91. 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: 4535; Downloads: 114
 Full text (1,29 MB) |
92. 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: 2919; Downloads: 0 |
93. 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: 3807; Downloads: 0
This document has many files! More... |
94. PHOTO-EXCITATION ENERGY INFLUENCE ON THE PHOTOCONDUCTIVITY OF ORGANIC SEMICONDUCTORSNadiia Pastukhova, 2018, doctoral dissertation Abstract: In this work, we experimentally studied the influence of photoexcitation energy
influence on the charge transport in organic semiconductors. Organic semiconductors
were small molecules like corannulene, perylene and pentacene derivatives, polymers
such as polythiophene and benzothiophene derivatives, and graphene, along with
combinations of these materials in heterojunctions or composites.
The first part of this study is focused on the photoexcitation energy influence on
the transient photoconductivity of non-crystalline curved π-conjugated corannulene
layers. The enhanced photoconductivity, in the energy range where optical absorption
is absent, is deduced from theoretical predictions of corannulene gas-phase excited
state spectra. Theoretical analysis reveals a consistent contribution involving
transitions to Super Atomic Molecular Orbitals (SAMOs), a unique set of diffuse
orbitals typical of curved π-conjugated molecules. More, the photoconductivity of the
curved corannulene was compared to the π-conjugated planar N,N′-1H,1H-
perfluorobutyldicyanoperylene-carboxydi-imide
(PDIF-CN2),
where
the
photoexcitation energy dependence of photocurrent closely follows the optical
absorption spectrum.
We next characterized charge transport in poly(3-hexylthiophene) (P3HT) layers
deposited from solution. Our results indicate that time-of-flight (TOF) mobility
depends on the photoexcitation energy. It is 0.4× 10 −3 cm 2 /Vs at 2.3 eV (530 nm) and
doubles at 4.8 eV (260 nm). TOF mobility was compared to field-effect (FET) mobility
of P3HT field-effect transistors (OFETs). The FET mobility was similar to the 2.3 eV
excitation TOF mobility. In order to improve charge mobility, graphene nanoparticles
were blended within a P3HT solution before the deposition. We found that the mobility
significantly improves upon the addition of graphene nanoparticles of a weight ratio
as low as 0.2 %. FET mobility increases with graphene concentration up to a value of
2.3× 10 −2 cm 2 /Vs at 3.2 %. The results demonstrate that phase segregation starts to
influence charge transport at graphene concentration of 0.8 % and above. Hence, the
graphene cannot form a bridged conduction channel between electrodes, which would
cancel the semiconducting effect of the polymer composite.
An alternative approach to enhance mobility is to optimize the molecular ordering
of organic semiconductors. For that purpose, we studied an innovative nanomesh
device. Free-standing nanomesh devices were used to form nanojunctions of N,N′-
iiDioctyl-3,4,9,10-perylenedicarboximide (PTCDI-C8) nanowires and crystalline
bis(triisopropylsilylethinyl)pentacene (TIPS-PEN). We characterized the photocurrent
response time of this novel nanomesh scaffold device. The photoresponse time
depends on the photon energy. It is between 4.5 − 5.6 ns at 500 nm excitation
wavelength and between 6.7 − 7.7 ns at 700 nm excitation wavelength. In addition, we
found that thermal annealing reduces charge carrier trapping in crystalline nanowires.
This confirms that the structural defects are crucial to obtaining high photon-to-charge
conversion efficiency and subsequent transport from pn junction in heterostructured
materials.
Structural defects also influence the power conversion efficiency of organic
heterostructured photovoltaics (OPVs). Anticipating that polymers with different
backbone lengths produce different level of structural defects, we examined charge
transport
dependence
on
the
molecular
weight
of
poly[4,8-bis(5-(2-
ethylhexyl)thiophen-2-yl)benzo[1,2-b;4,5-b']dithiophene-2,6-diyl-alt-(4-(2-
ethylhexyl)-3-fluorothieno[3,4-b]thiophene-)-2-carboxylate-2-6-diyl]
(PTB7-Th)
from 50 kDa to 300 kDa. We found p-type hopping transport in PTB7-Th,
characterized by 0.1 – 3× 10 −2 cm 2 /Vs mobility, which increases with temperature and
electric field. The polymer molecular weight exhibits a non-trivial influence on charge
transport. FET mobility in the saturation regime increases with molecular weight. A
similar trend is observed in TOF mobility and FET mobility in the linear regime,
except for the 100kDa polymer, which manifests in the highest mobility due to reduced
charge trapping. The lowest trapping at the dielectric interface of OFET is observed at
200 kDa. In addition, the 200 kDa polymer exhibits the lowest activation energy of the
charge transport. Although the 100 kDa polymer indicates the highest mobility, OPVs
using the 200 kDa polymer exhibit the best performance in terms of power conversion
efficiency.
Keywords: organic
semiconductors, optical
absorption
spectroscopy, time-of-flight
photoconductivity, transient photocurrent spectroscopy, organic thin film transistors, atomic force microscopy, superatomic molecular orbitals, pn heterojunction, organic
nanowires, graphene, composites, charge mobility, charge trapping, temperature
dependence, photodetector, photovoltaic, solar cell, organic electronics
Published in RUNG: 08.10.2018; Views: 5560; Downloads: 164
Full text (4,56 MB) |
95. Effects of Different Copper Loadings on the Photocatalytic Activity of TiO2-SiO2 Prepared at a Low Temperature for the Oxidation of Organic Pollutants in WaterT. Čižmar, Iztok Arčon, Mattia Fanetti, Urška Lavrenčič Štangar, 2018, original scientific article Abstract: The objective of this research is to examine how Cu modification can improve the photocatalytic activity of TiO2-SiO2, to explainthe correlation between the Cu concentration and the chemical state of Cu cations in the TiO2-SiO2 matrix, and the photocatalytic activity under UV/solar irradiation. The Cu-modified TiO2-SiO2 photocatalysts were prepared by a low-temperature sol–gel method from organic Cu, Si and Ti precursors with various Cu concentrations (0.05–3 mol %). The sol–gels were dried at 150 8C to obtain the photocatalysts in a powder form. The photocatalytic activity was determined by using a fluorescence- based method of terephthalic acid decomposition. An up to three times increase in photocatalytic activity is obtained if the TiO2-SiO2 matrix is modified with Cu in a narrow concentration
range from 0.05 to 0.1 mol%. At higher Cu loadings,
the photocatalytic activity of the Cu-modified photocatalysts is lower than that of the un-modified reference TiO2-SiO2 photocatalyst. XRD was used to show that all Cu-modified TiO2-SiO2 composites with different Cu concentrations have the same crystalline structure as un-modified TiO2-SiO2 composites. The addition of Cu does not change the relative ratio between the anatase and brookite phases or unit cell parameters of the two TiO2 crystalline structures. We used Cu K-edge X-ray absorption near edge structure and extended X-ray absorption fine structure analyses to determine the valence state and local structure of Cu cations in the Cu-modified TiO2-SiO2 photocatalysts. The results elucidate the mechanism responsible for the improved photocatalytic activity. In samples with a low Cu content,
which exhibit the highest activity, Cu@O@Ti connections
are formed, which suggests that the activity enhancement is
caused by the attachment of CuII cations on the surface of the photocatalytically active TiO2 nanoparticles, so CuII cations may act as free-electron traps, which reduce the intensity of recombination between electrons and holes at the TiO2 photocatalyst surface. At higher Cu loadings no additional Cu@O@Ti connections are formed, instead only Cu@O@Cu connections are established. This indicates the formation of amorphous or nanocrystalline
copper oxide, which hinders the photocatalytic activity
of TiO2.
Keywords: Cu modified TiO2-SiO2 photocatalyst
Cu EXAFS, XANES, Organic pollutants
Published in RUNG: 30.08.2018; Views: 3639; Downloads: 0
This document has many files! More... |
96. Negative field‐dependent charge mobility in crystalline organic semiconductors with delocalized transportFei Tong, Andrey Kadashchuk, Egon Pavlica, Gvido Bratina, 2018, original scientific article Abstract: Charge-carrier mobility has been investigated by time-of-flight (TOF) transient photocurrent in a lateral transport con- figuration in highly crystalline thin films of 2,7-dioctyl[1]benzothieno [3,2-b][1] benzothiophene (C8-BTBT) grown by a zone-casting alignment technique. High TOF mobility has been revealed that it is consistent with the delocalized nature of the charge transport in this material, yet it featured a positive temperature dependence at T ≥ 295 K. Moreover, the mobility was surprisingly found to decrease with electric field in the high-temperature region. These observations are not compat- ible with the conventional band-transport mechanism. We have elaborated an analytic model based on effective-medium approximation to rationalize the puzzling findings. The model considers the delocalized charge transport within the energy landscape formed by long-range transport band-edge variations in imperfect organic crystalline materials and accounts for the field-dependent effective dimensionality of charge transport percolative paths. The results of the model calculations are found to be in good agreement with experimental data.
Keywords: time of flight, organic semiconductors, single crystals
Published in RUNG: 07.05.2018; Views: 5349; Downloads: 0
This document has many files! More... |
97. |
98. |
99. Extraction of Organochlorine Pesticides from Plastic Pellets and Plastic Type AnalysisMaryline Pflieger, Petra Makorič, Manca Kovač Viršek, Špela Koren, 2017, review article Abstract: Plastic resin pellets, categorized as microplastics (≤5 mm in diameter), are small granules that can be unintentionally released to the
environment during manufacturing and transport. Because of their environmental persistence, they are widely distributed in the oceans and
on beaches all over the world. They can act as a vector of potentially toxic organic compounds (e.g., polychlorinated biphenyls) and might
consequently negatively affect marine organisms. Their possible impacts along the food chain are not yet well understood. In order to assess the
hazards associated with the occurrence of plastic pellets in the marine environment, it is necessary to develop methodologies that allow for rapid
determination of associated organic contaminant levels. The present protocol describes the different steps required for sampling resin pellets,
analyzing adsorbed organochlorine pesticides (OCPs) and identifying the plastic type. The focus is on the extraction of OCPs from plastic pellets
by means of a pressurized fluid extractor (PFE) and on the polymer chemical analysis applying Fourier Transform-InfraRed (FT-IR) spectroscopy.
The developed methodology focuses on 11 OCPs and related compounds, including dichlorodiphenyltrichloroethane (DDT) and its two main
metabolites, lindane and two production isomers, as well as the two biologically active isomers of technical endosulfan. This protocol constitutes
a simple and rapid alternative to existing methodology for evaluating the concentration of organic contaminants adsorbed on plastic pieces.
Keywords: Environmental Sciences, Issue 125, Microplastics, resin pellets, pesticides, persistent organic pollutants, organochlorine pesticides, dichlorodiphenyltrichloroethane, endosulfan, hexachlorocyclohexane, lindane, Fourier transform infrared spectroscopy, pressurized fluid extractor
Published in RUNG: 10.07.2017; Views: 4544; Downloads: 0 |
100. Interface-controlled growth of organic semiconductors on grapheneJinta Mathews, Saim Emin, Egon Pavlica, Matjaž Valant, Gvido Bratina, 2017, original scientific article Abstract: We have studied submonolayer coverages of N,N-1H,1H-perfluorobutyl dicyanoperylenecarboxydiimide (PDIF-CN2) on mechanically exfoliated graphene transferred onto SiO2 substrates. Our atomic force microscopy (AFM) data show that PDIF-CN2 forms irregularly-shaped 1.4 nm-high islands. From the selected area diffraction performed with transmission electron microscope (TEM) we conclude that this height corresponds to π−π
stacks of molecules, which are inclined for 43° relative to the graphene surface. AFM also showed complete absence of PDIF-CN2 on single-layer graphene (SLG). Electric force microscopy revealed a marked difference in surface charge density between a single-layer graphene and bilayer graphene, with a higher surface charge on SLG than on the bilayer graphene. We associate this behavior with p−
type doping of graphene due to the electrostatic dipole induced by the molecular water layer present at the graphene/SiO2 interface. The crucial role of the graphene/SiO2 interface in determining growth of PDIF-CN2 was further confirmed by TEM examination of PDIF-CN2 deposited onto unsupported SLG.
Keywords: afm, organic semiconductors, graphene
Published in RUNG: 18.05.2017; Views: 4891; Downloads: 0
This document has many files! More... |
