introduction: Infections such as ventilator-associated pneumonia (VAP) can be caused by one or more pathogens. Current methods for identifying these pathogenic microbes often require invasive sampling, and can be time consuming, due to the requirement for prolonged cultural enrichment along with selective and differential plating steps. This results in delays in diagnosis which in such critically ill patients can have potentially life-threatening consequences. Therefore, a non-invasive and timely diagnostic method is required. Detection of microbial volatile organic compounds (VOCs) in exhaled breath is proposed as an alternative method for identifying these pathogens and may distinguish between mono- and poly-microbial infections. Objectives: To investigate volatile metabolites that discriminate between bacterial mono- and co-cultures. Methods: VAP-associated pathogens Enterobacter cloacae and Pseudomonas aeruginosa were cultured individually and together in artificial sputum medium for 24 h and their headspace was analysed for potential discriminatory VOCs by thermal desorption gas chromatography–mass spectrometry. Results: Of the 70 VOCs putatively identified, 23 were found to significantly increase during bacterial culture (i.e. likely to be released during metabolism) and 13 decreased (i.e. likely consumed during metabolism). The other VOCs showed no transformation (similar concentrations observed as in the medium). Bacteria-specific VOCs including 2-methyl-1-propanol, 2-phenylethanol, and 3-methyl-1-butanol were observed in the headspace of axenic cultures of E. cloacae, and methyl 2-ethylhexanoate in the headspace of P. aeruginosa cultures which is novel to this investigation. Previously reported VOCs 1-undecene and pyrrole were also detected. The metabolites 2-methylbutyl acetate and methyl 2-methylbutyrate, which are reported to exhibit antimicrobial activity, were elevated in co-culture only. Conclusion: The observed VOCs were able to differentiate axenic and co-cultures. Validation of these markers in exhaled breath specimens could prove useful for timely pathogen identification and infection type diagnosis.
Keywords: Bacteria, Enterobacter cloacae, Gas Chromatography-Mass Spectrometry, Infection, Pseudomonas aeruginosa, Volatile organic compounds
Published in RUNG: 18.07.2019; Views: 4454; Downloads: 114
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79. Headspace volatile organic compounds from bacteria implicated in ventilator-associated pneumonia analysed by TD-GC/MSOluwasola Lawal, Howbeer Muhamadali, Waqar M Ahmed, Iain R. White, Tamara M E Nijsen, Roy Goodacre, Stephen J Fowler, 2018, original scientific article Abstract: Ventilator-associated pneumonia (VAP) is a healthcare-acquired infection arising from the invasion of the lower respiratory tract by opportunistic pathogens in ventilated patients. The current method of diagnosis requires the culture of an airway sample such as bronchoalveolar lavage, which is invasive to obtain and may take up to seven days to identify a causal pathogen, or indeed rule out infection. While awaiting results, patients are administered empirical antibiotics; risks of this approach include lack of effect on the causal pathogen, contribution to the development of antibiotic resistance and downstream effects such as increased length of intensive care stay, cost, morbidity and mortality. Specific biomarkers which could identify causal pathogens in a timely manner are needed as they would allow judicious use of the most appropriate antimicrobial therapy. Volatile organic compound (VOC) analysis in exhaled breath is proposed as an alternative due to its non-invasive nature and its potential to provide rapid diagnosis at the patient's bedside. VOCs in exhaled breath originate from exogenous, endogenous, as well as microbial sources. To identify potential markers, VAP-associated pathogens Escherichia coli, Klebsiella pneumoniae, Pseudomonas aeruginosa, and Staphylococcus aureus were cultured in both artificial sputum medium and nutrient broth, and their headspaces were sampled and analysed for VOCs. Previously reported volatile markers were identified in this study, including indole and 1-undecene, alongside compounds that are novel to this investigation, cyclopentanone and 1-hexanol. We further investigated media components (substrates) to identify those that are essential for indole and cyclopentanone production, with potential implications for understanding microbial metabolism in the lung.
Keywords: bacteria, exhaled breath, infection, ventilator-associated pneumonia, volatile organic compounds
Published in RUNG: 18.07.2019; Views: 2832; Downloads: 0 |
80. Characterisation of charge carrier transport in thin organic semiconductor T layers by time-of-flight photocurrent measurementsGvido Bratina, Egon Pavlica, 2019, review article Abstract: The paper reviews recent advances in characterisation of charge carrier transport in organic semiconductor layers by time-of-flight photocurrent measurements, with the emphasis on the measurements of the samples with co-planar electrodes. These samples comprised an organic semiconductor layer whose thickness is on the order of a μm or less, and thus mimic the structures of organic thin film transistors. In the review we emphasise the importance of considering spatial variation of electric field in these, essentially two-dimensional structures, in interpretation of photocurrent transients. We review the experimental details of this type of measurements and give examples that demonstrate exceptional sensitivity of the method to minute concentration of electrically active defects in the organic semiconductors as well as the capability of probing charge transport along the channels of different mobility that reside in the same sample.
Keywords: organic semiconductors, time of flight, mobiulity
Published in RUNG: 24.10.2018; Views: 3710; Downloads: 0
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