Designed synthesis and supramolecular architectures of furan-substituted perylene diimide.

PubMed

Yu, Yanwen; Li, Yongjun; Qin, Zhihong; Jiang, Runsheng; Liu, Huibiao; Li, Yuliang

2013-06-01

Novel furan-substituted perylene diimides are successfully synthesized and an efficient supramolecular architecture approach to construct zero/one-dimensional nano- and micro-structures by controlling solvents has been demonstrated. The aggregate structure conversion in different molecular structures can be controlled in the form of sphere-like, rod-like, and vesicle-like structures. As expected, these solid supramolecular rod-like architectures displayed interesting optical waveguide behavior, which indicates the aggregate structure materials of furan-substituted perylene diimides have the potential application as micro-scale photonic elements. Copyright © 2013 Elsevier Inc. All rights reserved.

The electrical and dielectrical behavior of n-conducting perylene tetracarboxylic diimide derivatives

NASA Astrophysics Data System (ADS)

Lehmann, Daniel; Zahn, Dietrich R. T.

2009-04-01

A comparison of the electrical characteristics of organic field-effect transistors (OFETs) based on derivatives of the electron-conductor perylene tetracarboxylic diimide (PTCDI) in top-contact configuration is presented. The derivatives used are N,N'-dimethyl-3,4,9,10-perylene-tetracarboxylic-diimide (DiMe-PTCDI), N,N'-diphenyl-3,4,9,10-perylene-tetracarboxylic-diimide (DiPhenyl-PTCDI), N,N'-dimethoxyethyl-3,4,9,10-perylene-tetracarboxylic-diimide (DiMethoxyethyl-PTCDI), N,N'-di(3-pentyl)-3,4,9,10-perylene-tetracarboxylic-diimide (Di3Pentyl-PTCDI), and N,N'-diheptyl-3,4,9,10-perylene-tetracarboxylic-diimide (DiHeptyl-PTCDI). Current/voltage measurements were first performed in situ and later ex situ. Additionally, the effect of annealing and bias stress was probed in situ. A strong influence of the different side groups on the order of magnitude of the electron mobility is revealed, ranging from 4×10-6 cm2/V s for DiMethoxyethyl-PTCDI to 5×10-2 cm2/V s for DiHeptyl-PTCDI. While none of the devices was stable in air after exposition to air, only the DiMe-PTCDI one resumed its functionality after restoring vacuum conditions. The dielectric functions of the derivatives was derived, additionally revealing optical isotropy for all films and varying surface roughness. While DiHeptyl-PTCDI and Di3Pentyl-PTCDI, yielding also the highest electron mobilities, form smooth layers with negligible surface roughness, strong island formation was be observed for DiPhenyl-PTCDI and DiMethoxyethyl-PTCDI, yielding low mobilities. This island growth was also confirmed by atomic force microscopy measurements. Ageing of the samples for several months under ambient conditions leads to increased roughness for the very rough samples. Layers with smooth surface, on the other hand, showed no significant change in the dielectric behavior of the sample.

Perylene-Based All-Organic Redox Battery with Excellent Cycling Stability.

PubMed

Iordache, Adriana; Delhorbe, Virginie; Bardet, Michel; Dubois, Lionel; Gutel, Thibaut; Picard, Lionel

2016-09-07

Organic materials derived from biomass can constitute a viable option as replacements for inorganic materials in lithium-ion battery electrodes owing to their low production costs, recyclability, and structural diversity. Among them, conjugated carbonyls have become the most promising type of organic electrode material as they present high theoretical capacity, fast reaction kinetics, and quasi-infinite structural diversity. In this letter, we report a new perylene-based all-organic redox battery comprising two aromatic conjugated carbonyl electrode materials, the prelithiated tetra-lithium perylene-3,4,9,10-tetracarboxylate (PTCLi6) as negative electrode material and the poly(N-n-hexyl-3,4,9,10-perylene tetracarboxylic)imide (PTCI) as positive electrode material. The resulting battery shows promising long-term cycling stability up to 200 cycles. In view of the enhanced cycling performances, the two organic materials studied herein are proposed as suitable candidates for the development of new all-organic lithium-ion batteries.

New fluorescent symmetrically substituted perylene-3,4,9,10-dianhydride-azohybrid dyes: Synthesis and spectroscopic studies

NASA Astrophysics Data System (ADS)

Saeed, Aamer; Shabir, Ghulam

2014-12-01

Five phenolic azo-dyes (3a-e) were synthesized by diazo coupling of the suitably substituted anilines (1a-e) with phenol at low temperature in alkaline medium. The resulting dyes have low solubility in aqueous medium due to lack of carboxylic or sulfonic solubilizing functionalities. The hybridization of perylene dianhydride with phenolic azo-dyes was achieved by the nucleophilic aromatic substitution (SNAr) reaction of perylene-3,4,9,10-dianhydride 4 with phenolic azo-dyes 3a-e in basic medium. The hybrid dyes exhibit absorption maxima λmax in the range 440-460 nm in aqueous medium due to presence of azo linkage and highly conjugated system of π bonds. Fluorescence spectra of these dyes in water show sharp emission peaks with small band widths. The structures of perylene-azo dyes were confirmed by FTIR and NMR spectroscopy.

Photoinduced Fluorescence from the Perylene Cation Isolated in Ne and Ar Matrices

NASA Technical Reports Server (NTRS)

Joblin, C.; Salama, F.; Allamandola, L.

1995-01-01

The fluorescence and fluorescence excitation spectra of the perylene cation isolated in neon and argon matrices are reported. This is the first report of the fluorescence spectrum of a polycyclic aromatic hydrocarbon ion in any phase.

Infrared study on the molecular orientation in bulk-heterojunction films based on perylene and 3,4,9,10-perylenetetracarboxylic dianhydride

NASA Astrophysics Data System (ADS)

Seto, Keisuke; Pham, John; Furukawa, Yukio

2012-03-01

Solid-state structures of thin blend films of perylene and 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) formed on the Au surface have been studied by a combination of infrared reflection-absorption spectroscopy and the RATIO method of Debe. In the blend films, PTCDA molecules take the face-on orientation in the whole range of PTCDA contents from 7.5 to 88 mol%. On the other hand, the molecular orientation of perylene molecules changes from edge-on toward random as the PTCDA content increases.

Benzo[g,h,i]perylene

Integrated Risk Information System (IRIS)

Benzo [ g , h , i ] perylene ; CASRN 191 - 24 - 2 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Nonc

Vesicular perylene dye nanocapsules as supramolecular fluorescent pH sensor systems.

PubMed

Zhang, Xin; Rehm, Stefanie; Safont-Sempere, Marina M; Würthner, Frank

2009-11-01

Water-soluble, self-assembled nanocapsules composed of a functional bilayer membrane and enclosed guest molecules can provide smart (that is, condition responsive) sensors for a variety of purposes. Owing to their outstanding optical and redox properties, perylene bisimide chromophores are interesting building blocks for a functional bilayer membrane in a water environment. Here, we report water-soluble perylene bisimide vesicles loaded with bispyrene-based energy donors in their aqueous interior. These loaded vesicles are stabilized by in situ photopolymerization to give nanocapsules that are stable over the entire aqueous pH range. On the basis of pH-tunable spectral overlap of donors and acceptors, the donor-loaded polymerized vesicles display pH-dependent fluorescence resonance energy transfer from the encapsulated donors to the bilayer dye membrane, providing ultrasensitive pH information on their aqueous environment with fluorescence colour changes covering the whole visible light range. At pH 9.0, quite exceptional white fluorescence could be observed for such water-soluble donor-loaded perylene vesicles.

Fluorescent Hydrogel Generated Conveniently from a Perylene Tetracarboxylate Derivative of Titanium(IV) Alkoxide.

PubMed

Zou, Dan-Hong; Wang, Peng; Luo, Wen; Hou, Jin-Le; Zhu, Qin-Yu; Dai, Jie

2018-02-05

Organic gelators and metal-coordination frameworks based on perylene derivatives as functional materials have attracted great attention because of their intense fluorescence emission as well as unique electronic and photonic properties. We report here the structures and properties of a luminescent titanium(IV) coordination compound of a perylene tetracarboxylate (PTC) derivative, [Ti 2 (O i Pr) 6 (L 1 )(phen) 2 ] (1), along with its two naphthalene analogues, [Ti 2 (O i Pr) 6 (L 2 )(phen) 2 ] (2) and [Ti 2 (O i Pr) 6 (L 2 )(bpy) 2 ] (3), where L 1 = 3,9-dicarboxylate-(4,10-diisopropanolcarboxylate)perylene, phen = 1,10-phenanthroline, L 2 = 1,5-dicarboxylate-(2,6-diisopropanolcarboxylate)naphthalene, and bpy = 2,2'-bipyridine. Compound 1 is a rare early-transition-metal PTC coordination compound that can be simply prepared in one pot as crystals by a low-heat synthesis. Unlike those of paramagnetic late-transition-metal PTC compounds, compound 1 showed intense fluorescence emission. More remarkably, the crystals of 1 can be turned immediately to a fluorescent hydrogel just through a simple procedure, putting the crystals in water and then treating with ultrasound. No acid catalyst or pH adjustment is needed. Hydrolysis of the titanium isopropanol group in water and π-π interaction of the perylene and phen play important roles in the gelation process. The film prepared from the gel can be used as a visual fluorescence sensor for aromatic amines and phenols, which are hazards for the human and environment.

Proton triggered circularly polarized luminescence in orthogonal- and co-assemblies of chiral gelators with achiral perylene bisimide.

PubMed

Han, Dongxue; Han, Jianlei; Huo, Shengwei; Qu, Zuoming; Jiao, Tifeng; Liu, Minghua; Duan, Pengfei

2018-05-29

The orthogonal- or co-assembly of achiral perylene bisimide (PBI) with chiral gelators can be regulated by solvents. While the coassembly leads to the formation of chiroptical nanofibers through chirality transfer, the orthogonal assemblies could not. Moreover, protonation on the coassembled nanofibers could light up the circularly polarized luminescence (CPL).

Air-stable n-channel organic thin-film transistors with high field-effect mobility based on N ,N'-bis(heptafluorobutyl)-3,4:9,10-perylene diimide

NASA Astrophysics Data System (ADS)

Oh, Joon Hak; Liu, Shuhong; Bao, Zhenan; Schmidt, Rüdiger; Würthner, Frank

2007-11-01

The thin-film transistor characteristics of n-channel organic semiconductor, N ,N'-bis(2,2,3,3,4,4,4-heptafluorobutyl)-perylene tetracarboxylic diimide, are described. The slip-stacked face-to-face molecular packing allows a very dense parallel arrangement of the molecules, leading to field-effect mobility as high as 0.72cm2V-1s-1. The mobility only slightly decreased after exposure to air and remained stable for more than 50days. Our results reveal that molecular packing effects such as close stacking of perylene diimide units and segregation effects imparted by the fluorinated side chains are crucial for the air stability.

Crystallochromy of perylene pigments: Influence of an enlarged polyaromatic core region

NASA Astrophysics Data System (ADS)

Gisslén, L.; Scholz, R.

2011-04-01

As demonstrated in a recent model study of several perylene pigments crystallizing in the monoclinic space group P21/c, the optical properties in the crystalline phase are determined by the interference between neutral molecular excitations and charge transfer states via electron and hole transfer. In the present work, we apply this exciton model to three further perylene compounds crystallizing in the space groups P21/n, P1̲, and P21/c, involving two chromophores with an enlarged polyaromatic core. In all cases, the charge transfer between stack neighbors increases the second moment of the optical response, whereas a larger conjugated core results in a red shift of the neutral excitation energy of each chromophore.

Coupled sensitizer-catalyst dyads: electron-transfer reactions in a perylene-polyoxometalate conjugate.

PubMed

Odobel, Fabrice; Séverac, Marjorie; Pellegrin, Yann; Blart, Errol; Fosse, Céline; Cannizzo, Caroline; Mayer, Cédric R; Elliott, Kristopher J; Harriman, Anthony

2009-01-01

Ultrafast discharge of a single-electron capacitor: A variety of intramolecular electron-transfer reactions are apparent for polyoxometalates functionalized with covalently attached perylene monoimide chromophores, but these are restricted to single-electron events. (et=electron transfer, cr=charge recombination, csr=charge-shift reaction, PER=perylene, POM=polyoxometalate).A new strategy is introduced that permits covalent attachment of an organic chromophore to a polyoxometalate (POM) cluster. Two examples are reported that differ according to the nature of the anchoring group and the flexibility of the linker. Both POMs are functionalized with perylene monoimide units, which function as photon collectors and form a relatively long-lived charge-transfer state under illumination. They are reduced to a stable pi-radical anion by electrolysis or to a protonated dianion under photolysis in the presence of aqueous triethanolamine. The presence of the POM opens up an intramolecular electron-transfer route by which the charge-transfer state reduces the POM. The rate of this process depends on the molecular conformation and appears to involve through-space interactions. Prior reduction of the POM leads to efficient fluorescence quenching, again due to intramolecular electron transfer. In most cases, it is difficult to resolve the electron-transfer products because of relatively fast reverse charge shift that occurs within a closed conformer. Although the POM can store multiple electrons, it has not proved possible to use these systems as molecular-scale capacitors because of efficient electron transfer from the one-electron-reduced POM to the excited singlet state of the perylene monoimide.

Detection of three-base deletion by exciplex formation with perylene derivatives.

PubMed

Kashida, Hiromu; Kondo, Nobuyo; Sekiguchi, Koji; Asanuma, Hiroyuki

2011-06-14

Here, we synthesized fluorescent DNA probes labeled with two perylene derivatives for the detection of a three-base deletion mutant. One such probe discriminated the three-base deletion mutant from the wild-type sequence by exciplex emission, and the deletion mutant was identifiable even by the naked eye. This journal is © The Royal Society of Chemistry 2011

2,5,8,11-Tetraalkenyl Perylene Bisimides: Direct Regioselective Synthesis and Enhanced π-π Stacking Interaction.

PubMed

Zhang, Li; He, Dezhi; Liu, Yudong; Wang, Kun; Guo, Zongxia; Lin, Jianbin; Zhang, Hui-Jun

2016-11-18

A series of 2,5,8,11-tetraalkenyl perylene bisimide (PBI) derivatives were synthesized through Ru(II)- or Rh(III)-catalyzed regio- and steroselective oxidative C-H olefination in one step. The optical electronic and self-assembly of the 2,5,8,11-substituted PBIs were investigated, which showed great potential in optoelectronic applications.

Topological ring currents in the "empty" ring of benzo-annelated perylenes.

PubMed

Dickens, Timothy K; Mallion, Roger B

2011-01-27

Cyclic conjugation in benzo-annelated perylenes is examined by means of the topological π-electron ring currents calculated for each of their constituent rings, in a study that is an exact analogy of a recent investigation by Gutman et al. based on energy-effect values for the corresponding rings in each of these structures. "Classical" approaches, such as Kekulé structures, Clar "sextet" formulas, and circuits of conjugation, predict that the central ring in perylene is "empty" and thus contributes negligibly to cyclic conjugation. However, conclusions from the present calculations of topological ring currents agree remarkably with those arising from the earlier study involving energy-effect values in that, contrary to what would be predicted from the classical approaches, rings annelated in an angular fashion relative to the central ring of these perylene structures materially increase the extent of that ring's involvement in cyclic conjugation. It is suggested that such close quantitative agreement between the predictions of these two superficially very different indices (energy effect and topological ring current) might be due to the fact that, ultimately, both depend, albeit in ostensibly quite different ways, only on an adjacency matrix that contains information about the carbon-carbon connectivity of the conjugated system in question.

Contamination of agricultural lands by polycyclic aromatic hydrocarbons (Tver region, Russia)

NASA Astrophysics Data System (ADS)

Zhidkin, Andrey; Koshovskii, Timur; Gennadiev, Alexander

2016-04-01

It is important to study sources and concentrations of polycyclic aromatic hydrocarbons (PAHs) in the agriculture soils within areas without intensive contaminations. Our studied object was soil and snow cover in the taiga zone (Tver region, Russia). A total of 52 surface (0-30 cm) and 31 subsurface (30-50 cm) soil samples, and 13 snow samples were collected in 35 soil pits, located in forest, crop and layland soils. Studied concentrations of the following 11 individual compounds: two-ring compounds (diphenyl and naphthalene homologues); three-ring compounds (fluorene, phenanthrene, anthracene); four-ring compounds (chrysene, pyrene, tetraphene); five-ring compounds (perylene, benzo[a]pyrene); and six-ring compounds (benzo[ghi]perylene). Analyses made by specrtofluorometry method at the temperature of liquid nitrogen. The total concentrations of all PAHs in soil samples ranged from 9 to 770 ng*g-1 with a median of 96 ng*g-1. The sum of high molecular weight PAHs was significantly lower than the sum of low molecular weight PAHs in the studied soils. The phenanthrene concentration was highest and ranged from 1.2 to 720 ng*g-1 (medium 72 ng*g-1). Compared PAHs reserves in snow cover (μg*m-2) with the reserves in topsoil layer (μg*m-2 in the upper 30 cm). Low molecular weight PAHs (fluorene, phenanthrene, diphenyl, naphthalene) reserves in snow was less than 20% from the reserves in the soil surface layer. High molecular weight PAHs (benzo[a]pyrene, chrysene, perylene, pyrene and tetraphene) reserves in snow was about 50-70% from the reserves in soil surface layer. High molecular weight PAHs (benzo[ghi]perylene and anthracene) reserves in snow was more than in topsoil. PAHs vertical distribution in soil profiles was statistically examined. The total concentration of all PAHs decreased with depth in all studied forest soils. In the arable soils was no significant trend in domination of PAHs total concentrations in the plowing and subsoil layers. The ratio of topsoil to subsoil concentrations of PAHs is different for differ congeners. Contents of phenanthrene and fluorene predominantly increase with the depth. Content of high molecular weight PAHs (benzo[a]pyrene, anthracene, tetraphene, perylene and pyrene) predominantly decreased with the depth. Other PAHs congeners have indistinct profile distributions in studied pits. Based on studied results PAHs divided to associations with different concentrations, sources and vertical distribution in soils: a) phenanthrene and fluorine; b) naphthalene, diphenyl; c) pyrene, benzo(a)pyrene, tetraphene, perylene, chrysene; d) anthracene and benzo(ghi)perylene. Research is funded by Russian Science Foundation (Project 14-27-00083).

Air-stable n-type semiconductor: core-perfluoroalkylated perylene bisimides.

PubMed

Li, Yan; Tan, Lin; Wang, Zhaohui; Qian, Hualei; Shi, Yubai; Hu, Wenping

2008-02-21

A series of core-perfluoroalkylated perylene bisimides (PBIs) have been efficiently synthesized by copper-mediated perfluoroalkylation of dibrominated PBIs. Their aromatic cores are highly twisted due to the steric encumbrance in the bay regions as revealed by single-crystal X-ray analysis. The organic field-effect transistors (OFETs) incorporating these new n-type semiconductors show remarkable air-stability and good field effect mobility.

Synthesis of pyridine-fused perylene imides with an amidine moiety for hydrogen bonding.

PubMed

Ito, Satoru; Hiroto, Satoru; Shinokubo, Hiroshi

2013-06-21

Pyridine-fused perylene tetracarboxylic acid bisimides (PBIs) were synthesized via Suzuki-Miyaura coupling and acid condensation. The fused PBIs with electron-donating substituents exhibited an intramolecular charge transfer interaction. One of the N-alkyl substituents was selectively removed with BBr3 to create an amidine guest binding site. A hydrogen bonding interaction with pentafluorobenzoic acid changed the absorption spectra and enhanced fluorescence.

Formation of non-spherical polymersomes driven by hydrophobic directional aromatic perylene interactions.

PubMed

Wong, Chin Ken; Mason, Alexander F; Stenzel, Martina H; Thordarson, Pall

2017-11-01

Polymersomes, made up of amphiphilic block copolymers, are emerging as a powerful tool in drug delivery and synthetic biology due to their high stability, chemical versatility, and surface modifiability. The full potential of polymersomes, however, has been hindered by a lack of versatile methods for shape control. Here we show that a range of non-spherical polymersome morphologies with anisotropic membranes can be obtained by exploiting hydrophobic directional aromatic interactions between perylene polymer units within the membrane structure. By controlling the extent of solvation/desolvation of the aromatic side chains through changes in solvent quality, we demonstrate facile access to polymersomes that are either ellipsoidal or tubular-shaped. Our results indicate that perylene aromatic interactions have a great potential in the design of non-spherical polymersomes and other structurally complex self-assembled polymer structures.

Visible-light driven oxidation of gaseous aliphatic alcohols to the corresponding carbonyls via TiO2 sensitized by a perylene derivative.

PubMed

Guarisco, Chiara; Palmisano, Giovanni; Calogero, Giuseppe; Ciriminna, Rosaria; Di Marco, Gaetano; Loddo, Vittorio; Pagliaro, Mario; Parrino, Francesco

2014-10-01

Sensitized P25 TiO2 was prepared by wet impregnation with a home-prepared perylene dye, i.e., N,N'-bis(2-(1-piperazino)ethyl)-3,4,9,10-perylene-tetracarboxylic acid diimide dichloride (PZPER). Energy levels of PZPER were found to be compatible with those of TiO2 allowing fast electron transfer. The obtained catalyst has been characterized and used in the gas-phase partial oxidation of aliphatic primary and secondary alcohols, i.e., methanol, ethanol, and 2-propanol. The reaction was carried out under cut-off (λ > 400 nm) simulated solar radiation in O2 atmosphere. The perylene derivative allowed a good absorbance of visible radiation thanks to its low optical energy gap (2.6 eV) which was evaluated by cyclic voltammetry. The optimal organic sensitizing amount was found to be 5.6 % w/w in terms of yield in carbonyl derivatives. Moreover, no change in reactivity/selectivity was observed after 10-h irradiation thus confirming the catalyst stability. Yields into formaldehyde, acetaldehyde, and acetone were 67, 70, and 96 %, respectively. No significant amounts of organic byproducts were detected but for methanol oxidation, whereas a minor amount of the substrate degraded to CO2.

21 CFR 73.3120 - 16,17-Dimethoxydinaphtho [1,2,3-cd:3′,2′,1′-lm] perylene-5,10-dione.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 1 2013-04-01 2013-04-01 false 16,17-Dimethoxydinaphtho [1,2,3-cd:3â²,2â²,1â²-lm] perylene-5,10-dione. 73.3120 Section 73.3120 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Medical Devices...

21 CFR 73.3120 - 16,17-Dimethoxydinaphtho [1,2,3-cd:3′,2′,1′-lm] perylene-5,10-dione.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 1 2011-04-01 2011-04-01 false 16,17-Dimethoxydinaphtho [1,2,3-cd:3â²,2â²,1â²-lm] perylene-5,10-dione. 73.3120 Section 73.3120 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Medical Devices...

21 CFR 73.3120 - 16,17-Dimethoxydinaphtho [1,2,3-cd:3′,2′,1′-lm] perylene-5,10-dione.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 1 2014-04-01 2014-04-01 false 16,17-Dimethoxydinaphtho [1,2,3-cd:3â²,2â²,1â²-lm] perylene-5,10-dione. 73.3120 Section 73.3120 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Medical Devices...

21 CFR 73.3120 - 16,17-Dimethoxydinaphtho [1,2,3-cd:3′,2′,1′-lm] perylene-5,10-dione.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 1 2012-04-01 2012-04-01 false 16,17-Dimethoxydinaphtho [1,2,3-cd:3â²,2â²,1â²-lm] perylene-5,10-dione. 73.3120 Section 73.3120 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Medical Devices...

21 CFR 73.3120 - 16,17-Dimethoxydinaphtho [1,2,3-cd:3′,2′,1′-lm] perylene-5,10-dione.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 1 2010-04-01 2010-04-01 false 16,17-Dimethoxydinaphtho [1,2,3-cd:3â²,2â²,1â²-lm] perylene-5,10-dione. 73.3120 Section 73.3120 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Medical Devices...

Perylene-diimide-based nanoparticles as highly efficient photoacoustic agents for deep brain tumor imaging in living mice

DOE PAGES

Fan, Quli; Cheng, Kai; Yang, Zhen; ...

2014-11-06

In order to promote preclinical and clinical applications of photoacoustic imaging, novel photoacoustic contrast agents are highly desired for molecular imaging of diseases, especially for deep tumor imaging. In this paper, perylene-3,4,9,10-tetracarboxylic diiimide-based near-infrared-absorptive organic nanoparticles are reported as an efficient agent for photoacoustic imaging of deep brain tumors in living mice with enhanced permeability and retention effect

Dendron-functionalized perylenes for red luminescent materials

NASA Astrophysics Data System (ADS)

Pan, Jianfeng; Zhu, Weihong; Li, Shangfeng; Tian, He

2005-01-01

This paper presents a novel series of dendrimers containing perylene diimide cores, Fréchet-type poly(arylether) dendrons, and peripheral functional units such as hole-transporting groups (carbazole) via a convergent synthetic approach with three generation. The higher generation dendrimer has an obvious site-isolation effect or dilution effect of dendrons, which results in a relatively small red-shift of absorption and emission spectra when they form a solid thin film for applications. The interactions between peripheral units and perylene diimide core in the dendrimers are studied by fluorescence spectra. The steady-state fluorescence shows there is no effective Förster intramolecular energy transfer. DSC results indicate that the incorporation of Fréchet-type poly(arylether) dendrons can improve the amorphous property and increase glass transition temperature (Tg). The preliminary EL results with a single-layer architecture demonstrate that these dendrimers could be utilized as a promising kind of active red luminescent emitters.

Dibenzo[a,f]perylene bisimide: effects of introducing two fused rings.

PubMed

Chaolumen; Enno, Hiroki; Murata, Michihisa; Wakamiya, Atsushi; Murata, Yasujiro

2014-11-01

Perylene bisimides (PBIs) are fascinating dyes with various potential applications. To study the effects of introducing a dibenzo-fused structure to the perylene moiety, π-extended PBI derivatives with a dibenzo-fused structure at both of the a and f bonds were synthesized. The twisted structure was characterized by X-ray crystal structure analysis. In the cyclic voltammograms, the dibenzo[a,f]-fused PBI showed a reversible oxidation wave at much less positive potential, relative to a dibenzo[a,o]-fused PBI derivative. These data indicated that two ring fusions at both sides of a naphthalene moiety, which construct a tetracene core, effectively raise the HOMO level compared to fusion of one ring at each naphthalene moiety (two anthracene cores). The dibenzo[a,f]-fused PBI derivative showed an absorption band at 735 nm with a shoulder band reaching 900 nm. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rearrangement of an aniline linked perylene bisimide under acidic conditions and visible to near-infrared emission from the intramolecular charge-transfer state of its fused derivatives.

PubMed

Kojima, Mitsuru; Tamoto, Akira; Aratani, Naoki; Yamada, Hiroko

2017-05-23

We have prepared a series of aniline-linked and fused perylene bisimides (PBIs) for making near-infrared (NIR) fluorophores. During this research, we found an unexpected rearrangement reaction on the PBI core for the first time. The aniline- and phenothiazine-fused PBIs exhibit excellent absorption ability and visible-to-NIR emission owing to their intramolecular charge transfer character.

An aggregated perylene-based broad-spectrum, efficient and label-free quencher for multiplexed fluorescent bioassays.

PubMed

Liu, Tao; Hu, Rong; Lv, Yi-Fan; Wu, Yuan; Liang, Hao; Huan, Shuang-Yan; Zhang, Xiao-Bing; Tan, Weihong; Yu, Ru-Qin

2014-08-15

Fluorescent sensing systems based on the quenching of fluorophores have found wide applications in bioassays. An efficient quencher will endow the sensing system a high sensitivity. The frequently used quenchers are based on organic molecules or nanomaterials, which usually need tedious synthesizing and modifying steps, and exhibit different quenching efficiencies to different fluorophores. In this work, we for the first time report that aggregated perylene derivative can serve as a broad-spectrum and label-free quencher that is able to efficiently quench a variety of fluorophores, such as green, red and far red dyes labeled on DNA. By choosing nucleases as model biomolecules, such a broad-spectrum quencher was then employed to construct a multiplexed bioassay platform through a label-free manner. Due to the high quenching efficiency of the aggregated perylene, the proposed platform could detect nuclease with high sensitivity, with a detection limit of 0.03U/mL for EcoRV, and 0.05U/mL for EcoRI. The perylene quencher does not affect the activity of nuclease, which makes it possible to design post-addition type bioassay platform. Moreover, the proposed platform allows simultaneous and multicolor analysis of nucleases in homogeneous solution, demonstrating its value of potential application in rapid screening of multiple bio-targets. Copyright © 2014 Elsevier B.V. All rights reserved.

Synthesis, photophysical, structural and electronic properties of novel regioisomerically pure 1,7-disubstituted perylene-3,4,9,10-tetracarboxylic monoimide dibutylester derivatives

NASA Astrophysics Data System (ADS)

Ozser, Mustafa E.; Mohiuddin, Obaidullah

2018-04-01

Three new isomerically pure 1,7-disubstituted perylene-3,4,9,10-tetracarboxylic monoimide dibutylester derivatives namely; N-[2-(diethylamino)ethyl]-1,7-dibromoperylene-3,4,9,10-tetracarboxy monoimide dibutylester (PMD-1), N-[2-(diethylamino)ethyl]-1,7-di(4-tert-butylphenoxy)perylene-3,4,9,10-tetracarboxy monoimide dibutylester (PMD-2) and N-[2-(diethylamino)ethyl]-1,7-di(pyrrolidinyl)perylene-3,4,9,10-tetracarboxy monoimide dibutylester (PMD-3), have been synthesized and their electronic absorption spectra, and steady-state fluorescence were investigated experimentally as well as by using density functional theory (DFT) calculations. All three compounds show good solubility in toluene and chloroform. Attachment of two tert-butylphenoxy groups at the 1,7-positions in PMD-2 resulted in a red shifted absorption band with an absorption maximum at 518 nm. UV/Vis absorption spectrum of PMD-3 bearing electron donating pyrrolidinyl groups at the 1,7-positions shows a broad absorption band within the visible region, extending to red region. Absorption maximum of lowest energy transition now shifts to 653 nm. In addition to the S0 → S1 absorption bands, bands belonging to S0 → S2 electronic transitions were observed at 378, 386, and 411 nm for PMD-1, PMD-2, and PMD-3 respectively. Compounds PMD-1, PMD-2 and PMD-3 display low fluorescence quantum yields of 0.027, 0.040 and 0.001, respectively in chloroform. DFT calculations revealed that the attachment of electron donating groups at 1,7-positions of perylene core, results in an increase in frontier orbitals energy levels. Observed energy increase in HOMO level is larger in each case, compared to the energy increase in LUMO levels, due to the higher contribution of side groups to HOMO. DFT calculated band gaps for PMD-1, PMD-2 and PMD-3 are 2.68, 2.63 and 2.29 eV respectively.

Biogenic polycyclic aromatic hydrocarbons in sediments of the San Joaquin River in California (USA), and current paradigms on their formation.

PubMed

Wakeham, Stuart G; Canuel, Elizabeth A

2016-06-01

Biogenic perylene and higher plant pentacyclic triterpenoid-derived alkylated and partially aromatized tetra- and pentacyclic derivatives of chrysene (3,4,7-trimethyl- and 3,3,7-trimethyl-1,2,3,4-tetrahydrochrysene, THC) and picene (1,2,9-trimethyl- and 2,2,9-trimethyl-1,2,3,4-tetrahydropicene, THP) were two- to four-fold more abundant than pyrogenic PAH in two sediment cores from the San Joaquin River in Northern California (USA). In a core from Venice Cut (VC), located in the river, PAH concentrations varied little downcore and the whole-core PAH concentration (biogenics + pyrogenics) was 250.6 ± 73.7 ng g(-1) dw; biogenic PAH constituted 67 ± 4 % of total PAH. THC were 26 ± 9 % of total biogenic PAH, THP were 36 ± 7 %, and perylene was 38 ± 7 %. PAH distributions in a core from Franks Tract (FT), a former wetland that was converted to an agricultural tract in the late 1800s and flooded in 1938, were more variable. Surface sediments were dominated by pyrogenic PAH so that biogenic PAH were only ~30 % of total PAH. Deeper in the core, biogenic PAH constituted 60-93 % of total PAH; THC, THP and perylene were 31 ± 28 %, 24 ± 32 %, and 45 ± 36 % of biogenic PAH. At 100-103 cm depth, THP constituted 80 % of biogenic PAH and at 120-123 cm perylene was 95 % of biogenic PAH. Current concepts related to precursors and transformation processes responsible for the diagenetic generation of perylene and triterpenoid-derived PAH are discussed. Distributions of biogenic PAH in VC and FT sediments suggest that they may not form diagenetically within these sediments but rather might be delivered pre-formed from the river's watershed.

Characterization of New Materials for Photovoltaic Thin Films: Aggregation Phenomena in Self-Assembled Perylene-Based Diimides

DTIC Science & Technology

2005-07-21

or solution-based methods such as spin casting or drop casting,’ 1ś󈧖 self-assembly,1922 Langmuir - Blodgett techniques,23 or electrochemical methods...and Langmuir - exist. Molecules containing a perylene diimide core have Blodgett techniques.’ 8 In many situations, the molecules also been proposed for...remain soluble in the W. J. Langmuir 1996, 12, 2169. absence of other ionic species. These systems represent (35) Antonietti, M.; Conrad, J. Angew

Rigidifying Nonplanar Perylene Diimides by Ring Fusion Toward Geometry-Tunable Acceptors for High-Performance Fullerene-Free Solar Cells.

PubMed

Zhong, Hongliang; Wu, Chen-Hao; Li, Chang-Zhi; Carpenter, Joshua; Chueh, Chu-Chen; Chen, Jung-Yao; Ade, Harald; Jen, Alex K-Y

2016-02-03

Rigid fused perylene diimide (PDI) dimers bridged with heterocycles exhibit superior photovoltaic performance compared to their unfused semiflexible analogues. Changing the chalcogen atoms in the aromatic bridges gradually increases the twist angles between the two PDI planes, leading to a varied morphology in which the one bridged by thiophene achieves a balance and shows the best efficiency of 6.72%. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High excimer-state emission of perylene bisimides and recognition of latent fingerprints.

PubMed

Wang, Ke-Rang; Yang, Zi-Bo; Li, Xiao-Liu

2015-04-07

High excimer-state emission in the H-type aggregate of a novel asymmetric perylene bisimide derivative, 6, with triethyleneglycol chains and lactose functionalization was achieved in water. Furthermore, its application for enhancing the visualization of transfer latent fingerprints from glass slides to the poly(vinylidene fluoride) (PVDF) membrane was explored, which showed clear images of the latent fingerprint in daylight and under 365 nm ultraviolet illumination. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Laser pulse control of ultrafast heterogeneous electron transfer: a computational study.

PubMed

Wang, Luxia; May, Volkhard

2004-10-22

Laser pulse control of the photoinduced 90 fs charge injection from perylene into the conduction band of TiO2 is studied theoretically. The approach accounts for the electronic-ground state of the dye, the first excited state, the ionized state formed after charge injection, and the continuum of the electronic states in the conduction band, all defined vs a single reaction coordinate. To address different control tasks optimal control theory is combined with a full quantum dynamical description of the electron-vibrational motion accompanying the charge injection process. First it is proved in which way the charge injection time can be changed by tailored laser pulses. In a second step a pump-dump scheme from the perylene ground state to the first excited electronic state and back to the ground state is discussed. Because of the strong coupling of the excited perylene state to the band continuum of TiO2 this control task is more suited to an experimental test than the direct control of the charge injection.

Time-resolved measurement of intramolecular photoinduced electron transfer processes in perylene diimides (Conference Presentation)

NASA Astrophysics Data System (ADS)

Döring, Robin Carl; Baal, Eduard; Sundermeyer, Jörg; Chatterjee, Sangam

2017-02-01

Perylene-3,4,9,10-tetracarboxylic acid (PTCDA) and respective derivatives (e.g. perylene diimide - PDI) are widely used as dyes but also for device applications such as organic field effect transistors or in organic photovoltaics. Due to their intrinsically high quantum efficiencies they are also used as spectroscopic standards. One major drawback of these materials is their low solubility in organic solvents which can be addressed by long alkyl substitutions. When introducing a tertiary amine into the molecule a mechanism known as photoinduced electron transfer (PET) can occur. Here, following an optically excited HOMO-LUMO transition of the core, an electron from the electron lone pair of the amine is transferred to the HOMO of the perylene core. Hence, radiative recombination is disallowed and photoluminescence effectively quenched. Here, we perform a systematic study of the distance dependence of the PET by introducing alkyle groups as spacer units between PDI core and the tertiary amine. Dynamics of the PET are extracted from ultrafast time-resolved photoluminescence measurement data. A rate equation model, simulating a three level system, reveals rate constant of the back electron transfer, otherwise not accessible with our experimental methods. Assuming a Marcus model of electron transfer, electronic coupling strength between the electronic states involved in the respective transitions can be calculated. In addition to the distance dependence, the effects of protonation and methylation of the the tertiary amine units are studied.

Perylene Bisimide Radicals and Biradicals: Synthesis and Molecular Properties.

PubMed

Schmidt, David; Son, Minjung; Lim, Jong Min; Lin, Mei-Jin; Krummenacher, Ivo; Braunschweig, Holger; Kim, Dongho; Würthner, Frank

2015-11-16

Unprecedented neutral perylene-3,4:9,10-tetracarboxylic acid bisimide (PBI) radicals and biradicals were synthesized by facile chemical oxidation of 4-hydroxyaryl-substituted PBIs. Subsequent characterization by optical and magnetic spectroscopic techniques, as well as quantum chemical calculations, revealed an open-shell singlet biradical ground state for the PBI biradical OS-2(..) (〈s(2)〉=1.2191) with a relatively small singlet-triplet energy gap of 0.041 eV and a large singlet biradical character of y=0.72. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photophysical and quantum chemical study on a J-aggregate forming perylene bisimide monomer.

PubMed

Ambrosek, David; Marciniak, Henning; Lochbrunner, Stefan; Tatchen, Jörg; Li, Xue-Qing; Würthner, Frank; Kühn, Oliver

2011-10-21

Perylene bisimides (PBIs) are excellent dyes and versatile building blocks for supramolecular structures. Only recently have PBIs been shown to depict absorption characteristics of J-aggregates. We apply electronic structure calculations and femtosecond pump-probe spectroscopy to the monomeric, bay-substituted building-block of a PBI aggregate in dichloromethane to investigate its electronically excited states in order to provide the ingredients for the description of excitons in the aggregates and their annihilation processes. The PBI S(1)←S(0) absorption spectrum and the S(1)→S(0) emission spectrum have been assigned based on time-dependent Density Functional Theory calculations for the geometry-optimized electronic ground state and excited state structures in the gas phase. The monomeric absorption spectrum contains a strong transition at 580 nm and a broad shoulder between 575-500 nm, both features are attributed to a vibrational progression with an effective vibrational mode of 1415 cm(-1) whose major contributing vibrational normal modes are breathing modes of the perylene body. The effective vibrational mode of the emission spectrum is characterized by a frequency of 1369 cm(-1), whose major contributing vibrational normal modes are characterized by perylene and phenol (bay-substituent) CH bendings. The S(n)←S(1) excited state absorption spectrum is assigned based on Multi-Reference Configuration Interaction methodology. Here, we identify three transitions which give rise to two broad experimental features, one being located between 500 and 600 nm and the other one ranging from 650 to 750 nm. This journal is © the Owner Societies 2011

A real-time fluorescence assay for protease activity and inhibitor screening based on the aggregation-caused quenching of a perylene probe.

PubMed

Wang, Yan; Zhang, Zhifang; Zhang, Ya; Yu, Cong

2018-06-01

We have established a real-time and label-free fluorescence turn-on strategy for protease activity detection and inhibitor screening via peptide-induced aggregation-caused quenching of a perylene probe. Because of electrostatic interactions and high hydrophilicity, poly-l-glutamic acid sodium salt (PGA; a negatively charged peptide) could induce aggregation of a positively charged perylene probe (probe 1) and the monomer fluorescence of probe 1 was effectively quenched. After a protease was added, PGA was enzymatically hydrolyzed into small fragments and probe 1 disaggregated. The fluorescence recovery of probe 1 was found to be proportional to the concentration of protease in the range from 0 to 1 mU/ml. The detection limit was down to 0.1 mU/ml. In the presence of a protease inhibitor, protease activity was inhibited and fluorescence recovery reduced. Moreover, we demonstrated the potential application of our method in a complex mixture sample including 1% human serum. Our method is simple, fast and cost effective. Copyright © 2018 John Wiley & Sons, Ltd.

Perylene dominates the organic contaminant profile in the Berau delta, East Kalimantan, Indonesia.

PubMed

Booij, Kees; Arifin, Zainal; Purbonegoro, Triyoni

2012-05-01

The geographical distributions of polyaromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), hexachlorobenzene, and 1,1-dichloro-2,2-bis(4-chlorophenyl)ethene (4,4'-DDE) were studied in the Berau delta (East Kalimantan, Indonesia), using sediment sampling and passive water sampling with semipermeable membrane devices. High concentrations of perylene were observed in sediments (54-580 ng g(-1) dry weight), and water (1-680 pg L(-1)). Perylene accounted for about 60% of the total concentrations of PAHs in the sediment. The relative abundance of the other PAHs was indicative of petrogenic sources. Concentrations of PCBs, hexachlorobenzene, and 4,4'-DDE in sediments were below or close to the detection limit (∼ 0.02 ng g(-1)). The analysis of a sediment core revealed no appreciable changes in the concentration of target compounds over the past three decades. We show that sediment sampling and passive water sampling are complementary techniques, and propose to bring the results of both methods to the same concentration scale, using locally derived sediment-water partition coefficients. Copyright © 2012 Elsevier Ltd. All rights reserved.

A Helicene Nanoribbon with Greatly Amplified Chirality.

PubMed

Schuster, Nathaniel J; Hernández Sánchez, Raúl; Bukharina, Daria; Kotov, Nicholas A; Berova, Nina; Ng, Fay; Steigerwald, Michael L; Nuckolls, Colin

2018-05-14

We report the synthesis and characterization of a chiral, shape-persistent, perylene-diimide-based nanoribbon. Specifically, the fusion of three perylene-diimide monomers with intervening naphthalene subunits resulted in a helical superstructure with two [6]helicene subcomponents. This π-helix-of-helicenes exhibits very intense electronic circular dichroism, including one of the largest Cotton effects ever observed in the visible range. It also displays more than an order of magnitude increase in circular dichroism for select wavelengths relative to its smaller homologue. These impressive chiroptical properties underscore the potential of this new nanoribbon architecture in the context of chiral electronic materials.

Isomeric N-Annulated Perylene Diimide Dimers for Organic Solar Cells.

PubMed

Ma, Zetong; Fu, Huiting; Meng, Dong; Jiang, Wei; Sun, Yanming; Wang, Zhaohui

2018-04-16

Two isomeric N-annulated perylene diimide dimers, namely, p-BDNP and m-BDNP were designed and synthesized via geometric tuning. The distinct molecular geometry and packing arrangements of isomers with almost identical optical and electrochemical properties rendered us an in-depth understanding of the molecular structure-aggregation state-photovoltaic performance relationship. Blended with the commercially available donor PCE-10, p-BDNP and m-BDNP showed distinct differences in photovoltaic performance with power conversion efficiencies (PCEs) of 5.01 % and 4.15 %, respectively. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A halochromic stimuli-responsive reversible fluorescence switching 3, 4, 9, 10-perylene tetracarboxylic acid dye for fabricating rewritable platform

NASA Astrophysics Data System (ADS)

Hariharan, P. S.; Pitchaimani, J.; Madhu, Vedichi; Anthony, Savarimuthu Philip

2017-02-01

3, 4, 9, 10-perylene tetracarboxylic acid (PTCA), a strongly fluorescent water soluble dye with halochromic functionality showed pH dependent reversible fluorescence switching. The strong fluorescence of PTCA (Φf = 0.67) in basic medium was completely quenched upon acidification. The fluorescent PTCA has been transferred on to a solid substrate (filter paper and glass plate) that also showed reversible off-on fluorescence switching by acid/base and drying/water vapor exposure. The reversible fluorescence switching of PTCA could be of potential interest for fabricating rewritable fluorescent medium.

Influence of chlorine atoms in bay positions of perylene-tetracarboxylic acids on their spectral properties in Langmuir-Blodgett films

NASA Astrophysics Data System (ADS)

Piosik, Emilia; Synak, Anna; Martyński, Tomasz

2018-01-01

The influence of chlorine atoms in the bay positions of the perylene-3,4,9,10-tetracarboxylic acids with the different alkyl chains length on their spectral properties in monomolecular films has been studied. The chlorinated (PCln) and for comparison non-chlorinated (Pn) perylene derivatives were deposited onto quartz plates using a Langmuir-Blodgett (LB) technique. The absorption spectra showed that the PCln and Pn dyes form in monolayers the I- and J-type aggregates, respectively. In turn, their steady-state and time-resolved emission spectra revealed presence of two emitter types, which we assigned to monomers and excimers. The luminescence lifetimes of the PCln monomers and excimers determined with a time-correlated single photon counting method (TCSPC) are significantly shorter than these obtained for the same emitter types in the Pn monolayers. In the case of the chlorinated dyes, the contribution of the monomer emission dominates over the excimer emission and is almost independent from the alkyl chain length. By contrast, the share of the Pn monomer emission increases strongly with a number of carbon atoms in their hydrocarbon chains. The luminescence quantum yields (LQY) of the Pn and PCln monolayers measured in an integrating sphere are in the range of 0.06-0.11. The presented results reveal that the PCln dyes exhibit lower tendency for aggregation than the non-chlorinated derivatives. It can be explained by limited intermolecular interaction between neighbouring PCln molecules caused by deformation of the perylene core as a result of strongly electronegative chlorine atoms in the bay positions of these dyes. Moreover, the strong influence of the alkyl chain length on the Pn aggregation contrary to the case of the PCln derivatives was observed.

Effect of five-membered ring and heteroatom substitution on charge transport properties of perylene discotic derivatives: A theoretical approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Navarro, Amparo, E-mail: anavarro@ujaen.es; Fernández-Liencres, M. Paz; Peña-Ruiz, Tomás

2016-08-07

Density functional theory calculations were carried out to investigate the evolvement of charge transport properties of a set of new discotic systems as a function of ring and heteroatom (B, Si, S, and Se) substitution on the basic structure of perylene. The replacement of six-membered rings by five-membered rings in the reference compound has shown a prominent effect on the electron reorganization energy that decreases ∼0.2 eV from perylene to the new carbon five-membered ring derivative. Heteroatom substitution with boron also revealed to lower the LUMO energy level and increase the electron affinity, therefore lowering the electron injection barrier comparedmore » to perylene. Since the rate of the charge transfer between two molecules in columnar discotic systems is strongly dependent on the orientation of the stacked cores, the total energy and transfer integral of a dimer as a disc is rotated with respect to the other along the stacking axis have been predicted. Aimed at obtaining a more realistic approach to the bulk structure, the molecular geometry of clusters made up of five discs was fully optimized, and charge transfer rate and mobilities were estimated for charge transport along a one dimensional pathway. Heteroatom substitution with selenium yields electron transfer integral values ∼0.3 eV with a relative disc orientation of 25°, which is the preferred angle according to the dimer energy profile. All the results indicate that the tetraselenium-substituted derivative, not synthetized so far, could be a promising candidate among those studied in this work for the fabrication of n-type semiconductors based on columnar discotic liquid crystals materials.« less

Effect of five-membered ring and heteroatom substitution on charge transport properties of perylene discotic derivatives: A theoretical approach.

PubMed

Navarro, Amparo; Fernández-Liencres, M Paz; Peña-Ruiz, Tomás; García, Gregorio; Granadino-Roldán, José M; Fernández-Gómez, Manuel

2016-08-07

Density functional theory calculations were carried out to investigate the evolvement of charge transport properties of a set of new discotic systems as a function of ring and heteroatom (B, Si, S, and Se) substitution on the basic structure of perylene. The replacement of six-membered rings by five-membered rings in the reference compound has shown a prominent effect on the electron reorganization energy that decreases ∼0.2 eV from perylene to the new carbon five-membered ring derivative. Heteroatom substitution with boron also revealed to lower the LUMO energy level and increase the electron affinity, therefore lowering the electron injection barrier compared to perylene. Since the rate of the charge transfer between two molecules in columnar discotic systems is strongly dependent on the orientation of the stacked cores, the total energy and transfer integral of a dimer as a disc is rotated with respect to the other along the stacking axis have been predicted. Aimed at obtaining a more realistic approach to the bulk structure, the molecular geometry of clusters made up of five discs was fully optimized, and charge transfer rate and mobilities were estimated for charge transport along a one dimensional pathway. Heteroatom substitution with selenium yields electron transfer integral values ∼0.3 eV with a relative disc orientation of 25°, which is the preferred angle according to the dimer energy profile. All the results indicate that the tetraselenium-substituted derivative, not synthetized so far, could be a promising candidate among those studied in this work for the fabrication of n-type semiconductors based on columnar discotic liquid crystals materials.

Synthesis of perylene-porphyrin building blocks and polymers thereof for the production of light-harvesting arrays

DOEpatents

Loewe, Robert S.; Tomizaki, Kin-ya; Lindsey, Jonathan S.

2005-07-12

The present invention provides methods, compounds, and compositions for the synthesis of light harvesting arrays, such arrays comprising: (a) a first substrate comprising a first electrode; and (b) a layer of light harvesting rods electrically coupled to said first electrode, each of said light harvesting rods comprising a polymer of Formula I: wherein m is at least 1; X.sup.1 is a charge separation group, and X.sup.2 through X.sup.m+1 are chromophores. At least one of X.sup.2 through X.sup.m+1 has at least one perylene group coupled thereto.

Low temperature exciton dynamics and structural changes in perylene bisimide aggregates

NASA Astrophysics Data System (ADS)

Wolter, Steffen; Magnus Westphal, Karl; Hempel, Magdalena; Würthner, Frank; Kühn, Oliver; Lochbrunner, Stefan

2017-09-01

The temperature dependent exciton dynamics of J-aggregates formed by a perylene bisimide dye is investigated down to liquid nitrogen temperature (77 K) by femtosecond pump-probe spectroscopy. The analysis of the transient absorption data using a diffusion model for the excitons does not only reveal an overall decrease of the exciton mobility, but also a change in the dimensionality of the exciton transport at low temperatures. This change in dimensionality is further investigated by kinetic Monte Carlo simulations, identifying weakly interlinked one-dimensional aggregate chains as the most likely structure at low temperatures. This causes the exciton transport to be highly anisotropic.

Ultra-bright red-emitting photostable perylene bisimide dyes: new indicators for ratiometric sensing of high pH or carbon dioxide.

PubMed

Pfeifer, David; Klimant, Ingo; Borisov, Sergey M

2018-05-08

New pH sensitive perylene bisimide indicator dyes were synthesised and used for fabrication of optical sensors. The highly photostable dyes show absorption/emission bands in the red/near-infrared (NIR) region of the electromagnetic spectrum, high molar absorption coefficients (up to 100 000 M-1 cm-1) and fluorescence quantum yields close to unity. The absorption and emission spectra show strong bathochromic shift upon deprotonation of imidazole nitrogen which makes the dyes promising as ratiometric fluorescent indicators. Physical entrapment of the indicators into polyurethane hydrogel enables pH determination in alkaline pH. It is also shown that plastic carbon dioxide solid state sensor can be manufactured via immobilization of the pH indicator in a hydrophilic polymer, along with a quaternary ammonium base. The influence of plasticizer, different lipophilic bases and humidity on the sensitivity of the sensor material were systematically investigated. The disubstituted perylene, particularly, features two deprotonation equilibria enabling sensing over a very broad range from 0.5 to 1000 hPa pCO2. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and Characterization of Superhydrophobic, Self-cleaning NIR-reflective Silica Nanoparticles

NASA Astrophysics Data System (ADS)

Sriramulu, Deepa; Reed, Ella Louise; Annamalai, Meenakshi; Venkatesan, Thirumalai Venky; Valiyaveettil, Suresh

2016-11-01

Multifunctional coatings offer many advantages towards protecting various surfaces. Here we apply aggregation induced segregation of perylene diimide (PDI) to control the surface morphology and properties of silica nanoparticles. Differentially functionalized PDI was incorporated on the surface of silica nanoparticles through Si-O-Si bonds. The absorption and emission spectra of the resultant functionalised nanoparticles showed monomeric or excimeric peaks based on the amounts of perylene molecules present on the surface of silica nanoparticles. Contact angle measurements on thin films prepared from nanoparticles showed that unfunctionalised nanoparticles were superhydrophilic with a contact angle (CA) of 0°, whereas perylene functionalised silica particles were hydrophobic (CA > 130°) and nanoparticles functionalised with PDI and trimethoxy(octadecyl)silane (TMODS) in an equimolar ratio were superhydrophobic with static CA > 150° and sliding angle (SA) < 10°. In addition, the near infrared (NIR) reflectance properties of PDI incorporated silica nanoparticles can be used to protect various heat sensitive substrates. The concept developed in this paper offers a unique combination of super hydrophobicity, interesting optical properties and NIR reflectance in nanosilica, which could be used for interesting applications such as surface coatings with self-cleaning and NIR reflection properties.

Theoretical insights into aggregation-induced helicity modulation of a perylene bisimide derivative.

PubMed

Liang, Lijun; Li, Xin

2018-02-12

Formation of helical chiroptical self-assemblies via noncovalent interaction is a widely observed phenomenon in nature, the mechanism of which remains insufficiently understood. Employing an amphiphilic perylene-sugar dyad molecule (PBI-HAG) as an example, we report that the modulatable supramolecular helicity may emerge from an aggregating process that is dominated by competition between two types of noncovalent interaction: hydrogen bonding and π-π stacking. The interplay between these two driving forces, which is greatly affected by the solvent environment, determines the morphology the supramolecular assembly of PBI-HAGs. In particular, a non-layered supramolecular structure was formed in octane owing to stabilization effects of intermolecular hydrogen bonds, whereas a layered supramolecular structure was formed in water because of energetically favorable π-π stacking of aromatic rings. The formation of distinct supramolecular architectures in different solvents was reinforced by simulated circular dichroism spectra, which show opposite signals consistent with experimental observations. The results of this study could help us understand aggregation-induced supramolecular chirality of noncovalent self-assemblies. Graphical abstract Left Typical structures of amphiphilic perylene-sugar dyad (PBI-HAG) aggregates in different octane and water. Right Simulated CD and UV-Vis spectra of core PBIs aggregates in octane and water.

Dynamic Stacking Pathway of Perylene Dimers in Aromatic and Nonaromatic Solvents.

PubMed

Hollfelder, Manuel; Gekle, Stephan

2015-08-13

Using molecular dynamics simulations, we elucidate in detail the dynamics of the π-π stacking process of a perylene bisimide (PBI) dimer solvated in toluene. Our calculations show that the transition from the open (unstacked) to the stacked configuration is hindered by a small free energy barrier of approximately 1kBT in toluene but not in the nonaromatic solvent hexane. A similar effect is observed tor two non-covalently linked monomers. The origin of this barrier is traced back to π-π interactions between perylene and the aromatic solvent which are very similar in nature to those between two PBI monomers. The stacking process proceeds in three phases via two well-defined transition states: (i) in the first phase, the two PBI molecules share part of their respective solvation shells forming the first transition state. Further approach needs to squeeze out the shared solvent layer, thus creating the energy barrier. (ii) After removal of the separating solvent, the two PBIs form a second transition state with one monomer located at a random position in the other's solvation shell. (iii) Finally, the two PBIs slide on top of each other into their final stacked position.

Noncharged and Charged Monodendronised Perylene Bisimides as Highly Fluorescent Labels and their Bioconjugates.

PubMed

Huth, Katharina; Heek, Timm; Achazi, Katharina; Kühne, Christian; Urner, Leonhard H; Pagel, Kevin; Dernedde, Jens; Haag, Rainer

2017-04-06

A series of water-soluble, hydroxylated and sulphated, polyglycerol (PG) dendronised, monofunctional perylene bisimides (PBIs) were synthesised in three generations. Their photophysical properties were determined by absorption and emission spectroscopy and their suitability as potential biolabels examined by biological in vitro studies after bioconjugation. It could be shown that the photophysical properties of the PBI labels can be improved by increasing the sterical demand and ionic charge of the attached dendron. Thereby, charged labels show superior suppression of aggregation over charge neutral labels owing to electrostatic repulsion forces on the PG-dendron. The ionic charges also enabled a reduction in dendron generation while retaining the labels' outstanding fluorescence quantum yields (FQYs) up to 100 %. These core-unsubstituted perylene derivatives were successfully applied as fluorescent labels upon bioconjugation to the therapeutic antibody cetuximab. The dye-antibody conjugates showed a strongly enhanced aggregation tendency compared to the corresponding free dyes. Biological evaluation by receptor-binding, cellular uptake, and cytotoxicity studies revealed that labelling did not affect the antibody's function, which renders the noncharged and charged dendronised PBIs suitable candidates as fluorescent labels in biological imaging. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A helical perylene diimide-based acceptor for non-fullerene organic solar cells: synthesis, morphology and exciton dynamics

NASA Astrophysics Data System (ADS)

Chen, Li; Wu, Mingliang; Shao, Guangwei; Hu, Jiahua; He, Guiying; Bu, Tongle; Yi, Jian-Peng; Xia, Jianlong

2018-05-01

Helical perylene diimide-based (hPDI) acceptors have been established as one of the most promising candidates for non-fullerene organic solar cells (OSCs). In this work, we report a novel hPDI-based molecule, hPDI2-CN2, as an electron acceptor for OSCs. Combining the hPDI2-CN2 with a low-bandgap polymeric donor (PTB7-Th), the blending film morphology exhibited high sensitivity to various treatments (such as thermal annealing and addition of solvent additives), as evidenced by atomic force microscope studies. The power conversion efficiency (PCE) was improved from 1.42% (as-cast device) to 2.76% after thermal annealing, and a PCE of 3.25% was achieved by further addition of 1,8-diiodooctane (DIO). Femtosecond transient absorption (TA) spectroscopy studies revealed that the improved thin-film morphology was highly beneficial for the charge carrier transport and collection. And a combination of fast exciton diffusion rate and the lowest recombination rate contributed to the best performance of the DIO-treated device. This result further suggests that the molecular conformation needs to be taken into account in the design of perylene diimide-based acceptors for OSCs.

Photoionization Efficiencies of Five Polycyclic Aromatic Hydrocarbons.

PubMed

Johansson, K Olof; Campbell, Matthew F; Elvati, Paolo; Schrader, Paul E; Zádor, Judit; Richards-Henderson, Nicole K; Wilson, Kevin R; Violi, Angela; Michelsen, Hope A

2017-06-15

We have measured photoionization-efficiency curves for pyrene, fluoranthene, chrysene, perylene, and coronene in the photon energy range of 7.5-10.2 eV and derived their photoionization cross-section curves in this energy range. All measurements were performed using tunable vacuum ultraviolet (VUV) radiation generated at the Advanced Light Source synchrotron at Lawrence Berkeley National Laboratory. The VUV radiation was used for photoionization, and detection was performed using a time-of-flight mass spectrometer. We measured the photoionization efficiency of 2,5-dimethylfuran simultaneously with those of pyrene, fluoranthene, chrysene, perylene, and coronene to obtain references of the photon flux during each measurement from the known photoionization cross-section curve of 2,5-dimethylfuran.

Multifunctional Diketopyrrolopyrrole-Based Conjugated Polymers with Perylene Bisimide Side Chains.

PubMed

Li, Cheng; Yu, Changshi; Lai, Wenbin; Liang, Shijie; Jiang, Xudong; Feng, Guitao; Zhang, Jianqi; Xu, Yunhua; Li, Weiwei

2017-11-24

Two conjugated polymers based on diketopyrrolopyrrole (DPP) in the main chain with different content of perylene bisimide (PBI) side chains are developed. The influence of PBI side chain on the photovoltaic performance of these DPP-based conjugated polymers is systematically investigated. This study suggests that the PBI side chains can not only alter the absorption spectrum and energy level but also enhance the crystallinity of conjugated polymers. As a result, such polymers can act as electron donor, electron acceptor, and single-component active layer in organic solar cells. These findings provide a new guideline for the future molecular design of multifunctional conjugated polymers. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

3'-O-Substituted 5-(perylen-3-ylethynyl)-2'-deoxyuridines as tick-borne encephalitis virus reproduction inhibitors.

PubMed

Proskurin, Gleb V; Orlov, Alexey A; Brylev, Vladimir A; Kozlovskaya, Liubov I; Chistov, Alexey A; Karganova, Galina G; Palyulin, Vladimir A; Osolodkin, Dmitry I; Korshun, Vladimir A; Aralov, Andrey V

2018-05-26

A series of analogues of potent antiviral perylene nucleoside dUY11 with methylthiomethyl (MTM), azidomethyl (AZM) and HO-C 1-4 -alkyl-1,2,3-triazol-1,4-diyl groups at 3'-O-position as well as the two products of copper-free alkyne-azide cycloaddition of the AZM derivative were prepared and evaluated against tick-borne encephalitis virus (TBEV). Four compounds (4, 6, 8a, 8b) showed EC 50  ≤ 10 nM, thus appearing the most potent TBEV inhibitors to date. Moreover, these nucleosides have higher lipophilicity (clogP) and increased solubility in aq. DMSO vs. parent compound dUY11. Copyright © 2018 Elsevier Masson SAS. All rights reserved.

Irregular bilayer structure in vesicles prepared from Halobacterium cutirubrum lipids

NASA Technical Reports Server (NTRS)

Lanyi, J. K.

1974-01-01

Fluorescent probes were used to study the structure of the cell envelope of Halobacterium cutirubrum, and, in particular, to explore the effect of the heterogeneity of the lipids in this organism on the structure of the bilayers. The fluorescence polarization of perylene was followed in vesicles of unfractionated lipids and polar lipids as a function of temperature in 3.4 M solutions of NaCl, NaNO3, and KSCN, and it was found that vesicles of unfractionated lipids were more perturbed by chaotropic agents than polar lipids. The dependence of the relaxation times of perylene on temperature was studied in cell envelopes and in vesicles prepared from polar lipids, unfractionated lipids, and mixtures of polar and neutral lipids.

Living Supramolecular Polymerization of a Perylene Bisimide Dye into Fluorescent J-Aggregates.

PubMed

Wagner, Wolfgang; Wehner, Marius; Stepanenko, Vladimir; Ogi, Soichiro; Würthner, Frank

2017-12-11

The self-assembly of a new perylene bisimide (PBI) organogelator with 1,7-dimethoxy substituents in the bay position affords non-fluorescent H-aggregates at high cooling rates and fluorescent J-aggregates at low cooling rates. Under properly adjusted conditions, the kinetically trapped "off-pathway" H-aggregates are transformed into the thermodynamically favored J-aggregates, a process that can be accelerated by the addition of J-aggregate seeds. Spectroscopic studies revealed a subtle interplay of π-π interactions and intra- and intermolecular hydrogen bonding for monomeric, H-, and J-aggregated PBIs. Multiple polymerization cycles initiated from the seed termini demonstrate the living character of this chain-growth supramolecular polymerization process. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst

PubMed Central

Theriot, Jordan C.; Ryan, Matthew D.; French, Tracy A.; Pearson, Ryan M.; Miyake, Garret M.

2016-01-01

A standardized technique for atom transfer radical polymerization of vinyl monomers using perylene as a visible-light photocatalyst is presented. The procedure is performed under an inert atmosphere using air- and water-exclusion techniques. The outcome of the polymerization is affected by the ratios of monomer, initiator, and catalyst used as well as the reaction concentration, solvent, and nature of the light source. Temporal control over the polymerization can be exercised by turning the visible light source off and on. Low dispersities of the resultant polymers as well as the ability to chain-extend to form block copolymers suggest control over the polymerization, while chain end-group analysis provides evidence supporting an atom-transfer radical polymerization mechanism. PMID:27166728

Photoionization Efficiencies of Five Polycyclic Aromatic Hydrocarbons

DOE PAGES

Johansson, K. Olof; Campbell, Matthew F.; Elvati, Paolo; ...

2017-05-18

We have measured photoionization-efficiency curves for pyrene, fluoranthene, chrysene, perylene, and coronene in the photon energy range of 7.5-10.2 eV and derived their photoionization cross-section curves in this energy range. All measurements were performed using tunable vacuum ultraviolet (VUV) radiation generated at the Advanced Light Source synchrotron at Lawrence Berkeley National Laboratory. The VUV radiation was used for photoionization, and detection was performed using a time-of-flight mass spectrometer. We measured the photoionization efficiency of 2,5-dimethylfuran simultaneously with those of pyrene, fluoranthene, chrysene, perylene, and coronene to obtain references of the photon flux during each measurement from the known photoionization cross-sectionmore » curve of 2,5- dimethylfuran.« less

Development of a magnetic solid-phase extraction coupled with high-performance liquid chromatography method for the analysis of polyaromatic hydrocarbons.

PubMed

Ma, Yan; Xie, Jiawen; Jin, Jing; Wang, Wei; Yao, Zhijian; Zhou, Qing; Li, Aimin; Liang, Ying

2015-07-01

A novel magnetic solid phase extraction coupled with high-performance liquid chromatography method was established to analyze polyaromatic hydrocarbons in environmental water samples. The extraction conditions, including the amount of extraction agent, extraction time, pH and the surface structure of the magnetic extraction agent, were optimized. The results showed that the amount of extraction agent and extraction time significantly influenced the extraction performance. The increase in the specific surface area, the enlargement of pore size, and the reduction of particle size could enhance the extraction performance of the magnetic microsphere. The optimized magnetic extraction agent possessed a high surface area of 1311 m(2) /g, a large pore size of 6-9 nm, and a small particle size of 6-9 μm. The limit of detection for phenanthrene and benzo[g,h,i]perylene in the developed analysis method was 3.2 and 10.5 ng/L, respectively. When applied to river water samples, the spiked recovery of phenanthrene and benzo[g,h,i]perylene ranged from 89.5-98.6% and 82.9-89.1%, respectively. Phenanthrene was detected over a concentration range of 89-117 ng/L in three water samples withdrawn from the midstream of the Huai River, and benzo[g,h,i]perylene was below the detection limit. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Green Perylene Bisimide Dyes: Synthesis, Photophysical and Electrochemical Properties

PubMed Central

Chang, Che-Wei; Tsai, Hsing-Yang; Chen, Kew-Yu

2014-01-01

Three asymmetric amino-substituted perylene bisimide dyes with different n-alkyl chain lengths (n = 6, 12, or 18), 1-(N,N-dialkylamino)perylene bisimides (1a–1c), were synthesized under mild condition in high yields and were characterized by 1H NMR, 13C NMR (nuclear magnetic resonance), HRMS (High Resolution Mass Spectrometer), UV-Vis and fluorescence spectra, as well as cyclic voltammetry (CV). These molecules show intense green color in both solution and solid state and are highly soluble in dichloromethane and even in nonpolar solvents, such as hexane. The shapes of the absorption spectra of 1a–1c in solid state and in solution were found to be virtually the same, indicating that the long alkyl chains could efficiently prevent aggregation. They exhibit a unique charge transfer emission in the near-infrared region, of which the peak wavelengths show strong solvatochromism. The dipole moments of the compounds have been estimated using the Lippert-Mataga equation, and upon excitation, they show larger dipole moment changes than that of 1-aminoperylene bisimide (2). Furthermore, all of the compounds exhibit two quasi-reversible one-electron oxidations and two quasi-reversible one-electron reductions in dichloromethane at modest potentials. Complementary density functional theory (DFT) calculations performed on these dyes are reported in order to rationalize their molecular structures and electronic properties. PMID:28788140

1,7-Bis-(N,N-dialkylamino)perylene Bisimides: Facile Synthesis and Characterization as Near-Infrared Fluorescent Dyes

PubMed Central

Chen, Kew-Yu; Chang, Che-Wei

2014-01-01

Three symmetric alkylamino-substituted perylene bisimides with different n-alkyl chain lengths (n = 6, 12, or 18), 1,7-bis-(N,N-dialkylamino)perylene bisimides (1a–1c), were synthesized under mild condition and were characterized by 1H NMR, 13C NMR and high resolution mass spectroscopy. Their optical and electrochemical properties were measured using UV-Vis and emission spectroscopic techniques as well as cyclic voltammetry (CV). These compounds show deep green color in both solution and solid state, and are highly soluble in dichloromethane and even in nonpolar solvents such as hexane. The shapes of the absorption spectra of 1a–1c in the solution and solid state were found to be almost the same, indicating that the long alkyl chains could efficiently prevent intermolecular contact and aggregation. They show a unique charge transfer emission in the near-infrared region, of which the peak wavelengths exhibit strong solvatochromism. The dipole moments of the molecules have been estimated using the Lippert–Mataga equation, and upon excitation, they show larger dipole moment changes than that of 1,7-diaminoperylene bisimide (2). Moreover, all the dyes exhibit two irreversible one-electron oxidations and two quasi-reversible one-electron reductions in dichloromethane at modest potentials. Complementary density functional theory calculations performed on these chromophores are reported in order to rationalize their electronic structure and optical properties. PMID:28788262

Spectroscopic, electrochemical and photovoltaic properties of Pt(ii) and Pd(ii) complexes of a chelating 1,10-phenanthroline appended perylene diimide.

PubMed

Işık Büyükekşi, Sebile; Şengül, Abdurrahman; Erdönmez, Seda; Altındal, Ahmet; Orman, Efe Baturhan; Özkaya, Ali Rıza

2018-02-20

In this study, a bis-chelating bridging perylene diimide ditopic ligand, namely N,N'-di(1,10-phenanthroline)-1,6,7,12-tetrakis-(4-methoxyphenoxy)perylene tetracarboxylic acid diimide (1), was synthesized and characterized. Further reactions of 1 with d 8 metal ions such as Pt(ii) and Pd(ii) having preferential square-planar geometry afforded the novel triads [(Cl 2 )M(ii)-(1)-M(ii)(Cl 2 )] where M(ii) = Pt(ii) (2), and Pd(ii) (3), respectively. The isolated triads and the key precursor were fully characterized by FT-IR, 1D-NMR ( 1 H NMR and 13 C DEPT NMR), 2D-NMR ( 1 H- 1 H COSY, 1 H- 13 C HSQC, 1 H- 13 C HMBC), MALDI-TOF mass and UV/Vis spectroscopy. The electrochemical properties of 1, 2 and 3 were investigated by cyclic voltammetry as well as in situ spectroelectrochemistry and also in situ electrocolorimetric measurements. These compounds were shown to exhibit net colour changes suitable for electrochromic applications. The compounds exhibited remarkably narrow HOMO-LUMO gaps, leading to their ease of reduction at low negative potentials. More importantly, dye-sensitized solar cells (DSSCs) were also fabricated using 1-3 to clarify the potential use of these complexes as a sensitizer. Analysis of the experimental data indicated that 2 has good potential as a sensitizer material for DSSCs.

Molecular Engineering of Perylene Imides for High-Performance Lithium Batteries: Diels-Alder Extension and Chiral Dimerization.

PubMed

Li, Lei; Hong, Yu-Jian; Chen, Dong-Yang; Lin, Mei-Jin

2017-11-21

The search for high-performance electrode materials in organic rechargeable batteries remains a key challenge. Reported herein is a molecular structural modification of perylene imides, a promising class of redox-active electrode materials, for improved battery performance. The Diels-Alder extension of perylene imides at the lateral position led to the simultaneous incorporation of two electron-withdrawing carbonyl groups and extension of the π system, which is supposed to favor high specific capacity, operating voltage, and electronic conductivity. After the chiral dimerization of the extended species with 1,2-diaminocyclohexane, it was anticipated that the porosity and coulombic interactions with lithium ions would be promoted, which would be beneficial for fast reaction kinetics and long cycling life. As expected, in lithium batteries, the obtained chiral and π-extended tweezer, which features six imide groups and a porous solid-state network of 42.2 % accessible cell volume, was found to deliver a reversible capacity of 92.1 mA h g -1 at a charge/discharge rate of 1 C within an operating voltage window of 1.60-2.80 V versus Li + /Li, around 75 and 50 % of which was maintained after 100 and 300 galvanostatic cycles, respectively, much better than those of unmodified species. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electronic Interactions of n-Doped Perylene Diimide Groups Appended to Polynorbornene Chains: Implications for Electron Transport in Organic Electronics.

PubMed

Nguyen, Minh T; Biberdorf, Joshua D; Holliday, Bradley J; Jones, Richard A

2017-11-01

A polymer consisting of a polynorbornene backbone with perylene diimide (PDI) pendant groups on each monomeric unit is synthesized via ring opening metathesis polymerization. The PDI pendant groups along the polymer backbone, studied by UV-vis absorption, fluorescence emission, and electron paramagnetic resonance spectroscopy in addition to electrochemical methods, show evidence of molecular aggregation and corresponding electronic coupling with neighboring groups, which forms pathways for efficient electron transport from one group to another in a specific reduced form. When n-doped, the title polymer shows redox conductivity of 5.4 × 10 -3 S cm -1 , comparable with crystalline PDI materials, and is therefore a promising material for use in organic electronics. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Perylene bisimide hydrogels and lyotropic liquid crystals with temperature-responsive color change.

PubMed

Görl, Daniel; Soberats, Bartolome; Herbst, Stefanie; Stepanenko, Vladimir; Würthner, Frank

2016-11-01

The self-assembly of perylene bisimide (PBI) dyes bearing oligo ethylene glycol (OEG) units in water affords responsive functional nanostructures characterized by their lower critical solution temperature (LCST). Tuning of the LCST is realized by a supramolecular approach that relies on two structurally closely related PBI-OEG molecules. The two PBIs socially co-assemble in water and the resulting nanostructures exhibit a single LCST in between the transition temperatures of the aggregates formed by single components. This permits to precisely tune the transition from a hydrogel to a lyotropic liquid crystal state at temperatures between 26 and 51 °C by adjusting the molar fraction of the two PBIs. Owing to concomitant changes in PBI-PBI interactions this phase transition affords a pronounced color change with "fluorescence-on" response that can be utilized as a smart temperature sensory system.

Cyclic perylene diimide: Selective ligand for tetraplex DNA binding over double stranded DNA.

PubMed

Vasimalla, Suresh; Sato, Shinobu; Takenaka, Fuminori; Kurose, Yui; Takenaka, Shigeori

2017-12-15

Synthesized cyclic perylene diimide, cPDI, showed the binding constant of 6.3 × 10 6  M -1 with binding number of n = 2 with TA-core as a tetraplex DNA in 50 mM Tris-HCl buffer (pH = 7.4) containing 100 mM KCl using Schatchard analysis and showed a higher preference for tetraplex DNA than for double stranded DNA with over 10 3 times. CD spectra showed that TA-core induced its antiparallel conformation upon addition of cPDI in the absence or presence of K + or Na + ions. The cPDI inhibits the telomerase activity with IC 50 of 0.3 µM using TRAP assay which is potential anti-cancer drug with low side effect. Copyright © 2017 Elsevier Ltd. All rights reserved.

Electronic Absorption Spectra of Neutral Perylene (C20H12), Terrylene (C30H16), and Quaterrylene (C40H20) and their Positive and Negative Ions: Ne Matrix-Isolation Spectroscopy and Time Dependent Density Functional Theory Calculations

NASA Technical Reports Server (NTRS)

Halasinski, Thomas M.; Weisman, Jennifer L.; Lee, Timothy J.; Salama, Farid; Head-Gordon, Martin; Kwak, Dochan (Technical Monitor)

2002-01-01

We present a full experimental and theoretical study of an interesting series of polycyclic aromatic hydrocarbons, the oligorylenes. The absorption spectra of perylene, terrylene and quaterrylene in neutral, cationic and anionic charge states are obtained by matrix-isolation spectroscopy in Ne. The experimental spectra are dominated by a bright state that red shifts with growing molecular size. Excitation energies and state symmetry assignments are supported by calculations using time dependent density functional theory methods. These calculations also provide new insight into the observed trends in oscillator strength and excitation energy for the bright states: the oscillator strength per unit mass of carbon increases along the series.

Novel EDTA-ligands containing an integral perylene bisimide (PBI) core as an optical reporter unit.

PubMed

Marcia, Mario; Singh, Prabhpreet; Hauke, Frank; Maggini, Michele; Hirsch, Andreas

2014-09-28

The synthesis, characterization and metal complexation of a new class of perylene bisimides (PBIs) as an integral part of ethylenediaminetetraacetic acid (EDTA) are reported. The simplest representative, namely derivative 1a, was synthesized both by a convergent as well as a direct approach while the elongated derivatives, 1b and 1c, were obtained only via a convergent synthetic pathway. All these new prototypes of water-soluble perylenes are bolaamphiphiles and were fully characterized by (1)H- and (13)C-NMR spectroscopy, matrix assisted laser desorption ionization-time of flight (MALDI-TOF) mass spectrometry and IR spectroscopy. In order to acquaint ourselves with the behaviour in solution of our PBIs bearing dendritic wedges, the simplest derivative, 1a, was chosen and tested by means of UV/Vis and fluorescence spectroscopy as well as by zeta-potential measurements. A photoexcitation induced intramolecular photo-electron transfer (PET) can be observed in these molecules. Therefore their potential applications as sensors can be imagined. Model compound 1a efficiently coordinates trivalent metal cations both in water and dimethyl sulfoxide (DMSO). Significantly, the effects of the complexation strongly depend on the aggregation state of the PBI molecules in solution. As a matter of fact, in water, the presence of M(3+) ions triggers the formation of light emitting supramolecular aggregates (excimers). On the other hand, in DMSO-rich solutions metal complexation leads to the suppression of the PET and leads to a strong fluorescence enhancement.

Crystallochromy of perylene pigments: Interference between Frenkel excitons and charge-transfer states

NASA Astrophysics Data System (ADS)

Gisslén, Linus; Scholz, Reinhard

2009-09-01

The optical properties of perylene-based pigments are arising from the interplay between neutral molecular excitations and charge transfer between adjacent molecules. In the crystalline phase, these excitations are coupled via electron and hole transfer, two quantities relating directly to the width of the conduction and valence band in the crystalline phase. Based on the crystal structure determined by x-ray diffraction, density-functional theory (DFT) and Hartree-Fock are used for the calculation of the electronic states of a dimer of stacked molecules. The resulting transfer parameters for electron and hole are used in an exciton model for the coupling between Frenkel excitons and charge-transfer states. The deformation of the positively or negatively charged molecular ions with respect to the neutral ground state is calculated with DFT and the geometry in the optically excited state is deduced from time-dependent DFT and constrained DFT. All of these deformations are interpreted in terms of the elongation of an effective internal vibration which is used subsequently in the exciton model for the crystalline phase. A comparison between the calculated dielectric function and the observed optical spectra allows to deduce the relative energetic position of Frenkel excitons and the charge-transfer state involving stack neighbors, a key parameter for various electronic and optoelectronic device applications. For five out of six perylene pigments studied in the present work, this exciton model results in excellent agreement between calculated and observed optical properties.

Structural and electronic properties of extremely long perylene bisimide nanofibers formed through a stoichiometrically mismatched, hydrogen-bonded complexation.

PubMed

Yagai, Shiki; Seki, Tomohiro; Murayama, Haruno; Wakikawa, Yusuke; Ikoma, Tadaaki; Kikkawa, Yoshihiro; Karatsu, Takashi; Kitamura, Akihide; Honsho, Yoshihito; Seki, Shu

2010-12-06

Extremely long nanofibers, whose lengths reach the millimeter regime, are generated via co-aggregation of a melamine-appended perylene bisimide semiconductor and a substituted cyanurate, both of which are ditopic triple-hydrogen-bonding building blocks; they co-aggregate in an unexpected stoichiometrically mismatched 1:2 ratio. Various microscopic and X-ray diffraction studies suggest that hydrogen-bonded polymeric chains are formed along the long axis of the nanofibers by the 1:2 complexation of the two components, which further stack along the short axis of the nanofibers. The photocarrier generation mechanism in the nanofibers is investigated by time-of-flight (TOF) experiments under electric and magnetic fields, revealing the birth and efficient recombination of singlet geminate electron-hole pairs. Flash-photolysis time-resolved microwave conductivity (FP-TRMC) measurements revealed intrinsic 1D electron mobilities up to 0.6 cm(2) V(-1) s(-1) within nanofibers.

Influence of the morphology of organic heterojunction on the photovoltaic cell performance

NASA Astrophysics Data System (ADS)

Podhájecká, K.; Pfleger, J.

2006-12-01

We present a series of organic photovoltaic (PV) cells based on the bulk-distributed heterojunction where π -conjugated polymer poly[1-(4-trimethylsilylphenyl)-2-phenylvinylene], PSDPhV, acts as the donor upon photoexcitation and the substituted perylene based low-molecular-weight compound: N,N`-di(pent-3-yl)-perylene-3,4:9,10-bis(dicarboximide), DPe-PTCDI, as the acceptor of photogenerated electrons. According to both absorption spectra and AFM images of the thin films spin-coated from solution of DPe-PTCDI and PSDPhV in toluene, the DPe-PTCDI is molecularly dissolved in conjugated polymer matrix. Upon exposition of layers to toluene vapors, microcrystals of DPe-PTCDI are progressively formed. The influence of the morphology of DPe-PTCDI inside the polymer matrix on PV cell performance is investigated. This paper has been presented at “ECHOS06”, Paris, 28 30 juin 2006.

An ambient stable core-substituted perylene bisimide dianion: isolation and single crystal structure analysis† †Electronic supplementary information (ESI) available: Synthesis, spectroelectrochemistry, UV-vis, electrochemistry, X-ray diffraction, NMR and mass spectra. CCDC 1032959. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4sc03671a Click here for additional data file. Click here for additional data file.

PubMed Central

Seifert, Sabine; Schmidt, David

2015-01-01

Here we report the first example of an isolable, ambient stable perylene bisimide (PBI) dianion which was synthesized by catalytic reduction of a highly electron deficient PBI derivative. The remarkable stability of this unprecedented dianion in air for months facilitated its complete characterization by different methods, including single crystal X-ray analysis. Furthermore, solvent dependent cyclic and square wave voltammetry studies revealed that the formation of PBI dianions is preferred in more polar solvents, whereas the generation of PBI radical anions should be favoured in less polar solvents. PMID:28717450

Supramolecular block copolymers by kinetically controlled co-self-assembly of planar and core-twisted perylene bisimides

PubMed Central

Görl, Daniel; Zhang, Xin; Stepanenko, Vladimir; Würthner, Frank

2015-01-01

New synthetic methodologies for the formation of block copolymers have revolutionized polymer science within the last two decades. However, the formation of supramolecular block copolymers composed of alternating sequences of larger block segments has not been realized yet. Here we show by transmission electron microscopy (TEM), 2D NMR and optical spectroscopy that two different perylene bisimide dyes bearing either a flat (A) or a twisted (B) core self-assemble in water into supramolecular block copolymers with an alternating sequence of (AmBB)n. The highly defined ultralong nanowire structure of these supramolecular copolymers is entirely different from those formed upon self-assembly of the individual counterparts, that is, stiff nanorods (A) and irregular nanoworms (B), respectively. Our studies further reveal that the as-formed supramolecular block copolymer constitutes a kinetic self-assembly product that transforms into thermodynamically more stable self-sorted homopolymers upon heating. PMID:25959777

Fully conjugated tri(perylene bisimides): an approach to the construction of n-type graphene nanoribbons.

PubMed

Qian, Hualei; Negri, Fabrizia; Wang, Chunru; Wang, Zhaohui

2008-12-31

We present an experimental study encompassing synthesis and characterization of fully conjugated tri(perylene bisimides) (triPBIs), having 19 six-membered carbon rings in the core and six imide groups at the edges. Two structural isomers of triPBIs resulting from the two probable coupling positions were successfully separated by HPLC. To assist the identification of the two structural isomers, quantum-chemical calculations of electronic structure, NMR, and optical spectra were carried out. Calculations predict stable helical and nonhelical configurations for both triPBIs isomers and allow the assignment of triPBIs 6 unequivocally to the most bathochromically shifted absorption spectrum. Increasing the number of PBI units in oligo-PBIs leads to an expansion of the pi system, in turn associated with a reduction of the transport and optical band gaps, and a remarkable increase in electron affinities, which make oligo-PBIs promising n-type functional components in optoelectronic devices.

A new fluorogenic sensing platform for salicylic acid derivatives based on π-π and NH-π interactions between electron-deficient and electron-rich aromatics.

PubMed

Pandith, Anup; Hazra, Giridhari; Kim, Hong-Seok

2017-05-05

A novel simple fluorescent probe was designed for the recognition of electron-rich salicylic acid derivatives (SAs). The imidazole-appended aminomethyl perylene probe 1 selectively differentiated between electron-rich amino-SAs and electron-deficient nitro-SAs in EtOH, exhibiting the highest selectivity and sensitivity toward 5-aminosalicylic acid (5-ASA) and showing strong 1:1 binding (K a =1.37×10 7 M -1 ). This high selectivity and sensitivity resulted from the synergistic multiple hydrogen bonding interactions of secondary amine and imidazole units and π-π interactions between electron-rich and electron-deficient rings, along with the unusual NH-π interactions between 5-ASA and the perylene moiety of 1. The limit of detection (LOD) for 5-ASA in EtOH was 0.012ppb. Copyright © 2017 Elsevier B.V. All rights reserved.

Observations of cavity polaritons in one-dimensional photonic crystals containing a liquid-crystalline semiconductor based on perylene bisimide units

NASA Astrophysics Data System (ADS)

Sakata, T.; Suzuki, M.; Yamamoto, T.; Nakanishi, S.; Funahashi, M.; Tsurumachi, N.

2017-10-01

We investigated the optical transmission properties of one-dimensional photonic crystal (1D-PC) microcavity structures containing the liquid-crystalline (LC) perylene tetracarboxylic bisimide (PTCBI) derivative. We fabricated the microcavity structures for this study by two different methods and observed the cavity polaritons successfully in both samples. For one sample, since the PTCBI molecules were aligned in the cavity layer of the 1D-PC by utilizing a friction transfer method, vacuum Rabi splitting energy was strongly dependent on the polarization of the incident light produced by the peculiar optical features of the LC organic semiconductor. For the other sample, we did not utilize the friction transfer method and did not observe such polarization dependence. However, we did observe a relatively large Rabi splitting energy of 187 meV, probably due to the improvement of optical confinement effect.

STM-induced light emission enhanced by weakly coupled organic ad-layers

NASA Astrophysics Data System (ADS)

Cottin, M. C.; Ekici, E.; Bobisch, C. A.

2018-03-01

We analyze the light emission induced by the tunneling current flowing in a scanning tunneling microscopy experiment. In particular, we study the influence of organic ad-layers on the light emission on the initial monolayer of bismuth (Bi) on Cu(111) in comparison to the well-known case of organic ad-layers on Ag(111). On the Bi/Cu(111)-surface, we find that the scanning tunneling microscopy-induced light emission is considerably enhanced if an organic layer, e.g., the fullerene C60 or the perylene derivate perylene-tetracarboxylic-dianhydride, is introduced into the tip-sample junction. The enhancement can be correlated with a peculiarly weak interaction between the adsorbed molecules and the underlying Bi/Cu(111) substrate as compared to the Ag(111) substrate. This allows us to efficiently enhance and tune the coupling of the tunneling current to localized excitations of the tip-sample junction, which in turn couple to radiative decay channels.

Core Perylene Diimide Designs via Direct Bay- and ortho-(Poly)trifluoromethylation: Synthesis, Isolation, X-Ray Structures, Optical and Electronic Properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clikeman, Tyler T.; Bukovsky, Eric V.; Wang, Xue-Bin

2015-09-22

We developed an efficient solvent- and catalyst-free direct polytrifluoromethylation of solid perylene-3,4,9,10-tetracarboxylic dianhydride that produced a new family of (poly)perfluoroalkyl bay- and ortho-substituted PDIs with two different imide substituents. Direct hydrogen substitution with CN group led to the synthesis of a cyanated perfluoroalkyl PDI derivative for the first time. Absorption, steady-state and time-resolved emission, X-ray diffraction, electrochemical, and gas-phase electron affinity data allowed for systematic studies of substitution effects at bay, ortho, and imide positions in the new PDIs. Solid-state packing showed remarkable variations in the intermolecular interactions that are important for charge transport and photophysical properties. Moreover, analysis ofmore » the electrochemical data for 143 electron poor PDIs, including newly reported compounds, revealed some general trends and peculiar effects from substituting electron-withdrawing groups at all three positions.« less

Core Perylene Diimide Designs via Direct Bay and Ortho (Poly)trifluoromethylation: Synthesis, Isolation, X-ray Structures, Optical and Electronic Properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clikeman, Tyler T.; Bukovsky, Eric V.; Wang, Xue B.

2015-09-22

We developed an efficient solvent- and catalyst-free direct polytrifluoromethylation of solid perylene-3,4,9,10-tetracarboxylic dianhydride that produced a new family of (poly)perfluoroalkyl bay and ortho substituted PDIs with two different imide substituents. Direct hydrogen substitution with CN group led to the synthesis of a cyanated perfluoroalkyl PDI derivative for the first time. Absorption, steady-state and time-resolved emission, X-ray diffraction, electrochemical, and gas-phase electron affinity data allowed for systematic studies of substitution effects at bay, ortho, and imide positions in the new PDIs. Solid-state packing showed remarkable variations in the intermolecular interactions that are important for charge transport and photophysical properties. Analysis ofmore » the electrochemical data for 143 electron poor PDIs, including newly reported compounds, revealed some general trends and peculiar effects of electron withdrawing group substitution at all three positions.« less

1D Self-Assembly and Ice Recrystallization Inhibition Activity of Antifreeze Glycopeptide-Functionalized Perylene Bisimides.

PubMed

Adam, Madeleine K; Jarrett-Wilkins, Charles; Beards, Michael; Staykov, Emiliyan; MacFarlane, Liam R; Bell, Toby D M; Matthews, Jacqueline M; Manners, Ian; Faul, Charl F J; Moens, Pierre D J; Ben, Robert N; Wilkinson, Brendan L

2018-06-04

Antifreeze glycoproteins (AFGPs) are polymeric natural products that have drawn considerable interest in diverse research fields owing to their potent ice recrystallization inhibition (IRI) activity. Self-assembled materials have emerged as a promising class of biomimetic ice growth inhibitor, yet the development of AFGP-based supramolecular materials that emulate the aggregative behavior of AFGPs have not yet been reported. This work reports the first example of the 1D self-assembly and IRI activity of AFGP-functionalized perylene bisimides (AFGP-PBIs). Glycopeptide-functionalized PBIs underwent 1D self-assembly in water and showed modest IRI activity, which could be tuned through substitution of the PBI core. This work presents essential proof-of-principle for the development of novel IRIs as potential supramolecular cryoprotectants and glycoprotein mimics. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quantifying highly efficient incoherent energy transfer in perylene-based multichromophore arrays.

PubMed

Webb, James E A; Chen, Kai; Prasad, Shyamal K K; Wojciechowski, Jonathan P; Falber, Alexander; Thordarson, Pall; Hodgkiss, Justin M

2016-01-21

Multichromophore perylene arrays were designed and synthesized to have extremely efficient resonance energy transfer. Using broadband ultrafast photoluminescence and transient absorption spectroscopies, transfer timescales of approximately 1 picosecond were resolved, corresponding to efficiencies of up to 99.98%. The broadband measurements also revealed spectra corresponding to incoherent transfer between localized states. Polarization resolved spectroscopy was used to measure the dipolar angles between donor and acceptor chromophores, thereby enabling geometric factors to be fixed when assessing the validity of Förster theory in this regime. Förster theory was found to predict the correct magnitude of transfer rates, with measured ∼2-fold deviations consistent with the breakdown of the point-dipole approximation at close approach. The materials presented, along with the novel methods for quantifying ultrahigh energy transfer efficiencies, will be valuable for applications demanding extremely efficient energy transfer, including fluorescent solar concentrators, optical gain, and photonic logic devices.

Photoinduced electron transfer in perylene-TiO2 nanoassemblies.

PubMed

Llansola-Portoles, Manuel J; Bergkamp, Jesse J; Tomlin, John; Moore, Thomas A; Kodis, Gerdenis; Moore, Ana L; Cosa, Gonzalo; Palacios, Rodrigo E

2013-01-01

The photosensitization effect of three perylene dye derivatives on titanium dioxide nanoparticles (TiO2 NPs) has been investigated. The dyes used, 1,7-dibromoperylene-3,4,9,10-tetracarboxy dianhydride (1), 1,7-dipyrrolidinylperylene-3,4,9,10-tetracarboxy dianhydride (2) and 1,7-bis(4-tert-butylphenyloxy)perylene-3,4,9,10-tetracarboxy dianhydride (3) have in common bisanhydride groups that convert into TiO2 binding groups upon hydrolysis. The different substituents on the bay position of the dyes enable tuning of their redox properties to yield significantly different driving forces for photoinduced electron transfer (PeT). Recently developed TiO2 NPs having a small average size and a narrow distribution (4 ± 1 nm) are used in this work to prepare the dye-TiO2 systems under study. Whereas successful sensitization was obtained with 1 and 2 as evidenced by steady-state spectral shifts and transient absorption results, no evidence for the attachment of 3 to TiO2 was observed. The comparison of the rates of PeT (kPeT ) for 1- and 2-TiO2 systems studied in this work with those obtained for previously reported analogous systems, having TiO2 NPs covered by a surfactant layer (Hernandez et al. [2012] J. Phys. Chem. B., 117, 4568-4581), indicates that kPeT for the former systems is slower than that for the later. These results are interpreted in terms of the different energy values of the conduction band edge in each system. © 2013 The American Society of Photobiology.

Mechanisms of low-power noncoherent photon upconversion in metalloporphyrin-organic blue emitter systems in solution.

PubMed

Sugunan, Sunish K; Tripathy, Umakanta; Brunet, Sophie M K; Paige, Matthew F; Steer, Ronald P

2009-07-30

The mechanisms of noncoherent photon upconversion that involve triplet-triplet annihilation (TTA) in solution have been investigated for two model systems. ZnTPP (meso-tetraphenylporphine zinc) is used as the model visible light-absorbing metalloporphyrin because its S(1) fluorescence intensity can be used to monitor the initial rate of porphyrin triplet state production and because its S(2) fluorescence intensity can be used as a direct measure of the rate of porphyrin TTA. When perylene, which has a triplet energy lower than that of ZnTPP, is added as a signaling blue emitter (BE), the mechanism of photon upconversion involves triplet energy transfer from the porphyrin to the BE followed by TTA in the BE to form the fluorescent perylene S(1) state. The kinetics of this process have been characterized and are unremarkable. When coumarin 343 (C343), which has photophysical properties similar to those of perylene except that it has a much higher triplet energy than ZnTPP, is added as the signaling BE, emission from the ZnTPP S(2) state is quenched and fluorescence from the C343 grows in. Contrary to previous suggestions, the mechanism of photon upconversion in this system does not involve singlet energy transfer from the porphyrin S(2) state to the BE. Instead, ground-state C343 complexes with the ZnTPP triplet to form a triplet exciplex, which then undergoes TTA with a second ZnTPP triplet to give the fluorescent state of the BE in a three-center process.

Source apportionment of elevated wintertime PAHs by compound-specific radiocarbon analysis

NASA Astrophysics Data System (ADS)

Sheesley, R. J.; Kruså, M.; Krecl, P.; Johansson, C.; Gustafsson, Ã.-.

2008-12-01

Natural abundance radiocarbon analysis facilitates distinct source apportionment between contemporary biomass/biofuel (14C "alive") versus fossil fuel (14C "dead") combustion. Here, the first compound-specific radiocarbon analysis (CSRA) of atmospheric polycylic aromatic hydrocarbons (PAHs) was demonstrated for a set of samples collected in Lycksele, Sweden a small town with frequent episodes of severe atmospheric pollution in the winter. Renewed interest in residential wood combustion means than this type of seasonal pollution is of increasing concern in many areas. Five individual/paired PAH isolates from three pooled fortnight-long filter collections were analyzed by CSRA: phenanthrene, fluoranthene, pyrene, benzo[b+k]fluoranthene and indeno[cd]pyrene plus benzo[ghi]perylene; phenanthrene was the only compound also analyzed in the gas phase. The measured Δ14C for PAHs spanned from -138.3‰ to 58.0‰. A simple isotopic mass balance model was applied to estimate the fraction biomass (fbiomass) contribution that was constrained to a range of 71% for indeno[cd]pyrene+benzo[ghi]perylene to 87% for the gas phase phenanthrene and particulate fluoranthene, respectively. Indeno[cd]pyrene plus benzo[ghi]perylene, known to be enhanced in gasoline-powered motor vehicle exhaust compared to diesel exhaust, had the lowest contribution of biomass combustion of the measured PAHs by 9%. The total organic carbon (TOC, defined as carbon remaining after removal of inorganic carbon) fbiomass was estimated to be 77%, which falls within the range for PAHs. This CSRA data of atmospheric PAHs demonstrate the non-uniformity of biomass combustion contribution to different PAHs even in a location with limited local emission sources and illustrates that regulatory efforts would not evenly reduce all PAHs.

Effect of core twisting on self-assembly and optical properties of perylene bisimide dyes in solution and columnar liquid crystalline phases.

PubMed

Chen, Zhijian; Baumeister, Ute; Tschierske, Carsten; Würthner, Frank

2007-01-01

A series of highly soluble and fluorescent core-twisted perylene bisimide dyes (PBIs) 3 a-f with different substituents at the bay area (1,6,7,12 positions of the perylene core) were synthesized and fully characterized by (1)H NMR, UV/Vis spectroscopy, MS spectrometry, and elemental analysis. The pi-pi aggregation properties of these new functional dyes were investigated in detail both in solution and in condensed phase by UV/Vis and fluorescence spectroscopy, vapor pressure osmometry (VPO), differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and X-ray diffraction. Concentration-dependent UV/Vis measurements and VPO analysis revealed that these core-twisted pi-conjugated systems show distinct self-dimerization equilibria in apolar solvent methylcyclohexane (MCH) with dimerization constants between 1.3x10(4) and 30 M(-1). The photoluminescence spectra of the dimers of PBIs 3 a-f exhibit bathochromic shifts of quite different magnitude which could be attributed to different longitudinal or rotational offsets between the dyes as well as differences in the respective pi-pi stacking distance. In condensed state, quite a few of these PBIs form luminescent rectangular or hexagonal columnar liquid crystalline phases with low isotropization temperatures. The effects of the distortion of the pi systems on their pi-pi stacking and the optical properties of the resultant stacks in solution and in LC phases have been explored in detail. In one case (3 a) a particularly interesting phase change from crystalline into liquid crystalline could be observed upon annealing that was accompanied by a transformation from non-fluorescent H-type into strongly fluorescent J-type packing of the dyes.

Sensitization of Nanocrystalline Metal Oxides with a Phosphonate-Functionalized Perylene Diimide for Photoelectrochemical Water Oxidation with a CoOx Catalyst.

PubMed

Kirner, Joel T; Finke, Richard G

2017-08-23

A planar organic thin film composed of a perylene diimide dye (N,N'-bis(phosphonomethyl)-3,4,9,10-perylenediimide, PMPDI) with photoelectrochemically deposited cobalt oxide (CoO x ) catalyst was previously shown to photoelectrochemically oxidize water (DOI: 10.1021/am405598w). Herein, the same PMPDI dye is studied for the sensitization of different nanostructured metal oxide (nano-MO x ) films in a dye-sensitized photoelectrochemical cell architecture. Dye adsorption kinetics and saturation decreases in the order TiO 2 > SnO 2 ≫ WO 3 . Despite highest initial dye loading on TiO 2 films, photocurrent with hydroquinone (H 2 Q) sacrificial reductant in pH 7 aqueous solution is much higher on SnO 2 films, likely due to a higher driving force for charge injection into the more positive conduction band energy of SnO 2 . Dyeing conditions and SnO 2 film thickness were subsequently optimized to achieve light-harvesting efficiency >99% at the λ max of the dye, and absorbed photon-to-current efficiency of 13% with H 2 Q, a 2-fold improvement over the previous thin-film architecture. A CoO x water-oxidation catalyst was photoelectrochemically deposited, allowing for photoelectrochemical water oxidation with a faradaic efficiency of 31 ± 7%, thus demonstrating the second example of a water-oxidizing, dye-sensitized photoelectrolysis cell composed entirely of earth-abundant materials. However, deposition of CoO x always results in lower photocurrent due to enhanced recombination between catalyst and photoinjected electrons in SnO 2 , as confirmed by open-circuit photovoltage measurements. Possible future studies to enhance photoanode performance are discussed, including alternative catalyst deposition strategies or structural derivatization of the perylene dye.

Perylene Diimide as a Precise Graphene-like Superoxide Dismutase Mimetic

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jalilov, Almaz S.; Nilewski, Lizanne G.; Berka, Vladimir

Here we show that the active portion of a graphitic nanoparticle can be mimicked by a perylene diimide (PDI) to explain the otherwise elusive biological and electrocatalytic activity of the nanoparticle construct. Development of molecular analogues that mimic the antioxidant properties of oxidized graphenes, in this case the poly(ethylene glycolated) hydrophilic carbon clusters (PEG–HCCs), will afford important insights into the highly efficient activity of PEG–HCCs and their graphitic analogues. PEGylated perylene diimides (PEGn–PDI) serve as well-defined molecular analogues of PEG–HCCs and oxidized graphenes in general, and their antioxidant and superoxide dismutase-like (SOD-like) properties were studied. PEGn–PDIs have two reversible reductionmore » peaks, which are more positive than the oxidation peak of superoxide (O2•–). This is similar to the reduction peak of the HCCs. Thus, as with PEG–HCCs, PEGn–PDIs are also strong single-electron oxidants of O2•–. Furthermore, reduced PEGn–PDI, PEGn–PDI•–, in the presence of protons, was shown to reduce O2•– to H2O2 to complete the catalytic cycle in this SOD analogue. The kinetics of the conversion of O2•– to O2 and H2O2 by PEG8–PDI was measured using freeze-trap EPR experiments to provide a turnover number of 133 s–1; the similarity in kinetics further supports that PEG8–PDI is a true SOD mimetic. Finally, PDIs can be used as catalysts in the electrochemical oxygen reduction reaction in water, which proceeds by a two-electron process with the production of H2O2, mimicking graphene oxide nanoparticles that are otherwise difficult to study spectroscopically.« less

Sensitization of Nanocrystalline Metal Oxides with a Phosphonate-Functionalized Perylene Diimide for Photoelectrochemical Water Oxidation with a CoO x Catalyst

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kirner, Joel T.; Finke, Richard G.

A planar organic thin film composed of a perylene diimide dye (N,N'-bis(phosphonomethyl)-3,4,9,10-perylenediimide, PMPDI) with photoelectrochemically deposited cobalt oxide (CoO x) catalyst was previously shown to photoelectrochemically oxidize water (DOI: 10.1021/am405598w). Herein, the same PMPDI dye is studied for the sensitization of different nanostructured metal oxide (nano-MO x) films in a dye-sensitized photoelectrochemical cell architecture. Dye adsorption kinetics and saturation decreases in the order TiO 2 > SnO 2 >> WO 3. Despite highest initial dye loading on TiO 2 films, photocurrent with hydroquinone (H 2Q) sacrificial reductant in pH 7 aqueous solution is much higher on SnO 2 films, likelymore » due to a higher driving force for charge injection into the more positive conduction band energy of SnO 2. Dyeing conditions and SnO 2 film thickness were subsequently optimized to achieve light-harvesting efficiency >99% at the λmax of the dye, and absorbed photon-to-current efficiency of 13% with H 2Q, a 2-fold improvement over the previous thin-film architecture. A CoO x water-oxidation catalyst was photoelectrochemically deposited, allowing for photoelectrochemical water oxidation with a faradaic efficiency of 31 ± 7%, thus demonstrating the second example of a water-oxidizing, dye-sensitized photoelectrolysis cell composed entirely of earth-abundant materials. However, deposition of CoO x always results in lower photocurrent due to enhanced recombination between catalyst and photoinjected electrons in SnO 2, as confirmed by open-circuit photovoltage measurements. Possible future studies to enhance photoanode performance are also discussed, including alternative catalyst deposition strategies or structural derivatization of the perylene dye.« less

Spectral characteristics and photosensitization of TiO2 nanoparticles in reverse micelles by perylenes.

PubMed

Hernández, Laura I; Godin, Robert; Bergkamp, Jesse J; Llansola Portolés, Manuel J; Sherman, Benjamin D; Tomlin, John; Kodis, Gerdenis; Méndez-Hernández, Dalvin D; Bertolotti, Sonia; Chesta, Carlos A; Mariño-Ochoa, Ernesto; Moore, Ana L; Moore, Thomas A; Cosa, Gonzalo; Palacios, Rodrigo E

2013-04-25

We report on the photosensitization of titanium dioxide nanoparticles (TiO2 NPs) synthesized inside AOT (bis(2-ethylhexyl) sulfosuccinate sodium salt) reverse micelles following photoexcitation of perylene derivatives with dicarboxylate anchoring groups. The dyes, 1,7-dibromoperylene-3,4,9,10-tetracarboxy dianhydride (1), 1,7-dipyrrolidinylperylene-3,4,9,10-tetracarboxy dianhydride (2), and 1,7-bis(4-tert-butylphenyloxy)perylene-3,4,9,10-tetracarboxy dianhydride (3), have considerably different driving forces for photoinduced electron injection into the TiO2 conduction band, as estimated by electrochemical measurements and quantum mechanical calculations. Fluorescence anisotropy measurements indicate that dyes 1 and 2 are preferentially solubilized in the micellar structure, creating a relatively large local concentration that favors the attachment of the dye to the TiO2 surface. The binding process was followed by monitoring the hypsochromic shift of the dye absorption spectra over time for 1 and 2. Photoinduced electron transfer from the singlet excited state of 1 and 2 to the TiO2 conduction band (CB) is indicated by emission quenching of the TiO2-bound form of the dyes and confirmed by transient absorption measurements of the radical cation of the dyes and free carriers (injected electrons) in the TiO2 semiconductor. Steady state and transient spectroscopy indicate that dye 3 does not bind to the TiO2 NPs and does not photosensitize the semiconductor. This observation was rationalized as a consequence of the bulky t-butylphenyloxy groups which create a strong steric impediment for deep access of the dye within the micelle structure to reach the semiconductor oxide surface.

Sensitization of Nanocrystalline Metal Oxides with a Phosphonate-Functionalized Perylene Diimide for Photoelectrochemical Water Oxidation with a CoO x Catalyst

DOE PAGES

Kirner, Joel T.; Finke, Richard G.

2017-07-20

A planar organic thin film composed of a perylene diimide dye (N,N'-bis(phosphonomethyl)-3,4,9,10-perylenediimide, PMPDI) with photoelectrochemically deposited cobalt oxide (CoO x) catalyst was previously shown to photoelectrochemically oxidize water (DOI: 10.1021/am405598w). Herein, the same PMPDI dye is studied for the sensitization of different nanostructured metal oxide (nano-MO x) films in a dye-sensitized photoelectrochemical cell architecture. Dye adsorption kinetics and saturation decreases in the order TiO 2 > SnO 2 >> WO 3. Despite highest initial dye loading on TiO 2 films, photocurrent with hydroquinone (H 2Q) sacrificial reductant in pH 7 aqueous solution is much higher on SnO 2 films, likelymore » due to a higher driving force for charge injection into the more positive conduction band energy of SnO 2. Dyeing conditions and SnO 2 film thickness were subsequently optimized to achieve light-harvesting efficiency >99% at the λmax of the dye, and absorbed photon-to-current efficiency of 13% with H 2Q, a 2-fold improvement over the previous thin-film architecture. A CoO x water-oxidation catalyst was photoelectrochemically deposited, allowing for photoelectrochemical water oxidation with a faradaic efficiency of 31 ± 7%, thus demonstrating the second example of a water-oxidizing, dye-sensitized photoelectrolysis cell composed entirely of earth-abundant materials. However, deposition of CoO x always results in lower photocurrent due to enhanced recombination between catalyst and photoinjected electrons in SnO 2, as confirmed by open-circuit photovoltage measurements. Possible future studies to enhance photoanode performance are also discussed, including alternative catalyst deposition strategies or structural derivatization of the perylene dye.« less

Anti-cooperative supramolecular polymerization: a new K2-K model applied to the self-assembly of perylene bisimide dye proceeding via well-defined hydrogen-bonded dimers.

PubMed

Gershberg, Jana; Fennel, Franziska; Rehm, Thomas H; Lochbrunner, Stefan; Würthner, Frank

2016-03-01

A perylene bisimide dye bearing amide functionalities at the imide positions derived from amino acid l-alanine and a dialkoxy-substituted benzyl amine self-assembles into tightly bound dimers by π-π-stacking and hydrogen bonding in chloroform. In less polar or unpolar solvents like toluene and methylcyclohexane, and in their mixtures, these dimers further self-assemble into extended oligomeric aggregates in an anti-cooperative process in which even numbered aggregates are highly favoured. The stepwise transition from dimers into oligomers can not be properly described by conventional K 2 - K model, and thus a new K 2 - K aggregation model has been developed, which interpretes the present anti-cooperative supramolecular polymerization more appropriately. The newly developed K 2 - K model will be useful to describe self-assembly processes of a plethora of other π-conjugated molecules that are characterized by a favored dimer species.

3D Aerogel of Graphitic Carbon Nitride Modified with Perylene Imide and Graphene Oxide for Highly Efficient Nitric Oxide Removal under Visible Light.

PubMed

Hu, Jundie; Chen, Dongyun; Li, Najun; Xu, Qingfeng; Li, Hua; He, Jinghui; Lu, Jianmei

2018-05-01

3D materials are considered promising for photocatalytic applications in air purification because of their large surface areas, controllability, and recyclability. Here, a series of aerogels consisting of graphitic-carbon nitride (g-C 3 N 4 ) modified with a perylene imide (PI) and graphene oxide (GO) are prepared for nitric oxide (NO) removal under visible-light irradiation. All of the photocatalysts exhibit excellent activity in NO removal because of the strong light absorption and good planarity of PI-g-C 3 N 4 coupled with the favorable charge transport properties of GO, which slow the recombination of electron-hole pairs. The aerogel containing thiophene displays the most efficient NO removal of the aerogel series, with a removal ratio of up to 66%. Density functional theory calculations are conducted to explain this result and recycling experiments are carried out to verify the stability and recyclability of these photocatalysts. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Effect of Reduction Potential on the Generation of the Perylene Diimide Radical Anions

NASA Astrophysics Data System (ADS)

Zhao, Y. Z.; Li, K. X.; Ding, S. Y.; Zhu, M.; Ren, H. P.; Ma, Q.; Guo, Z.; Tian, S. P.; Zhang, H. Q.; Miao, Z. C.

2018-07-01

Perylene diimide derivatives (PDIs) with different substituents in the bay positions (Un-PDI, DFPDI and THBPDI) were chosen in this report to investigate the effect of potential on the reduction of PDIs through base (hydrazine, 1,2-ethanediamine and triethylamine)-driven keto-enol anion tautomerism. The reduction potentials (PDI/PDI•-) of these compounds determined via cyclic voltammetry are -0.51, ‒0.34, and -0.098 V for Un-PDI, DFPDI, and THBPDI, respectively. The reduction of Un-PDI, DFPDI and THBPDI by hydrazine can produce corresponding radical anions and dianions, but the volume of hydrazine added at which the radicals started to appear is different and depends on their reduction potential. The similar phenomenon was observed using 1,2-ethylenediamine and triethylamine. However, only the radical anion was obtained even in a large excess of 1,2-ethanediamine or triethylamine. Moreover, the reduction of these PDIs with different bases added in the same amount was investigated, and the correlation with their basicity was shown.

Conjugated ionic state and its distribution in perylene bisimide doped film: A characterization of Z-scanning in confocal Raman spectroscopy.

PubMed

Zhou, Xuehong; Zhang, Wenqiang; Wang, Cong; Zhou, Jiadong; Liu, Linlin; Xie, Zengqi; Ma, Yuguang

2018-04-27

Ion-doped states are significant for improving the performance in organic semiconductor-based devices, which require clear characterization to understand their relationship with conductivity and charge transporting mechanisms. In this paper, Raman spectroscopy is used to track the evolution of a dianion-anion-neutral mixture in a perylene bisimide (PBI)-doped film under air, with z-scanning carried out in the confocal mode. The precise distribution for the different states along the film depth is realized within 3.5 μm. The whole film is clearly divided into three regions: the ion-poor state, transition region and ion-rich state. The ion ratio and distribution are strongly related to the film conductivity and the onset voltage shift. Changes in the distribution of the ionic species during oxidation and electrode catalysis are clearly recorded by z-scanning, which is beneficial for understanding the charge transfer properties as well as the mechanism underlying working devices. Copyright © 2018 Elsevier B.V. All rights reserved.

Photoelectrochemical processes in organic semiconductor: Ambipolar perylene diimide thin film

NASA Astrophysics Data System (ADS)

Kim, Jung Yong; Chung, In Jae

2018-03-01

A thin film of N,N‧-dioctadecyl-3,4,9,10-perylene tetracarboxylic diimide (PTCDI-C18) is spin-coated on indium tin oxide (ITO) glass. Using the PTCDI-C18/ITO electrode, we fabricate a photoelectrochemical cell with the ITO/PTCDI-C18/Redox Electrolyte/Pt configuration. The electrochemical properties of this device are investigated as a function of hydroquinone (HQ) concentration, bias voltage, and wavelength of light. Anodic photocurrent is observed at V ≥ -0.2 V vs. Ag/AgCl, indicating that the PTCDI-C18 film acts as an n-type semiconductor as usual. However, when benzoquinone (BQ) is inserted into the electrolyte system instead of HQ, cathodic photocurrent is observed at V ≤ 0.0 V, displaying that PTCDI-C18 abnormally serves as a p-type semiconductor. Hence the overall results reveal that the PTCDI-C18 film can be an ambipolar functional semiconductor depending on the redox couple in the appropriate voltage.

Enhancement of the Rate Capability of LiFePO4 by a New Highly Graphitic Carbon-Coating Method.

PubMed

Song, Jianjun; Sun, Bing; Liu, Hao; Ma, Zhipeng; Chen, Zhouhao; Shao, Guangjie; Wang, Guoxiu

2016-06-22

Low lithium ion diffusivity and poor electronic conductivity are two major drawbacks for the wide application of LiFePO4 in high-power lithium ion batteries. In this work, we report a facile and efficient carbon-coating method to prepare LiFePO4/graphitic carbon composites by in situ carbonization of perylene-3,4,9,10-tetracarboxylic dianhydride during calcination. Perylene-3,4,9,10-tetracarboxylic dianhydride containing naphthalene rings can be easily converted to highly graphitic carbon during thermal treatment. The ultrathin layer of highly graphitic carbon coating drastically increased the electronic conductivity of LiFePO4. The short pathway along the [010] direction of LiFePO4 nanoplates could decrease the Li(+) ion diffusion path. In favor of the high electronic conductivity and short lithium ion diffusion distance, the LiFePO4/graphitic carbon composites exhibit an excellent cycling stability at high current rates at room temperature and superior performance at low temperature (-20 °C).

Fine-Tuning the Quasi-3D Geometry: Enabling Efficient Nonfullerene Organic Solar Cells Based on Perylene Diimides.

PubMed

Liu, Zhitian; Zhang, Linhua; Shao, Ming; Wu, Yao; Zeng, Di; Cai, Xiang; Duan, Jiashun; Zhang, Xiaolu; Gao, Xiang

2018-01-10

The geometries of acceptors based on perylene diimides (PDIs) are important for improving the phase separation and charge transport in organic solar cells. To fine-tune the geometry, biphenyl, spiro-bifluorene, and benzene were used as the core moiety to construct quasi-three-dimensional nonfullerene acceptors based on PDI building blocks. The molecular geometries, energy levels, optical properties, photovoltaic properties, and exciton kinetics were systematically studied. The structure-performance relationship was discussed as well. Owing to the finest phase separation, the highest charge mobility and smallest nongeminate recombination, the power conversion efficiency of nonfullerene solar cells using PDI derivatives with biphenyl core (BP-PDI 4 ) as acceptor reached 7.3% when high-performance wide band gap donor material poly[(2,6-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-benzo[1,2-b:4,5-b']dithiophene))-alt-(5,5-(1',3'-di-2-thienyl-5',7'-bis(2-ethylhexyl)benzo[1',2'-c:4',5'-c']dithiophene-4,8-dione))] was blended.

Morphological Transformation between Nanocoils and Nanoribbons via Defragmentation Structural Rearrangement or Fragmentation-recombination Mechanism

NASA Astrophysics Data System (ADS)

Zhang, Yibin; Zheng, Yingxuan; Xiong, Wei; Peng, Cheng; Zhang, Yifan; Duan, Ran; Che, Yanke; Zhao, Jincai

2016-06-01

Kinetic control over the assembly pathways towards novel metastable functional materials or far-from-equilibrium systems has been much less studied compared to the thermodynamic equilibrium self-assembly. Herein, we report the distinct morphological transformation between nanocoils and nanoribbons in the self-assembly of unsymmetric perylene diimide (PDI) molecules. We demonstrate that the morphological transformation of the kinetically trapped assemblies into the thermodynamically stable forms proceeds via two distinct mechanisms, i.e., a direct structural rearrangement (molecule 1 or 2) and a fragmentation-recombination mechanism (molecule 4), respectively. The subtle interplay of the steric hindrance of the bulky substituents and the flexibility of the linker structure between the bulky moiety and the perylene core was demonstrated to enable the effective modulation of the energetic landscape of the assemblies and thus modulation of the assembly pathways. Herein, our work presents a new approach to control the self-assembly pathways and thereby can be used to achieve novel far-from-equilibrium systems.

D1((2)B2g) to D0((2)Au) Fluorescence from the Matrix-Isolated Perylene Cation Following Laser Excitation into the D5(2)B3g) and D2 ((2)B3g) Electronic States

NASA Technical Reports Server (NTRS)

Chillier, Xavier D. F.; Stone, Bradley M.; Joblin, Christine; Salama, Farid; Allamandola, Louis J.; DeVincenzi, Donald L. (Technical Monitor)

2001-01-01

Fluorescence spectra of the perylene cation, pumped by direct laser excitation via the D(sub 2)((2)B(sub 3g)) (left arrow) D(sub 0)((2)A(sub u)) and D(sub 5)(2)B(sub 3g)) (left arrow) D(sub 0)((2)A(sub u)) transitions, are presented. Direct excitation into the D5 or D2 states is followed by rapid non-radiative relaxation to D1 that, in turn,relaxes radiatively. Excitation spectroscopy across the D(sub 2)((2)B(sub 3g)) (left arrow) D(sub 0)((2)A(sub u)) transition near 730 nm shows that site splitting plays little or no role in determining the spectral substructure in the ion spectra. Tentative assignments for ground state vibrational frequencies are made by comparison of spectral intervals with calculated normal mode frequencies.

Distinct Interfacial Fluorescence in Oil-in-Water Emulsions via Exciton Migration of Conjugated Polymers.

PubMed

Koo, Byungjin; Swager, Timothy M

2017-09-01

Commercial dyes are extensively utilized to stain specific phases for the visualization applications in emulsions and bioimaging. In general, dyes emit only one specific fluorescence signal and thus, in order to stain various phases and/or interfaces, one needs to incorporate multiple dyes and carefully consider their compatibility to avoid undesirable interactions with each other and with the components in the system. Herein, surfactant-type, perylene-endcapped fluorescent conjugated polymers that exhibit two different emissions are reported, which are cyan in water and red at oil-water interfaces. The interfacially distinct red emission results from enhanced exciton migration from the higher-bandgap polymer backbone to the lower-bandgap perylene endgroup. The confocal microscopy images exhibit the localized red emission exclusively from the circumference of oil droplets. This exciton migration and dual fluorescence of the polymers in different physical environments can provide a new concept of visualization methods in many amphiphilic colloidal systems and bioimaging. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Direct observation of ultrafast coherent exciton dynamics in helical π-stacks of self-assembled perylene bisimides

PubMed Central

Sung, Jooyoung; Kim, Pyosang; Fimmel, Benjamin; Würthner, Frank; Kim, Dongho

2015-01-01

Ever since the discovery of dye self-assemblies in nature, there have been tremendous efforts to exploit biomimetic supramolecular assemblies for tailored artificial photon processing materials. This feature necessarily has resulted in an increasing demand for understanding exciton dynamics in the dye self-assemblies. In a sharp contrast with J-type aggregates, however, the detailed observation of exciton dynamics in H-type aggregates has remained challenging. In this study, as we succeed in measuring transient fluorescence from Frenkel state of π-stacked perylene tetracarboxylic acid bisimide dimer and oligomer aggregates, we present an experimental demonstration on Frenkel exciton dynamics of archetypal columnar π–π stacks of dyes. The analysis of the vibronic peak ratio of the transient fluorescence spectra reveals that unlike the simple π-stacked dimer, the photoexcitation energy in the columnar π-stacked oligomer aggregates is initially delocalized over at least three molecular units and moves coherently along the chain in tens of femtoseconds, preceding excimer formation process. PMID:26492820

Temperature-dependent vibrational spectroscopy to study order-disorder transitions in charge transfer complexes

NASA Astrophysics Data System (ADS)

Isaac, Rohan; Goetz, Katelyn P.; Roberts, Drew; Jurchescu, Oana D.; McNeil, L. E.

2018-02-01

Charge-transfer (CT) complexes are a promising class of materials for the semiconductor industry because of their versatile properties. This class of compounds shows a variety of phase transitions, which are of interest because of their potential impact on the electronic characteristics. Here temperature-dependent vibrational spectroscopy is used to study structural phase transitions in a set of organic CT complexes. Splitting and broadening of infrared-active phonons in the complex formed between pyrene and pyromellitic dianhydride (PMDA) confirm the structural transition is of the order-disorder type and complement previous x-ray diffraction (XRD) results. We show that this technique is a powerful tool to characterize transitions, and apply it to a range of binary CT complexes composed of polyaromatic hyrdocarbons (anthracene, perylene, phenanthrene, pyrene, and stilbene) and PMDA. We extend the understanding of transitions in perylene-PMDA and pyrene-PMDA, and show that there are no order-disorder transitions present in anthracene-PMDA, stilbene-PMDA and phenanthrene-PMDA in the temperature range investigated here.

Interaction between perylene-derivated molecules observed by low temperature scanning tunneling microscopy

NASA Astrophysics Data System (ADS)

Vernisse, Loranne; Guillermet, Olivier; Gourdon, André; Coratger, Roland

2018-03-01

Derivative perylene molecules deposited on Ag(111) and on NaCl(001) ultrathin layers have been investigated using low temperature STM and NC-AFM. When the metallic substrate is held at ambient temperature during evaporation, the molecules form characteristic trimers on the Ag(111) surface and interact through their polar groups. Close to the steps, the molecules form linear structures and seems to stand side by side. On the other hand, after deposition on a substrate cooled at liquid helium temperature, single molecules are observed both on metal and on NaCl. On the ultrathin insulator layers, the STM images present characteristic contrasts related to the molecular orbitals which favors the localization of aldehyde groups. In this case, the lateral molecular interactions may induce the formation of small assemblies in which the electronic levels are slightly shifted. A possible interpretation of this phenomenon is to take into account polar interactions and charge transfer between neighboring molecules.

Perylene bisimide hydrogels and lyotropic liquid crystals with temperature-responsive color change† †Electronic supplementary information (ESI) available: Detailed procedures and results for all reported experiments, along with synthetic details for PBI 1. See DOI: 10.1039/c6sc02249a Click here for additional data file.

PubMed Central

Görl, Daniel; Soberats, Bartolome; Herbst, Stefanie; Stepanenko, Vladimir

2016-01-01

The self-assembly of perylene bisimide (PBI) dyes bearing oligo ethylene glycol (OEG) units in water affords responsive functional nanostructures characterized by their lower critical solution temperature (LCST). Tuning of the LCST is realized by a supramolecular approach that relies on two structurally closely related PBI–OEG molecules. The two PBIs socially co-assemble in water and the resulting nanostructures exhibit a single LCST in between the transition temperatures of the aggregates formed by single components. This permits to precisely tune the transition from a hydrogel to a lyotropic liquid crystal state at temperatures between 26 and 51 °C by adjusting the molar fraction of the two PBIs. Owing to concomitant changes in PBI–PBI interactions this phase transition affords a pronounced color change with “fluorescence-on” response that can be utilized as a smart temperature sensory system. PMID:28451124

Visualization of Membrane Rafts Using a Perylene Monoimide Derivative and Fluorescence Lifetime Imaging

PubMed Central

Margineanu, Anca; Hotta, Jun-ichi; Van der Auweraer, Mark; Ameloot, Marcel; Stefan, Alina; Beljonne, David; Engelborghs, Yves; Herrmann, Andreas; Müllen, Klaus; De Schryver, Frans C.; Hofkens, Johan

2007-01-01

A new membrane probe, based on the perylene imide chromophore, with excellent photophysical properties (high absorption coefficient, quantum yield (QY) ≈ 1, high photostability) and excited in the visible domain is proposed for the study of membrane rafts. Visualization of separation between the liquid-ordered (Lo) and the liquid-disordered (Ld) phases can be achieved in artificial membranes by fluorescence lifetime imaging due to the different decay times of the membrane probe in the two phases. Rafts on micrometer-scale in cell membranes due to cellular activation can also be observed by this method. The decay time of the dye in the Lo phase is higher than in organic solvents where its QY is 1. This allows proposing a (possible general) mechanism for the decay time increase in the Lo phase, based on the local field effects of the surrounding molecules. For other fluorophores with QY < 1, the suggested mechanism could also contribute, in addition to effects reducing the nonradiative decay pathways, to an increase of the fluorescence decay time in the Lo phase. PMID:17573424

Tethered tertiary amines as solid-state n-type dopants for solution-processable organic semiconductors

DOE PAGES

Russ, Boris; Robb, Maxwell J.; Popere, Bhooshan C.; ...

2015-12-09

A scarcity of stable n-type doping strategies compatible with facile processing has been a major impediment to the advancement of organic electronic devices. Localizing dopants near the cores of conductive molecules can lead to improved efficacy of doping. We and others recently showed the effectiveness of tethering dopants covalently to an electron-deficient aromatic molecule using trimethylammonium functionalization with hydroxide counterions linked to a perylene diimide core by alkyl spacers. In this work, we demonstrate that, contrary to previous hypotheses, the main driver responsible for the highly effective doping observed in thin films is the formation of tethered tertiary amine moietiesmore » during thin film processing. Furthermore, we demonstrate that tethered tertiary amine groups are powerful and general n-doping motifs for the successful generation of free electron carriers in the solid-state, not only when coupled to the perylene diimide molecular core, but also when linked with other small molecule systems including naphthalene diimide, diketopyrrolopyrrole, and fullerene derivatives. Our findings help expand a promising molecular design strategy for future enhancements of n-type organic electronic materials.« less

Tethered tertiary amines as solid-state n-type dopants for solution-processable organic semiconductors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Russ, Boris; Robb, Maxwell J.; Popere, Bhooshan C.

A scarcity of stable n-type doping strategies compatible with facile processing has been a major impediment to the advancement of organic electronic devices. Localizing dopants near the cores of conductive molecules can lead to improved efficacy of doping. We and others recently showed the effectiveness of tethering dopants covalently to an electron-deficient aromatic molecule using trimethylammonium functionalization with hydroxide counterions linked to a perylene diimide core by alkyl spacers. In this work, we demonstrate that, contrary to previous hypotheses, the main driver responsible for the highly effective doping observed in thin films is the formation of tethered tertiary amine moietiesmore » during thin film processing. Furthermore, we demonstrate that tethered tertiary amine groups are powerful and general n-doping motifs for the successful generation of free electron carriers in the solid-state, not only when coupled to the perylene diimide molecular core, but also when linked with other small molecule systems including naphthalene diimide, diketopyrrolopyrrole, and fullerene derivatives. Our findings help expand a promising molecular design strategy for future enhancements of n-type organic electronic materials.« less

Perylene Diimide Based ``Nanofabric'' Thin Films for Organic Photovoltaic Cells

NASA Astrophysics Data System (ADS)

Carter, Austin; Park, June Hyoung; Min, Yong; Epstein, Arthur

2011-03-01

We report progress in using a perylene diimide (PDI) nanofabric as an effective electron accepting nanostructure for organic photovoltaics (OPV). A key challenge in OPV continues to be the recovery of electrons after charge separation due to the relatively poor mobility of C60 and related materials. A series of PDI compounds and complexes have been synthesized and used to fabricate nanofibers and thin films using solution and vacuum deposition techniques. Overlaping PDI-based nanofibers form a fast electron-transporting ``nanofabric'' that has been characterized (AFM, PL, UV-vis, etc.) and can be blended with electron donating materials. A solution-processible OPV configuration containing a nanofabric heterojunction (FHJ) of poly(3-hexylthiophene) and the PDI nanofabric was investigated. We observed a significant improvement in power-conversion efficiency due in part to expansion of the interfacial area and the presence of high mobility electron pathways to the LiF/Al electrode. This work is supported by the Wright Center for Photovoltaic Innovation and Commercialization, the Institute for Materials Research and the Center for Affordable Nanoengineering of Polymeric Biomedical Devices.

Excited-State Vibrational Coherence in Perylene Bisimide Probed by Femtosecond Broadband Pump-Probe Spectroscopy.

PubMed

Son, Minjung; Park, Kyu Hyung; Yoon, Min-Chul; Kim, Pyosang; Kim, Dongho

2015-06-18

Broadband laser pulses with ultrashort duration are capable of triggering impulsive excitation of the superposition of vibrational eigenstates, giving rise to quantum beating signals originating from coherent wave packet motions along the potential energy surface. In this work, coherent vibrational wave packet dynamics of an N,N'-bis(2,6-dimethylphenyl)perylene bisimide (DMP-PBI) were investigated by femtosecond broadband pump-probe spectroscopy which features fast and balanced data acquisition with a wide spectral coverage of >200 nm. Clear modulations were observed in the envelope of the stimulated emission decay profiles of DMP-PBI with the oscillation frequencies of 140 and 275 cm(-1). Fast Fourier transform analysis of each oscillatory mode revealed characteristic phase jumps near the maxima of the steady-state fluorescence, indicating that the observed vibrational coherence originates from an excited-state wave packet motion. Quantum calculations of the normal modes at the low-frequency region suggest that low-frequency C-C (C═C) stretching motions accompanied by deformation of the dimethylphenyl substituents are responsible for the manifestation of such coherent wave packet dynamics.

High-performance air-stable n-channel organic thin film transistors based on halogenated perylene bisimide semiconductors.

PubMed

Schmidt, Rüdiger; Oh, Joon Hak; Sun, Ya-Sen; Deppisch, Manuela; Krause, Ana-Maria; Radacki, Krzysztof; Braunschweig, Holger; Könemann, Martin; Erk, Peter; Bao, Zhenan; Würthner, Frank

2009-05-06

The syntheses and comprehensive characterization of 14 organic semiconductors based on perylene bisimide (PBI) dyes that are equipped with up to four halogen substituents in the bay area of the perylene core and five different highly fluorinated imide substituents are described. The influence of the substituents on the LUMO level and the solid state packing of PBIs was examined by cyclic voltammetry and single crystal structure analyses of seven PBI derivatives, respectively. Top-contact/bottom-gate organic thin film transistor (OTFT) devices were constructed by vacuum deposition of these PBIs on SiO(2) gate dielectrics that had been pretreated with n-octadecyl triethoxysilane in vapor phase (OTS-V) or solution phase (OTS-S). The electrical characterization of all devices was accomplished in a nitrogen atmosphere as well as in air, and the structural features of thin films were explored by grazing incidence X-ray diffraction (GIXD) and atomic force microscopy (AFM). Several of those PBIs that bear only hydrogen or up to two fluorine substitutents at the concomitantly flat PBI core afforded excellent n-channel transistors, in particular, on OTS-S substrate and even in air (mu > 0.5 cm(2) V(-1) s(-1); I(on)/I(off) > 10(6)). The best OTFTs were obtained for 2,2,3,3,4,4,4-heptafluorobutyl-substituted PBI 1a ("PTCDI-C4F7") on OTS-S with n-channel field effect mobilities consistently >1 cm(2) V(-1) s(-1) and on-to-off current rations of 10(6) in a nitrogen atmosphere and in air. For distorted core-tetrahalogenated (fluorine, chlorine, or bromine) PBIs, less advantageous solid state packing properties were found and high performance OTFTs were obtained from only one tetrachlorinated derivative (2d on OTS-S). The excellent on-to-off current modulation combined with high mobility in air makes these PBIs suitable for a wide range of practical applications.

Applications of Nonlinear Hole Burning Spectroscopy.

DTIC Science & Technology

1987-08-31

benerate a spectral hole through the generation of phonons interacting with the local environment of the surrounding glass. The key advantage to this...phthalocyanine, porphine, octaethylporphine, tetraphenylporphine, pentacene , and perylene. The host materials included methyl tetrahydrofuran, n-octane, benzoic...polymethyl methacrylate doped with either pentacene or phthalocyanne. There were also a number of experimental difficulties that had to be addressed

Self-assembled containers based on extended tetrathiafulvalene.

PubMed

Bivaud, Sébastien; Goeb, Sébastien; Croué, Vincent; Dron, Paul I; Allain, Magali; Sallé, Marc

2013-07-10

Two original self-assembled containers constituted each by six electroactive subunits are described. They are synthesized from a concave tetratopic π-extended tetrathiafulvalene ligand bearing four pyridyl units and cis-M(dppf)(OTf)2 (M = Pd or Pt; dppf = 1,1'-bis(diphenylphosphino)ferrocene; OTf = trifluoromethane-sulfonate) complexes. Both fully characterized assemblies present an oblate spheroidal cavity that can incorporate one perylene molecule.

Soft plasma processing of organic nanowires: a route for the fabrication of 1D organic heterostructures and the template synthesis of inorganic 1D nanostructures.

PubMed

Alcaire, Maria; Sanchez-Valencia, Juan R; Aparicio, Francisco J; Saghi, Zineb; Gonzalez-Gonzalez, Juan C; Barranco, Angel; Zian, Youssef Oulad; Gonzalez-Elipe, Agustin R; Midgley, Paul; Espinos, Juan P; Groening, Pierangelo; Borras, Ana

2011-11-01

Hierarchical (branched) and hybrid metal-NPs/organic supported NWs are fabricated through controlled plasma processing of metalloporphyrin, metallophthalocyanine and perylene nanowires. The procedure is also applied for the development of a general template route for the synthesis of supported metal and metal oxide nanowires.

Ultrafast Exciton Delocalization, Localization, and Excimer Formation Dynamics in a Highly Defined Perylene Bisimide Quadruple π-Stack.

PubMed

Kaufmann, Christina; Kim, Woojae; Nowak-Król, Agnieszka; Hong, Yongseok; Kim, Dongho; Würthner, Frank

2018-03-28

An adequately designed, bay-tethered perylene bisimide (PBI) dimer Bis-PBI was synthesized by Pd/Cu-catalyzed Glaser-type oxidative homocoupling of the respective PBI building block. This newly synthesized PBI dimer self-assembles exclusively and with high binding constants of up to 10 6 M -1 into a discrete π-stack of four chromophores. Steady-state absorption and emission spectra show the signatures of H-type excitonic coupling among the dye units. Broadband fluorescence upconversion spectroscopy (FLUPS) reveals an ultrafast dynamics in the optically excited state. An initially coherent Frenkel exciton state that is delocalized over the whole quadruple stack rapidly (τ = ∼200 fs) loses its coherence and relaxes into an excimer state. Comparison with Frenkel exciton dynamics in PBI dimeric and oligomeric H-aggregates demonstrates that in the quadruple stack coherent exciton propagation is absent due to its short length of aggregates, thereby it has only one relaxation pathway to the excimer state. Furthermore, the absence of pump-power dependence in transient absorption experiments suggests that multiexciton cannot be generated in the quadruple stack, which is in line with time-resolved fluorescence measurements.

On the possibility of singlet fission in crystalline quaterrylene

NASA Astrophysics Data System (ADS)

Wang, Xiaopeng; Liu, Xingyu; Cook, Cameron; Schatschneider, Bohdan; Marom, Noa

2018-05-01

Singlet fission (SF), the spontaneous down-conversion of a singlet exciton into two triplet excitons residing on neighboring molecules, is a promising route to improve organic photovoltaic (OPV) device efficiencies by harvesting two charge carriers from one photon. However, only a few materials have been discovered that exhibit intermolecular SF in the solid state, most of which are acene derivatives. Recently, there has been a growing interest in rylenes as potential SF materials. We use many-body perturbation theory in the GW approximation and the Bethe-Salpeter equation to investigate the possibility of intermolecular SF in crystalline perylene and quaterrylene. A new method is presented for determining the percent charge transfer (%CT) character of an exciton wave-function from double-Bader analysis. This enables relating exciton probability distributions to crystal packing. Based on comparison to known and predicted SF materials with respect to the energy conservation criterion (ES-2ET) and %CT, crystalline quaterrylene is a promising candidate for intermolecular SF. Furthermore, quaterrylene is attractive for OPV applications, thanks to its high stability and narrow optical gap. Perylene is not expected to exhibit SF; however, it is a promising candidate for harvesting sub-gap photons by triplet-triplet annihilation.

New fluorescent perylene bisimide indicators--a platform for broadband pH optodes.

PubMed

Aigner, Daniel; Borisov, Sergey M; Klimant, Ingo

2011-06-01

Asymmetric perylene bisimide (PBI) dyes are prepared and are shown to be suitable for the preparation of fluorescence chemosensors for pH. They carry one amino-functional substituent which introduces pH sensitivity via photoinduced electron transfer (PET) while the other one increases solubility. The luminescence quantum yields for the new indicators exceed 75% in the protonated form. The new indicators are non-covalently entrapped in polyurethane hydrogel D4 and poly(hydroxyalkylmethacrylates). Several PET functions including aliphatic and aromatic amino groups were successfully used to tune the dynamic range of the sensor. Because of their virtually identical spectral properties, various PBIs with selected PET functions can easily be integrated into a single sensor with enlarged dynamic range (over 4 pH units). PBIs with two different substitution patterns in the bay position are investigated and possess variable spectral properties. Compared with their tetrachloro analogues, tetra-tert-butyl-substituted PBIs yield more long-wave excitable sensors which feature excellent photostability. Cross-sensitivity to ionic strength was found to be negligible. The practical applicability of the sensors may be compromised by the long response times (especially in case of tetra-tert-butyl-substituted PBIs).

Chiral J-aggregates of atropo-enantiomeric perylene bisimides and their self-sorting behavior.

PubMed

Xie, Zengqi; Stepanenko, Vladimir; Radacki, Krzysztof; Würthner, Frank

2012-06-04

Herein we report on structural, morphological, and optical properties of homochiral and heterochiral J-aggregates that were created by nucleation-elongation assembly of atropo-enantiomerically pure and racemic perylene bisimides (PBIs), respectively. Our detailed studies with conformationally stable biphenoxy-bridged chiral PBIs by UV/Vis absorption, circular dichroism (CD) spectroscopy, and atomic force microscopy (AFM) revealed structurally as well as spectroscopically quite different kinds of J-aggregates for enantiomerically pure and racemic PBIs. AFM investigations showed that enantiopure PBIs form helical nanowires of unique diameter and large length-to-width ratio by self-recognition, while racemic PBIs provide irregular-sized particles by self-discrimination of the enantiomers at the stage of nucleation. Steady-state fluorescence spectroscopy studies revealed that the photoluminescence efficiency of homochiral J-aggregated nanowires (47±3%) is significantly higher than that of heterochiral J-aggregated particle-like aggregates (12±3%), which is explained in terms of highly ordered molecular stacking in one-dimensional nanowires of homochiral J-aggregates. Our present results demonstrate the high impact of homochirality on the construction of well-defined nanostructures with unique optical properties. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Energy transfer within self-assembled cyclic multichromophoric arrays based on orthogonally arranged donor-acceptor building blocks.

PubMed

Karakostas, Nikolaos; Kaloudi-Chantzea, Antonia; Martinou, Elisabeth; Seintis, Kostas; Pitterl, Florian; Oberacher, Herbert; Fakis, Mihalis; Kallitsis, Joannis K; Pistolis, George

2015-01-01

We herein present the coordination-driven supramolecular synthesis and photophysics of a [4+4] and a [2+2] assembly, built up by alternately collocated donor-acceptor chromophoric building blocks based, respectively, on the boron dipyrromethane (Bodipy) and perylene bisimide dye (PBI). In these multichromophoric scaffolds, the intensely absorbing/emitting dipoles of the Bodipy subunit are, by construction, cyclically arranged at the corners and aligned perpendicular to the plane formed by the closed polygonal chain comprising the PBI units. Steady-state and fs time-resolved spectroscopy reveal the presence of efficient energy transfer from the vertices (Bodipys) to the edges (PBIs) of the polygons. Fast excitation energy hopping - leading to a rapid excited state equilibrium among the low energy perylene-bisimide chromophores - is revealed by fluorescence anisotropy decays. The dynamics of electronic excitation energy hopping between the PBI subunits was approximated on the basis of a theoretical model within the framework of Förster energy transfer theory. All energy-transfer processes are quantitatively describable with Förster theory. The influence of structural deformations and orientational fluctuations of the dipoles in certain kinetic schemes is discussed.

Synthesis of Perylene Imide Diones as Platforms for the Development of Pyrazine Based Organic Semiconductors.

PubMed

de Echegaray, Paula; Mancheño, María J; Arrechea-Marcos, Iratxe; Juárez, Rafael; López-Espejo, Guzmán; López Navarrete, J Teodomiro; Ramos, María Mar; Seoane, Carlos; Ortiz, Rocío Ponce; Segura, José L

2016-11-18

There is a great interest in peryleneimide (PI)-containing compounds given their unique combination of good electron accepting ability, high abosorption in the visible region, and outstanding chemical, thermal, and photochemical stabilities. Thus, herein we report the synthesis of perylene imide derivatives endowed with a 1,2-diketone functionality (PIDs) as efficient intermediates to easily access peryleneimide (PI)-containing organic semiconductors with enhanced absorption cross-section for the design of tunable semiconductor organic materials. Three processable organic molecular semiconductors containing thiophene and terthiophene moieties, PITa, PITb, and PITT, have been prepared from the novel PIDs. The tendency of these semiconductors for molecular aggregation have been investigated by NMR spectroscopy and supported by quantum chemical calculations. 2D NMR experiments and theoretical calculations point to an antiparallel π-stacking interaction as the most stable conformation in the aggregates. Investigation of the optical and electrochemical properties of the materials is also reported and analyzed in combination with DFT calculations. Although the derivatives presented here show modest electron mobilities of ∼10 -4 cm 2 V -1 s -1 , these preliminary studies of their performance in organic field effect transistors (OFETs) indicate the potential of these new building blocks as n-type semiconductors.

Organic Semiconductors based on Dyes and Color Pigments.

PubMed

Gsänger, Marcel; Bialas, David; Huang, Lizhen; Stolte, Matthias; Würthner, Frank

2016-05-01

Organic dyes and pigments constitute a large class of industrial products. The utilization of these compounds in the field of organic electronics is reviewed with particular emphasis on organic field-effect transistors. It is shown that for most major classes of industrial dyes and pigments, i.e., phthalocyanines, perylene and naphthalene diimides, diketopyrrolopyrroles, indigos and isoindigos, squaraines, and merocyanines, charge-carrier mobilities exceeding 1 cm(2) V(-1) s(-1) have been achieved. The most widely investigated molecules due to their n-channel operation are perylene and naphthalene diimides, for which even values close to 10 cm(2) V(-1) s(-1) have been demonstrated. The fact that all of these π-conjugated colorants contain polar substituents leading to strongly quadrupolar or even dipolar molecules suggests that indeed a much larger structural space shows promise for the design of organic semiconductor molecules than was considered in this field traditionally. In particular, because many of these dye and pigment chromophores demonstrate excellent thermal and (photo-)chemical stability in their original applications in dyeing and printing, and are accessible by straightforward synthetic protocols, they bear a particularly high potential for commercial applications in the area of organic electronics. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multi-source apportionment of polycyclic aromatic hydrocarbons using simultaneous linear equations

NASA Astrophysics Data System (ADS)

Marinaite, Irina; Semenov, Mikhail

2014-05-01

A new approach to identify multiple sources of polycyclic aromatic hydrocarbons (PAHs) and to evaluate the source contributions to atmospheric deposition of particulate PAHs is proposed. The approach is based on differences in concentrations of sums of PAHs with the same molecular weight among the sources. The data on PAHs accumulation in snow as well as the source profiles were used for calculations. Contributions of aluminum production plant, oil-fired central heating boilers, and residential wood and coal combustion were calculated using the linear mixing models. The concentrations of PAH pairs such as Benzo[b]fluorantene + Benzo[k]fluorantene and Benzo[g,h,i]perylene + Indeno[1,2,3-c,d]pyrene normalized to Benzo[a]antracene + Chrysene were used as tracers in mixing equations. The results obtained using ratios of sums of PAHs were compared with those obtained using molecular diagnostic ratios such as Benzo[a]antracene/Chrysene and Benzo[g,h,i]perylene/Indeno[1,2,3-c,d]pyrene. It was shown that the results obtained using diagnostic ratios as tracers are less reliable than results obtained using ratios of sums of PAHs. Funding was provided by Siberian Branch of Russian Academy of Sciences grant No. 8 (2012-2014).

On the possibility of singlet fission in crystalline quaterrylene.

PubMed

Wang, Xiaopeng; Liu, Xingyu; Cook, Cameron; Schatschneider, Bohdan; Marom, Noa

2018-05-14

Singlet fission (SF), the spontaneous down-conversion of a singlet exciton into two triplet excitons residing on neighboring molecules, is a promising route to improve organic photovoltaic (OPV) device efficiencies by harvesting two charge carriers from one photon. However, only a few materials have been discovered that exhibit intermolecular SF in the solid state, most of which are acene derivatives. Recently, there has been a growing interest in rylenes as potential SF materials. We use many-body perturbation theory in the GW approximation and the Bethe-Salpeter equation to investigate the possibility of intermolecular SF in crystalline perylene and quaterrylene. A new method is presented for determining the percent charge transfer (%CT) character of an exciton wave-function from double-Bader analysis. This enables relating exciton probability distributions to crystal packing. Based on comparison to known and predicted SF materials with respect to the energy conservation criterion (E S -2E T ) and %CT, crystalline quaterrylene is a promising candidate for intermolecular SF. Furthermore, quaterrylene is attractive for OPV applications, thanks to its high stability and narrow optical gap. Perylene is not expected to exhibit SF; however, it is a promising candidate for harvesting sub-gap photons by triplet-triplet annihilation.

Rigid amphipathic fusion inhibitors demonstrate antiviral activity against African swine fever virus.

PubMed

Hakobyan, Astghik; Galindo, Inmaculada; Nañez, Almudena; Arabyan, Erik; Karalyan, Zaven; Chistov, Alexey A; Streshnev, Philipp P; Korshun, Vladimir A; Alonso, Covadonga; Zakaryan, Hovakim

2018-01-01

Rigid amphipathic fusion inhibitors (RAFIs) are a family of nucleoside derivatives that inhibit the infectivity of several enveloped viruses by interacting with virion envelope lipids and inhibiting fusion between viral and cellular membranes. Here we tested the antiviral activity of two RAFIs, 5-(Perylen-3-ylethynyl)-arabino-uridine (aUY11) and 5-(Perylen-3-ylethynyl)uracil-1-acetic acid (cm1UY11) against African swine fever virus (ASFV), for which no effective vaccine is available. Both compounds displayed a potent, dose-dependent inhibitory effect on ASFV infection in Vero cells. The major antiviral effect was observed when aUY11 and cm1UY11 were added at early stages of infection and maintained during the complete viral cycle. Furthermore, virucidal assay revealed a significant extracellular anti-ASFV activity for both compounds. We also found decrease in the synthesis of early and late viral proteins in Vero cells treated with cm1UY11. Finally, the inhibitory effect of aUY11 and cm1UY11 on ASFV infection in porcine alveolar macrophages was confirmed. Overall, our study has identified novel anti-ASFV compounds with potential for future therapeutic developments.

Self-sorted photoconductive xerogels† †Electronic supplementary information (ESI) available: Full experimental details, rheological data, pK a titrations, further NMR data, full details of the photoconductivity set-up, further photoconductivity measurements. See DOI: 10.1039/c6sc02644c Click here for additional data file.

PubMed Central

Draper, Emily R.; Lee, Jonathan R.; Wallace, Matthew; Jäckel, Frank; Cowan, Alexander J.

2016-01-01

We show that a perylene bisimide (PBI)-based gelator forms self-sorted mixtures with a stilbene-based gelator. To form the self-sorted gels, we use a slow pH change induced by the hydrolysis of glucono-δ-lactone (GdL) to gluconic acid. We prove that self-sorting occurs using NMR spectroscopy, UV-Vis spectroscopy, rheology, and viscometry. The corresponding xerogels are photoconductive. Importantly, the wavelength dependence of the photoconductive films is different to that of the films formed from the perylene bisimide alone. Transient absorption spectroscopy of the xerogels reveals changes in the spectrum of the PBI on the picosecond timescale in the presence of stilbene with a PBI radical anion being formed within 10 ps when the stilbene is present. The ability to form the PBI radical anion under visible light leads to the enhanced spectral response of the multicomponent gels. These systems therefore have potential as useful visible-active optoelectronics. PMID:28451108

Electron Acceptors Based on α-Substituted Perylene Diimide (PDI) for Organic Solar Cells

DOE PAGES

Zhao, Donglin; Wu, Qinghe; Cai, Zhengxu; ...

2016-02-20

The ortho-position functionalized perylene diimide derivatives (αPPID, αPBDT) were synthesized and used as the electron acceptors in nonfullerene organic photovoltaics. Due to the good planarity of ortho-position functionalized PDI, the αPPID and αPBDT show strong tendency to form aggregate because of their enhanced intermolecular pie-pie interaction. Moreover, they maintain the pure domains and the same packing order as in the pure film if they are blended with PBT7-TH and the SCLC measurement also shows the high electron mobility. The inverted OPVs employing αPDI-based compounds as acceptor and PBT7-TH as the donor give the highest PCE of 4.92 % for αPBDTmore » based device and 3.61 % for αPPID based device, which is 39 % and 4 % higher than that for their counterpart βPBDT and βPPID. The charge separation study shows the more efficient exciton dissociation at interfaces between PDI based compounds and PBT7-TH. In conclusion, the results suggest that compared to beta-substituted ones, alpha-substituted PDI derivatives are more promising electron acceptors for OPV.« less

Silicon/organic hybrid heterojunction infrared photodetector operating in the telecom regime.

PubMed

Bednorz, Mateusz; Matt, Gebhard J; Głowacki, Eric D; Fromherz, Thomas; Brabec, Christoph J; Scharber, Markus C; Sitter, Helmut; Sariciftci, N Serdar

2013-05-01

The authors report on the fabrication of a silicon/organic heterojunction based IR photodetector. It is demonstrated that an Al/ p -Si/perylene-derivative/Al heterostructure exhibits a photovoltaic effect up to 2.7 μm (0.46 eV), a value significantly lower than the bandgap of either material. Although the devices are not optimized, at room temperature a rise time of 300 ns, a responsivity of ≈0.2 mA/W with a specific detectivity of D ∗  ≈ 7 × 10 7 Jones at 1.55 μm is found. The achieved responsivity is two orders of magnitude higher compared to our previous efforts [1,2]. It will be outlined that the photocurrent originates from an absorption mechanism involving excitation of an electron from the Si valence band into the extended LUMO state in the perylene-derivative, with possible participation of intermediate localized surface state in the organic material. The non-invasive deposition of the organic interlayer onto the Si results in compatibility with the CMOS process, making the presented approach a potential alternative to all inorganic device concepts.

Effect of the Molecular Configuration of Perylene Diimide Acceptors on Charge Transfer and Device Performance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qu, Jianfei; Mu, Zhao; Lai, Hanjian

Three perylene diimides (PDI)-based small molecules, T2-SePDI2, T3B-SePDI3, and T4B-SePDI4, with different molecular configurations are synthesized. Due to a large steric hindrance, the molecular configuration of T3B-SePDI3 is the most distorted, followed by T4BSePDI4, while T2-SePDI2 shows the smallest steric hindrance. Inverted bulk heterojunction solar cells based on T3B-SePDI3 and PBDB-T show the highest power conversion efficiency (PCE) of 5.82% with an open-circuit voltage of 0.98 V, a high short-circuit current density of 10.52 mA/cm2, and a fill factor of 56.31%. The PCEs of the T2-SePDI2- and T4B-SePDI4- based devices are 4.10% and 5.10%, respectively. Furthermore, the results demonstrate thatmore » the molecular configuration of the PDI-based small molecule acceptor is critical and that increasing the steric hindrance is helpful in suppressing aggregation and improving device performance.« less

Assessment of atmospheric distribution of polycyclic aromatic hydrocarbons using a molecular structure model

NASA Astrophysics Data System (ADS)

Turk Sekulić, Maja; Okuka, Marija; Šenk, Nevena; Radonić, Jelena; Vojinović Miloradov, Mirjana; Vidicki, Branko

2013-07-01

In this paper, a comparison of experimentally obtained and SPARC software v4.6 modelled values of gas/particle partitioning coefficients was conducted to determine whether the evaluation of atmospheric distribution of PAH molecules can be performed using a molecular structure model. Partitioning coefficients were calculated for sixteen EPA PAHs, in thirty-nine samples of ambient air collected at nineteen urban, industrial, highly contaminated and background sites in the Republic of Serbia and Bosnia and Herzegovina. For obtaining samples of ambient air, the conventional high volume (Hi-Vol) methodology was applied, whereby gaseous and particulate phase data collection was conducted simultaneously by glass fibre filters (GFFs) and polyurethane foam filters (PUFs). The best prediction was for PAHs with 5 or more rings (benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, indeno(1,2,3-cd)perylene and benzo(ghi)perylene). For evaluating the applicability of SPARC software predictions of gas/particle partitioning coefficients for the existing conditions, the results were compared with those obtained by applying other frequently used and highly ranked theoretical models of phase distributions, namely Junge-Pankow adsorption model, KOA absorption model, Dachs-Eisenreich dual model and PP-LFER model.

Effect of the Molecular Configuration of Perylene Diimide Acceptors on Charge Transfer and Device Performance

DOE PAGES

Qu, Jianfei; Mu, Zhao; Lai, Hanjian; ...

2018-01-25

Three perylene diimides (PDI)-based small molecules, T2-SePDI2, T3B-SePDI3, and T4B-SePDI4, with different molecular configurations are synthesized. Due to a large steric hindrance, the molecular configuration of T3B-SePDI3 is the most distorted, followed by T4BSePDI4, while T2-SePDI2 shows the smallest steric hindrance. Inverted bulk heterojunction solar cells based on T3B-SePDI3 and PBDB-T show the highest power conversion efficiency (PCE) of 5.82% with an open-circuit voltage of 0.98 V, a high short-circuit current density of 10.52 mA/cm2, and a fill factor of 56.31%. The PCEs of the T2-SePDI2- and T4B-SePDI4- based devices are 4.10% and 5.10%, respectively. Furthermore, the results demonstrate thatmore » the molecular configuration of the PDI-based small molecule acceptor is critical and that increasing the steric hindrance is helpful in suppressing aggregation and improving device performance.« less

Novel electrochemiluminescence of perylene derivative and its application to mercury ion detection based on a dual amplification strategy.

PubMed

Zhao, Jing; Lei, Yan-Mei; Chai, Ya-Qin; Yuan, Ruo; Zhuo, Ying

2016-12-15

In this paper, a novel covalently crosslinked perylene derivative (PTC-PEI) composed of polyethylenimine (PEI) and perylenetetracarboxylic acid (PTCA) has been first investigated for cathodic electrochemiluminescence (ECL) in an aqueous system with dissolved O2 as coreactant. The promising novel ECL materials of PTC-PEI exhibited admirable physical and chemical stability and high ECL intensity, which held an alternative way to construct ECL sensor with improved sensitivity. Thus, it was applied to construct a dual amplified "signal-on" mercury ion (Hg(2+)) sensor by the employment of nicking endonuclease (NEase)-assisted target recycling and rolling circle amplification (RCA) for signal amplification. Herein, a long G-rich sequence was generated by RCA process to capture abundant hemin on the electrode surface, and then a significantly amplified ECL signal of PTC-PEI was obtained. Based on dual signal amplification strategy, the devised sensor showed a linear range from 0.1pM to 0.1μΜ with a detection limit down to 33fM (S/N=3), and was successfully used in the direct detection of real water sample with high sensitivity and selectivity. Copyright © 2016 Elsevier B.V. All rights reserved.

Tetrahedral Arrangements of Perylene Bisimide Columns via Supramolecular Orientational Memory.

PubMed

Sahoo, Dipankar; Peterca, Mihai; Aqad, Emad; Partridge, Benjamin E; Heiney, Paul A; Graf, Robert; Spiess, Hans W; Zeng, Xiangbing; Percec, Virgil

2017-01-24

Chiral, shape, and liquid crystalline memory effects are well-known to produce commercial macroscopic materials with important applications as springs, sensors, displays, and memory devices. A supramolecular orientational memory effect that provides complex nanoscale arrangements was only recently reported. This supramolecular orientational memory was demonstrated to preserve the molecular orientation and packing within supramolecular units of a self-assembling cyclotriveratrylene crown at the nanoscale upon transition between its columnar hexagonal and Pm3̅n cubic periodic arrays. Here we report the discovery of supramolecular orientational memory in a dendronized perylene bisimide (G2-PBI) that self-assembles into tetrameric crowns and subsequently self-organizes into supramolecular columns and spheres. This supramolecular orientation memory upon transition between columnar hexagonal and body-centered cubic (BCC) mesophases preserves the 3-fold cubic [111] orientations rather than the 4-fold [100] axes, generating an unusual tetrahedral arrangement of supramolecular columns. These results indicate that the supramolecular orientational memory concept may be general for periodic arrays of self-assembling dendrons and dendrimers as well as for other periodic and quasiperiodic nanoscale organizations comprising supramolecular spheres, generated from other organized complex soft matter including block copolymers and surfactants.

An amplified electrochemiluminescent aptasensor using Au nanoparticles capped by 3,4,9,10-perylene tetracarboxylic acid-thiosemicarbazide functionalized C60 nanocomposites as a signal enhancement tag

NASA Astrophysics Data System (ADS)

Ma, Meng-Nan; Zhang, Xia; Zhuo, Ying; Chai, Ya-Qin; Yuan, Ruo

2015-01-01

A novel electrochemiluminescent (ECL) signal tag of Au nanoparticles capped by 3,4,9,10-perylene tetracarboxylic acid-thiosemicarbazide functionalized C60 nanocomposites (AuNPs/TSC-PTC/C60NPs) was developed for thrombin (TB) aptasensor construction based on the peroxydisulfate/oxygen (S2O82-/O2) system. For signal tag fabrication, the C60 nanoparticles (C60NPs) were prepared and then coated with 3,4,9,10-perylene tetracarboxylic acid (PTCA) by π-π stacking interactions. Afterwards, thiosemicarbazide (TSC) was linked with PTCA functionalized C60NPs via amidation for further assembling Au nanoparticles (AuNPs). Finally, detection aptamer of thrombin (TBA 2) was labeled on the ECL signal amplification tag of AuNPs/TSC-PTC/C60NPs. Herein, TSC, with the active groups of -NH2 and -SH, was selected and introduced into the ECL S2O82-/O2 system for the first time, which could not only offer the active groups of -SH to absorb AuNPs for TBA 2 anchoring but also remarkably enhance the ECL signal of the S2O82-/O2 system by the formation of TSC-PTC/C60NPs for signal amplification. Meanwhile, the sensing interface of a glassy carbon electrode (GCE) was modified by AuNPs/graphene (AuNPs/GR) nanocomposites with the large specific surface area and the active sites, followed by immobilization of thiol-terminated thrombin capture aptamer (TBA 1). With the formation of the sandwich-type structure of TBA 1, TB, and TBA 2 signal probes, a desirable enhanced ECL signal was measured in the testing buffer of an S2O82-/O2 solution for detecting TB. The aptasensor exhibited a good linear relationship for TB detection in the range of 1 × 10-5-10 nM with a detection limit of 3.3 fM.A novel electrochemiluminescent (ECL) signal tag of Au nanoparticles capped by 3,4,9,10-perylene tetracarboxylic acid-thiosemicarbazide functionalized C60 nanocomposites (AuNPs/TSC-PTC/C60NPs) was developed for thrombin (TB) aptasensor construction based on the peroxydisulfate/oxygen (S2O82-/O2) system. For signal tag fabrication, the C60 nanoparticles (C60NPs) were prepared and then coated with 3,4,9,10-perylene tetracarboxylic acid (PTCA) by π-π stacking interactions. Afterwards, thiosemicarbazide (TSC) was linked with PTCA functionalized C60NPs via amidation for further assembling Au nanoparticles (AuNPs). Finally, detection aptamer of thrombin (TBA 2) was labeled on the ECL signal amplification tag of AuNPs/TSC-PTC/C60NPs. Herein, TSC, with the active groups of -NH2 and -SH, was selected and introduced into the ECL S2O82-/O2 system for the first time, which could not only offer the active groups of -SH to absorb AuNPs for TBA 2 anchoring but also remarkably enhance the ECL signal of the S2O82-/O2 system by the formation of TSC-PTC/C60NPs for signal amplification. Meanwhile, the sensing interface of a glassy carbon electrode (GCE) was modified by AuNPs/graphene (AuNPs/GR) nanocomposites with the large specific surface area and the active sites, followed by immobilization of thiol-terminated thrombin capture aptamer (TBA 1). With the formation of the sandwich-type structure of TBA 1, TB, and TBA 2 signal probes, a desirable enhanced ECL signal was measured in the testing buffer of an S2O82-/O2 solution for detecting TB. The aptasensor exhibited a good linear relationship for TB detection in the range of 1 × 10-5-10 nM with a detection limit of 3.3 fM. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr05918b

Pronounced Effects of a Triazine Core on Photovoltaic Performance-Efficient Organic Solar Cells Enabled by a PDI Trimer-Based Small Molecular Acceptor.

PubMed

Duan, Yuwei; Xu, Xiaopeng; Yan, He; Wu, Wenlin; Li, Zuojia; Peng, Qiang

2017-02-01

A novel-small molecular acceptor with electron-deficient 1,3,5-triazine as the core and perylene diimides as the arms is developed as the acceptor material for efficient bulk heterojunction organic solar cells with an efficiency of 9.15%. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Laboratory evidence for ionized polycyclic aromatic hydrocarbons in the interstellar medium

NASA Technical Reports Server (NTRS)

Szczepanski, Jan; Vala, Martin

1993-01-01

The infrared absorption from neutrals and cations of four PAHs - naphthalene, anthracene, pyrene, and perylene - integrated over the spectral regions corresponding to the interstellar bands are compared with astronomical observations. It is found that the interstellar bands cannot be explained solely on the basis of neutral PAH species, but that cations must be a significant, and in some cases dominant, component.

5-(Perylen-3-yl)Ethynyl-arabino-Uridine (aUY11), an Arabino-Based Rigid Amphipathic Fusion Inhibitor, Targets Virion Envelope Lipids To Inhibit Fusion of Influenza Virus, Hepatitis C Virus, and Other Enveloped Viruses

PubMed Central

Colpitts, Che C.; Ustinov, Alexey V.; Epand, Raquel F.; Epand, Richard M.; Korshun, Vladimir A.

2013-01-01

Entry of enveloped viruses requires fusion of viral and cellular membranes. Fusion requires the formation of an intermediate stalk structure, in which only the outer leaflets are fused. The stalk structure, in turn, requires the lipid bilayer of the envelope to bend into negative curvature. This process is inhibited by enrichment in the outer leaflet of lipids with larger polar headgroups, which favor positive curvature. Accordingly, phospholipids with such shape inhibit viral fusion. We previously identified a compound, 5-(perylen-3-yl)ethynyl-2′-deoxy-uridine (dUY11), with overall shape and amphipathicity similar to those of these phospholipids. dUY11 inhibited the formation of the negative curvature necessary for stalk formation and the fusion of a model enveloped virus, vesicular stomatitis virus (VSV). We proposed that dUY11 acted by biophysical mechanisms as a result of its shape and amphipathicity. To test this model, we have now characterized the mechanisms against influenza virus and HCV of 5-(perylen-3-yl)ethynyl-arabino-uridine (aUY11), which has shape and amphipathicity similar to those of dUY11 but contains an arabino-nucleoside. aUY11 interacted with envelope lipids to inhibit the infectivity of influenza virus, hepatitis C virus (HCV), herpes simplex virus 1 and 2 (HSV-1/2), and other enveloped viruses. It specifically inhibited the fusion of influenza virus, HCV, VSV, and even protein-free liposomes to cells. Furthermore, aUY11 inhibited the formation of negative curvature in model lipid bilayers. In summary, the arabino-derived aUY11 and the deoxy-derived dUY11 act by the same antiviral mechanisms against several enveloped but otherwise unrelated viruses. Therefore, chemically unrelated compounds of appropriate shape and amphipathicity target virion envelope lipids to inhibit formation of the negative curvature required for fusion, inhibiting infectivity by biophysical, not biochemical, mechanisms. PMID:23283943

Molecular design and nanoscale engineering of organic nanofibril donor-acceptor heterojunctions

NASA Astrophysics Data System (ADS)

Huang, Helin

Organic nanofibril heterojunction materials have gained increasing research interest due to their broad applications in organic semiconductor devices. In order to enhance the device performance, we have investigated the structure-property relationship of these nanostructures by designing and synthesizing functional building block molecules, selfassembling the molecules into well-defined nanofibers, fabricating the nanofibers into optical and electrical devices, and testing their photoconductivity and sensor properties. In Chapter 2, we present a simple approach to fabricate efficient nanofibril heterojunctions by interfacial engineering of electron donor (D) coating onto acceptor (A) nanofibers. The nanofibers both create a large D/A interface for increased charge separation and act as long-range transport pathways for photogenerated charge carriers towards the electrodes, and the alkyl groups modified at the A molecules not only enable effective surface adsorption of D molecules on the nanofibers for effective electron-transfer communication, but also spatially separate the photogenerated charge carriers to prevent their recombination. In Chapter 3, we further investigated the effect of D molecular structure and coating morphology on photoconductivity of organic nanofiber materials. A series of D molecules with varying side-chain modifications were synthesized and investigated for the different intermolecular arrangements caused by pi-pi stacking in balance with steric hindrance of side-chains. Different molecular assemblies of D resulted in distinctive phase segregation between D and A nanofiber, which significantly affects the interfacial charge separation. In Chapter 4, we developed an alternative nanofibril heterojunction structure that is composed of D as the nanofiber, onto which a monolayer of A molecule was coated. Due to the strong redox (charge transfer) interaction between D and A, the nanofibril junction demonstrated high conductivity even without light illumination, which makes this material suitable for applications in chemiresistor sensors for detection of amines. In Chapter 5, a series of perylene tetracarboxylic monoimides were synthesized through a one-step reaction between cycloalkyl amines and the parent perylene dianhydride. The selection of appropriate reaction medium is the most critical for achieving the high purity of product. This approach opens up a new way for large scale production of the monoimides, which are the precursor for making a variety of perylene based building block molecules.

Charge versus Energy Transfer Effects in High-Performance Perylene Diimide Photovoltaic Blend Films.

PubMed

Singh, Ranbir; Shivanna, Ravichandran; Iosifidis, Agathaggelos; Butt, Hans-Jürgen; Floudas, George; Narayan, K S; Keivanidis, Panagiotis E

2015-11-11

Perylene diimide (PDI)-based organic photovoltaic devices can potentially deliver high power conversion efficiency values provided the photon energy absorbed is utilized efficiently in charge transfer (CT) reactions instead of being consumed in nonradiative energy transfer (ET) steps. Hitherto, it remains unclear whether ET or CT primarily drives the photoluminescence (PL) quenching of the PDI excimer state in PDI-based blend films. Here, we affirm the key role of the thermally assisted PDI excimer diffusion and subsequent CT reaction in the process of PDI excimer PL deactivation. For our study we perform PL quenching experiments in the model PDI-based composite made 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-ethylhexanoyl)-thieno[3,4-b]thiophene)-2-6-diyl] (PBDTTT-CT) polymeric donor mixed with the N,N'-bis(1-ethylpropyl)-perylene-3,4,9,10-tetracarboxylic diimide (PDI) acceptor. Despite the strong spectral overlap between the PDI excimer PL emission and UV-vis absorption of PBDTTT-CT, two main observations indicate that no significant ET component operates in the overall PL quenching: the PL intensity of the PDI excimer (i) increases with decreasing temperature and (ii) remains unaffected even in the presence of 10 wt % content of the PBDTTT-CT quencher. Temperature-dependent wide-angle X-ray scattering experiments further indicate that nonradiative resonance ET is highly improbable due to the large size of PDI domains. The dominance of the CT over the ET process is verified by the high performance of devices with an optimum composition of 30:70 PBDTTT-CT:PDI. By adding 0.4 vol % of 1,8-diiodooctane we verify the plasticization of the polymer side chains that balances the charge transport properties of the PBDTTT-CT:PDI composite and results in additional improvement in the device efficiency. The temperature-dependent spectral width of the PDI excimer PL band suggests the presence of energetic disorder in the PDI excimer excited state manifold.

Porous and non-porous water soluble polymer nanospheres

NASA Astrophysics Data System (ADS)

Henselwood, Fred William

Water soluble polymer nanospheres have been prepared from the photo-cross-linking of diblock copolymer micelles formed either in water or in N,N-dimethylformamide/water mixtures. The diblock copolymers utilized in this study were poly(2-cinnamoyl-ethyl methacrylate)-block-poly(acrylic acid), poly ((2-cinnamoylethyl methacrylate)-random-(2-octanoylethyl methacrylate)) -block-poly(acrylic acid), and poly ((2-cinnamoyl-ethyl methacrylate)-random-(2-oleoylethyl methacrylate)) -block-poly(acrylic acid). These polymers were synthesized by the functionalization of diblock copolymers prepared by anionic polymerization. The photo-cross-linking was achieved through the dimerization of cinnamoyl groups by ultraviolet irradiation. Transmission electron microscopy confirmed that the polymer nanospheres had an inner core region formed by the cinnamoyl containing polymer blocks, and an outer shell layer formed by the acrylic acid polymer blocks. The hydrodynamic radius of the polymer nanospheres in water was approximately 50 to 75 nm as determined by dynamic light scattering. It has been found that the polymer nanospheres, when in water, could be readily impregnated with organic molecules. Fluorescence measurements showed that the polymer nanospheres could uptake polyaromatic hydrocarbons by the direct mixing of polyaromatic hydrocarbons with the polymer nanospheres in water. Perylene was found to be between 2.0 × 10sp5 and 4.0 × 10sp5 times more soluble in the core region of the polymer nanospheres than in water. The addition of divalent cations was shown to induce aggregation of the polymer nanospheres and resulted in the precipitation of the polymer nanospheres along with any captured perylene. This suggests that the polymer nanospheres may be useful in water remediation. Porous polymer nanospheres were prepared by the incorporation of low molecular weight polymeric porogens within the core region of the polymer nanospheres. Following photo-cross-linking the polymeric porogens were extracted out of the polymer nanospheres resulting in pore formation. Perylene loading experiments revealed that the loading of the porous polymer nanospheres was 41% higher than that achieved for non-porous polymer nanospheres prepared from the same initial diblock copolymer. This indicates that the porous polymer nanospheres may be preferred over the non-porous polymer nanospheres in applications such as drug delivery.

Guest and solvent modulated photo-driven charge separation and triplet generation in a perylene bisimide cyclophane

DOE PAGES

Spenst, Peter; Young, Ryan M.; Wasielewski, Michael R.; ...

2016-05-18

Cofacial positioning of two perylene bisimide (PBI) chromophores at a distance of 6.5 Å in a cyclophane structure prohibits the otherwise common excimer formation and directs photoexcited singlet state relaxation towards intramolecular symmetry-breaking charge separation (τ CS = 161 ± 4 ps) in polar CH 2Cl 2, which is thermodynamically favored with a Gibbs free energy of ΔG CS = –0.32 eV. The charges then recombine slowly in τ CR = 8.90 ± 0.06 ns to form the PBI triplet excited state, which can be used subsequently to generate singlet oxygen in 27% quantum yield. This sequence of events ismore » eliminated by dissolving the PBI cyclophane in non-polar toluene, where only excited singlet state decay occurs. In contrast, complexation of electron-rich aromatic hydrocarbons by the host PBI cyclophane followed by photoexcitation of PBI results in ultrafast electron transfer (<10 ps) from the guest to the PBI in CH 2Cl 2. As a result, the rate constants for charge separation and recombination increase as the guest molecules become easier to oxidize, demonstrating that charge separation occurs close to the peak of the Marcus curve and the recombination lies far into the Marcus inverted region.« less

Localization/delocalization of charges in bay-linked perylene bisimides.

PubMed

Jiang, Wei; Xiao, Chengyi; Hao, Linxiao; Wang, Zhaohui; Ceymann, Harald; Lambert, Christoph; Di Motta, Simone; Negri, Fabrizia

2012-05-29

The copper-mediated Ullmann coupling of 1,7-dibromoperylene bisimides afforded structurally perfect singly-linked perylene bisimide (PBI) arrays, whilst the homo-coupling of 1,12-dibromoperylene bisimides gave doubly-linked and triply-linked diperylene bisimides. The interactions of three bay-linked diperylene bisimides that differed in their linkage (singly, doubly, and triply) were investigated in their neutral and reduced forms (mono-anion to tetra-anion). UV/Vis absorption and fluorescence spectroscopy revealed different degrees of interaction, which was explained by exciton coupling and conjugation effects. The electrochemical properties and spectroelectrochemistry also showed quite-different degrees of PBI interactions in the reduced mixed-valence species, which was apparent by the observation of CT bands. The interpretation of the experimental findings was supported by spin-restricted and -unrestricted DFT and time-dependent TD-DFT calculations with the long-range-corrected CAM-B3LYP functional. Accordingly, the degree of interaction in both the neutral and reduced forms of the bay-linked PBIs was qualitatively in the order doubly linked

Photoinduced electron transfer (PET) versus excimer formation in supramolecular p/n-heterojunctions of perylene bisimide dyes and implications for organic photovoltaics.

PubMed

Nowak-Król, Agnieszka; Fimmel, Benjamin; Son, Minjung; Kim, Dongho; Würthner, Frank

2015-01-01

Foldamer systems comprised of two perylene bisimide (PBI) dyes attached to the conjugated backbones of 1,2-bis(phenylethynyl)benzene and phenylethynyl-bis(phenylene)indane, respectively, were synthesized and investigated with regard to their solvent-dependent properties. UV/Vis absorption and steady-state fluorescence spectra show that both foldamers exist predominantly in a folded H-aggregated state consisting of π-π-stacked PBIs in THF and in more random conformations with weaker excitonic coupling between the PBIs in chloroform. Time-resolved fluorescence spectroscopy and transient absorption spectroscopy reveal entirely different relaxation pathways for the photoexcited molecules in the given solvents, i.e. photoinduced electron transfer leading to charge separated states for the open conformations (in chloroform) and relaxation into excimer states with red-shifted emission for the stacked conformations (in THF). Supported by redox data from cyclic voltammetry and Rehm-Weller analysis we could relate the processes occurring in these solution-phase model systems to the elementary processes in organic solar cells. Accordingly, only if relaxation pathways such as excimer formation are strictly avoided in molecular semiconductor materials, excitons may diffuse over larger distances to the heterojunction interface and produce photocurrent via the formation of electron/hole pairs by photoinduced electron transfer.

Dimer formation of perylene: An ultracold spectroscopic and computational study

NASA Astrophysics Data System (ADS)

Birer, Ö.; Yurtsever, E.

2015-10-01

The electronic spectra of perylene inside helium nanodroplets recorded by the depletion method are presented. The results show two broad peaks in addition to sharp monomer vibronic transitions due to dimer formation. In order to understand the details of the spectra, first the dimer formation is studied by DFT and SCS-MP2 calculations and then the electronic spectra are calculated at the minima of the potential energy surface (PES). Theoretical calculations show that there are two low-lying energetically degenerate dimer structures; namely a parallel displaced one and a rotated stacked one. PES around these minima is very flat with a number of local minima at higher energies which at the experimental temperatures cannot be populated. Even though thermodynamically these two structures are equally populated, dynamical considerations point out that in helium droplet the parallel displaced geometry is encouraged by the natural alignment of the molecules due to the acquired angular momentum following the pick-up process. The calculated spectrum of the parallel displaced geometry predicts the positions of the dimer transitions within 30 nm of the experimental spectrum. Furthermore, the difference between the two dimer transitions is accurately predicted to be about 25 nm while the experimental difference was about 20 nm. Such a small difference could only be detected due to the ultracold conditions helium nanodroplets provided.

Hydrocarbon Status of Alluvial Soils in the Istra Morphostructural Node (Moscow Oblast)

NASA Astrophysics Data System (ADS)

Pikovskiy, Yu. I.; Gennadiev, A. N.; Kovach, R. G.; Khlynina, N. I.; Khlynina, A. V.

2017-12-01

The effect of the current block structure of the earth's crust and its most active sites (morphostructural nodes) on the natural hydrocarbon status of alluvial soils has been considered. Studies have been performed in the Istra district of Moscow oblast within the Istra morphostructural node. The node represents an area of increased geodynamic activity of the earth's crust located at the convergence or intersection of block boundaries: mobile linear zones following large river valleys with alluvial soils. Soil cover mainly consists of alluvial humic-gley soils (Eutric Gleyic Fluvisols) of different depths and alluvial mucky-gley soils (Eutric Gleyic Histic Fluvisols). Some soils manifest stratification. Two factors forming the hydrocarbon status of soils are considered: soil processes and the effect of geodynamic activity, which is manifested within the morphostructural node. The contents of bitumoids and retained methane and butanes in alluvial soils appreciably increase at the entry of river valley into the node. The occurrence frequency of 5-6-ring polycyclic aromatic hydrocarbons (perylene and benzo[ghi]perylene) in mineral horizons increases. It has been concluded that alluvial soils within the Istra morphostructural node are characterized by the biogeochemical type of hydrocarbon status with signs of emanation type at sites with the highest geodynamic activity.

Nanostructured polyurethane perylene bisimide ester assemblies with tuneable morphology and enhanced stability

NASA Astrophysics Data System (ADS)

Zhang, Xiaoxiao; Gong, Tingyuan; Chi, Hong; Li, Tianduo

2018-03-01

Size control has been successfully achieved in inorganic materials, but it remains a challenge in polymer nanomaterials due to their polydispersity. Here, we report a facile approach to tailor the diameters of polyurethane (PU) nanoparticles (490 nm, 820 nm and 2.1 µm) via perylene bisimide (PBI) assisted self-assembly. The formed morphologies such as spindle, spherical and core-shell structures depend on the ratio of PBI and polymer concentrations. It is shown that the formation of PU nanoparticles is directed by π-π stacking of PBI and the morphology transition is not only affected by the amount of PBI incorporated, but also influenced by solvent, which controls the initial evaporation balance. Furthermore, the prepared PUs exhibit retained optical stability and enhanced thermal stability. The PUs, designed to have conjugated PBI segments in backbones, were synthesized via ring-opening and condensation reactions. Compared with the neat PU, gel permeation chromatography shows narrower molecular weight distribution. Fluorescence spectra and ultraviolet-visible spectra indicate retained maximum emission wavelength of PBI at 574 nm and 5.2% quantum yields. Thermo-gravimetric analysis and differential scanning calorimetry reveal 79°C higher decomposition temperature and 22°C higher glass transition temperature. This study provides a new way to fabricate well-defined nanostructures of functionalized PUs.

Infrared spectroscopy of matrix-isolated polycyclic aromatic hydrocarbon cations. 2. The members of the thermodynamically most favorable series through coronene

NASA Technical Reports Server (NTRS)

Hudgins, D. M.; Allamandola, L. J.

1995-01-01

Gaseous, ionized polycyclic aromatic hydrocarbons (PAHs) are thought to be responsible for a very common family of interstellar infrared emission bands. Here the near- and mid-infrared spectra of the cations of the five most thermodynamically favored PAHs up to coronene:phenanthrene, pyrene, benzo[e]pyrene, benzo[ghi]perylene, and coronene, are presented to test this hypothesis. For those molecules that have been studied previously (pyrene, pyrene-d10, and coronene), band positions and relative intensities are in agreement. In all of these cases we report additional features. Absolute integrated absorbance values are given for the phenanthrene, perdeuteriophenanthrene, pyrene, benzo[ghi]perylene, and coronene cations. With the exception of coronene, the cation bands corresponding to the CC modes are typically 2-5 times more intense than those of the CH out-of-plane bending vibrations. For the cations, the CC stretching and CH in-plane bending modes give rise to bands that are an order of magnitude stronger than those of the neutral species, and the CH out-of-plane bends produce bands that are 5-20 times weaker than those of the neutral species. This behavior is similar to that found in most other PAH cations studied to date. The astronomical implications of these PAH cation spectra are also discussed.

Impact of Linear Alkyl Length on the Assembly of Twisted Perylene Bisimides: From Molecular Arrangement to Nanostructures.

PubMed

Guo, Zongxia; Wang, Kun; Yu, Ping; Wang, Xiangnan; Lan, Shusha; Sun, Kai; Yi, Yuanping; Li, Zhibo

2017-11-02

The effect of the length of linear alkyl chains substituted at imine positions on the assembly of tetrachlorinated perylene bisimides (1: PBI with -C 6 H 13 ; 2: PBI with -C 12 H 25 ) has been investigated. Solvent-induced assembly was performed in solutions of THF and methanol with varying volume ratios. Morphological (SEM, AFM, and TEM) and spectral (UV/Vis, fluorescence, FTIR, and XRD) methods were used to characterize the assembled nanostructures and the molecular arrangement in the aggregates. It was found that uniform structures could be obtained for both molecules in solutions with a high ratio of methanol. PBI 1 formed rigid nanosheets, whereas 2 assembled into longer nanostripes with a high ratio of length to width. On combining the morphological data with the spectral data, it was suggested that π-π stacking predominated in assemblies of 1, and the synergetic effect of van der Waals interactions from the long alkyl chains and π-π stacking between neighboring building blocks facilitated the growth of the long-range-ordered nanostructures of 2. By changing the linear chain length, the hierarchical assembly of PBIs modified on bay positions could be manipulated effectively. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Infrared Spectroscopy of Matrix-Isolated Polycyclic Aromatic Hydrocarbon Cations

NASA Technical Reports Server (NTRS)

Hudgins, D. M.; Allamandola, L. J.

1995-01-01

Gaseous, ionized polycyclic aromatic hydrocarbons (PAHs) are thought to be responsible for a very common family of interstellar infrared emission bands. Here the near- and mid-infrared spectra of the cations of the five most thermodynamically favored PAHs up to coronene: phenanthrene, pyrene, benzo(e)pyrene, benzo-(ghi)perylene, and coronene, are presented to test this hypothesis. For those molecules that have been studied previously (pyrene, pyrene-d(sub 10), and coronene), band positions and relative intensities are in agreement. In all of these cases we report additional features. Absolute integrated absorbance values are given for the phenanthrene, perdeuteriophenanthrene, pyrene, benzo(ghi]perylene, and coronene cations. With the exception of coronene, the cation bands corresponding to the CC modes are typically 2-5 times more intense than those of the CH out-of-plane bending vibrations. For the cations, the CC stretching and CH in-plane bending modes give rise to bands that are an order of magnitude stronger than those of the neutral species, and the CH out-of-plane bends produce bands that are 5-20 times weaker than those of the neutral species. This behavior is similar to that found in most other PAH cations studied to date. The astronomical implications of these PAH cation spectra are also discussed.

High-Performance Non-Fullerene Organic Solar Cells Based on a Selenium-Containing Polymer Donor and a Twisted Perylene Bisimide Acceptor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Tao; Meng, Dong; Cai, Yunhao

2016-04-23

A novel polymer donor (PBDTS-Se) is designed to match with a non-fullerene acceptor (SdiPBI-S). The corresponding solar cells show a high efficiency of 8.22%, which result from synergetic improvements of light harvesting, charge carrier transport and collection, and morphology. The results indicate that rational design of novel donor materials is important for non-fullerene organic solar cells.

Cellules photovoltaïques à base de semi-conducteurs organiques

NASA Astrophysics Data System (ADS)

Videlot, C.; Fichou, D.; Garnier, F.

1998-06-01

We describe here the elaboration and performances of photovoltaic cells using organic p type (pentacene) and n type (perylene) semiconductors in a pn heterojunction configuration. Nous décrivons ici l'élaboration et les performances de cellules photovoltaïques à base de semi-conducteurs organiques de type p (pentacène) et de type n (pérylène) dans une hétérojonction pn.

Elemental carbon and polycyclic aromatic compounds in a 150-year sediment core from Lake Qinghai, Tibetan Plateau, China: influence of regional and local sources and transport pathways.

PubMed

Han, Y M; Wei, C; Bandowe, B A M; Wilcke, W; Cao, J J; Xu, B Q; Gao, S P; Tie, X X; Li, G H; Jin, Z D; An, Z S

2015-04-07

Elemental carbon (EC) and polycyclic aromatic compounds (PACs) are potential proxies for the reconstruction of change in human activities and the origin of air masses in historic times. In this study, the historic deposition of char and soot (the two subtypes of EC) and PACs in a 150-year sediment core from different topographic subbasins of Lake Qinghai on the Qinghai Tibetan Plateau (QTP) were reconstructed. The objective was to explore how the variations in the concentrations of EC and PACs, in the ratios of char to soot and of oxygenated polycyclic aromatic hydrocarbons (OPAHs) to parent PAHs, and in the composition of the PAC mixtures reflect historical changes in climate and human activity and the origin of air masses arriving at the QTP. The deposition fluxes of soot in the different subbasins were similar, averaging 0.18 (range of 0.15-0.25) and 0.16 (0.13-0.23) g m(-2) year(-1), respectively, but they varied for char (averaging 0.11 and 0.22 g m(-2) year(-1), respectively), suggesting ubiquitous atmospheric deposition of soot and local river inputs of char. The different vertical distributions of the char/soot ratios in the different subbasins can be interpreted in terms of the different transport mechanisms of char and soot. An abrupt increase in soot concentrations since 1980 coincides with results from the QTP ice cores that were interpreted to be indicative of soot transport from South Asia. Similar concentration patterns of PAHs with soot and 9,10-anthraquinone/anthracene (9,10-AQ/ANT) ratios all >2.0 suggest regional PAC sources. Increasing PAH/soot ratios and decreasing 9,10-AQ/ANT ratios since the beginning of the 1970s indicate increasing local emissions. The historical trends of these diagnostic ratios indicate an increase in the fossil-fuel contribution since the beginning of the 1970s. The increase of perylene concentrations with increasing core depth and the ratio of perylene to its penta-aromatic isomers indicate that perylene originates mainly from in situ biogenic diagenesis. We demonstrate that the concentrations of EC, char, soot, and PACs in sediments can be used to reconstruct local, regional, and remote sources and transport pathways of pollutants to the QTP.

Size- and Shape-Dependent Fluorescence Quenching of Gold Nanoparticles on Perylene Dye

DTIC Science & Technology

2013-01-01

Am. Chem. Soc. 2005 , 127 , 1216 . [10] S. Vukovic , S. Corni , B. Mennucci , J . Phys. Chem. C 2009 , 113 , 121 . procedure [ 11... J . Halas , S. Lal , W. S. Chang , S. Link , P. Nordlander , Chem. Rev. 2011 , 111 , 3913 . [3] S.-Y. Chen , J . J . Mock , R. T...Hill , A. Chilkoti , D. R. Smith , A. A. Lazarides , ACS Nano 2010 , 4 , 6535 . [4] C. J . Murphy , T. K. San , A. M. Gole , C. J

Fluorescent Polymer-Single-Walled Carbon Nanotube Complexes with Charged and Noncharged Dendronized Perylene Bisimides for Bioimaging Studies.

PubMed

Huth, Katharina; Glaeske, Mareen; Achazi, Katharina; Gordeev, Georgy; Kumar, Shiv; Arenal, Raúl; Sharma, Sunil K; Adeli, Mohsen; Setaro, Antonio; Reich, Stephanie; Haag, Rainer

2018-06-05

Fluorescent nanomaterials are expected to revolutionize medical diagnostic, imaging, and therapeutic tools due to their superior optical and structural properties. Their inefficient water solubility, cell permeability, biodistribution, and high toxicity, however, limit the full potential of their application. To overcome these obstacles, a water-soluble, fluorescent, cytocompatible polymer-single-walled carbon nanotube (SWNT) complex is introduced for bioimaging applications. The supramolecular complex consists of an alkylated polymer conjugated with neutral hydroxylated or charged sulfated dendronized perylene bisimides (PBIs) and SWNTs as a general immobilization platform. The polymer backbone solubilizes the SWNTs, decorates them with fluorescent PBIs, and strongly improves their cytocompatibility by wrapping around the SWNT scaffold. In photophysical measurements and biological in vitro studies, sulfated complexes exhibit superior optical properties, cellular uptake, and intracellular staining over their hydroxylated analogs. A toxicity assay confirms the highly improved cytocompatibility of the polymer-wrapped SWNTs toward surfactant-solubilized SWNTs. In microscopy studies the complexes allow for the direct imaging of the SWNTs' cellular uptake via the PBI and SWNT emission using the 1st and 2nd optical window for bioimaging. These findings render the polymer-SWNT complexes with nanometer size, dual fluorescence, multiple charges, and high cytocompatibility as valuable systems for a broad range of fluorescence bioimaging studies. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydroxypropyl cyclic β-(1 → 2)-D-glucans and epichlorohydrin β-cyclodextrin dimers as effective carbohydrate-solubilizers for polycyclic aromatic hydrocarbons.

PubMed

Choi, Jae Min; Jeong, Daham; Piao, Jinglan; Kim, Kyoungtea; Nguyen, Andrew Bao Loc; Kwon, Nak-Jung; Lee, Mi-Kyung; Lee, Im Soon; Yu, Jae-Hyuk; Jung, Seunho

2015-01-12

The removal of polycyclic aromatic hydrocarbons by soil washing using water is extremely difficult due to their intrinsic hydrophobic nature. In this study, the effective aqueous solubility enhancements of seven polycyclic aromatic hydrocarbons by chemically modified hydroxypropyl rhizobial cyclic β-(1 → 2)-D-glucans and epichlorohydrin β-cyclodextrin dimer have been investigated for the first time. In the presence of hydroxypropyl cyclic β-(1 → 2)-D-glucans, the solubility of benzo[a]pyrene is increased up to 38 fold of its native solubility. The solubility of pyrene and phenanthrene dramatically increased up to 160 and 359. Coronene, chrysene, perylene, and fluoranthene also show an increase of 11, 23, 23, and 97 fold, respectively, of enhanced solubility by complexation with synthetic epichlorohydrin β-cyclodextrin dimer. The physicochemical properties of the complex are characterized by Fourier-transform infrared spectra and differential scanning calorimetry. Utilizing a scanning electron microscopy, the morphological structures of native benzo[a]pyrene, pyrene, phenanthrene, coronene, chrysene, perylene, fluoranthene and their complex with novel carbohydrate-solubilizers are studied. These results elucidate that polycyclic aromatic hydrocarbons are able to form an efficient complex with hydroxypropyl cyclic β-(1 → 2)-D-glucans and β-cyclodextrin dimer, suggesting the potential usage of chemically modified novel carbohydrate-solubilizers. Copyright © 2014 Elsevier Ltd. All rights reserved.

Hierarchical Self-Organization of Perylene Bisimides into Supramolecular Spheres and Periodic Arrays Thereof.

PubMed

Sahoo, Dipankar; Peterca, Mihai; Aqad, Emad; Partridge, Benjamin E; Heiney, Paul A; Graf, Robert; Spiess, Hans W; Zeng, Xiangbing; Percec, Virgil

2016-11-09

Perylene bisimide derivatives (PBIs) are known to form only columnar or lamellar assemblies. There is no known example of a PBI self-assembling into a supramolecular sphere. Therefore, periodic and quasiperiodic arrays generated from spherical assemblies produced from PBIs are also not known. Here, a PBI functionalized at its imide groups with a second generation self-assembling dendron is reported to self-assemble into supramolecular spheres. These spheres self-organize in a body-centered cubic (BCC) periodic array, rarely encountered for self-assembling dendrons but often encountered in block copolymers. These supramolecular spheres also assemble into a columnar hexagonal array in which the supramolecular columns are unexpectedly and unprecedentedly made from spheres. At lower temperature, two additional columnar hexagonal phases consisting of symmetric and asymmetric tetrameric crowns of PBI are observed. Structural and retrostructural analysis via X-ray diffraction (XRD), molecular modeling, molecular simulation, and solid state NMR suggests that inversion of the symmetric tetrameric crowns at high temperature mediates their transformation into supramolecular spheres. The tetrameric crowns of PBIs are able to form an isotropic sphere in the cubic phase due to rapid molecular motion at high temperature, unobservable by XRD but demonstrated by solid state NMR studies. This mechanism of hierarchical self-organization of PBI into supramolecular spheres is most probably general and can be applied to other related planar molecules to generate new functions.

Solvent and substituent effects on aggregation constants of perylene bisimide π-stacks--a linear free energy relationship analysis.

PubMed

Chen, Zhijian; Fimmel, Benjamin; Würthner, Frank

2012-08-14

A series of six perylene bisimides (PBIs) with hydrophilic and hydrophobic side chains at the imide nitrogens were applied for a comparative study of the solvent and structural effects on the aggregation behaviour of this class of dyes. A comparison of the binding constants in tetrachloromethane at room temperature revealed the highest binding constant of about 10(5) M(-1) for a PBI bearing 3,4,5-tridodecyloxyphenyl substituents at the imide nitrogens, followed by 3,4,5-tridodecylphenyl and alkyl-substituted PBIs, whereas no aggregation could be observed in the accessible concentration range for PBIs equipped with bulky 2,6-diisopropylphenyl substituents at the imide nitrogens. The aggregation behaviour of three properly soluble compounds was investigated in 17 different solvents covering a broad polarity range from nonpolar n-hexane to highly polar DMSO and water. Linear free energy relationships (LFER) revealed a biphasic behaviour between Gibbs free energies of aggregation and common empirical solvent polarity scales indicating particularly strong π-π stacking interactions in nonpolar aliphatic and polar alcoholic solvents whilst the weakest binding is observed in dichloromethane and chloroform. Accordingly, PBI aggregation is dominated by electrostatic interactions in nonpolar solvents and by solvophobic interactions in protic solvents. In water, the aggregation constant is increased far beyond LFER expectations pointing at a pronounced hydrophobic effect.

Optimization and determination of polycyclic aromatic hydrocarbons in biochar-based fertilizers.

PubMed

Chen, Ping; Zhou, Hui; Gan, Jay; Sun, Mingxing; Shang, Guofeng; Liu, Liang; Shen, Guoqing

2015-03-01

The agronomic benefit of biochar has attracted widespread attention to biochar-based fertilizers. However, the inevitable presence of polycyclic aromatic hydrocarbons in biochar is a matter of concern because of the health and ecological risks of these compounds. The strong adsorption of polycyclic aromatic hydrocarbons to biochar complicates their analysis and extraction from biochar-based fertilizers. In this study, we optimized and validated a method for determining the 16 priority polycyclic aromatic hydrocarbons in biochar-based fertilizers. Results showed that accelerated solvent extraction exhibited high extraction efficiency. Based on a Box-Behnken design with a triplicate central point, accelerated solvent extraction was used under the following optimal operational conditions: extraction temperature of 78°C, extraction time of 17 min, and two static cycles. The optimized method was validated by assessing the linearity of analysis, limit of detection, limit of quantification, recovery, and application to real samples. The results showed that the 16 polycyclic aromatic hydrocarbons exhibited good linearity, with a correlation coefficient of 0.996. The limits of detection varied between 0.001 (phenanthrene) and 0.021 mg/g (benzo[ghi]perylene), and the limits of quantification varied between 0.004 (phenanthrene) and 0.069 mg/g (benzo[ghi]perylene). The relative recoveries of the 16 polycyclic aromatic hydrocarbons were 70.26-102.99%. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Perylene Diimide Based Fluorescent Dyes for Selective Sensing of Nitroaromatic Compounds: Selective Sensing in Aqueous Medium Across Wide pH Range.

PubMed

Hariharan, P S; Pitchaimani, J; Madhu, Vedichi; Anthony, Savarimuthu Philip

2016-03-01

Water soluble perylenediimide based fluorophore salt, N,N'-bis(ethelenetrimethyl ammoniumiodide)-perylene-3,4,9,10-tetracarboxylicbisimide (PDI-1), has been used for selective fluorescence sensing of picric acid (PA) and 4-nitroaniline (4-NA) in organic as well as aqueous medium across wide pH range (1.0 to 10.0). PDI-1 showed strong fluorescence in dimethylformamide (DMF) (Φf = 0.26 (DMF) and moderate fluorescence in water. Addition of picric acid (PA) and 4-nitroaniline (4-NA) into PDI-1 in DMF/aqueous solution selectively quenches the fluorescence. The concentration dependent studies showed decrease of fluorescence linearly with increase of PA and 4-NA concentration. The interference studies demonstrate high selectivity for PA and 4-NA. Interestingly, PDI-1 showed selective fluorescence sensing of PA and 4-NA across wide pH range (1.0 to 10.0). Selective fluorescence sensing of PA and 4-NA has also been observed with trifluoroacetate (PDI-2), sulfate (PDI-3) salt of PDI-1 as well as octyl chain substituted PDI (PDI-4) without amine functionality. These studies suggest that PA and 4-NA might be having preferential interaction with PDI aromatic core and quenches the fluorescence. Thus PDI based dyes have been used for selective fluorescent sensing of explosive NACs for the first time to the best our knowledge.

Interaction of albumin with perylene-diimides with aromatic substituents

NASA Astrophysics Data System (ADS)

Farooqi, Mohammed; Penick, Mark; Burch, Jessica; Negrete, George; Brancaleon, Lorenzo

2015-03-01

Polyaromatic hydrocarbons (PAH) binding to proteins remains one of the fundamental aspects of research in biophysics. Ligand binding can regulate the function of proteins. Binding to small ligands remains a very important aspect in the study of the function of many proteins. Perylene diimide or PDI derivatives have attracted initial interest as industrial dyes and pigments. Recently, much attention has been focused on their strong π - π stacks resulting from the large PDI aromatic core. These PDI stacks have distinct optical properties, and provide informative models that mimic the light-harvesting system and initial charge separation and charge transfer in the photosynthetic system. The absorption property of PDI derivatives may be largely tuned from visible to near-infrared region by chemical modifications at the bay-positions. We are currently studying a new class of PDI derivatives with substituents made of the side chains of aromatic amino acids (Tyrosine, Tryptophan and Phenylalanine). We have looked at the fluorescence absorption and emission of these PDIs in water and other organic solvents. PDIs show evidence of dimerization and possible aggregation. We also present binding studies of these PDIs with Human Serum Albumin (HSA). The binding was studied using fluorescence emission quenching of the HSA Tryptophan residue. Stern-Volmer equation is used to derive the quenching constants. PDI binding to HSA also has an effect on the fluorescence emission of the PDIs themselves by red shifting the spectra. Funded by RCMI grant.

Effect of Energy Alignment, Electron Mobility, and Film Morphology of Perylene Diimide Based Polymers as Electron Transport Layer on the Performance of Perovskite Solar Cells.

PubMed

Guo, Qiang; Xu, Yingxue; Xiao, Bo; Zhang, Bing; Zhou, Erjun; Wang, Fuzhi; Bai, Yiming; Hayat, Tasawar; Alsaedi, Ahmed; Tan, Zhan'ao

2017-03-29

For organic-inorganic perovskite solar cells (PerSCs), the electron transport layer (ETL) plays a crucial role in efficient electron extraction and transport for high performance PerSCs. Fullerene and its derivatives are commonly used as ETL for p-i-n structured PerSCs. However, these spherical small molecules are easy to aggregate with high annealing temperature and thus induce morphology stability problems. N-type conjugated polymers are promising candidates to overcome these problems due to the tunable energy levels, controllable aggregation behaviors, and good film formation abilities. Herein, a series of perylene diimide (PDI) based polymers (PX-PDIs), which contain different copolymeried units (X), including vinylene (V), thiophene (T), selenophene (Se), dibenzosilole (DBS), and cyclopentadithiophene (CPDT), are introduced as ETL for p-i-n structured PerSCs. The effect of energy alignment, electron mobility, and film morphology of these ETLs on the photovoltaic performance of the PerSCs are fully investigated. Among the PX-PDIs, PV-PDI demonstrates the deeper LUMO energy level, the highly delocalized LUMO electron density, and a better planar structure, making it the best electron transport material for PerSCs. The planar heterojunction PerSC with PV-PDI as ETL achieves a power conversion efficiency (PCE) of 10.14%, among the best values for non-fullerene based PerSCs.

Multicolor fluorescent biosensor for multiplexed detection of DNA.

PubMed

Hu, Rong; Liu, Tao; Zhang, Xiao-Bing; Huan, Shuang-Yan; Wu, Cuichen; Fu, Ting; Tan, Weihong

2014-05-20

Development of efficient methods for highly sensitive and rapid screening of specific oligonucleotide sequences is essential to the early diagnosis of serious diseases. In this work, an aggregated cationic perylene diimide (PDI) derivative was found to efficiently quench the fluorescence emission of a variety of anionic oligonucleotide-labeled fluorophores that emit at wavelengths from the visible to NIR region. This broad-spectrum quencher was then adopted to develop a multicolor biosensor via a label-free approach for multiplexed fluorescent detection of DNA. The aggregated perylene derivative exhibits a very high quenching efficiency on all ssDNA-labeled dyes associated with biosensor detection, having efficiency values of 98.3 ± 0.9%, 97 ± 1.1%, and 98.2 ± 0.6% for FAM, TAMRA, and Cy5, respectively. An exonuclease-assisted autocatalytic target recycling amplification was also integrated into the sensing system. High quenching efficiency combined with autocatalytic target recycling amplification afforded the biosensor with high sensitivity toward target DNA, resulting in a detection limit of 20 pM, which is about 50-fold lower than that of traditional unamplified homogeneous fluorescent assay methods. The quencher did not interfere with the catalytic activity of nuclease, and the biosensor could be manipulated in either preaddition or postaddition manner with similar sensitivity. Moreover, the proposed sensing system allows for simultaneous and multicolor analysis of several oligonucleotides in homogeneous solution, demonstrating its potential application in the rapid screening of multiple biotargets.

pn-Heterojunction effects of perylene tetracarboxylic diimide derivatives on pentacene field-effect transistor.

PubMed

Yu, Seong Hun; Kang, Boseok; An, Gukil; Kim, BongSoo; Lee, Moo Hyung; Kang, Moon Sung; Kim, Hyunjung; Lee, Jung Heon; Lee, Shichoon; Cho, Kilwon; Lee, Jun Young; Cho, Jeong Ho

2015-01-28

We investigated the heterojunction effects of perylene tetracarboxylic diimide (PTCDI) derivatives on the pentacene-based field-effect transistors (FETs). Three PTCDI derivatives with different substituents were deposited onto pentacene layers and served as charge transfer dopants. The deposited PTCDI layer, which had a nominal thickness of a few layers, formed discontinuous patches on the pentacene layers and dramatically enhanced the hole mobility in the pentacene FET. Among the three PTCDI molecules tested, the octyl-substituted PTCDI, PTCDI-C8, provided the most efficient hole-doping characteristics (p-type) relative to the fluorophenyl-substituted PTCDIs, 4-FPEPTC and 2,4-FPEPTC. The organic heterojunction and doping characteristics were systematically investigated using atomic force microscopy, 2D grazing incidence X-ray diffraction studies, and ultraviolet photoelectron spectroscopy. PTCDI-C8, bearing octyl substituents, grew laterally on the pentacene layer (2D growth), whereas 2,4-FPEPTC, with fluorophenyl substituents, underwent 3D growth. The different growth modes resulted in different contact areas and relative orientations between the pentacene and PTCDI molecules, which significantly affected the doping efficiency of the deposited adlayer. The differences between the growth modes and the thin-film microstructures in the different PTCDI patches were attributed to a mismatch between the surface energies of the patches and the underlying pentacene layer. The film-morphology-dependent doping effects observed here offer practical guidelines for achieving more effective charge transfer doping in thin-film transistors.

Infrared Spectroscopy of Matrix-Isolated Polycyclic Aromatic Hydrocarbon Cations. Part 2; The Members of the Thermodynamically Most Favorable Series through Coronene

NASA Technical Reports Server (NTRS)

Hudgins, D. M.; Allamandola, L. J.

1995-01-01

Gaseous, ionized polycyclic aromatic hydrocarbons (PAHS) are thought to be responsible for a very common family of interstellar infrared emission bands. Here the near- and mid-infrared spectra of the cations of the five most thermodynamically favored PAHs up to coronene: phenanthrene, pyrene, benzo[e]pyrene, benzo-[ghi]perylene, and coronene, are presented to test this hypothesis. For those molecules that have been studied previously (pyrene, pyrene-d(sub 10), and coronene), band positions and relative intensities are in agreement. In all of these cases we report additional features. Absolute integrated absorbance values are given for the phenanthrene, perdeuteriophenanthrene, pyrene, benzo[ghi]perylene, and coronene cations. With the exception of coronene, the cation bands corresponding to the CC modes are typically 2-5 times more intense than those of the CH out-of-plane bending vibrations. For the cations, the CC stretching and CH in-plane bending modes give rise to bands that are an order of magnitude stronger than those of the neutral species, and the CH out-of-plane bends produce bands that are 5-20 times weaker than those of the neutral species. This behavior is similar to that found in most other PAH cations studied to date. The astronomical implications of these PAH cation spectra are also discussed.

Impact of IrRu Oxygen Evolution Reaction Catalysts on Pt Nanostructured Thin Films under Start-Up/Shutdown Cycling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cullen, David A; More, Karren Leslie; Atanasoska, Liliana

Electron microscopy and X-ray photoelectron spectroscopy (XPS) methods have been utilized to study the role of oxygen evolution reaction (OER) catalysts in mitigating degradation arising from start-up/shutdown events. Pt nanostructured thin films (NSTF) were coated with a Ru0.1Ir0.9 OER catalyst at loadings ranging from 1 to 10 g/cm2 and submitted to 5,000 potential cycles within a membrane electrode assembly. Analysis of the as-deposited catalyst showed that Ir and Ru coating is primarily metallic, and further evidence is provided to support the previously reported interaction between Ru and the perylene-red support. Aberration-corrected scanning transmission electron microscopy and energy dispersive X-ray spectroscopymore » were used to observe the impact of the OER catalysts on Pt dissolution and migration through the membrane. Elemental mapping showed a high percentage of the Ir catalyst was maintained on the NSTF whisker surfaces following testing. The presence of the OER catalysts greatly reduced the smoothing of the Pt NSTF whiskers, which has been correlated with Pt dissolution and losses in electrochemically active surface area. The dissolution of both Ir and Pt led to the formation of IrPt nanoparticle clusters in the membrane close to the cathode, as well as the formation of a Pt band deeper in the membrane.« less

Water-quality monitoring for a pilot piling removal field evaluation, Coal Creek Slough, Washington, 2008-09

USGS Publications Warehouse

Nilsen, Elena B.; Alvarez, David A.

2011-01-01

Significant Findings Water and sediment quality monitoring was conducted before and after the removal of a piling field located in Coal Creek Slough near Longview, Washington. Passive chemical samplers and continuous water-quality monitoring instruments were deployed at the piling removal site, Coal Creek Slough Site 1 (CCS1), and at a comparison site, Coal Creek Slough Site 2 (CCS2), before (2008) and after (2009) piling removal. Surface and subsurface (core) sediment samples were collected before and after piling removal and were analyzed for grain size, organic carbon content, and chemicals of concern. Significant findings from this study include: * Phenanthrene was the only compound detected in wood piling samples analyzed for a large suite of semivolatile organic compounds and polycyclic aromatic hydrocarbons (PAHs). Metals potentially associated with wood treatment were detected in the wood piling samples at low concentrations. * Organic carbon was slightly lower in core samples from CCS1 in pre-removal (2008) and post-removal (2009) samples than in surface samples from both sites in both years. * Grain-size class distributions were relatively uniform between sites and years. * Thirty-four out of 110 chemicals of concern were detected in sediments. Eight of those detected were anthropogenic waste indicator (AWI) compounds, 18 were PAHs, 4 were sterols, and 4 were metals potentially associated with wood treatment. * Nearly all reported concentrations of chemicals of concern in sediments are qualified as estimates, primarily due to interferences in extracts resulting from complex sample matrices. Indole, perylene, and fluoranthene are reported without qualification for some of the samples, and the metals are reported without qualification for all samples. * The highest frequency of detection of chemicals of concern was seen in the pre-removal surface samples at both sites. * AWI compounds were detected less frequently and at lower concentrations during the post-removal sampling compared to the pre-removal sampling. * Several PAHs were detected at relatively high concentrations in core samples, likely indicating historical sources. * Most commonly detected PAHs in sediments were 2,6-dimethylnaphthalene, fluoranthene, perylene, and pyrene. * Most commonly detected AWIs in sediments were 3-methyl-1h-indole (skatol), acetophenone, indole, phenol, and paracresol. * Sedimentary concentrations of perylene exceeded available sediment quality guidelines. Perylene is widespread in the environment and has large potential natural sources in addition to its anthropogenic sources. * Concentrations of metals did not exceed sediment quality guidelines. * Multiple organochlorine pesticides, both banned and currently used, were detected at each site using passive samplers. * Commonly detected pesticides included hexachlorobenzene, pentachloroanisole (a degradation product of pentachlorophenol), diazinon, cis-chlordane, endosulfan, DDD, and endosulfan sulfate. * PBDE concentrations detected in passive sampler extracts were less than the method detection limit at all sites with the exception of PBDE-99, detected at a concentration less than the reporting limit. * The fragrance galaxolide was detected at a concentration greater than the method detection limit. * Common PAHs, such as phenanthrene, fluoranthene, and pyrene, were detected in every passive sampler. * Dissolved oxygen concentration was slightly higher at site CCS1 compared to site CCS2 in both years. * Overall, there was no systematic increase in chemicals of concern at the restoration site during post-removal monitoring compared to conditions during pre-removal monitoring. Any immediate, short-duration effects of piling removal on water quality could not be determined because monitoring was not conducted during the removal.

Simultaneous Luminescence Pressure and Temperature Mapping

NASA Technical Reports Server (NTRS)

Buck, Gregory M. (Inventor)

1998-01-01

A simultaneous luminescence pressure and temperature mapping system is developed including improved dye application techniques for surface temperature and pressure measurements from 5 torr to 1000 torr with possible upgrade to from 0.5 torr to several atmospheres with improved camera resolution. Adsorbed perylene dye on slip-cast silica is pressure (oxygen) sensitive and reusable to relatively high temperatures (-150 C). Adsorbed luminescence has an approximately linear color shift with temperature, which can be used for independent temperature mapping and brightness pressure calibration with temperature.

Transition metal catalyzed borylation of functional π-systems

PubMed Central

SHINOKUBO, Hiroshi

2014-01-01

Borylated functional π-systems are useful building blocks to enable efficient synthesis of novel molecular architectures with beautiful structures, intriguing properties and unique functions. Introduction of boronic ester substituents to a variety of extended π-systems can be achieved through either iridium-catalyzed direct C–H borylation or the two-step procedure via electrophilic halogenation followed by palladium-catalyzed borylation. This review article focuses on our recent progress on borylation of large π-conjugated systems such as porphyrins, perylene bisimides, hexabenzocoronenes and dipyrrins. PMID:24492644

Simultaneous Luminescence Pressure and Temperature Mapping System

NASA Technical Reports Server (NTRS)

Buck, Gregory M. (Inventor)

1995-01-01

A simultaneous luminescence pressure and temperature mapping system is developed including improved dye application techniques for surface temperature and pressure measurements from 5 torr to 1000 torr with possible upgrade to from 0.5 torr to several atmospheres with improved camera resolution. Adsorbed perylene dye on slip-cast silica is pressure (oxygen) sensitive and reusable to relatively high temperatures (approximately 150 C). Adsorbed luminescence has an approximately linear color shift with temperature, which can be used for independent temperature mapping and brightness pressure calibration with temperature.

An unsymmetrical non-fullerene acceptor: synthesis via direct heteroarylation, self-assembly, and utility as a low energy absorber in organic photovoltaic cells.

PubMed

Payne, Abby-Jo; Li, Shi; Dayneko, Sergey V; Risko, Chad; Welch, Gregory C

2017-09-12

This study reports on the design and synthesis of an unsymmetrical π-conjugated organic molecule composed of perylene diimide, thienyl diketopyrrolopyrrole, and indoloquinoxaline pieced together using direct heteroarylation. This material demonstrates unprecedented response in the thin-film upon post-deposition solvent vapor annealing, resulting in dramatic red-shifts in optical absorption. Such changes were utilized to enhance photocurrent generation in P3HT based organic solar cells.

Optical Spectra and Kinetics of Single Impurity Molecules in a Polymer: Spectral Diffusion and Persistent Spectral Hole-Burning

DTIC Science & Technology

1991-11-07

new area of opticAl sp,,ctroscopy of solids where truly unique single environments and quantum effects can be studied in detail. In the pentacene in p...observed. Until very recentlx, the reports of SMI) have concentrated on the crystalline system of pentacene in p-terphenyl. Owing to the complex physical...excessive PSIIB, pentacene in benzoi, acid, is described briefly. The advantages of the perylene in PF_. system become evident immediately when

Impulsive effects of phase-locked pulse pairs on nuclear motion in the electronic ground state

NASA Astrophysics Data System (ADS)

Cina, J. A.; Smith, T. J.

1993-06-01

The nonlinear effects of ultrashort phase-locked electronically resonant pulse pairs on the ground state nuclear motion are investigated theoretically. The pulse-pair propagator, momentum impulse, and displacement are determined in the weak field limit for pulse pairs separated by a time delay short on a nuclear time scale. Possible application to large amplitude vibrational excitation of the 104 cm-1 mode of α-perylene is considered and comparisons are made to other Raman excitation methods.

Passivation of Black Phosphorus via Self-Assembled Organic Monolayers by van der Waals Epitaxy.

PubMed

Zhao, Yinghe; Zhou, Qionghua; Li, Qiang; Yao, Xiaojing; Wang, Jinlan

2017-02-01

An effective passivation approach to protect black phosphorus (BP) from degradation based on multi-scale simulations is proposed. The self-assembly of perylene-3,4,9,10-tetracarboxylic dianhydride monolayers via van der Waals epitaxy on BP does not break the original electronic properties of BP. The passivation layer thickness is only 2 nm. This study opens up a new pathway toward fine passivation of BP. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Source apportionment of elevated wintertime PAHs by compound-specific radiocarbon analysis

NASA Astrophysics Data System (ADS)

Sheesley, R. J.; Kruså, M.; Krecl, P.; Johansson, C.; Gustafsson, Ã.-.

2009-05-01

Natural abundance radiocarbon analysis facilitates distinct source apportionment between contemporary biomass/biofuel (14C "alive") versus fossil fuel (14C "dead") combustion. Here, the first compound-specific radiocarbon analysis (CSRA) of atmospheric polycyclic aromatic hydrocarbons (PAHs) was demonstrated for a set of samples collected in Lycksele, Sweden a small town with frequent episodes of severe atmospheric pollution in the winter. Renewed interest in using residential wood combustion (RWC) means that this type of seasonal pollution is of increasing concern in many areas. Five individual/paired PAH isolates from three pooled fortnight-long filter collections were analyzed by CSRA: phenanthrene, fluoranthene, pyrene, benzo[b+k]fluoranthene and indeno[cd]pyrene plus benzo[ghi]perylene; phenanthrene was the only compound also analyzed in the gas phase. The measured Δ14C for PAHs spanned from -138.3‰ to 58.0‰. A simple isotopic mass balance model was applied to estimate the fraction biomass (fbiomass) contribution, which was constrained to 71-87% for the individual PAHs. Indeno[cd]pyrene plus benzo[ghi]perylene had an fbiomass of 71%, while fluoranthene and phenanthrene (gas phase) had the highest biomass contribution at 87%. The total organic carbon (TOC, defined as carbon remaining after removal of inorganic carbon) fbiomass was estimated to be 77%, which falls within the range for PAHs. This CSRA data of atmospheric PAHs established that RWC is the dominating source of atmospheric PAHs to this region of the boreal zone with some variations among RWC contributions to specific PAHs.

Sensing of Double-Stranded DNA/RNA Secondary Structures by Water Soluble Homochiral Perylene Bisimide Dyes.

PubMed

Gershberg, Jana; Radić Stojković, Marijana; Škugor, Marko; Tomić, Sanja; Rehm, Thomas H; Rehm, Stefanie; Saha-Möller, Chantu R; Piantanida, Ivo; Würthner, Frank

2015-05-18

A broad series of homochiral perylene bisimide (PBI) dyes were synthesized that are appended with amino acids and cationic side chains at the imide positions. Self-assembly behavior of these ionic PBIs has been studied in aqueous media by UV/Vis spectroscopy, revealing formation of excitonically coupled H-type aggregates. The interactions of these ionic PBIs with different ds-DNA and ds-RNA have been explored by thermal denaturation, fluorimetric titration and circular dichroism (CD) experiments. These PBIs strongly stabilized ds-DNA/RNA against thermal denaturation as revealed by high melting temperatures of the formed PBI/polynucleotide complexes. Fluorimetric titrations showed that these PBIs bind to ds-DNA/RNA with high binding constants depending on the number of the positive charges in the side chains. Thus, spermine-containing PBIs with six positive charges each showed higher binding constants (logKs =9.2-9.8) than their dioxa analogues (logKs =6.5-7.9) having two positive charges each. Induced circular dichroism (ICD) of PBI assemblies created within DNA/RNA grooves was observed. These ICD profiles are strongly dependent on the steric demand of the chiral substituents of the amino acid units and the secondary structure of the DNA or RNA. The observed ICD effects can be explained by non-covalent binding of excitonically coupled PBI dimer aggregates into the minor groove of DNA and major groove of RNA which is further supported by molecular modeling studies. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A universal aptameric biosensor: Multiplexed detection of small analytes via aggregated perylene-based broad-spectrum quencher.

PubMed

Hu, Rong; Zhang, Xi; Xu, Qiang; Lu, Dan-Qing; Yang, Yun-Hui; Xu, Quan-Qing; Ruan, Qiong; Mo, Liu-Ting; Zhang, Xiao-Bing

2017-06-15

A universal aptameric system based on the taking advantage of double-stranded DNA/perylene diimide (dsDNA/PDI) as the signal probe was developed for multiplexed detection of small molecules. Aptamers are single-stranded DNA or RNA oligonucleotides which are selected in vitro by a process known as systematic evolution of ligands by exponential enrichment. In this work, we synthesized a new kind of PDI and reported this aggregated PDI could quench the double-stranded DNA (dsDNA)-labeled fluorophores with a high quenching efficiency. The quenching efficiencies on the fluorescence of FAM, TAMRA and Cy5 could reach to 98.3%±0.9%, 97.2%±0.6% and 98.1%±1.1%, respectively. This broad-spectrum quencher was then adopted to construct a multicolor biosensor via a label-free approach. A structure-switching-triggered enzymatic recycling amplification was employed for signal amplification. High quenching efficiency combined with autocatalytic target recycling amplification afforded the biosensor with high sensitivity towards small analytes. For other targets, changing the corresponding aptamer can achieve the goal. The quencher did not interfere with the catalytic activity of nuclease. The biosensor could be manipulated with similar sensitivity no matter in pre-addition or post-addition manner. Moreover, simultaneous and multiplexed analysis of several small molecules in homogeneous solution was achieved, demonstrating its potential application in the rapid screening of multiple biotargets. Copyright © 2017 Elsevier B.V. All rights reserved.

Long-Lived Charge Separation at Heterojunctions between Semiconducting Single-Walled Carbon Nanotubes and Perylene Diimide Electron Acceptors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kang, Hyun Suk; Sisto, Thomas J.; Peurifoy, Samuel

Nonfullerene electron acceptors have facilitated a recent surge in the efficiencies of organic solar cells, although fundamental studies of the nature of exciton dissociation at interfaces with nonfullerene electron acceptors are still relatively sparse. Semiconducting single-walled carbon nanotubes (s-SWCNTs), unique one-dimensional electron donors with molecule-like absorption and highly mobile charges, provide a model system for studying interfacial exciton dissociation. Here, we investigate excited-state photodynamics at the heterojunction between (6,5) s-SWCNTs and two perylene diimide (PDI)-based electron acceptors. Each of the PDI-based acceptors, hPDI2-pyr-hPDI2 and Trip-hPDI2, is deposited onto (6,5) s-SWCNT films to form a heterojunction bilayer. Transient absorption measurements demonstratemore » that photoinduced hole/electron transfer occurs at the photoexcited bilayer interfaces, producing long-lived separated charges with lifetimes exceeding 1.0 us. Both exciton dissociation and charge recombination occur more slowly for the hPDI2-pyr-hPDI2 bilayer than for the Trip-hPDI2 bilayer. To explain such differences, we discuss the potential roles of the thermodynamic charge transfer driving force available at each interface and the different molecular structure and intermolecular interactions of PDI-based acceptors. As a result, detailed photophysical analysis of these model systems can develop the fundamental understanding of exciton dissociation between organic electron donors and nonfullerene acceptors, which has not been systematically studied.« less

Liquid crystalline perylene diimide outperforming nonliquid crystalline counterpart: higher power conversion efficiencies (PCEs) in bulk heterojunction (BHJ) cells and higher electron mobility in space charge limited current (SCLC) devices.

PubMed

Zhang, Youdi; Wang, Helin; Xiao, Yi; Wang, Ligang; Shi, Dequan; Cheng, Chuanhui

2013-11-13

In this work, we propose the application of liquid crystalline acceptors as a potential means to improve the performances of bulk heterojunction (BHJ) organic solar cells. LC-1, a structurally-simple perylene diimide (PDI), has been adopted as a model for thorough investigation. It exhibits a broad temperature range of liquid crystalline (LC) phase from 41 °C to 158 °C, and its LC properties have been characterized by differental scanning calorimetry (DSC), polarization optical microscopy (POM), and X-ray diffraction (XRD). The BHJ devices, using P3HT:LC-1 (1:2) as an organic photovoltaic active layer undergoing thermal annealing at 120 °C, shows an optimized efficiency of 0.94 %. By contrast, the devices based on PDI-1, a nonliquid crystalline PDI counterpart, only obtain a much lower efficiency of 0.22%. Atomic force microscopy (AFM) images confirm that the active layers composed of P3HT:LC-1 have smooth and ordered morphology. In space charge limited current (SCLC) devices fabricated via a spin-coating technique, LC-1 shows the intrinsic electron mobility of 2.85 × 10(-4) cm(2)/(V s) (at 0.3 MV/cm) which is almost 5 times that of PDI-1 (5.83 × 10(-5) cm(2)/(V s)) under the same conditions for thermal annealing at 120 °C.

Long-Lived Charge Separation at Heterojunctions between Semiconducting Single-Walled Carbon Nanotubes and Perylene Diimide Electron Acceptors

DOE PAGES

Kang, Hyun Suk; Sisto, Thomas J.; Peurifoy, Samuel; ...

2018-04-13

Nonfullerene electron acceptors have facilitated a recent surge in the efficiencies of organic solar cells, although fundamental studies of the nature of exciton dissociation at interfaces with nonfullerene electron acceptors are still relatively sparse. Semiconducting single-walled carbon nanotubes (s-SWCNTs), unique one-dimensional electron donors with molecule-like absorption and highly mobile charges, provide a model system for studying interfacial exciton dissociation. Here, we investigate excited-state photodynamics at the heterojunction between (6,5) s-SWCNTs and two perylene diimide (PDI)-based electron acceptors. Each of the PDI-based acceptors, hPDI2-pyr-hPDI2 and Trip-hPDI2, is deposited onto (6,5) s-SWCNT films to form a heterojunction bilayer. Transient absorption measurements demonstratemore » that photoinduced hole/electron transfer occurs at the photoexcited bilayer interfaces, producing long-lived separated charges with lifetimes exceeding 1.0 us. Both exciton dissociation and charge recombination occur more slowly for the hPDI2-pyr-hPDI2 bilayer than for the Trip-hPDI2 bilayer. To explain such differences, we discuss the potential roles of the thermodynamic charge transfer driving force available at each interface and the different molecular structure and intermolecular interactions of PDI-based acceptors. As a result, detailed photophysical analysis of these model systems can develop the fundamental understanding of exciton dissociation between organic electron donors and nonfullerene acceptors, which has not been systematically studied.« less

Nanoparticle Self-Assembled Grain Like Curcumin Conjugated ZnO: Curcumin Conjugation Enhances Removal of Perylene, Fluoranthene, and Chrysene by ZnO

PubMed Central

Moussawi, Rasha N.; Patra, Digambara

2016-01-01

Curcumin conjugated ZnO, referred as Zn(cur)O, nanostructures have been successfully synthesized, these sub-micro grain-like structures are actually self-assemblies of individual needle-shaped nanoparticles. The nanostructures as synthesized possess the wurtzite hexagonal crystal structure of ZnO and exhibit very good crystalline quality. FT-Raman and TGA analysis establish that Zn(cur)O is different from curcumin anchored ZnO (ZnO@cur), which is prepared by physically adsorbing curcumin on ZnO surfaces. Chemically Zn(cur)O is more stable than ZnO@cur. Diffuse reflectance spectroscopy indicates Zn(cur)O have more impurities compared to ZnO@cur. The solid-state photoluminescence of Zn(cur)O has been investigated, which demonstrates that increase of curcumin concentration in Zn(cur)O suppresses visible emission of ZnO prepared through the same method, this implies filling ZnO defects by curcumin. However, at excitation wavelength 425 nm the emission is dominated by fluorescence from curcumin. The study reveals that Zn(cur)O can remove to a far extent high concentrations of perylene, fluoranthene, and chrysene faster than ZnO. The removal depends on the extent of curcumin conjugation and is found to be faster for PAHs having smaller number of aromatic rings, particularly, it is exceptional for fluoranthene with 93% removal after 10 minutes in the present conditions. The high rate of removal is related to photo-degradation and a mechanism has been proposed. PMID:27080002

Structurally Simple and Easily Accessible Perylenes for Dye-Sensitized Solar Cells Applicable to Both 1 Sun and Dim-Light Environments.

PubMed

Chou, Hsien-Hsin; Liu, Yu-Chieh; Fang, Guanjie; Cao, Qiao-Kai; Wei, Tzu-Chien; Yeh, Chen-Yu

2017-11-01

The need for low-cost and highly efficient dyes for dye-sensitized solar cells under both the sunlight and dim light environments is growing. We have devised GJ-series push-pull organic dyes which require only four synthesis steps. These dyes feature a linear molecular structure of donor-perylene-ethynylene-arylcarboxylic acid, where donor represents N,N-diarylamino group and arylcarboxylic groups represent benzoic, thienocarboxylic, 2-cyano-3-phenylacrylic, 2-cyano-3-thienoacrylic, and 4-benzo[c][1,2,5]thiadiazol-4-yl-benzoic groups. In this study, we demonstrated that a dye without tedious and time-consuming synthesis efforts can perform efficiently. Under the illumination of AM1.5G simulated sunlight, the benzothiadiazole-benzoic-containing GJ-BP dye shows the best power conversion efficiency (PCE) of 6.16% with V OC of 0.70 V and J SC of 11.88 mA cm -2 using liquid iodide-based electrolyte. It also shows high performance in converting light of 6000 lx light intensity, that is, incident power of ca. 1.75 mW cm -2 , to power output of 0.28 mW cm -2 which equals a PCE of 15.79%. Interestingly, the benzoic-containing dye GJ-P with a simple molecular structure has comparable performance in generating power output of 0.26 mW cm -2 (PCE of 15.01%) under the same condition and is potentially viable toward future application.

Spatial Temperature Mapping within Polymer Nanocomposites Undergoing Ultrafast Photothermal Heating via Gold Nanorods

PubMed Central

Maity, Somsubhra; Wu, Wei-Chen; Xu, Chao; Tracy, Joseph B.; Gundogdu, Kenan; Bochinski, Jason R.; Clarke, Laura I.

2015-01-01

Heat emanates from gold nanorods (GNRs) under ultrafast optical excitation of the localized surface plasmon resonance. The steady state nanoscale temperature distribution formed within a polymer matrix embedded with GNRs undergoing pulsed femtosecond photothermal heating is determined experimentally using two independent ensemble optical techniques. Physical rotation of the nanorods reveals the average local temperature of the polymer melt in the immediate spatial volume surrounding them while fluorescence of homogeneously-distributed perylene molecules monitors temperature over sample regions at larger distances from the GNRs. Polarization-sensitive fluorescence measurements of the perylene probes provide an estimate of the average size of the quasi-molten region surrounding each nanorod (that is, the boundary between softened polymer and solid material as the temperature decreases radially away from each particle) and distinguishes the steady state temperature in the solid and melt regions. Combining these separate methods enables nanoscale spatial mapping of the average steady state temperature distribution caused by ultrafast excitation of the GNRs. These observations definitively demonstrate the presence of a steady-state temperature gradient and indicate that localized heating via the photothermal effect within materials enables nanoscale thermal manipulations without significantly altering the bulk sample temperature in these systems. These quantitative results are further verified by reorienting nanorods within a solid polymer nanofiber without inducing any morphological changes to the highly temperature-sensitive nanofiber surface. Temperature differences of 70 – 90 °C were observed over a distances of ~100 nm. PMID:25379775

Optical Sensing of Aromatic Amino Acids and Dipeptides by a Crown-Ether-Functionalized Perylene Bisimide Fluorophore.

PubMed

Weißenstein, Annike; Saha-Möller, Chantu R; Würthner, Frank

2018-06-04

The host-guest binding properties of a fluorescent perylene bisimide (PBI) receptor equipped with crown ether were studied in detail with a series of aromatic amino acids and dipeptides by UV/Vis, fluorescence and NMR spectroscopy. Fluorescence titration experiments showed that electron-rich aromatic amino acids and dipeptides strongly quench the fluorescence of the electron-poor PBI host molecule. Benesi-Hildebrand plots of fluorescence titration data confirmed the formation of host-guest complexes with 1:2 stoichiometry. Binding constants determined by global analysis of UV/Vis and fluorescence titration experiments revealed values between 10 3  m -1 and 10 5  m -1 in acetonitrile/methanol (9:1) at 23 °C. These data showed that amino acid l-Trp having an indole group and dipeptides containing this amino acid bind to the PBI receptor more strongly than other amino acids and dipeptides investigated here. For dipeptides containing l-Trp or l-Tyr, the binding strength is dependent on the distance between the ammonium group and the aromatic unit of the amino acids and dipeptides leading to a strong sensitivity for Ala-Trp dipeptide. 1D and 2D NMR experiments also corroborated 1:2 host-guest complexation and indicated formation of two diastereomeric species of host-guest complexes. The studies have shown that a properly functionalized PBI fluorophore functions as a molecular probe for the optical sensing of aromatic amino acids and dipeptides. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

New stable tunable solid-state dye laser in the red

NASA Astrophysics Data System (ADS)

Gvishi, Raz; Reisfeld, Renata; Burshtein, Zeev; Miron, Eli

1993-08-01

A red perylene derivative was impregnated into a composite silica-gel glass, and characterized as a dye laser material. The absorption spectrum in the range 480 - 600 nm belongs to the S0 - S1 electronic transition, with a structure reflecting the perylene skeletal vibrations, of typical energy 1100 - 1200 cm-1. An additional peak between 400 and 460 nm belongs to the S0 - S2 transition. The fluorescence exhibits a mirror image relative to the S0 - S1 absorption, with a Stokes shift of about 40 nm for the 0 - 0 transition. Laser tunability was obtained in the range 605 - 630 nm using a frequency-doubled Nd:YAG laser for pumping ((lambda) equals 532 nm). This wavelength range is important for medical applications, such as photodynamic therapy of some cancer tumors. Maximum laser efficiency of approximately 2.5% was obtained at 617 nm. Maximum output was approximately 0.36 mJ/pulse at a repetition rate of 10 Hz. Minimum laser threshold obtained was 0.45 mJ/pulse. The medium losses are attributed to an excited-state singlet-singlet absorption, with an upper limit cross-section of approximately 2.5 X 10-16 cm2. The laser output was stable over more than approximately 500,000 pulses, under excitation with the green line of a copper vapor laser (510 nm), of energy density approximately 40 mJ/cm2 per pulse. Good prospects exist for a considerable enhancement in laser output efficiency.

Size distribution of particle-phase molecular markers during a severe winter pollution episode.

PubMed

Kleeman, Michael J; Riddle, Sarah G; Jakober, Chris A

2008-09-01

Airborne particulate matter was collected using filter samplers and cascade impactors in six size fractions below 1.8 microm during a severe winter air pollution event at three sites in the Central Valley of California. The smallest size fraction analyzed was 0.056 < Dp <0.1 microm particle diameter, which accounts for the majority of the mass in the ultrafine (PM0.1) size range. Separate samples were collected during the daytime (10 a.m. to 6 p.m. PST) and nighttime (8 p.m. to 8 a.m. PST) to characterize diurnal patterns. Each sample was extracted with organic solvents and analyzed using gas chromatography mass spectrometry for molecular markers that can be used for size-resolved source apportionment calculations. Colocated impactor and filter measurements were highly correlated (R8 > 0.8) for retene, benzo[ghi]flouranthene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[e]pyrene, benzo[a]pyrene, perylene, indeno[1,2,3-cd]pyrene, benzo[ghi]perylene, coronene, MW302 polycyclic aromatic hydrocarbon (PAHs), 17beta(H)-21alpha(H)-30-norhopane, 17alpha(H)-21beta(H)-hopane, alphabetabeta-20R-C29-ethylcholestane, levoglucosan, and cholesterol. Of these compounds, levoglucosan was present in the highest concentration (60-2080 ng m(-3)) followed by cholesterol (6-35 ng m(-3)), PAHs (2-38 ng m(-3)), and hopanes and steranes (0-2 ng m(-3)). Nighttime concentrations were higher than daytime concentrations in all cases. Organic compound size distributions were generally similar to the total carbon size distributions during the nighttime but showed greater variability during the daytime. This may reflect the dominance of fresh emission in the stagnant surface layer during the evening hours and the presence of aged organic aerosol at the surface during the daytime when the atmosphere is better mixed. All of the measured organic compound particle size distributions had a single mode that peaked somewhere between 0.18 and 0.56 microm, but the width of each distribution varied by compound. Cholesterol generally had the broadest particle size distribution, while benzo[ghi]perylene and 17alpha(H)-21beta(H)-29-norhopane generally had sharper peaks. The difference between the size distributions of the various particle-phase organic compounds reflects the fact that these compounds exist in particles emitted from different sources. The results of the current study will prove useful for size-resolved source apportionment exercises.

New organic semiconductors with imide/amide-containing molecular systems.

PubMed

Liu, Zitong; Zhang, Guanxin; Cai, Zhengxu; Chen, Xin; Luo, Hewei; Li, Yonghai; Wang, Jianguo; Zhang, Deqing

2014-10-29

Due to their high electron affinities, chemical and thermal stabilities, π-conjugated molecules with imide/amide frameworks have received considerable attentions as promising candidates for high-performance optoelectronic materials, particularly for organic semiconductors with high carrier mobilities. The purpose of this Research News is to give an overview of recent advances in development of high performance imide/amide based organic semiconductors for field-effect transistors. It covers naphthalene diimide-, perylene diimide- and amide-based conjugated molecules and polymers for organic semiconductors. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Redox-Active Supramolecular Polymer Binders for Lithium–Sulfur Batteries That Adapt Their Transport Properties in Operando

DOE PAGES

Frischmann, Peter D.; Hwa, Yoon; Cairns, Elton J.; ...

2016-10-25

π-Stacked perylene bisimide (PBI) molecules are implemented here as highly networked, redox-active supramolecular polymer binders in sulfur cathodes for lightweight and energy-dense Li-S batteries. We show that the in operando reduction and lithiation of these PBI binders sustainably reduces Li-S cell impedance relative to nonredox active conventional polymer binders. This lower impedance enables high-rate cycling in Li-S cells with excellent durability, a critical step toward unlocking the full potential of Li-S batteries for electric vehicles and aviation.

Single-molecule studies of oligomer extraction and uptake of dyes in poly(dimethylsiloxane) films.

PubMed

Lange, Jeffrey J; Collinson, Maryanne M; Culbertson, Christopher T; Higgins, Daniel A

2009-12-15

Single-molecule microscopic methods were used to probe the uptake, mobility, and entrapment of dye molecules in cured poly(dimethylsiloxane) (PDMS) films as a function of oligomer extraction. The results are relevant to the use of PDMS in microfluidic separations, pervaporation, solid-phase microextraction, and nanofiltration. PDMS films were prepared by spin-casting dilute solutions of Sylgard 184 onto glass coverslips, yielding approximately 1.4 microm thick films after curing. Residual oligomers were subsequently extracted from the films by "spin extraction". In this procedure, 200 microL aliquots of isopropyl alcohol were repeatedly dropped onto the film surface and spun off at 2000 rpm. Samples extracted 5, 10, 20, and 40 times were investigated. Dye molecules were loaded into these films by spin-casting nanomolar dye solutions onto the films. Both neutral perylene diimide (N,N'-bis(butoxypropyl)perylene-3,4,9,10-tetracarboxylic diimide) and cationic rhodamine 6G (R6G) dyes were employed. The films were imaged by confocal fluorescence microscopy. The images obtained depict nonzero populations of fixed and mobile molecules in all films. Cross-correlation methods were used to quantitatively determine the population of fixed molecules in a given region, while a Bayesian burst analysis was used to obtain the total population of molecules. The results show that the total amount of dye loaded increases with increased oligomer extraction, while the relative populations of fixed and mobile molecules decrease and increase, respectively. Bulk R6G data also show greater dye loading with increased oligomer extraction.

Benzo[ghi]perylene activates the AHR pathway to exert biological effects on the NL-20 human bronchial cell line.

PubMed

Zaragoza-Ojeda, Montserrat; Eguía-Aguilar, Pilar; Perezpeña-Díazconti, Mario; Arenas-Huertero, Francisco

2016-08-10

Polycyclic aromatic hydrocarbons (PAH) are produced by incomplete combustion of organic material. In the Mexico City atmosphere, the most abundant PAH is benzo[ghi]perylene (BghiP), a gasoline combustion marker. At present, there are no reports of the effects of BghiP on human bronchial cells, so the aim of the study was to evaluate the effects in vitro of BghiP on the NL-20 cell line. Results showed that BghiP induced the formation of small vesicles throughout the cytoplasm, with absence of nuclear fragmentation. At 48h exposition, damage in cell membrane increased significantly at 1.24μg/mL of BghiP (p<0.05). Immunocytochemistry revealed that BghiP provokes nuclear translocation of AhR receptor, which indicates that this compound can induce transcription of genes via receptor binding (AhR pathway activation). BghiP induced a two-fold increase (p<0.05) in the expression of AhR and CYP4B1 (a lung-specific pathway effector). In the presence of the receptor antagonist CH-223191, the loss of viability, the nuclear translocation and the overexpression of genes decreased, though this did not prevent the formation of vesicles. BghiP induced oxidative stress and in presence of the receptor antagonist this increased significantly. In conclusion, BghiP can activate the overexpression of AhR and CYP4B1, and the effects are abated by the AhR receptor antagonist. This is the first report to prove that BghiP utilizes the AhR pathway to exert its toxic effects on the NL-20 human bronchial cell line . Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Supramolecularly engineered perylene bisimide assemblies exhibiting thermal transition from columnar to multilamellar structures.

PubMed

Yagai, Shiki; Usui, Mari; Seki, Tomohiro; Murayama, Haruno; Kikkawa, Yoshihiro; Uemura, Shinobu; Karatsu, Takashi; Kitamura, Akihide; Asano, Atsushi; Seki, Shu

2012-05-09

Perylene 3,4:9,10-tetracarboxylic acid bisimide (PBI) was functionalized with ditopic cyanuric acid to organize it into complex columnar architectures through the formation of hydrogen-bonded supermacrocycles (rosette) by complexing with ditopic melamines possessing solubilizing alkoxyphenyl substituents. The aggregation study in solution using UV-vis and NMR spectroscopies showed the formation of extended aggregates through hydrogen-bonding and π-π stacking interactions. The cylindrical fibrillar nanostructures were visualized by microscopic techniques (AFM, TEM), and the formation of lyotropic mesophase was confirmed by polarized optical microscopy and SEM. X-ray diffraction study revealed that a well-defined hexagonal columnar (Col(h)) structure was formed by solution-casting of fibrillar assemblies. All of these results are consistent with the formation of hydrogen-bonded PBI rosettes that spontaneously organize into the Col(h) structure. Upon heating the Col(h) structure in the bulk state, a structural transition to a highly ordered lamellar (Lam) structure was observed by variable-temperature X-ray diffraction, differential scanning calorimetry, and AFM studies. IR study showed that the rearrangement of the hydrogen-bonding motifs occurs during the structural transition. These results suggest that such a striking structural transition is aided by the reorganization in the lowest level of self-organization, i.e., the rearrangement of hydrogen-bonded motifs from rosette to linear tape. A remarkable increase in the transient photoconductivity was observed by the flash-photolysis time-resolved microwave conductivity (FP-TRMC) measurements upon converting the Col(h) structure to the Lam structure. Transient absorption spectroscopy revealed that electron transfer from electron-donating alkoxyphenyl groups of melamine components to electron-deficient PBI moieties takes place, resulting in a higher probability of charge carrier generation in the Lam structure compared to the Col(h) structure.

Fluorescent J-aggregates of core-substituted perylene bisimides: studies on structure-property relationship, nucleation-elongation mechanism, and sergeants-and-soldiers principle.

PubMed

Kaiser, Theo E; Stepanenko, Vladimir; Würthner, Frank

2009-05-20

A series of highly soluble and fluorescent, at core tetraaryloxy-substituted and in imide positions hydrogen atom containing perylene bisimide (PBI) dyes 1a-e with varying peripheral side chains have been synthesized and thoroughly characterized. The self-assembly of these PBIs has been studied in detail by UV/vis, linear dichroism (LD) and circular dichroism (CD) spectroscopy, and scanning probe microscopy (AFM, STM). These studies revealed that the present PBIs self-assemble into extended double string cables, which consist of two hydrogen-bonded supramolecular polymeric chains of densely packed and strongly excitonically coupled PBI chromophores, providing highly fluorescent J-aggregates. The aggregation strength ("melting" temperature) and the fluorescence properties of these J-aggregates are dependent on the number and chain length of the peripheral alkoxy substituents, thus revealing a structure-property relationship. In contrast to previously reported assemblies of PBIs, for which the aggregation process is described by the isodesmic (or equal K) model, a cooperative nucleation-elongation mechanism applies for the aggregation of the present assemblies as revealed by concentration-dependent UV/vis absorption studies with the chiral PBI 1e, providing equilibrium constants for dimerization (= nucleation) of K(2) = 13 +/- 11 L mol(-1) and for elongation of K = 2.3 +/- 0.1 x 10(6) L mol(-1) in methylcyclohexane (MCH). LD spectroscopic measurements have been performed to analyze the orientation of the monomers within the aggregates. The nonlinearity of chiral amplification in PBI aggregates directed by sergeants-and-soldiers principle has been elucidated by coaggregation experiments of different PBI dyes using CD spectroscopy. The dimensions as well as the molecular arrangement of the monomeric units in assemblies have been explored by atomic force microscopy (AFM) and scanning tunneling microscopy (STM).

Self-assembly of dendronized perylene bisimides into complex helical columns.

PubMed

Percec, Virgil; Peterca, Mihai; Tadjiev, Timur; Zeng, Xiangbing; Ungar, Goran; Leowanawat, Pawaret; Aqad, Emad; Imam, Mohammad R; Rosen, Brad M; Akbey, Umit; Graf, Robert; Sekharan, Sivakumar; Sebastiani, Daniel; Spiess, Hans W; Heiney, Paul A; Hudson, Steven D

2011-08-10

The synthesis of perylene 3,4:9,10-tetracarboxylic acid bisimides (PBIs) dendronized with first-generation dendrons containing 0 to 4 methylenic units (m) between the imide group and the dendron, (3,4,5)12G1-m-PBI, is reported. Structural analysis of their self-organized arrays by DSC, X-ray diffraction, molecular modeling, and solid-state (1)H NMR was carried out on oriented samples with heating and cooling rates of 20 to 0.2 °C/min. At high temperature, (3,4,5)12G1-m-PBI self-assemble into 2D-hexagonal columnar phases with intracolumnar order. At low temperature, they form orthorhombic (m = 0, 2, 3, 4) and monoclinic (m = 1) columnar arrays with 3D periodicity. The orthorhombic phase has symmetry close to hexagonal. For m = 0, 2, 3, 4 ,they consist of tetramers as basic units. The tetramers contain a pair of two molecules arranged side by side and another pair in the next stratum of the column, turned upside-down and rotated around the column axis at different angles for different m. In contrast, for m = 1, there is only one molecule in each stratum, with a four-strata 2(1) helical repeat. All molecules face up in one column, and down in the second column, of the monoclinic cell. This allows close and extended π-stacking, unlike in the disruptive up-down alteration from the case of m = 0, 2, 3, 4. Most of the 3D structures were observed only by cooling at rates of 1 °C/min or less. This complex helical self-assembly is representative for other classes of dendronized PBIs investigated for organic electronics and solar cells. © 2011 American Chemical Society

Modeling of experimental data on trace elements and organic compounds content in industrial waste dumps.

PubMed

Smoliński, Adam; Drobek, Leszek; Dombek, Václav; Bąk, Andrzej

2016-11-01

The main objective of the study presented was to investigate the differences between 20 mine waste dumps located in the Silesian Region of Poland and Czech Republic, in terms of trace elements and polycyclic aromatic hydrocarbons contents. The Principal Component Analysis and Hierarchical Clustering Analysis were applied in exploration of the studied data. Since the data set was affected by outlying objects, the employment of a relevant analysis strategy was necessary. The final PCA model was constructed with the use of the Expectation-Maximization iterative approach preceded by a correct identification of outliers. The analysis of the experimental data indicated that three mine waste dumps located in Poland were characterized by the highest concentrations of dibenzo(g,h,i)anthracene and benzo(g,h,i)perylene, and six objects located in Czech Republic and three objects in Poland were distinguished by high concentrations of chrysene and indeno (1.2.3-cd) pyrene. Three of studied mine waste dumps, one located in Czech Republic and two in Poland, were characterized by low concentrations of Cr, Ni, V, naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthen, benzo(a)anthracene, chrysene, benzo (b) fluoranthene, benzo (k) fluoranthene, benzo(a)pyrene, dibenzo(g,h,i)anthracene, benzo(g,h,i)perylene and indeno (1.2.3-cd) pyrene in comparison with the remaining ones. The analysis contributes to the assessment and prognosis of ecological and health risks related to the emission of trace elements and organic compounds (PAHs) from the waste dumps examined. No previous research of similar scope and aims has been reported for the area concerned. Copyright © 2016 Elsevier Ltd. All rights reserved.

High-performance peroxidase mimics for rapid colorimetric detection of H2O2 and glucose derived from perylene diimides functionalized Co3O4 nanoparticles.

PubMed

Ding, Yanan; Chen, Miaomiao; Wu, Kaili; Chen, Mingxing; Sun, Lifang; Liu, Zhenxue; Shi, Zhiqiang; Liu, Qingyun

2017-11-01

N,N'-di-caboxy methyl perylene diimides (PDI), as one of the most promising functional materials in optional chemosensing, was first used to combine with Co 3 O 4 nanoparticles through a facile two-step hydrothermal method and obtain the PDI functionalized Co 3 O 4 nanocomposites (PDI-Co 3 O 4 NCs). PDI-Co 3 O 4 NCs were characterized by a series of technical analysis including transmission electron microscope (TEM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR), respectively. The experimental results indicated that the as-prepared PDI-Co 3 O 4 NCs possessed the higher peroxidase-like activity than that of Co 3 O 4 nanoparticles without PDI, and could rapidly catalyze oxidation reaction of the chromogenic substrate TMB in the presence of H 2 O 2 to a blue product (oxTMB) observed by the naked eye. The improved catalytic activity of PDI-Co 3 O 4 NCs for colorimetric reactions could be attributed to the synergistic effects of PDI and Co 3 O 4 nanoparticles. On the basis of these experimental results, a convenient colorimetric system based on PDI-Co 3 O 4 as enzyme mimic that is highly sensitive and selective was developed for glucose detection. Meanwhile, the electron transfer between H 2 O 2 and TMB was responsible for the oxidation of TMB. The present work demonstrates a general strategy for the design of organic molecules functionalized oxide for different applications, such as nanocatalysts, biosensors and nanomedicine. Copyright © 2017 Elsevier B.V. All rights reserved.

S1(1A1)<--S0(1A1) transition of benzo[g,h,i]perylene in supersonic jets and rare gas matrices.

PubMed

Rouillé, G; Arold, M; Staicu, A; Krasnokutski, S; Huisken, F; Henning, Th; Tan, X; Salama, F

2007-05-07

The study of the S1(1A1)<--S0(1A1) transition of benzo[g,h,i]perylene (BghiP, C22H12) in supersonic jets and solid rare gas matrices is reported. In the jet-cooled spectrum, the origin band position is located at 25,027.1+/-0.2 cm-1, the assignment being supported by the analysis of vibrational shifts and rotational band contours. Except for the origin band, which is weak, all bands are attributed to the fundamental excitation of nontotally symmetric b1 vibrational modes of S1. The intensity pattern is interpreted as a consequence of the weak oscillator strength of the electronic transition combined with intensity-borrowing through vibronic interaction between the S1(1A1) and S2(1B1) states. The spectra of the S1(1A1)<--S0(1A1) and S2(1B1)<--S0(1A1) transitions have also been measured for BghiP in solid neon and argon matrices. The comparison of the redshifts determined for either transition reveals that the polarizability of BghiP is larger in its S2 than in its S1 state. Bandwidths of 2.7 cm-1 measured in supersonic jets, which provide conditions relevant for astrophysics, are similar to those of most diffuse interstellar bands. The electronic transitions of BghiP are found to lie outside the ranges covered by present databases. From the comparison between experimental spectra and theoretical computations, it is concluded that the accuracy of empirical and ab initio approaches in predicting electronic energies is still not sufficient to identify astrophysically interesting candidates for spectroscopic laboratory studies.

Perylene-Diimide Based Donor-Acceptor-Donor Type Small-Molecule Acceptors for Solution-Processable Organic Solar Cells

NASA Astrophysics Data System (ADS)

Ganesamoorthy, Ramasamy; Vijayaraghavan, Rajagopalan; Sakthivel, Pachagounder

2017-12-01

Development of nonfullerene acceptors plays an important role in the commercial availability of plastic solar cells. We report herein synthesis of bay-substituted donor-acceptor-donor (D-A-D)-type perylene diimide (PDI)-based small molecules (SM-1 to SM-4) by Suzuki coupling method and their use as acceptors in bulk heterojunction organic solar cells (BHJ-OSCs) with poly(3-hexylthiophene) (P3HT) polymer donor. We varied the number of electron-rich thiophene units and the solubilizing side chains and also evaluated the optical and electrochemical properties of the small molecules. The synthesized small molecules were confirmed by Fourier-transform infrared (FT-IR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, and high-resolution mass spectroscopy (HR-MS). The small molecules showed extensive and strong absorption in the ultraviolet-visible (UV-Vis) region up to 750 nm, with bandgap (E_{{g}}^{{opt}} ) reduced below <2 eV. The energy levels of small molecules SM-1 to SM-4 were suitable for use as electron-accepting materials. The small molecules showed good thermal stability up to 300°C. BHJ-OSCs with SM-1 and P3HT polymer donor showed maximum power conversion efficiency (PCE) of 0.19% with V oc of 0.30 V, J sc of 1.72 mA cm-2, and fill factor (FF) of 37%. The PCE decreased with the number of thiophene units. The PCE of SM-2 was lower than that of SM-1. This difference in PCE can be explained by the higher aggregation tendency of the bithiophene compared with the thiophene unit. Introduction of the solubilizing group in the bay position increased the aggregation property, leading to much lower PCE than for the small molecules without solubilizing group.

Emissions of particle-phase polycyclic aromatic hydrocarbons (PAHs) in the Fu Gui-shan Tunnel of Nanjing, China

NASA Astrophysics Data System (ADS)

Chen, Fei; Hu, Wei; Zhong, Qin

2013-04-01

Real-world vehicle emission factors for PM10 (particulate matter with aerodynamic diameter smaller than 10 μm) and particle-phase polycyclic aromatic hydrocarbons (PAHs) from mixed vehicles were quantified in the Fu Gui-shan Tunnel of Nanjing during summer and winter of 2010. Concentrations of PM10 and sixteen particle phase polycyclic aromatic hydrocarbons (PAHs) in the entrance and exit of the tunnel were studied. The results showed that the four most abundant particular phase polycyclic aromatic hydrocarbons (PAHs) of motor vehicle were benzo[ghi]perylene, benzo[k]fluoranthene, benz[a]anthracene and benzo[a]pyrene. The emission factors for PM10 and particle-phase PAHs were 687 mg veh- 1 km- 1 and 18.853 mg veh- 1 km- 1 in summer, 714 mg veh- 1 km- 1 and 20.374 mg veh- 1 km- 1 in winter. Higher particle-phase PAH emission factors were found to be associated with a high proportion of diesel-fueled vehicles (DV). The estimated PM10 emission factor of gasoline-fueled vehicles (GV) was 513 mg veh- 1 km- 1 and the value for DV was 914 mg veh- 1 km- 1, while EFDV of particulate PAH (31.290 mg veh- 1 km- 1) was nearly 4 times higher than EFGV (9.310 mg veh- 1 km- 1). The five highest emission factors of diesel-fueled vehicles (DV) were benzo[ghi]perylene, benzo[k]fluoranthene, Indeno[1,2,3-cd]pyrene, benz[a]anthracene and benzo[a]pyrene, which was similarly found in the gasoline-fueled vehicles (GV). The sum of these five emission factors accounted for ~ 69% of the total particle-phase PAH of DV and ~ 67% of GV.

Installation Restoration Program. Phase 2. Confirmation/Quantification, Stage 2 for Seymour Johnson Air Force Base, North Carolina. Volume 4

DTIC Science & Technology

1988-11-01

BENZIDINE 400 81)1 5 BENZO (a) ANTHRACENE 400 ODL 6 BENZ0 (a) PYRENE 400 61 )1 7 BENZO (b) FLUORANTHENE 400 61 )1 a BENZO (ghl) PERYLENE 1003 61 )1 9...BENZO (k) FLUIORANTHENE 400 61 )1 10 815 (2-CHOROEThOXY) METHANE 400 81)1 11 815 (2-CHOROETIIYL) ETHER 400 BDL 12 8(5 (2-CHLOROISOPROPYL) ETHER 400 BDL 13...CHOROPHENYL PHENYL ETHER 400 61 )1 18 CHRYSENE 400 B1)L - 19 DIBEIQO (ah) ANTHRACENE 400 81)1 20 1,2-DICHOROBENZENE 400 81)1 21 1 ,3-DICHLOROBENZENE

Direct Observation of Excimer-Mediated Intramolecular Electron Transfer in a Cofacially-Stacked Perylene Bisimide Pair.

PubMed

Sung, Jooyoung; Nowak-Król, Agnieszka; Schlosser, Felix; Fimmel, Benjamin; Kim, Woojae; Kim, Dongho; Würthner, Frank

2016-07-27

We have elucidated excimer-mediated intramolecular electron transfer in cofacially stacked PBIs tethered by two phenylene-butadiynylene loops. The electron transfer between energetically equivalent PBIs is revealed by the simultaneous observation of the PBI radical anion and cation bands in the transient absorption spectra. The fluorescence decay time of the excimer states is in good agreement with the rise time of PBI radical bands in transient absorption spectra suggesting that the electron transfer dynamics proceed via the excimer state. We can conclude that the excimer state effectuates the efficient charge transfer in the cofacially stacked PBI dimer.

Rylene and related diimides for organic electronics.

PubMed

Zhan, Xiaowei; Facchetti, Antonio; Barlow, Stephen; Marks, Tobin J; Ratner, Mark A; Wasielewski, Michael R; Marder, Seth R

2011-01-11

Organic electron-transporting materials are essential for the fabrication of organic p-n junctions, photovoltaic cells, n-channel field-effect transistors, and complementary logic circuits. Rylene diimides are a robust, versatile class of polycyclic aromatic electron-transport materials with excellent thermal and oxidative stability, high electron affinities, and, in many cases, high electron mobilities; they are, therefore, promising candidates for a variety of organic electronics applications. In this review, recent developments in the area of high-electron-mobility diimides based on rylenes and related aromatic cores, particularly perylene- and naphthalene-diimide-based small molecules and polymers, for application in high-performance organic field-effect transistors and photovoltaic cells are summarized and analyzed.

Novel fluorescent core-shell nanocontainers for cell membrane transport.

PubMed

Yin, Meizhen; Kuhlmann, Christoph R W; Sorokina, Ksenia; Li, Chen; Mihov, George; Pietrowski, Eweline; Koynov, Kaloian; Klapper, Markus; Luhmann, Heiko J; Müllen, Klaus; Weil, Tanja

2008-05-01

The synthesis and characterization of novel core-shell macromolecules consisting of a fluorescent perylene-3,4,9,10-tetracarboxdiimide chromophore in the center surrounded by a hydrophobic polyphenylene shell as a first and a flexible hydrophilic polymer shell as a second layer was presented. Following this strategy, several macromolecules bearing varying polymer chain lengths, different polymer shell densities, and increasing numbers of positive and negative charges were achieved. Because all of these macromolecules reveal a good water solubility, their ability to cross cellular membranes was investigated. In this way, a qualitative relationship between the molecular architecture of these macromolecules and the biological response was established.

Low Band Gap Thiophene-Perylene Diimide Systems with Tunable Charge Transport Properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Balaji, Ganapathy; Kale, Tejaswini S.; Keerthi, Ashok

2011-01-07

Perylenediimide-pentathiophene systems with varied architecture of thiophene units were synthesized. The photophysical, electrochemical, and charge transport behavior of the synthesized compounds were studied. Both molecules showed a low band gap of ~1.4 eV. Surprisingly, the molecule with pentathiophene attached via β-position to the PDI unit upon annealing showed a predominant hole mobility of 1 × 10 -4 cm 2 V -1 s -1 whereas the compound with branched pentathiophene attached via β-position showed an electron mobility of 9.8 × 10 -7 cm 2 V -1 s -1. This suggests that charge transport properties can be tuned by simply varying themore » architecture of pentathiophene units.« less

Role of organic interfacial modifiers in inverted polymers solar cells: An in-depth analysis of perylene vs fullerene organic modifiers

NASA Astrophysics Data System (ADS)

Kumar, S.; Panigrahi, D.; Dhar, A.

2018-03-01

Interfacial issues can significantly restrict the performance of photovoltaic devices by exacerbating the charge recombination channels, macroscopic phase separation, and providing a non-ideal contact for selective extraction of charges particularly in photovoltaic devices using organic and inorganic materials together. Organic interfacial modifiers (IMs) are often used to mitigate these issues by modifying the organic-inorganic interface. In order to extricate the role of these IMs on the photovoltaic performance we have made a comprehensive study on the application of perylene-based and fullerene small molecules having different molecular origin as organic IMs on ZnO electron extracting layers in inverted BHJs photovoltaic devices. We report an elaborate study on the electronic and surface altering properties of these IMs and correlated their effect on the different PV performance parameters of the inverted BHJ solar cells employing P3HT: PCBM photoactive layer. Our investigations demonstrate the role of these organic IMs in reducing the ZnO cathode work function and increasing its electron transportation property along with the passivation of superficial traps states present on ZnO which helps in selective extraction of charge carriers from the devices and minimize the recombination losses. These different aspects of IMs compete and their balanced effect decides the final outcome. As a result, we obtain a substantial improvement in the device performance with power conversion efficiency (PCE) of 3.0% for the C70/ZnO cathode device which shows over 60% improvement in contrast to the devices without any ZnO surface modification. The present investigation intents to exhibit the feasibility of vacuum sublimated organic small molecules in performance improvement in BHJ solar cells utilizing the ZnO ETLs and contrast their efficacy for the purpose rather than setting any benchmark device performance although the efficiencies obtained are typical for the active layer used in the study.

Interference between Coulombic and CT-mediated couplings in molecular aggregates: H- to J-aggregate transformation in perylene-based π-stacks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hestand, Nicholas J.; Spano, Frank C.

2015-12-28

The spectroscopic differences between J and H-aggregates are traditionally attributed to the spatial dependence of the Coulombic coupling, as originally proposed by Kasha. However, in tightly packed molecular aggregates wave functions on neighboring molecules overlap, leading to an additional charge transfer (CT) mediated exciton coupling with a vastly different spatial dependence. The latter is governed by the nodal patterns of the molecular LUMOs and HOMOs from which the electron (t{sub e}) and hole (t{sub h}) transfer integrals derive. The sign of the CT-mediated coupling depends on the sign of the product t{sub e}t{sub h} and is therefore highly sensitive tomore » small (sub-Angstrom) transverse displacements or slips. Given that Coulombic and CT-mediated couplings exist simultaneously in tightly packed molecular systems, the interference between the two must be considered when defining J and H-aggregates. Generally, such π-stacked aggregates do not abide by the traditional classification scheme of Kasha: for example, even when the Coulomb coupling is strong the presence of a similarly strong but destructively interfering CT-mediated coupling results in “null-aggregates” which spectroscopically resemble uncoupled molecules. Based on a Frenkel/CT Holstein Hamiltonian that takes into account both sources of electronic coupling as well as intramolecular vibrations, vibronic spectral signatures are developed for integrated Frenkel/CT systems in both the perturbative and resonance regimes. In the perturbative regime, the sign of the lowest exciton band curvature, which rigorously defines J and H-aggregation, is directly tracked by the ratio of the first two vibronic peak intensities. Even in the resonance regime, the vibronic ratio remains a useful tool to evaluate the J or H nature of the system. The theory developed is applied to the reversible H to J-aggregate transformations recently observed in several perylene bisimide systems.« less

Quantity and quality of stormwater collected from selected stormwater outfalls at industrial sites, Fort Gordon, Georgia, 2012

USGS Publications Warehouse

Nagle, Doug D.

2013-01-01

Samples from sites SWR11–3, SWR11–4, and SWR11–5 were analyzed for 83 volatile and semivolatile organic compounds. Eight polycyclic aromatic hydrocarbon compounds, benzo[a]pyrene, benzo[b]fluoranthene, benzo[ghi]perylene, benzo[k]fluoranthene, chrysene, indeno[1,2,3-cd]pyrene, phenanthrene, and pyrene, were detected at all three sites. Of the 86 volatile and semivolatile organic compounds that were analyzed in stormwater samples from heating and cooling sites, 15 (18 percent) were detected at site SWR11–3, 12 (14 percent) were detected at site SWR11–4, and 17 (20 percent) were detected at site SWR11–5.

Absorption spectra of PTCDI: A combined UV-Vis and TD-DFT study

NASA Astrophysics Data System (ADS)

Oltean, Mircea; Calborean, Adrian; Mile, George; Vidrighin, Mihai; Iosin, Monica; Leopold, Loredana; Maniu, Dana; Leopold, Nicolae; Chiş, Vasile

2012-11-01

Absorption spectra of PTCDI (3,4,9,10-perylene-tetracarboxylic-diimide) have been investigated in chloroform, N,N'-dimethylformamide (DMF) and dimethylsulfoxide (DMSO). While no signature of assembled PTCDI molecules is observed in chloroform solution, distinct bands assigned to their aggregation have been identified in DMF and DMSO solutions. PTCDI monomers show very similar absorption patterns in chloroform and DMSO solutions. Experimental data, including the vibronic structure of the absorption spectra were explained based on the Franck-Condon approximation and quantum chemical results obtained at PBE0-DCP/6-31+G(d,p) level of theory. Geometry optimization of the first excited state leads to a nice agreement between the calculated adiabatic transition energies and experimental data.

Photon Upconversion Using Baird-Type (Anti)Aromatic Quinoidal Naphthalene Derivative as a Sensitizer

DOE PAGES

Shokri, Siamak; Wiederrecht, Gary P.; Gosztola, David J.; ...

2017-10-02

In this study, a naphtho-p-quinodimethane (QDM) exhibiting Baird’s 4n - π antiaromaticity was used as green photonsharvesting chromophore to sensitize perylene (Per) leading to upconverted blue photoluminescence. The solution phase QDM → Per triplet energy transfer (TET) could not be unraveled via the Stern-Volmer method, but transient absorption measurements revealed that the kinetics of T 1 → T n for QDM (τ = 1.4 μs) was 1 order of magnitude reduced (τ= 0.17 μs) as a result of 3(Per)* formation. Lastly, we demonstrated that incident light with power densities in the microwatt regime is sufficient to perform photon upconversion usingmore » the present set of molecular systems.« less

Priority PAHs in orthodox black tea during manufacturing process.

PubMed

Grover, Inderpreet Singh; Singh, Satnam; Pal, Bonamali

2013-08-01

Orthodox black tea is obtained from fresh leaves followed by withering, rolling, fermentation and drying. The presence of 16 priority polycyclic aromatic hydrocarbons (PAHs) was studied in fresh leaves and at various stages of manufacturing. Benzo(a)pyrene (2A: probable human carcinogen) was found in dried tea leaves only whereas, naphthalene (2B: probable human carcinogen) was present during all the stages of manufacturing. Dry tea leaves showed higher content of total 16 PAHs (∑PAHs) about 3 and 211 times than present in withered and dried leaves, respectively. Chrysene, benzo[g,h,i]perylene, indendo[1,2,3-c,d]pyrene, dibenzo[a,h]pyrene and benzo[a]antracene were not found during manufacturing stages of tea.

Sediments from stormwater drainage system as sorbents of organic and inorganic pollutants

NASA Astrophysics Data System (ADS)

Sałata, Aleksandra; Dąbek, Lidia

2017-11-01

The study presents the results of tests aimed at determining variations in concentrations of polycyclic aromatic hydrocarbons (naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenzo[a, h]anthracene, benzo[g, h, i]perylene and indeno[1, 2, 3-c, d]pyrene) and heavy metals (copper, cadmium, chromium, nickel, lead and zinc) in the sediments from the stormwater sewer system. Results of this study were then compared to Polish regulations and established ecological screening values to determine their potential risk to environment. The results suggest that stormwater sediments are moderately contaminated with PAHs and heavy metals according to domestic regulations and highly contaminated according to ecological benchmarks.

Polycyclic aromatic hydrocarbons associated with airborne particulate matter at a Pathumthani location, 40 km north of Bangkok, Thailand

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oanh, N.T.K.; Reutergardh, L.B.; Dung, N.T.

Total suspended particulate matter in ambient air was sampled by high volume samplers at four sites at the Asian Institute of Technology campus, west of the Phahonyothin Road, Phathumthani Province, 40 km North of Bangkok, Thailand. The concentrations of 18 polycyclic aromatic hydrocarbons (PAHs), were measured by gas liquid chromatography with flame ionization and/or liquid solid chromatography with fluorescence detection. The PAH profile with relatively high concentrations of benzo(ghi)perylene and coronene, decreasing with the distance from the road, suggested a substantial contribution from the traffic. The concentrations in the core of the campus were compatible to those reported for residentialmore » areas in Bangkok, but higher than some western metropolitan areas.« less

Efficient fluorescence "turn-on" sensing of dissolved oxygen by electrochemical switching.

PubMed

Shin, Ik-Soo; Hirsch, Thomas; Ehrl, Benno; Jang, Dong-Hak; Wolfbeis, Otto S; Hong, Jong-In

2012-11-06

We report on a novel method for sensing oxygen that is based on the use of a perylene diimide dye (1) which is electrochemically reduced to its nonfluorescent dianion form (1(2-)). In the presence of oxygen, the dianion is oxidized to its initial form via an electron-transfer reaction with oxygen upon which fluorescence is recovered. As a result, the fluorescence intensity of the dianion solution increases upon the addition of oxygen gas. Results demonstrate that high sensitivity is obtained, and the emission intensity shows a linear correlation with oxygen content (0.0-4.0% v/v) at ambient barometric pressure. In addition, using electrochemical reduction, oxygen determination becomes regenerative, and no significant degradation is observed over several turnovers. The limit of detection is 0.4% oxygen in argon gas.

Temperature-Responsive Luminescent Solar Concentrators: Tuning Energy Transfer in a Liquid Crystalline Matrix.

PubMed

Sol, Jeroen A H P; Dehm, Volker; Hecht, Reinhard; Würthner, Frank; Schenning, Albertus P H J; Debije, Michael G

2018-01-22

Temperature-responsive luminescent solar concentrators (LSCs) have been fabricated in which the Förster resonance energy transfer (FRET) between a donor-acceptor pair in a liquid crystalline solvent can be tuned. At room temperatures, the perylene bisimide (PBI) acceptor is aggregated and FRET is inactive; while after heating to a temperature above the isotropic phase of the liquid crystal solvent, the acceptor PBI completely dissolves and FRET is activated. This unusual temperature control over FRET was used to design a color-tunable LSC. The device has been shown to be highly stable towards consecutive heating and cooling cycles, making it an appealing device for harvesting otherwise unused solar energy. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

First Principles Optical Absorption Spectra of Organic Molecules Adsorbed on Titania Nanoparticles

NASA Astrophysics Data System (ADS)

Baishya, Kopinjol; Ogut, Serdar; Mete, Ersen; Gulseren, Oguz; Ellialtioglu, Sinasi

2012-02-01

We present results from first principles computations on passivated rutile TiO2 nanoparticles in both free-standing and dye-sensitized configurations to investigate the size dependence of their optical absorption spectra. The computations are performed using time-dependent density functional theory (TDDFT) as well as GW-Bethe-Salpeter-Equation (GWBSE) methods and compared with each other. We interpret the first principles spectra for free-standing TiO2 nanoparticles within the framework of the classical Mie-Gans theory using the bulk dielectric function of TiO2. We investigate the effects of the titania support on the absorption spectra of a particular set of perylene-diimide (PDI) derived dye molecules, namely brominated PDI (Br2C24H8N2O4) and its glycine and aspartine derivatives.

Layer-by-Layer Assembled Films of Perylene Diimide- and Squaraine-Containing Metal-Organic Frameworks- like Materials: Solar Energy Capture and Directional Energy Transfer

DOE PAGES

Park, Hea Jung; So, Monica C.; Gosztola, David J.

2016-09-28

We demonstrate that thin films of metal organic framework (MOF)-like materials, containing two perylenedlimides (PDICl4, PDIOPh2) and a squaraine dye (S1); can be fabricated by, layer-by-layer assembly (LbL). Interestingly, these LbL films absorb across the visible light region (400-750 nm) and facilitate directional energy transfer. Due to the high spectral overlap and oriented transition dipole moments of the donor (PDICl4 and PDIOPh2) and acceptor (S1) components, directional long-range energy transfer from the bluest to reddest absorber was successfully demonstrated in the multicomponent MOF-like films. These findings have significant implications for the development of solar energy conversion devices based on MOFs.

Fluorescent supramolecular micelles for imaging-guided cancer therapy

NASA Astrophysics Data System (ADS)

Sun, Mengmeng; Yin, Wenyan; Dong, Xinghua; Yang, Wantai; Zhao, Yuliang; Yin, Meizhen

2016-02-01

A novel smart fluorescent drug delivery system composed of a perylene diimide (PDI) core and block copolymer poly(d,l-lactide)-b-poly(ethyl ethylene phosphate) is developed and named as PDI-star-(PLA-b-PEEP)8. The biodegradable PDI-star-(PLA-b-PEEP)8 is a unimolecular micelle and can self-assemble into supramolecular micelles, called as fluorescent supramolecular micelles (FSMs), in aqueous media. An insoluble drug camptothecin (CPT) can be effectively loaded into the FSMs and exhibits pH-responsive release. Moreover, the FSMs with good biocompatibility can also be employed as a remarkable fluorescent probe for cell labelling because the maximum emission of PDI is beneficial for bio-imaging. The flow cytometry and confocal laser scanning microscopy analysis demonstrate that the micelles are easily endocytosed by cancer cells. In vitro and in vivo tumor growth-inhibitory studies reveal a better therapeutic effect of FSMs after CPT encapsulation when compared with the free CPT drug. The multifunctional FSM nanomedicine platform as a nanovehicle has great potential for fluorescence imaging-guided cancer therapy.A novel smart fluorescent drug delivery system composed of a perylene diimide (PDI) core and block copolymer poly(d,l-lactide)-b-poly(ethyl ethylene phosphate) is developed and named as PDI-star-(PLA-b-PEEP)8. The biodegradable PDI-star-(PLA-b-PEEP)8 is a unimolecular micelle and can self-assemble into supramolecular micelles, called as fluorescent supramolecular micelles (FSMs), in aqueous media. An insoluble drug camptothecin (CPT) can be effectively loaded into the FSMs and exhibits pH-responsive release. Moreover, the FSMs with good biocompatibility can also be employed as a remarkable fluorescent probe for cell labelling because the maximum emission of PDI is beneficial for bio-imaging. The flow cytometry and confocal laser scanning microscopy analysis demonstrate that the micelles are easily endocytosed by cancer cells. In vitro and in vivo tumor growth-inhibitory studies reveal a better therapeutic effect of FSMs after CPT encapsulation when compared with the free CPT drug. The multifunctional FSM nanomedicine platform as a nanovehicle has great potential for fluorescence imaging-guided cancer therapy. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr00450d

Impact of molecular solvophobicity vs. solvophilicity on device performances of dimeric perylene diimide based solution-processed non-fullerene organic solar cells.

PubMed

Lu, Zhenhuan; Zhang, Xin; Zhan, Chuanlang; Jiang, Bo; Zhang, Xinliang; Chen, Lili; Yao, Jiannian

2013-07-21

Because of their outstanding molecular optoelectronic properties, perylene diimides (PDIs) are promising alternatives to the commonly used PCBM. However, the overly strong aggregation ability, poor solution-processability and compatibility of PDIs severely limit their photovoltaic applications. We turned to borrowing the amphiphile concept to improve these supramolecular properties. Practically, we fine-tuned the molecular solvophobicity with respect to the molecular solvophilicity, e.g. F(solvophob/solvophil), by changing the number of the weakly solvophobic 2-methoxyethoxyl (EG) groups in the bay-region of the thienyl-bridged dimeric PDI backbone, forming three PDI dimers of Bis-PDI-T (0 EG), Bis-PDI-T-EG (2 EG) and Bis-PDI-T-di-EG (4 EG) (Scheme 1). The photovoltaic properties using these dimers as the solution-processed non-fullerene electron-acceptor and P3HT as the electron-donor were investigated via the device configuration of ITO/PEDOT:PSS/P3HT:PDI dimer/Ca/Al. Bis-PDI-T exhibited overly strong aggregation ability and very poor solution-processability, which severely limited compatibility, giving a very poor power conversion efficiency (PCE) of 0.007%. When two EG groups were attached at the 1,1'-positions, the resulted Bis-PDI-T-EG showed dramatically reduced aggregation ability, improved solution-processability, compatibility and proper phase separation. Small sized phases (∼20 nm) dominated in the active layer and the best PCE was increased to 0.39%. When four solvophobic EG functions were introduced, affording Bis-PDI-T-di-EG with excellent supramolecular properties, particularly, the improvement of the phase separation with an increased phase size of 24 nm and the enhanced electron and hole mobilities, by 2-4 times, with respect to that of Bis-PDI-T-EG. The best PCE was further enhanced to 0.88%. After using 1-chloronaphthalene as the co-solvent of 1,2-dichlorobenzene to further improve the compatibility, the PCE was improved further up to 0.41% for Bis-PDI-T, 0.76% for Bis-PDI-T-EG and 1.54% for Bis-PDI-T-di-EG.

Genotoxicity-Related Chemistry of Human Metabolites of Benzo[ghi]perylene (B[ghi]P) Investigated using Electro-optical Arrays and DNA/Microsome Biocolloid Reactors with LC-MS/MS

PubMed Central

Pan, Shenmin; Li, Dandan; Zhao, Linlin; Schenkman, John B.; Rusling, James F.

2013-01-01

There is limited and sometimes contradictory information about the genotoxicity of polycyclic aromatic hydrocarbon benzo[ghi]perylene (B[ghi]P). Using recently developed metabolic toxicity screening arrays and a biocolloid reactor-LC-MS/MS approach, both featuring films of DNA and human metabolic enzymes, we demonstrated relatively low reactivity of metabolically activated B[ghi]P towards DNA. Electro-optical toxicity screening arrays showed that B[ghi]P metabolites damage DNA at a 3-fold lower rate than benzo[a]pyrene (B[a]P), whose metabolites have a strong and well-understood propensity for DNA damage. Metabolic studies using magnetic bead biocolloid reactors coated with microsomal enzymes in 96-well plates showed that cyt P450s 1A1 and 1B1 provide high activity for B[ghi]P and B[a]P conversion. Consistent with published results, the major metabolism of B[ghi]P involved oxidations at 3,4 and 11,12 positions, leading to formation of B[ghi]P 3,4-oxide and B[ghi]P 3,4,11,12-bisoxide. B[ghi]P 3,4-oxide was synthesized and reacted with deoxyadenosine at N6 and N7 positions and with deoxyguanosine at the N2 position. B[ghi]P 3,4-oxide is hydrolytically unstable and transforms into the 3,4-diol or converts to 3- or 4-hydroxy B[ghi]P. LC-MS/MS of reaction products from the magnetic biocolloid reactor particles coated with DNA and human enzymes revealed for the first time that a major DNA adduct results from reaction between B[ghi]P 3,4,11,12-bisoxide and deoxyguanosine. Results also demonstrated 5-fold lower formation rates of the major DNA adduct for B[ghi]P metabolites compared to B[a]P. Overall, results from both ECL array and biocolloid reactor-LC-MS/MS consistently suggest a lower human genotoxicity profile of B[ghi]P than B[a]P. PMID:23879290

Work function and temperature dependence of electron tunneling through an N-type perylene diimide molecular junction with isocyanide surface linkers.

PubMed

Smith, Christopher E; Xie, Zuoti; Bâldea, Ioan; Frisbie, C Daniel

2018-01-18

Conducting probe atomic force microscopy (CP-AFM) was employed to examine electron tunneling in self-assembled monolayer (SAM) junctions. A 2.3 nm long perylene tetracarboxylic acid diimide (PDI) acceptor molecule equipped with isocyanide linker groups was synthesized, adsorbed onto Ag, Au and Pt substrates, and the current-voltage (I-V) properties were measured by CP-AFM. The dependence of the low-bias resistance (R) on contact work function indicates that transport is LUMO-assisted ('n-type behavior'). A single-level tunneling model combined with transition voltage spectroscopy (TVS) was employed to analyze the experimental I-V curves and to extract the effective LUMO position ε l = E LUMO - E F and the effective electronic coupling (Γ) between the PDI redox core and the contacts. This analysis revealed a strong Fermi level (E F ) pinning effect in all the junctions, likely due to interface dipoles that significantly increased with increasing contact work function, as revealed by scanning Kelvin probe microscopy (SKPM). Furthermore, the temperature (T) dependence of R was found to be substantial. For Pt/Pt junctions, R varied more than two orders of magnitude in the range 248 K < T < 338 K. Importantly, the R(T) data are consistent with a single step electron tunneling mechanism and allow independent determination of ε l , giving values compatible with estimates of ε l based on analysis of the full I-V data. Theoretical analysis revealed a general criterion to unambiguously rule out a two-step transport mechanism: namely, if measured resistance data exhibit a pronounced Arrhenius-type temperature dependence, a two-step electron transfer scenario should be excluded in cases where the activation energy depends on contact metallurgy. Overall, our results indicate (1) the generality of the Fermi level pinning phenomenon in molecular junctions, (2) the utility of employing the single level tunneling model for determining essential electronic structure parameters (ε l and Γ), and (3) the importance of changing the nature of the contacts to verify transport mechanisms.

Laser-Induced Fluorescence Emission (L.I.F.E.): searching for Mars organics with a UV-enhanced PanCam.

PubMed

Storrie-Lombardi, Michael C; Muller, Jan-Peter; Fisk, Martin R; Cousins, Claire; Sattler, Birgit; Griffiths, Andrew D; Coates, Andrew J

2009-12-01

The European Space Agency will launch the ExoMars mission in 2016 with a primary goal of surveying the martian subsurface for evidence of organic material. We have recently investigated the utility of including either a 365 nm light-emitting diode or a 375 nm laser light source in the ExoMars rover panoramic camera (PanCam). Such a modification would make it feasible to monitor rover drill cuttings optically for the fluorescence signatures of aromatic organic molecules and map the distribution of polycyclic aromatic hydrocarbons (PAHs) as a function of depth to the 2 m limit of the ExoMars drill. The technique described requires no sample preparation, does not consume irreplaceable resources, and would allow mission control to prioritize deployment of organic detection experiments that require sample destruction, expenditure of non-replaceable consumables, or both. We report here for the first time laser-induced fluorescence emission (L.I.F.E.) imaging detection limits for anthracene, pyrene, and perylene targets doped onto a Mars analog granular peridotite with a 375 nm Nichia laser diode in optically uncorrected wide-angle mode. Data were collected via the Beagle 2 PanCam backup filter wheel fitted with original blue (440 nm), green (530 nm), and red (670 nm) filters. All three PAH species can be detected with the PanCam green (530 nm) filter. Detection limits in the green band for signal-to-noise ratios (S/N) > 10 are 49 parts per million (ppm) for anthracene, 145 ppm for pyrene, and 20 ppm for perylene. The anthracene detection limit improves to 7 ppm with use of the PanCam blue filter. We discuss soil-dependent detection limit constraints; use of UV excitation with other rover cameras, which provides higher spatial resolution; and the advantages of focused and wide-angle laser modes. Finally, we discuss application of L.I.F.E. techniques at multiple wavelengths for exploration of Mars analog extreme environments on Earth, including Icelandic hydrothermally altered basalts and the ice-covered lakes and glaciers of Dronning Maud Land, Antarctica.

Donor-acceptor cocrystal based on hexakis(alkoxy)triphenylene and perylenediimide derivatives with an ambipolar transporting property

NASA Astrophysics Data System (ADS)

Su, Yajun; Li, Yan; Liu, Jiangang; Xing, Rubo; Han, Yanchun

2015-01-01

An organic donor-acceptor cocrystal with an ambipolar transporting property was constructed based on N,N'-bis(1-ethylpropyl)-perylene-3,4,9,10-tetracarboxylic diimide (EP-PDI) and 2,3,6,7,10,11-hexakis-(hexyloxy)-triphenylene (H6TP). The cocrystal with an alternating stacking of H6TP and EP-PDI molecules was formed through both drop-casting and spin-coating processes, especially at the optimized ratios of H6TP/EP-PDI (2/1, 1/1). The formation of the cocrystal was driven by the strong π-π interaction and the weaker steric hindrance, resulting from the smaller side groups, between the donor and acceptor molecules. Field effect transistors (FETs) based on the H6TP/EP-PDI cocrystal exhibited relatively balanced hole/electron transport, with a hole mobility of 1.14 × 10-3 cm2 V-1 s-1 and an electron mobility of 1.40 × 10-3 cm2 V-1 s-1.An organic donor-acceptor cocrystal with an ambipolar transporting property was constructed based on N,N'-bis(1-ethylpropyl)-perylene-3,4,9,10-tetracarboxylic diimide (EP-PDI) and 2,3,6,7,10,11-hexakis-(hexyloxy)-triphenylene (H6TP). The cocrystal with an alternating stacking of H6TP and EP-PDI molecules was formed through both drop-casting and spin-coating processes, especially at the optimized ratios of H6TP/EP-PDI (2/1, 1/1). The formation of the cocrystal was driven by the strong π-π interaction and the weaker steric hindrance, resulting from the smaller side groups, between the donor and acceptor molecules. Field effect transistors (FETs) based on the H6TP/EP-PDI cocrystal exhibited relatively balanced hole/electron transport, with a hole mobility of 1.14 × 10-3 cm2 V-1 s-1 and an electron mobility of 1.40 × 10-3 cm2 V-1 s-1. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr05915h

A 150-year record of polycyclic aromatic compound (PAC) deposition from high Andean Cajas National Park, southern Ecuador.

PubMed

Bandowe, Benjamin A Musa; Fränkl, Lea; Grosjean, Martin; Tylmann, Wojciech; Mosquera, Pablo V; Hampel, Henrietta; Schneider, Tobias

2018-04-15

The temporal profiles of polycyclic aromatic compounds (PACs) in lake sediments reflect past changes in emissions, transport and deposition of these pollutants and, thus, record natural and anthropogenic processes. We document fluxes of PACs [(polycyclic aromatic hydrocarbons (PAHs), oxygenated PAHs (OPAHs) and azaarenes (AZAs)] deposited in two tropical high-altitude lakes in the Cajas National Park (Ecuadorian Andes, 2°50'S, 79°10'W). In remote and high elevation Laguna Fondococha (4130m a.s.l.), the temporal fluxes of OPAHs and AZAs were similar to those of PAHs suggesting similar sources. A significant increase of PAC deposition after the 1950s reflects Ecuador's economic development. PAH fluxes were relatively low (∑27PAHs (without retene and perylene): 0.86-11.21ngcm -2 yr -1 ) with a composition pattern typical for long-range atmospheric transport (high 9-fluorenone/fluorene ratios) and biomass burning (30% low molecular weight PAHs). PAHs diagnostic of high temperature combustion (industry, traffic) make up 20-25% of total PAHs. Perylene concentrations increase linearly with increasing sediment depth suggesting diagenetic in-situ production. At lower elevations (Laguna Llaviucu, 3140m a.s.l.) and closer to urban areas, PAC fluxes in the past decades were 4-5 times higher than in the remote high-elevation lake. Laguna Llaviucu also showed higher concentrations of high molecular weight pyrogenic PAHs and a greater diversity of AZAs. Individual OPAHs and AZAs reflect mainly combustion activities. In Laguna Llaviucu, which is at a lower elevation (3140m a.s.l.) and closer to the city, molecular ratios suggest short-range atmospheric transport and deposition of PACs. A very foggy climate (170 rainy days per year) with the precipitation maximum at 3500m removes PACs very efficiently (by wet deposition) from the atmosphere at very short distances from emission sources. This partly explains why L. Llaviucu shows higher fluxes of PACs than the higher elevation L. Fondococha. This study presents the first historical record of organic pollutants from environmental archives in Ecuador. Copyright © 2017 Elsevier B.V. All rights reserved.

Plasmon enhanced heterogeneous electron transfer with continuous band energy model

NASA Astrophysics Data System (ADS)

Zhao, Dandan; Niu, Lu; Wang, Luxia

2017-08-01

Photoinduced charge injection from a perylene dye molecule into the conduction band of a TiO2 system decorated by a metal nanoparticles (MNP) is studied theoretically. Utilizing the density matrix theory the charge transfer dynamics is analyzed. The continuous behavior of the TiO2 conduction band is accounted for by a Legendre polynomials expansion. The simulations consider optical excitation of the dye molecule coupled to the MNP and the subsequent electron injection into the TiO2 semiconductor. Due to the energy transfer coupling between the molecule and the MNP optical excitation and subsequent charge injection into semiconductor is strongly enhanced. The respective enhancement factor can reach values larger than 103. Effects of pulse duration, coupling strength and energetic resonances are also analyzed. The whole approach offers an efficient way to increase charge injection in dye-sensitized solar cells.

Laser-Induced Acoustic Desorption Atmospheric Pressure Photoionization via VUV-Generating Microplasmas.

PubMed

Benham, Kevin; Hodyss, Robert; Fernández, Facundo M; Orlando, Thomas M

2016-11-01

We demonstrate the first application of laser-induced acoustic desorption (LIAD) and atmospheric pressure photoionization (APPI) as a mass spectrometric method for detecting low-polarity organics. This was accomplished using a Lyman-α (10.2 eV) photon generating microhollow cathode discharge (MHCD) microplasma photon source in conjunction with the addition of a gas-phase molecular dopant. This combination provided a soft desorption and a relatively soft ionization technique. Selected compounds analyzed include α-tocopherol, perylene, cholesterol, phenanthrene, phylloquinone, and squalene. Detectable surface concentrations as low as a few pmol per spot sampled were achievable using test molecules. The combination of LIAD and APPI provided a soft desorption and ionization technique that can allow detection of labile, low-polarity, structurally complex molecules over a wide mass range with minimal fragmentation. Graphical Abstract ᅟ.

Synthesis, Photophysical, and Biological Evaluation of Sulfated Polyglycerol Dendronized Perylenebisimides (PBIs)--A Promising Platform for Anti-Inflammatory Theranostic Agents?

PubMed

Heek, T; Kühne, C; Depner, H; Achazi, K; Dernedde, J; Haag, R

2016-03-16

A set of four water-soluble perylene bisimides (PBI) based on sulfated polyglycerol (PGS) dendrons were developed, their photophysical properties determined via UV/vis and fluorescence spectroscopy, and their performance as possible anti-inflammatory agents evaluated via biological in vitro studies. It could be shown that in contrast to charge neutral PG-PBIs the introduction of the additional electrostatic repulsion forces leads to a decrease in the dendron generation necessary for aggregation suppression, allowing the preparation of PBIs with fluorescence quantum yields of >95% with a considerable decreased synthetic effort. Furthermore, the values determined for L-selectin binding down to the nanomolar range, their limited impact on blood coagulation, and their minor activation of the complement system renders these systems ideal for anti-inflammatory purposes.

Reduction of the 3,4,9,10-perylenediimides and the formation of eletrodeposited films based on their radical anions

NASA Astrophysics Data System (ADS)

Zhu, Yuan-Yuan; Gu, Shuang-Xi

2014-09-01

The reduction of the two 3,4,9,10-perylene diimide (PDI) derivatives in the mixture of hydrazine hydrate and N,N-dimethylformamide was investigated by the UV-vis absorption spectra, fluorescence spectra (FL) and electron spin resonance spectroscopy (ESR). The time dependence of the PDI content, as well as the structure of PDI aggregates were also investigated and discussed. Combining the electro-migration behavior of PDI-· with the molecular self-assembly properties, the films of two PDI derivatives (PDI-32 and PDI-123) were successfully fabricated via anode electro-deposition (AED). The difference of aggregation state between the two PDI films was studied by UV-vis absorption spectra, XRD and SEM. Based on these, the formation mechanism of PDI films was also deduced.

Spectral densities for Frenkel exciton dynamics in molecular crystals: A TD-DFTB approach

NASA Astrophysics Data System (ADS)

Plötz, Per-Arno; Megow, Jörg; Niehaus, Thomas; Kühn, Oliver

2017-02-01

Effects of thermal fluctuations on the electronic excitation energies and intermonomeric Coulomb couplings are investigated for a perylene-tetracarboxylic-diimide crystal. To this end, time dependent density functional theory based tight binding (TD-DFTB) in the linear response formulation is used in combination with electronic ground state classical molecular dynamics. As a result, a parametrized Frenkel exciton Hamiltonian is obtained, with the effect of exciton-vibrational coupling being described by spectral densities. Employing dynamically defined normal modes, these spectral densities are analyzed in great detail, thus providing insight into the effect of specific intramolecular motions on excitation energies and Coulomb couplings. This distinguishes the present method from approaches using fixed transition densities. The efficiency by which intramolecular contributions to the spectral density can be calculated is a clear advantage of this method as compared with standard TD-DFT.

Putting corannulene in its place. Reactivity studies comparing corannulene with other aromatic hydrocarbons.

PubMed

George, Stephen R D; Frith, Thomas D H; Thomas, Donald S; Harper, Jason B

2015-09-14

A series of aromatic hydrocarbons were investigated so as to compare the reactivity of corannulene with planar aromatic hydrocarbons. Corannulene was found to be more reactive than benzene, naphthalene and triphenylene to Friedel-Crafts acylation whilst electrophilic aromatic bromination was also used to confirm that triphenylene was less reactive than corannulene and that pyrene, perylene and acenaphthene were more so. The stabilisation of a neighbouring carbocation by the various aromatic systems was investigated through consideration of the rates of methanolysis of a series of benzylic alcohols. The reactivity series was found to parallel that observed for the electrophilic aromatic substitutions and both series are supported by computational studies. As such, a reactivity scale was devised that showed that corannulene was less reactive than would be expected for an aromatic planar species of similar pi electron count.

Approach to the characterization of the airborne organic matter (benzene soluble) in the atmosphere of Mexico City

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bravo, H.; Baez, A.P.

1961-01-01

Three areas of Mexico City were chosen from which to obtain samples of aromatic airborne particles. The samples were analyzed in order to have a broad idea of the composition of the material. The downtown area contained the highest concentration of organic benzene soluble material in the airborne particles, with the highest concentrations during the winter months. A combined sample (Ciudad Universitaria and Tacuba) was analyzed and gave the following figures of benzene soluble material in mg/g: fluoranthene - 160; pyrene - 210; benzo(a)anthracene - 47; benzo(a)pyrene - 82; benzo(e)pyrene - 150; benzo(g,h,i)perylene - 340; coronene - 160. A moremore » complete study is recommended in order to establish the actual parameters of the organic content in Mexico City's atmosphere.« less

High-brightness blue organic light emitting diodes with different types of guest-host systems

NASA Astrophysics Data System (ADS)

Wang, Xiao; Zhang, Jing-shuang; Peng, Cui-yun; Guo, Kun-ping; Wei, Bin; Zhang, Hao

2016-03-01

We demonstrate high-brightness blue organic light emitting diodes (OLEDs) using two types of guest-host systems. A series of blue OLEDs were fabricated using three organic emitters of dibenz anthracene (perylene), di(4-fluorophenyl) amino-di (styryl) biphenyl (DSB) and 4,4'-bis[2-(9-ethyl-3-carbazolyl)vinyl]biphenyl (BCzVBi) doped into two hosting materials of 4,4'-bis(9-carbazolyl) biphenyl (CBP) and 2-(4-biphenylyl)-5(4-tert-butyl-phenyl)-1,3,4-oxadiazole (PBD) as blue emitting layers, respectively. We achieve three kinds of devices with colors of deep-blue, pure-blue and sky-blue with the Commission Internationale de L'Eclairage (CIE) coordinates of (0.16, 0.10), (0.15, 0.15) and (0.17, 0.24), respectively, by employing PBD as host material. In addition, we present a microcavity device using the PBD guest-host system and achieve high-purity blue devices with narrowed spectrum.

Enhanced Efficiency in Fullerene-Free Polymer Solar Cell by Incorporating Fine-designed Donor and Acceptor Materials.

PubMed

Ye, Long; Sun, Kai; Jiang, Wei; Zhang, Shaoqing; Zhao, Wenchao; Yao, Huifeng; Wang, Zhaohui; Hou, Jianhui

2015-05-06

Among the diverse nonfullerene acceptors, perylene bisimides (PBIs) have been attracting much attention due to their excellent electron mobility and tunable molecular and electronic properties by simply engineering the bay and head linkages. Herein, guided by two efficient small molecular acceptors, we designed, synthesized, and characterized a new nonfullerene small molecule PPDI with fine-tailored alkyl chains. Notably, a certificated PCE of 5.40% is realized in a simple structured fullerene-free polymer solar cell comprising PPDI as the electron acceptor and a fine-tailored 2D-conjugated polymer PBDT-TS1 as the electron donor. Moreover, the device behavior, morphological feature, and origin of high efficiency in PBDT-TS1/PPDI-based fullerene-free PSC were investigated. The synchronous selection and design of donor and acceptor materials reported here offer a feasible strategy for realizing highly efficient fullerene-free organic photovoltaics.

Surface supported gold-organic hybrids: on-surface synthesis and surface directed orientation.

PubMed

Zhang, Haiming; Franke, Jörn-Holger; Zhong, Dingyong; Li, Yan; Timmer, Alexander; Arado, Oscar Díaz; Mönig, Harry; Wang, Hong; Chi, Lifeng; Wang, Zhaohui; Müllen, Klaus; Fuchs, Harald

2014-04-09

The surface-assisted synthesis of gold-organic hybrids on Au (111) and Au (100) surfaces is repotred by thermally initiated dehalogenation of chloro-substituted perylene-3,4,9,10-tetracarboxylic acid bisimides (PBIs). Structures and surface-directed alignment of the Au-PBI chains are investigated by scanning tunnelling microscopy in ultra high vacuum conditions. Using dichloro-PBI as a model system, the mechanism for the formation of Au-PBI dimer is revealed with scanning tunnelling microscopy studies and density functional theory calculations. A PBI radical generated from the homolytic C-Cl bond dissociation can covalently bind a surface gold atom and partially pull it out of the surface to form stable PBI-Au hybrid species, which also gives rise to the surface-directed alignment of the Au-PBI chains on reconstructed Au (100) surfaces. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Controlling Photoconductivity in PBI Films by Supramolecular Assembly.

PubMed

Draper, Emily R; Archibald, Lewis J; Nolan, Michael C; Schweins, Ralf; Zwijnenburg, Martijn A; Sproules, Stephen; Adams, Dave J

2018-03-15

Perylene bisimides (PBIs) self-assemble in solution. The solubility of the PBIs is commonly changed through the choice of substituents at the imide positions. It is generally assumed this substitution does not affect the electronic properties of the PBI, and that the properties of the self-assembled aggregate are essentially that of the isolated molecule. However, substituents do affect the self-assembly, resulting in potentially different packing in the formed aggregates. Here, we show that the photoconductivity of films formed from a library of substituted PBIs varies strongly with the substituent and demonstrate that this is due to the different ways in which they pack. Our results open the possibility for tuning the optoelectronic properties of self-assembled PBIs by controlling the aggregate structure through careful choice of substituent, as demonstrated by us here optimising the photoconductivity of PBI films in this way. © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Controlling Photoconductivity in PBI Films by Supramolecular Assembly

PubMed Central

Archibald, Lewis J.; Nolan, Michael C.; Schweins, Ralf; Zwijnenburg, Martijn A.; Sproules, Stephen

2018-01-01

Abstract Perylene bisimides (PBIs) self‐assemble in solution. The solubility of the PBIs is commonly changed through the choice of substituents at the imide positions. It is generally assumed this substitution does not affect the electronic properties of the PBI, and that the properties of the self‐assembled aggregate are essentially that of the isolated molecule. However, substituents do affect the self‐assembly, resulting in potentially different packing in the formed aggregates. Here, we show that the photoconductivity of films formed from a library of substituted PBIs varies strongly with the substituent and demonstrate that this is due to the different ways in which they pack. Our results open the possibility for tuning the optoelectronic properties of self‐assembled PBIs by controlling the aggregate structure through careful choice of substituent, as demonstrated by us here optimising the photoconductivity of PBI films in this way. PMID:29405458

A supramolecular approach to fabricate highly emissive smart materials

PubMed Central

Liu, Kai; Yao, Yuxing; Kang, Yuetong; Liu, Yu; Han, Yuchun; Wang, Yilin; Li, Zhibo; Zhang, Xi

2013-01-01

The aromatic chromophores, for example, perylene diimides (PDIs) are well known for their desirable absorption and emission properties. However, their stacking nature hinders the exploitation of these properties and further applications. To fabricate emissive aggregates or solid-state materials, it has been common practice to decrease the degree of stacking of PDIs by incorporating substituents into the parent aromatic ring. However, such practice often involves difficultorganic synthesis with multiple steps. A supramolecular approach is established here to fabricate highly fluorescent and responsive soft materials, which has greatly decreases the number of required synthetic steps and also allows for a system with switchable photophysical properties. The highly fluorescent smart material exhibits great adaptivity and can be used as a supramolecular sensor for the rapid detection of spermine with high sensitivity and selectivity, which is crucial for the early diagnosis of malignant tumors. PMID:23917964

Intermolecular vs molecule–substrate interactions: A combined STM and theoretical study of supramolecular phases on graphene/Ru(0001)

PubMed Central

Roos, Michael; Uhl, Benedikt; Künzel, Daniela; Hoster, Harry E; Groß, Axel

2011-01-01

Summary The competition between intermolecular interactions and long-range lateral variations in the substrate–adsorbate interaction was studied by scanning tunnelling microscopy (STM) and force field based calculations, by comparing the phase formation of (sub-) monolayers of the organic molecules (i) 2-phenyl-4,6-bis(6-(pyridin-3-yl)-4-(pyridin-3-yl)pyridin-2-yl)pyrimidine (3,3'-BTP) and (ii) 3,4,9,10-perylene tetracarboxylic-dianhydride (PTCDA) on graphene/Ru(0001). For PTCDA adsorption, a 2D adlayer phase was formed, which extended over large areas, while for 3,3'-BTP adsorption linear or ring like structures were formed, which exclusively populated the areas between the maxima of the moiré structure of the buckled graphene layer. The consequences for the competing intermolecular interactions and corrugation in the adsorption potential are discussed and compared with the theoretical results. PMID:22003444

Polycyclic aromatic hydrocarbon (PAH)-phase associations in Washington coastal sediment

NASA Astrophysics Data System (ADS)

Prahl, Fredrick G.; Carpenter, Roy

1983-06-01

Polycyclic aromatic (PAH) and aliphatic hydrocarbon compositions, organic carbon, nitrogen and lignin contents were determined in whole, unfractionated sediment from the Washington continental shelf and in discrete sediment fractions separated by particle size and density. At least 20 to 25% of perylene and PAH derived from pyrolytic processes and 50% of the retene measured in whole sediment are contained within organic C- and lignin-rich panicles of density ≤ 1.9 g/cc. These particles, which include primarily vascular plant remains and bits of charcoal, comprise less than 1% of the total sediment weight. In contrast, a series of methylated phenanthrene homologs, possibly of fossil origin, are concentrated in some component of the more dense, lithic matrix of the sediment. Equilibrium models of PAH sorption/desorption from aqueous phase onto small particles of high surface area do not appear applicable to the behavior of the major PAH types identified in this aquatic environment.

Characterization of polycyclic aromatic hydrocarbons and carbonyl compounds in diesel exhaust emissions.

PubMed

Mabilia, Rosanna; Cecinato, Angelo; Tomasi Scianò, Maria Concetta; Di Palo, Vincenzo; Possanzini, Massimiliano

2004-01-01

Exhaust emissions from a recent model heavy-duty diesel vehicle (city bus) in a chassis dynamometer were measured during a transient driving cycle. Particle-bound polycyclic aromatic hydrocarbons (PAHs) and gaseous carbonyls, substances that create health hazards and are, as yet, unregulated were collected, the former on filters and the latter on dinitrophenylhydrazine (DNPH)-coated silica cartridges and analysed by GC-MS and HPLC, respectively. PAH emission rates decreased with the number of benzene fused rings. They averaged 0.2 mg km(-1) for a total of 11 PAHs ranging from fluoranthene to benzo(ghi)perylene. Fluoranthene and pyrene accounted for 90% of total PAHs. The sum of emission rates of C1 approximately C6 carbonyls averaged 174 mg km(-1), even if formaldehyde alone represented approximately 70% of the total carbonyl mass, followed by acetaldehyde (13%). Results obtained were compared with emission data reported in previous studies.

High-Mobility, Ultrathin Organic Semiconducting Films Realized by Surface-Mediated Crystallization.

PubMed

Vladimirov, I; Kellermeier, M; Geßner, T; Molla, Zarah; Grigorian, S; Pietsch, U; Schaffroth, L S; Kühn, M; May, F; Weitz, R T

2018-01-10

The functionality of common organic semiconductor materials is determined by their chemical structure and crystal modification. While the former can be fine-tuned via synthesis, a priori control over the crystal structure has remained elusive. We show that the surface tension is the main driver for the plate-like crystallization of a novel small organic molecule n-type semiconductor at the liquid-air interface. This interface provides an ideal environment for the growth of millimeter-sized semiconductor platelets that are only few nanometers thick and thus highly attractive for application in transistors. On the basis of the novel high-performance perylene diimide, we show in as-grown, only 3 nm thin crystals electron mobilities of above 4 cm 2 /(V s) and excellent bias stress stability. We suggest that the established systematics on solvent parameters can provide the basis of a general framework for a more deterministic crystallization of other small molecules.

Understanding Structure and Bonding of Multilayered Metal–Organic Nanostructures

PubMed Central

2013-01-01

For organic and hybrid electronic devices, the physicochemical properties of the contained interfaces play a dominant role. To disentangle the various interactions occurring at such heterointerfaces, we here model a complex, yet prototypical, three-component system consisting of a Cu–phthalocyanine (CuPc) film on a 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) monolayer adsorbed on Ag(111). The two encountered interfaces are similar, as in both cases there would be no bonding without van der Waals interactions. Still, they are also distinctly different, as only at the Ag(111)–PTCDA interface do massive charge-rearrangements occur. Using recently developed theoretical tools, we show that it has become possible to provide atomistic insight into the physical and chemical processes in this comparatively complex nanostructure distinguishing between interactions involving local rearrangements of the charge density and long-range van der Waals attraction. PMID:23447750

Use of constant wavelength synchronous spectrofluorimetry for identification of polycyclic aromatic hydrocarbons in air particulate samples

NASA Astrophysics Data System (ADS)

Sharma, Homdutt; Jain, V. K.; Khan, Zahid H.

2013-05-01

We have developed a simple, rapid, inexpensive method for the identification of fluoranthene (Flan), benz(a)anthracene (BaA), benzo(a)pyrene (BaP), benzo(k)fluoranthene (BkF), pyrene (Pyr), benz(ghi)perylene (BghiP) in suspended particulate matter in an urban environment of Delhi. Suspended particulate matter samples of 24 h duration were collected on glass fiber filter papers. Polycyclic aromatic hydrocarbons (PAHs) were extracted from the filter papers using dichloromethane (DCM) and hexane with ultrasonication method. Comparison of the characteristic emission of spectra of PAHs with standard spectra indicated the degree of condensation of aromatic compounds present in investigated mixtures. It was also possible to identify some individual compounds. However, this identification could be more effective with the use of the respective values of Δλ parameter for each particular component of the mixture.

Polycyclic aromatic hydrocarbon levels and risk assessment for food from service facilities in Korea.

PubMed

Park, Shin-Woong; Jeong, Jun-Hyun; Her, Jae-Young; Kim, Mina K; Lee, Kwang-Geun

2017-06-01

In this study, levels of benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene (BaP), dibenzo[a,h]anthracene, benzo[g,h,i]perylene and indeno[1,2,3-c,d]pyrene in 412 food items collected from food service facilities in Korea were analysed. The concentrations of the eight polycyclic aromatic hydrocarbons (PAHs) ranged 0.13-0.48 μg/kg. The concentrations of benzo[a]pyrene in all food samples were <1 μg/kg, which is the lowest maximum limit in foods regulated by European Union legislation. PAH contents were employed to conduct exposure and risk assessment. The chronic daily intake of PAHs from 412 food samples was 5.48 × 10 -6 -4.70 ×x 10 -4  µg-TEQ BaP /kg/day with margins of exposure of 1.04 × 10 9 -1.16 × 10 11 .

Linear conduction in N-type organic field effect transistors with nanometric channel lengths and graphene as electrodes

NASA Astrophysics Data System (ADS)

Chianese, F.; Candini, A.; Affronte, M.; Mishra, N.; Coletti, C.; Cassinese, A.

2018-05-01

In this work, we test graphene electrodes in nanometric channel n-type Organic Field Effect Transistors (OFETs) based on thermally evaporated thin films of the perylene-3,4,9,10-tetracarboxylic acid diimide derivative. By a thorough comparison with short channel transistors made with reference gold electrodes, we found that the output characteristics of the graphene-based devices respond linearly to the applied bias, in contrast with the supralinear trend of gold-based transistors. Moreover, short channel effects are considerably suppressed in graphene electrode devices. More specifically, current on/off ratios independent of the channel length (L) and enhanced response for high longitudinal biases are demonstrated for L down to ˜140 nm. These results are rationalized taking into account the morphological and electronic characteristics of graphene, showing that the use of graphene electrodes may help to overcome the problem of Space Charge Limited Current in short channel OFETs.

A new efficient method for calculation of Frenkel exciton parameters in molecular aggregates

NASA Astrophysics Data System (ADS)

Plötz, Per-Arno; Niehaus, Thomas; Kühn, Oliver

2014-05-01

The Frenkel exciton Hamiltonian is at the heart of many simulations of excitation energy transfer in molecular aggregates. It separates the aggregate into Coulomb-coupled monomers. Here it is shown that the respective parameters, i.e., monomeric excitation energies and Coulomb couplings between transition densities can be efficiently calculated using time-dependent tight-binding-based density functional theory (TD-DFTB). Specifically, Coulomb couplings are expressed in terms of self-consistently determined Mulliken transition charges. The approach is applied to two dimer systems. First, formaldehyde oxime for which a detailed comparison with standard DFT using the B3LYP and the PBE functionals as well as with SCS-CC2 is provided. Second, the Coulomb coupling is explored in dependence on the intermolecular coordinates for a perylene bisimide dimer. This provides structural evidence for the previously observed biphasic aggregation behavior of this dye.

Infrared frequencies and intensities for astrophysically important polycyclic aromatic hydrocarbon cations

NASA Technical Reports Server (NTRS)

Szczepanski, Jan; Vala, Martin

1993-01-01

Polycyclic aromatic hydrocarbons (PAHs) have been implicated as the carriers of the 'unidentified infrared' (UIR) emission bands observed from the interstellar medium. It has long been thought that these molecules, if present, probably exist as cations. In this paper we present infrared spectra of the cations of five moderate-sized PAHs. The PAH cations have been produced by low-energy electron impact and then trapped and stabilized in argon matrices at 12 K. To date, results have been obtained on naphthalene, anthracene, pyrene, perylene, and coronene. A common feature of the infrared spectra of all these cations is the very different intensity pattern of the ions compared to the neutral parents. Visible and (partial) infrared spectra of the coronene cation are also presented. It is shown that the out-of-plane CH bending mode shifts to a position very close to the UIR band at 11.3 microns. The astrophysical impact of these observations is discussed.

Influence of the adsorption geometry of PTCDA on Ag(111) on the tip-molecule forces in non-contact atomic force microscopy.

PubMed

Langewisch, Gernot; Falter, Jens; Schirmeisen, André; Fuchs, Harald

2014-01-01

Perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) adsorbed on a metal surface is a prototypical organic-anorganic interface. In the past, scanning tunneling microscopy and scanning tunneling spectroscopy studies of PTCDA adsorbed on Ag(111) have revealed differences in the electronic structure of the molecules depending on their adsorption geometry. In the work presented here, high-resolution 3D force spectroscopy measurements at cryogenic temperatures were performed on a surface area that contained a complete PTCDA unit cell with the two possible geometries. At small tip-molecule separations, deviations in the tip-sample forces were found between the two molecule orientations. These deviations can be explained by a different electron density in both cases. This result demonstrates the capability of 3D force spectroscopy to detect even small effects in the electronic properties of organic adsorbates.

Superpoissonian shot noise in organic magnetic tunnel junctions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cascales, Juan Pedro; Martinez, Isidoro; Aliev, Farkhad G., E-mail: farkhad.aliev@uam.es

Organic molecules have recently revolutionized ways to create new spintronic devices. Despite intense studies, the statistics of tunneling electrons through organic barriers remains unclear. Here, we investigate conductance and shot noise in magnetic tunnel junctions with 3,4,9,10-perylene-teracarboxylic dianhydride (PTCDA) barriers a few nm thick. For junctions in the electron tunneling regime, with magnetoresistance ratios between 10% and 40%, we observe superpoissonian shot noise. The Fano factor exceeds in 1.5–2 times the maximum values reported for magnetic tunnel junctions with inorganic barriers, indicating spin dependent bunching in tunneling. We explain our main findings in terms of a model which includes tunnelingmore » through a two level (or multilevel) system, originated from interfacial bonds of the PTCDA molecules. Our results suggest that interfaces play an important role in the control of shot noise when electrons tunnel through organic barriers.« less

Exploring High-Performance n-Type Thermoelectric Composites Using Amino-Substituted Rylene Dimides and Carbon Nanotubes.

PubMed

Wu, Guangbao; Zhang, Zhi-Guo; Li, Yongfang; Gao, Caiyan; Wang, Xin; Chen, Guangming

2017-06-27

Taking advantage of the high electrical conductivity of a single-walled carbon nanotube (SWCNT) and the large Seebeck coefficient of rylene diimide, a convenient strategy is proposed to achieve high-performance n-type thermoelectric (TE) composites containing a SWCNT and amino-substituted perylene diimide (PDINE) or naphthalene diimide (NDINE). The obtained n-type composites display greatly enhanced TE performance with maximum power factors of 112 ± 8 (PDINE/SWCNT) and 135 ± 14 (NDINE/SWCNT) μW m -1 K -2 . A short doping time of 0.5 h can ensure high TE performance. The corresponding TE module consisting of five p-n junctions reaches a large output power of 3.3 μW under a 50 °C temperature gradient. In addition, the n-type composites exhibit high air stability and excellent thermal stability. This design strategy benefits the future fabricating of high-performance n-type TE materials and devices.

DOE Office of Scientific and Technical Information (OSTI.GOV)

O`Clair, C.E.; Short, J.W.; Rice, S.D.

Sediments were collected at ten locations in Prince William Sound in July 1993 to determine the geographical and bathymetric distribution of oil from the Exxon Valdez oil spill in the low intertidal zone and subtidal region. The authors sampled sediments at mean lower low water (0 m) and at five subtidal depths from 3 to 100 m. No Exxon Valdez oil was found in sediments at 0 m where the greatest mean intertidal concentration of total polynuclear aromatic hydrocarbons excluding perylene (54 ng/g) was observed at Moose Lips Bay. Subtidal sediments showed polynuclear aromatic hydrocarbon composition patterns similar to Exxonmore » Valdez oil at three sites, Herring Bay, Northwest Bay and Sleepy Bay. Contamination of sediments by Exxon Valdez oil reached a depth of 20 m at Northwest Bay and Sleepy Bay. In deep sediments (> or = 40 m) the authors found no evidence of weathered Exxon Valdez oil.« less

Characteristics of polycyclic aromatic hydrocarbons in PM2.5 emitted from different cooking activities in China.

PubMed

Li, Yun-Chun; Qiu, Jia-Qian; Shu, Man; Ho, Steven Sai Hang; Cao, Jun-Ji; Wang, Ge-Hui; Wang, Xian-Xiang; Zhao, Xiao-Qing

2018-02-01

Nineteen polycyclic aromatic hydrocarbons (PAHs) in PM 2.5 emitted from five different cooking activities were characterized, and their influencing factors were determined. The total quantified particle-bounded PAH concentrations (ΣPAHs) in the airs from the cooking activities were 4.2-36.5-fold higher than those in corresponding backgrounds. The highest ΣPAHs were seen in cafeteria frying (783 ± 499 ng/m 3 ), followed by meat roasting (420 ± 191 ng/m 3 ), fish roasting (210 ± 105 ng/m 3 ), snack-street boiling (202 ± 230 ng/m 3 ), and cafeteria boiling (150 ± 65 ng/m 3 ). The main influencing factors on the PAH emissions were cooking methods, fat contents in raw materials, and oil consumptions. Four- to six-ringed PAHs had the highest contributions to the ΣPAHs (avg. 87.5%). Diagnostic ratios of individual PAH were similar between the two charbroiling and other three conventional Chinese cooking methods, respectively, demonstrating the dominance of cooking methods in the PAH emissions. Remarkably high benzo(b)fluoranthene/benzo(k)fluoranthene (BbF/BkF) ratio (8.31) was seen in the snack-street boiling, attributed to the coal combustion as cooking fuel. Both fluoranthene/(fluoranthene + pyrene) [FLT/(FLT + PYR)] and benzo(a)anthracene/(benzo(a)anthracene + chrysene) [BaA/(BaA + CHR)] ratios were higher for the oil-based cooking than those from the water-based ones. In addition, two ratios of indeno(1,2,3-cd)pyrene/(indeno(1,2,3-cd)pyrene + benzo(g,h,i)perylene) [IPY/(IPY + BPE)] and benzo(a)pyrene/(benzo(a)pyrene + benzo(g,h,i)perylene) [BaP/(BaP + BPE)] were higher for two charbroiling than the three conventional Chinese cooking methods. The characterization work in this study is particularly important since cooking is a potential contributor of atmospheric PAHs in urban China. Carcinogenic potencies of PAHs were assessed by comparison with the air quality guideline and health risk estimation. The BaP and BaP equivalent were higher for the oil-based than the water-based cooking activities.

Improved optimization of polycyclic aromatic hydrocarbons (PAHs) mixtures resolution in reversed-phase high-performance liquid chromatography by using factorial design and response surface methodology.

PubMed

Andrade-Eiroa, Auréa; Diévart, Pascal; Dagaut, Philippe

2010-04-15

A new procedure for optimizing PAHs separation in very complex mixtures by reverse phase high performance (RPLC) is proposed. It is based on changing gradually the experimental conditions all along the chromatographic procedure as a function of the physical properties of the compounds eluted. The temperature and speed flow gradients allowed obtaining the optimum resolution in large chromatographic determinations where PAHs with very different medium polarizability have to be separated. Whereas optimization procedures of RPLC methodologies had always been accomplished regardless of the physico-chemical properties of the target analytes, we found that resolution is highly dependent on the physico-chemical properties of the target analytes. Based on resolution criterion, optimization process for a 16 EPA PAHs mixture was performed on three sets of difficult-to-separate PAHs pairs: acenaphthene-fluorene (for the optimization procedure in the first part of the chromatogram where light PAHs elute), benzo[g,h,i]perylene-dibenzo[a,h]anthracene and benzo[g,h,i]perylene-indeno[1,2,3-cd]pyrene (for the optimization procedure of the second part of the chromatogram where the heavier PAHs elute). Two-level full factorial designs were applied to detect interactions among variables to be optimized: speed flow, temperature of column oven and mobile-phase gradient in the two parts of the studied chromatogram. Experimental data were fitted by multivariate nonlinear regression models and optimum values of speed flow and temperature were obtained through mathematical analysis of the constructed models. An HPLC system equipped with a reversed phase 5 microm C18, 250 mm x 4.6mm column (with acetonitrile/water mobile phase), a column oven, a binary pump, a photodiode array detector (PDA), and a fluorimetric detector were used in this work. Optimum resolution was achieved operating at 1.0 mL/min in the first part of the chromatogram (until 45 min) and 0.5 mL/min in the second one (from 45 min to the end) and by applying programmed temperature gradient (15 degrees C until 30 min and progressively increasing temperature until reaching 40 degrees C at 45 min). (c) 2009 Elsevier B.V. All rights reserved.

Towards radiation hard converter material for SiC-based fast neutron detectors

NASA Astrophysics Data System (ADS)

Tripathi, S.; Upadhyay, C.; Nagaraj, C. P.; Venkatesan, A.; Devan, K.

2018-05-01

In the present work, Geant4 Monte-Carlo simulations have been carried out to study the neutron detection efficiency of the various neutron to other charge particle (recoil proton) converter materials. The converter material is placed over Silicon Carbide (SiC) in Fast Neutron detectors (FNDs) to achieve higher neutron detection efficiency as compared to bare SiC FNDs. Hydrogenous converter material such as High-Density Polyethylene (HDPE) is preferred over other converter materials due to the virtue of its high elastic scattering reaction cross-section for fast neutron detection at room temperature. Upon interaction with fast neutrons, hydrogenous converter material generates recoil protons which liberate e-hole pairs in the active region of SiC detector to provide a detector signal. The neutron detection efficiency offered by HDPE converter is compared with several other hydrogenous materials viz., 1) Lithium Hydride (LiH), 2) Perylene, 3) PTCDA . It is found that, HDPE, though providing highest efficiency among various studied materials, cannot withstand high temperature and harsh radiation environment. On the other hand, perylene and PTCDA can sustain harsh environments, but yields low efficiency. The analysis carried out reveals that LiH is a better material for neutron to other charge particle conversion with competent efficiency and desired radiation hardness. Further, the thickness of LiH has also been optimized for various mono-energetic neutron beams and Am-Be neutron source generating a neutron fluence of 109 neutrons/cm2. The optimized thickness of LiH converter for fast neutron detection is found to be ~ 500 μm. However, the estimated efficiency for fast neutron detection is only 0.1%, which is deemed to be inadequate for reliable detection of neutrons. A sensitivity study has also been done investigating the gamma background effect on the neutron detection efficiency for various energy threshold of Low-Level Discriminator (LLD). The detection efficiency of a stacked structure concept has been explored by juxtaposing several converter-detector layers to improve the efficiency of LiH-SiC-based FNDs . It is observed that approximately tenfold efficiency improvement has been achieved—0.93% for ten layers stacked configuration vis-à-vis 0.1% of single converter-detector layer configuration. Finally, stacked detectors have also been simulated for different converter thicknesses to attain the efficiency as high as ~ 3.25% with the help of 50 stacked layers.

Improved efficiency of extraction of polycyclic aromatic hydrocarbons (PAHs) from the National Institute of Standards and Technology (NIST) Standard Reference Material Diesel Particulate Matter (SRM 2975) using accelerated solvent extraction.

PubMed

Masala, Silvia; Ahmed, Trifa; Bergvall, Christoffer; Westerholm, Roger

2011-12-01

The efficiency of extraction of polycyclic aromatic hydrocarbons (PAHs) with molecular masses of 252, 276, 278, 300, and 302 Da from standard reference material diesel particulate matter (SRM 2975) has been investigated using accelerated solvent extraction (ASE) with dichloromethane, toluene, methanol, and mixtures of toluene and methanol. Extraction of SRM 2975 using toluene/methanol (9:1, v/v) at maximum instrumental settings (200 °C, 20.7 MPa, and five extraction cycles) with 30-min extraction times resulted in the following elevations of the measured concentration when compared with the certified and reference concentrations reported by the National Institute of Standards and Technology (NIST): benzo[b]fluoranthene, 46%; benzo[k]fluoranthene, 137%; benzo[e]pyrene, 103%; benzo[a]pyrene, 1,570%; perylene, 37%; indeno[1,2,3-cd]pyrene, 41%; benzo[ghi]perylene, 163%; and coronene, 361%. The concentrations of the following PAHs were comparable to the reference values assigned by NIST: indeno[1,2,3-cd]fluoranthene, dibenz[a,h]anthracene, and picene. The measured concentration of dibenzo[a,e]-pyrene was lower than the information value reported by the NIST. The measured concentrations of other highly carcinogenic PAHs (dibenzo[a,l]pyrene, dibenzo[a,i]pyrene, and dibenzo[a,h]pyrene) in SRM 2975 are also reported. Comparison of measurements using the optimized ASE method and using similar conditions to those applied by the NIST for the assignment of PAH concentrations in SRM 2975 indicated that the higher values obtained in the present study were associated with more complete extraction of PAHs from the diesel particulate material. Re-extraction of the particulate samples demonstrated that the deuterated internal standards were more readily recovered than the native PAHs, which may explain the lower values reported by the NIST. The analytical results obtained in the study demonstrated that the efficient extraction of PAHs from SRM 2975 is a critical requirement for the accurate determination of PAHs with high molecular masses in this standard reference material and that the optimization of extraction conditions is essential to avoid underestimation of the PAH concentrations. The requirement is especially relevant to the human carcinogen benzo[a]pyrene, which is commonly used as an indicator of the carcinogenic risk presented by PAH mixtures.

Optical gating with organic building blocks. A quantitative model for the fluorescence modulation of photochromic perylene bisimide dithienylcyclopentene triads

PubMed Central

Pärs, Martti; Gradmann, Michael; Gräf, Katja; Bauer, Peter; Thelakkat, Mukundan; Köhler, Jürgen

2014-01-01

We investigated the capability of molecular triads, consisting of two strong fluorophores that were covalently linked to a photochromic molecule, for optical gating. Therefore we monitored the fluorescence intensity of the fluorophores as a function of the isomeric state of the photoswitch. From the analysis of our data we develop a kinetic model that allows us to predict quantitatively the degree of the fluorescence modulation as a function of the mutual intensities of the lasers that are used to induce the fluorescence and the switching of the photochromic unit. We find that the achievable contrast for the modulation of the fluorescence depends mainly on the intensity ratio of the two light beams and appears to be very robust against absolute changes of these intensities. The latter result provides valuable information for the development of all-optical circuits which would require to handle different signal strengths for the input and output levels. PMID:24614963

Fluorescent nanocolloids for differential labeling of the endocytic pathway and drug delivery applications

NASA Astrophysics Data System (ADS)

Delehanty, James B.; Spillmann, Christopher M.; Naciri, Jawad; Algar, W. Russ; Ratna, Banahalli R.; Medintz, Igor L.

2013-02-01

The demonstration of fine control over nanomaterials within biological systems, particularly in live cells, is integral for the successful implementation of nanoparticles (NPs) in biomedical applications. Here, we show the ability to differentially label the endocytic pathway of mammalian cells in a spatiotemporal manner utilizing fluorescent nanocolloids (NCs) doped with a perylene-based dye. EDC-based conjugation of green- and red-emitting NCs to the iron transport protein transferrin resulted in stable bioconjugates that were efficiently endocytosed by HEK 293T/17 cells. The staggered delivery of the bioconjugates allowed for the time-resolved, differential labeling of distinct vesicular compartments along the endocytic pathway in a nontoxic manner. We further demonstrated the ability of the NCs to be impregnated with the anticancer therapeutic, doxorubicin. Delivery of the drug-doped nanoconjugates resulted in the intracellular release and nuclear accumulation of doxorubicin in a time- and dose-dependent manner. We discuss our results in the context of the utility of such materials for NP-mediated drug delivery applications.

Tetrachlorinated Polycyclic Aromatic Dicarboximides: New Electron-Poor Π-Scaffolds and NIR Emitters by Palladium-Catalyzed Annulation Reaction.

PubMed

Mahl, Magnus; Shoyama, Kazutaka; Rühe, Jessica; Grande, Vincenzo; Würthner, Frank

2018-04-24

Herein we report a palladium-catalyzed annulation reaction consisting of a Suzuki-Miyaura cross-coupling and a C-H arylation cascade for the synthesis of tetrachlorinated polycyclic aromatic dicarboximides (PADIs). This convergent synthetic route afforded a broad series of hitherto unknown electron-deficient PADIs under optimized reaction conditions by coupling of a dibromo-tetrachloro-perylene dicarboximide with different polycyclic aromatic hydrocarbon (PAH) boronic acid pinacol esters in up to 89% yields. The new PADI compounds show broad absorption in the visible range and some of them emit in the near-infrared (NIR) region. Cyclic and square wave voltammetric studies revealed that these tetrachlorinated PADIs are more electron-deficient than a non-chlorinated reference compound and they possess lower lying frontier orbitals. Thus, the newly synthesized electron-poor PADIs are potential n-type semiconductors. Moreover, these chlorinated PADIs are interesting building blocks for the construction of large π-extended arrays by metal-mediated coupling reactions. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A triaxial supramolecular weave

NASA Astrophysics Data System (ADS)

Lewandowska, Urszula; Zajaczkowski, Wojciech; Corra, Stefano; Tanabe, Junki; Borrmann, Ruediger; Benetti, Edmondo M.; Stappert, Sebastian; Watanabe, Kohei; Ochs, Nellie A. K.; Schaeublin, Robin; Li, Chen; Yashima, Eiji; Pisula, Wojciech; Müllen, Klaus; Wennemers, Helma

2017-11-01

Despite recent advances in the synthesis of increasingly complex topologies at the molecular level, nano- and microscopic weaves have remained difficult to achieve. Only a few diaxial molecular weaves exist—these were achieved by templation with metals. Here, we present an extended triaxial supramolecular weave that consists of self-assembled organic threads. Each thread is formed by the self-assembly of a building block comprising a rigid oligoproline segment with two perylene-monoimide chromophores spaced at 18 Å. Upon π stacking of the chromophores, threads form that feature alternating up- and down-facing voids at regular distances. These voids accommodate incoming building blocks and establish crossing points through CH-π interactions on further assembly of the threads into a triaxial woven superstructure. The resulting micrometre-scale supramolecular weave proved to be more robust than non-woven self-assemblies of the same building block. The uniform hexagonal pores of the interwoven network were able to host iridium nanoparticles, which may be of interest for practical applications.

Energy transfer dynamics in Light-Harvesting Dendrimers

NASA Astrophysics Data System (ADS)

Melinger, Joseph S.; McMorrow, Dale; Kleiman, Valeria D.

2002-03-01

We explore energy transfer dynamics in light-harvesting phenylacetylene symmetric and asymmetric dendrimers. Femtosecond pump-probe spectroscopy is used to probe the ultrafast dynamics of electronic excitations in these dendrimers. The backbone of the macromolecule consists of branches of increasing conjugation length, creating an energy gradient, which funnels energy to an accepting perylene trap. In the case of the symmetric dendrimer (nanostar), the energy transfer efficiency is known to approach nearly unity, although the nature and timescale of the energy transfer process is still unknown. For the asymmetric dendrimers, energy transfer efficiencies are very high, with the possibility of more complex transfer processes. We experimentally monitor the transport of excitons through the light-harvesting dendrimer. The transients show a number of components, with timescales ranging from <300fs to several tens of picoseconds, revealing the complex photophysics taking place in these macromolecules. We interpret our results in terms of the Förster mechanism in which energy transfer occurs through dipole-dipole interactions.

Biotransformation of petroleum asphaltenes and high molecular weight polycyclic aromatic hydrocarbons by Neosartorya fischeri.

PubMed

Hernández-López, E Lorena; Perezgasga, Lucia; Huerta-Saquero, Alejandro; Mouriño-Pérez, Rosa; Vazquez-Duhalt, Rafael

2016-06-01

Neosartorya fischeri, an Aspergillaceae fungus, was evaluated in its capacity to transform high molecular weight polycyclic aromatics hydrocarbons (HMW-PAHs) and the recalcitrant fraction of petroleum, the asphaltenes. N. fischeri was able to grow in these compounds as sole carbon source. Coronene, benzo(g,h,i)perylene, and indeno(1,2,3-c,d)pyrene, together with the asphaltenes, were assayed for fungal biotransformation. The transformation of the asphaltenes and HMW-PAHs was confirmed by reverse-phase high-performance liquid chromatography (HPLC), nano-LC mass spectrometry, and IR spectrometry. The formation of hydroxy and ketones groups on the PAH molecules suggest a biotransformation mediated by monooxygenases such as cytochrome P450 system (CYP). A comparative microarray with the complete genome from N. fischeri showed three CYP monooxygenases and one flavin monooxygenase genes upregulated. These findings, together with the internalization of aromatic substrates into fungal cells and the microsomal transformation of HMW-PAHs, strongly support the role of CYPs in the oxidation of these recalcitrant compounds.

Distributions of polycyclic aromatic hydrocarbons and alkylated polycyclic aromatic hydrocarbons in Osaka Bay, Japan.

PubMed

Miki, Shizuho; Uno, Seiichi; Ito, Kazuki; Koyama, Jiro; Tanaka, Hiroyuki

2014-08-30

Contaminations in sediments by polycyclic aromatic hydrocarbons (PAHs) and alkylated PAHs were investigated at 44 sites in Osaka Bay, Japan. Concentrations of total PAHs and alkylated PAHs were in the range 6.40-7800 ng/g dry weights and 13.7-1700 ng/g dry weights, respectively. The PAH concentrations tended to be higher along the shoreline in the vicinities of big ports, industrialized areas, and densely populated regions such as the cities of Osaka and Kobe. The major sources appeared to be pyrogenic or both pyrogenic and petrogenic at most of the sites. PAH concentrations were remarkably high at a site near Kobe, where the concentrations of dibenzo(a,h)anthracene and benzo(g,h,i)perylene exceeded the effects-range-medium concentration and eight PAHs were above the corresponding effects-range-low concentrations. Those PAHs may have been derived from the great fire associated with the large earthquake in 1995. Copyright © 2014 Elsevier Ltd. All rights reserved.

Green and Red Fluorescent Dyes for Translational Applications in Imaging and Sensing Analytes: A Dual‐Color Flag

PubMed Central

Oliveira, Elisabete; Bértolo, Emilia; Núñez, Cristina; Pilla, Viviane; Santos, Hugo M.; Fernández‐Lodeiro, Javier; Fernández‐Lodeiro, Adrian; Djafari, Jamila; Capelo, José Luis

2017-01-01

Abstract Red and green are two of the most‐preferred colors from the entire chromatic spectrum, and red and green dyes are widely used in biochemistry, immunohistochemistry, immune‐staining, and nanochemistry applications. Selective dyes with green and red excitable chromophores can be used in biological environments, such as tissues and cells, and can be irradiated with visible light without cell damage. This critical review, covering a period of five years, provides an overview of the most‐relevant results on the use of red and green fluorescent dyes in the fields of bio‐, chemo‐ and nanoscience. The review focuses on fluorescent dyes containing chromophores such as fluorescein, rhodamine, cyanine, boron–dipyrromethene (BODIPY), 7‐nitobenz‐2‐oxa‐1,3‐diazole‐4‐yl, naphthalimide, acridine orange, perylene diimides, coumarins, rosamine, Nile red, naphthalene diimide, distyrylpyridinium, benzophosphole P‐oxide, benzoresorufins, and tetrapyrrolic macrocycles. Metal complexes and nanomaterials with these dyes are also discussed. PMID:29318095

Petroleum hydrocarbons in the surface water of two estuaries in the Southeastern united states

NASA Astrophysics Data System (ADS)

Bidleman, T. F.; Castleberry, A. A.; Foreman, W. T.; Zaranski, M. T.; Wall, D. W.

1990-01-01

Surface water samples from Charleston Harbor, SC and Winyah Bay, SC were analysed for total hydrocarbons by gas chromatography (GC) and for petroleum residues (expressed as crude oil equivalents) by fluorescence spectrometry. Cleanup by column chromatography and saponification was necessary to reduce the background from extraneous fluorescing materials. Oil concentrations determined by FS ranged from 0·5-25 μg l -1 in Charleston Harbor and <0·23-9·6 μg l -1 in Winyah Bay. Hydrocarbons determined by GC were significantly correlated ( P < 0·01) with crude oil equivalents determined by FS, but the data showed considerable scatter as indicated by r2 = 0·45. Polycyclic aromatic hydrocarbons were determined by gas chromatography—mass spectrometry for one set of Winyah Bay samples. The sum of nonalkylated polycyclic aromatic hydrocarbons having ≥ 3 rings ranged from 7-64 ng l -1 at different stations. Perylene, possibly originating from sediment dredging, was one of the more abundant polycyclic aromatic hydrocarbons.

A solution-based single-molecule study of surface-bound PBIs: solvent-mediated environmental effects on molecular flexibility.

PubMed

Lee, Ji-Eun; Han, Ye Ri; Ham, Sujin; Jun, Chul-Ho; Kim, Dongho

2017-11-08

We have investigated the fundamental photophysical properties of surface-bound perylene bisimide (PBI) molecules in a solution-phase at the single-molecule level. By efficient immobilization of single PBIs on glass, we were able to simultaneously monitor fluorescence intensity trajectories, fluorescence lifetimes, and emission spectra of individual PBIs in organic and aqueous media using confocal microscopy. We showed that the fluorescence dynamics of single PBIs in the solution phase is highly dependent on their local and chemical environments. Furthermore, we visualized different spatial-fluctuations of surface-bound PBIs using defocused wide-field imaging. While PBIs show more steric flexibility in organic media, the flexible motion of PBI molecules in aqueous solution is relatively prohibited due to a cage effect by a hydrogen bonding network, which is previously unobserved. Our method opens up a new possibility to investigate the photophysical properties of multi-chromophoric systems in various solvents at the single-molecule level for developing optimal molecular devices such as water-proof devices.

Donor-acceptor cocrystal based on hexakis(alkoxy)triphenylene and perylenediimide derivatives with an ambipolar transporting property.

PubMed

Su, Yajun; Li, Yan; Liu, Jiangang; Xing, Rubo; Han, Yanchun

2015-02-07

An organic donor-acceptor cocrystal with an ambipolar transporting property was constructed based on N,N'-bis(1-ethylpropyl)-perylene-3,4,9,10-tetracarboxylic diimide (EP-PDI) and 2,3,6,7,10,11-hexakis-(hexyloxy)-triphenylene (H6TP). The cocrystal with an alternating stacking of H6TP and EP-PDI molecules was formed through both drop-casting and spin-coating processes, especially at the optimized ratios of H6TP/EP-PDI (2/1, 1/1). The formation of the cocrystal was driven by the strong π-π interaction and the weaker steric hindrance, resulting from the smaller side groups, between the donor and acceptor molecules. Field effect transistors (FETs) based on the H6TP/EP-PDI cocrystal exhibited relatively balanced hole/electron transport, with a hole mobility of 1.14 × 10(-3) cm(2) V(-1) s(-1) and an electron mobility of 1.40 × 10(-3) cm(2) V(-1) s(-1).

Nanostructured films employed as sensing units in an "electronic tongue" system.

PubMed

da Silva, B A; Antunes, P A; Pasquini, D; Curvelo, A A S; Aroca, R F; Riul, A Júnior; Constantino, C J L

2007-02-01

Nanostructured films of lignin (macromolecule extracted from sugar cane bagasse), polypyrrole (conducting polymer) and bis butylimido perylene (organic dye) were used in the detection of trace levels of fluorine (from H2SiF6), chlorine (from NaClO), Pb(+2), Cu(+2), and Cd(+2) in aqueous solutions. Langmuir monolayers on ultrapure water were characterised by surface pressure-mean molecular area (II-A) isotherms. Langmuir-Blodgett (LB) films were transferred onto gold interdigitated electrodes and used as individual sensing units of an electronic tongue system. Impedance spectroscopy measurements were taken with the sensor immersed into aqueous solutions containing the ions described above in different molar concentrations. Fourier transform infrared absorption (FTIR) was employed to identify possible interactions between the LB films and the analytes in solution, and no significant changes could be observed in the FTIR spectra of BuPTCD and Ppy. Therefore, the results for lignin point to an interaction involving the electronic cloud of the phenyl groups with the metallic ions.

Comparison of polycyclic aromatic hydrocarbons level between suspended solid and sediment samples of Pengkalan Chepa River, Kelantan state, Malaysia

NASA Astrophysics Data System (ADS)

Muslim, Noor Zuhartini Md; Babaheidari, Seyedreza Hashemi; Zakaria, Mohamad Pauzi

2015-09-01

Sixteen type of common Polycyclic Aromatic Hydrocarbons (PAHs) which consist of naphthalene, acenaphthene, acenaphthylene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, benzo[ghi]-perylene, indeno[1,2,3-cd]-pyrene and dibenz[a,h]-anthracene in suspended solid and sediment samples of Pengkalan Chepa River, Kelantan state, Malaysia were investigated. The analysis samples were taken from six different sites of Pengkalan Chepa River during sunny day. The samples were subjected to a series of pre-treatment before the level of PAHs can be determined. A Gas Chromatography-Mass Spectrometry (GC-MS) was the prime method for the analysis of PAHs level. A total of 16 PAHs concentration in suspended solid of the whole Pengkalan Chepa River was found to be 2144.6 ng/g dry weights. This concentration was about eight times more than 16 PAHs concentration in sediment which found to be 266.5 ng/g dry weights.

The identification of synthetic organic pigments in modern paints and modern paintings using pyrolysis-gas chromatography-mass spectrometry.

PubMed

Russell, Joanna; Singer, Brian W; Perry, Justin J; Bacon, Anne

2011-05-01

A collection of more than 70 synthetic organic pigments were analysed using pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS). We report on the analysis of diketo-pyrrolo-pyrrole, isoindolinone and perylene pigments which are classes not previously reported as being analysed by this technique. We also report on a number of azo pigments (2-naphthol, naphthol AS, arylide, diarylide, benzimidazolone and disazo condensation pigments) and phthalocyanine pigments, the Py-GC-MS analysis of which has not been previously reported. The members of each class were found to fragment in a consistent way and the pyrolysis products are reported. The technique was successfully applied to the analysis of paints used by the artist Francis Bacon (1909-1992), to simultaneously identify synthetic organic pigments and synthetic binding media in two samples of paint taken from Bacon's studio and micro-samples taken from three of his paintings and one painting attributed to him.

Environmentally benign Friedel-Crafts benzylation over nano-TiO2/SO4 2-

NASA Astrophysics Data System (ADS)

Devi, Kalathiparambil RPS; Sreeja, Puthenveetil B.; Sugunan, Sankaran

2013-05-01

During the past decade, much attention has been paid to the replacement of homogeneous catalysts by solid acid catalysts. Friedel-Crafts benzylation of toluene with benzyl chloride (BC) in liquid phase was carried out over highly active, nano-crystalline sulfated titania systems. These catalysts were prepared using the sol gel method. Modification was done by loading 3% of transition metal oxides over sulfated titania. Reaction parameters such as catalyst mass, molar ratio, temperature, and time have been studied. More than 80% conversion of benzyl chloride and 100% selectivity are shown by all the catalysts under optimum conditions. Catalytic activity is correlated with Lewis acidity obtained from perylene adsorption studies. The reaction appears to proceed by an electrophile, which involves the reaction of BC with the acidic titania catalyst. The catalyst was regenerated and reused up to four reaction cycles with equal efficiency as in the first run. The prepared systems are environmentally friendly and are easy to handle.

Photothermal heating as a methodology for post processing of polymeric nanofibers

NASA Astrophysics Data System (ADS)

Gorga, Russell; Clarke, Laura; Bochinski, Jason; Viswanath, Vidya; Maity, Somsubhra; Dong, Ju; Firestone, Gabriel

2015-03-01

Metal nanoparticles embedded within polymeric systems can be made to act as localized heat sources thereby aiding in-situ polymer processing. This is made possible by the surface plasmon resonance (SPR) mediated photothermal effect of metal (in this case gold) nanoparticles, wherein incident light absorbed by the nanoparticle generates a non-equilibrium electron distribution which subsequently transfers this energy into the surrounding medium, resulting in a temperature increase in the immediate region around the particle. Here we demonstrate this effect in polymer nanocomposite systems, specifically electrospun polyethylene oxide nanofibrous mats, which have been annealed at temperatures above the glass transition. A non-contact temperature measurement technique utilizing embedded fluorophores (perylene) has been used to monitor the average temperature within samples. The effect of annealing methods (conventional and photothermal) and annealing conditions (temperature and time) on the fiber morphology, overall crystallinity, and mechanical properties is discussed. This methodology is further utilized in core-sheath nanofibers to crosslink the core material, which is a pre-cured epoxy thermoset. NSF Grant CMMI-1069108.

Tube radial distribution phenomenon with a two-phase separation solution of a fluorocarbon and hydrocarbon organic solvent mixture in a capillary tube and metal compounds separation.

PubMed

Kitaguchi, Koichi; Hanamura, Naoya; Murata, Masaharu; Hashimoto, Masahiko; Tsukagoshi, Kazuhiko

2014-01-01

A fluorocarbon and hydrocarbon organic solvent mixture is known as a temperature-induced phase-separation solution. When a mixed solution of tetradecafluorohexane as a fluorocarbon organic solvent and hexane as a hydrocarbon organic solvent (e.g., 71:29 volume ratio) was delivered in a capillary tube that was controlled at 10°C, the tube radial distribution phenomenon (TRDP) of the solvents was clearly observed through fluorescence images of the dye, perylene, dissolved in the mixed solution. The homogeneous mixed solution (single phase) changed to a heterogeneous solution (two phases) with inner tetradecafluorohexane and outer hexane phases in the tube under laminar flow conditions, generating the dynamic liquid-liquid interface. We also tried to apply TRDP to a separation technique for metal compounds. A model analyte mixture, copper(II) and hematin, was separated through the capillary tube, and detected with a chemiluminescence detector in this order within 4 min.

Geochemistry of polycyclic aromatic hydrocarbons in the bottom sediments of the eastern Arctic shelf

NASA Astrophysics Data System (ADS)

Petrova, V. I.; Batova, G. I.; Kursheva, A. V.; Litvinenko, I. V.; Savinov, V. M.; Savinova, T. N.

2008-04-01

Sources and pathways of supply of polycyclic aromatic hydrocarbons (PAH) in the surface sediments of the Laptev and East Siberian seas were identified based on an analysis of the lithological-geochemical characteristics and distribution of organic matter (OM). The distribution of organic carbon, humic acids, bitumoids, and hydrocarbons demonstrates the determining role of the riverine runoff in the formation of the recent sediments. The total average content of PAH in the sediments of this region approximates 37 ng/g, not exceeding 80 ng/g of dry sediment. The biogenic components of the PAH (alkylphenanthrenes, alkylchrysenes, perylene) dominate in the estuarine-shelf and coastal-shelf sediments enriched with plant detritus and significantly decrease in the pelagic zone. The anthropogenic influence is observed in sediments of the port of Tiksi, where the total content of PAH with dominant pyrogenic components is two orders of magnitude higher as compared with the background values in the study region.

Imaging the wave functions of adsorbed molecules

PubMed Central

Lüftner, Daniel; Ules, Thomas; Reinisch, Eva Maria; Koller, Georg; Soubatch, Serguei; Tautz, F. Stefan; Ramsey, Michael G.; Puschnig, Peter

2014-01-01

The basis for a quantum-mechanical description of matter is electron wave functions. For atoms and molecules, their spatial distributions and phases are known as orbitals. Although orbitals are very powerful concepts, experimentally only the electron densities and -energy levels are directly observable. Regardless whether orbitals are observed in real space with scanning probe experiments, or in reciprocal space by photoemission, the phase information of the orbital is lost. Here, we show that the experimental momentum maps of angle-resolved photoemission from molecular orbitals can be transformed to real-space orbitals via an iterative procedure which also retrieves the lost phase information. This is demonstrated with images obtained of a number of orbitals of the molecules pentacene (C22H14) and perylene-3,4,9,10-tetracarboxylic dianhydride (C24H8O6), adsorbed on silver, which are in excellent agreement with ab initio calculations. The procedure requires no a priori knowledge of the orbitals and is shown to be simple and robust. PMID:24344291

Ultrafast Photoinduced Symmetry-Breaking Charge Separation and Electron Sharing in Perylenediimide Molecular Triangles.

PubMed

Wu, Yilei; Young, Ryan M; Frasconi, Marco; Schneebeli, Severin T; Spenst, Peter; Gardner, Daniel M; Brown, Kristen E; Würthner, Frank; Stoddart, J Fraser; Wasielewski, Michael R

2015-10-21

We report on a visible-light-absorbing chiral molecular triangle composed of three covalently linked 1,6,7,12-tetra(phenoxy)perylene-3,4:9,10-bis(dicarboximide) (PDI) units. The rigid triangular architecture reduces the electronic coupling between the PDIs, so ultrafast symmetry-breaking charge separation is kinetically favored over intramolecular excimer formation, as revealed by femtosecond transient absorption spectroscopy. Photoexcitation of the PDI triangle dissolved in CH2Cl2 gives PDI(+•)-PDI(-•) in τCS = 12.0 ± 0.2 ps. Fast subsequent intramolecular electron/hole hopping can equilibrate the six possible energetically degenerate ion-pair states, as suggested by electron paramagnetic resonance/electron-nuclear double resonance spectroscopy, which shows that one-electron reduction of the PDI triangle results in complete electron sharing among the three PDIs. Charge recombination of PDI(+•)-PDI(-•) to the ground state occurs in τCR = 1.12 ± 0.01 ns with no evidence of triplet excited state formation.

Self-assembling hydrogel scaffolds for photocatalytic hydrogen production

DOE PAGES

Weingarten, Adam S.; Kazantsev, Roman V.; Palmer, Liam C.; ...

2014-10-05

Integration into a soft material of all the molecular components necessary to generate storable fuels is an interesting target in supramolecular chemistry. The concept is inspired by the internal structure of photosynthetic organelles, such as plant chloroplasts, which colocalize molecules involved in light absorption, charge transport and catalysis to create chemical bonds using light energy. We report in this paper on the light-driven production of hydrogen inside a hydrogel scaffold built by the supramolecular self-assembly of a perylene monoimide amphiphile. The charged ribbons formed can electrostatically attract a nickel-based catalyst, and electrolyte screening promotes gelation. We found the emergent phenomenonmore » that screening by the catalyst or the electrolytes led to two-dimensional crystallization of the chromophore assemblies and enhanced the electronic coupling among the molecules. Finally, photocatalytic production of hydrogen is observed in the three-dimensional environment of the hydrogel scaffold and the material is easily placed on surfaces or in the pores of solid supports.« less

Combining Fullerenes and Zwitterions in non-Conjugated Polymer Interlayers to Raise Solar Cell Efficiency.

PubMed

Liu, Yao; Sheri, Madhu; Cole, Marcus D; Emrick, Todd; Russell, Thomas P

2018-06-12

Polymer zwitterions were synthesized by nucleophilic ring-opening of 3,3'-(but-2-ene-1,4-diyl)bis(1,2-oxathiolane 2,2-dioxide) (a bis-sultone) with functional perylene diimide (PDI) or fullerene monomers. Integration of these polymers into solar cell devices as cathode interlayers boosted efficiencies of fullerene-based organic photovoltaics (OPVs) from 2.75% to 10.74%, and of non-fullerene-based OPVs from 4.25% to 10.10%, demonstrating the versatility of these interlayer materials in OPVs. The fullerene-containing polymer zwitterion (C60-PZ) showed a higher interfacial dipole (∆) value and electron mobility than its PDI counterpart (PDI-PZ), affording solar cells with high efficiency. The power of PDI-PZ and C60-PZ to improve electron injection and extraction processes when positioned between metal electrodes and organic semiconductors highlights their promise to overcome energy barriers at the hard-soft materials interface of organic electronics. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of Nanostructure on the Exciton Dynamics of Multichromophore Donor–Acceptor Block Copolymers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xia, Jianlong; Busby, Erik; Sanders, Samuel N.

Here, we explore the synthesis and photophysics of nanostructured block copolymers that mimic light-harvesting complexes. We find that the combination of a polar and electron-rich boron dipyrromethene (BODIPY) block with a nonpolar electron-poor perylene diimide (PDI) block yields a polymer that self-assembles into ordered “nanoworms”. Numerical simulations are used to determine optimal compositions to achieve robust self-assembly. Photoluminescence spectroscopy is used to probe the rich exciton dynamics in these systems. Using controls, such as homopolymers and random copolymers, we analyze the mechanisms of the photoluminescence from these polymers. With this understanding it allows us to probe in detail the photophysicsmore » of the block copolymers, including the effects of their self-assembly into nanostructures on their excited-state properties. Similar to natural systems, ordered nanostructures result in properties that are starkly different than the properties of free polymers in solution, such as enhanced rates of electronic energy transfer and elimination of excitonic emission from disordered PDI trap states.« less

Influence of Nanostructure on the Exciton Dynamics of Multichromophore Donor–Acceptor Block Copolymers

DOE PAGES

Xia, Jianlong; Busby, Erik; Sanders, Samuel N.; ...

2017-03-27

Here, we explore the synthesis and photophysics of nanostructured block copolymers that mimic light-harvesting complexes. We find that the combination of a polar and electron-rich boron dipyrromethene (BODIPY) block with a nonpolar electron-poor perylene diimide (PDI) block yields a polymer that self-assembles into ordered “nanoworms”. Numerical simulations are used to determine optimal compositions to achieve robust self-assembly. Photoluminescence spectroscopy is used to probe the rich exciton dynamics in these systems. Using controls, such as homopolymers and random copolymers, we analyze the mechanisms of the photoluminescence from these polymers. With this understanding it allows us to probe in detail the photophysicsmore » of the block copolymers, including the effects of their self-assembly into nanostructures on their excited-state properties. Similar to natural systems, ordered nanostructures result in properties that are starkly different than the properties of free polymers in solution, such as enhanced rates of electronic energy transfer and elimination of excitonic emission from disordered PDI trap states.« less

Anisotropy Changes of a Fluorescent Probe during the Micellar Growth and Clouding of a Nonionic Detergent.

PubMed

Komaromy-Hiller; von Wandruszka R

1996-01-15

The effects of temperature and Triton X-114 (TX-114) concentration on the fluorescence anisotropy of perylene were investigated before and after detergent clouding. The measured anisotropy values were used to estimate the microviscosity of the micellar interior. In the lower detergent concentration range, an anisotropy maximum was observed at the critical micelle concentration (CMC), while the values decreased in the range immediately above the CMC. This was ascribed to the micellar volume increase, which, in the case of TX-114, was not accompanied by a more ordered internal environment. A gradual decrease of anisotropy and microviscosity with increasing temperature below the cloud point was observed. At the cloud point, no abrupt changes were found to occur. Compared to detergents with more flexible hydrophobic moieties, TX-114 micelles have a relatively ordered micellar interior indicated by the microviscosity and calculated fusion energy values. In the separated micellar phase formed after clouding, the probe anisotropy increased as water was eliminated at higher temperatures.

Particulate polycyclic aromatic hydrocarbons (PAH) in the atmosphere of Bizerte city, Tunisia.

PubMed

Ben Hassine, S; Hammami, B; Ben Ameur, W; El Megdiche, Y; Barhoumi, B; Driss, M R

2014-09-01

The particle-phase concentrations of polycyclic aromatic hydrocarbons (PAH) were determined in 13 air samples collected in an urban area of Bizerte (Tunisia) during 2009-2010. Atmospheric particulate samples were extracted by ultrasonic bath and analyzed by high-performance liquid chromatography with fluorescence detection. PAH were found in all the analyzed air samples and the most abundant compounds were pyrene, fluoranthene, benzo[g,h,i]perylene, benzo[b]fluoranthene, chrysene and benzo[a]pyrene. ∑14-PAH concentrations ranging from 9.38 to 44.81 ng m(-3) with mean value of 25.39 ng m(-3). PAH diagnostic ratio source analysis revealed gasoline and diesel vehicular emissions as major sources. The mean total benzo[a]pyrene toxicity equivalent calculated for samples was 3.66 ng m(-3) and the mean contribution of the carcinogenic potency of benzo[a]pyrene was determined to be 55.8 %. Concentrations of particulate PAH in Bizerte city atmosphere were approximately eight times greater than sampled at a nearby rural site.

The Mid-Infrared Absorption Spectra of Neutral PAHs in Dense Interstellar Clouds

NASA Technical Reports Server (NTRS)

Bernstein, M. P.; Sandford, S. A.; Allamandola, L. J.

2005-01-01

Polycyclic aromatic hydrocarbons (PAHs) are common throughout the universe and are expected to be present in dense interstellar clouds. In these environments, some P.4Hs may be present in the gas phase, but most should be frozen into ice mantles or adsorbed onto dust grains and their spectral features are expected to be seen in absorption. Here we extend our previous work on the infrared spectral properties of the small PAH naphthalene (C10H8) in several media to include the full mid-infrared laboratory spectra of 11 other PAHs and related aromatic species frozen in H2O ices. These include the molecules 1,2-dihydronaphthalene, anthracene, 9,1O-dihydroanthracene, phenanthrene, pyrene, benzo[e]pyrene, perylene, benzo(k)fluoranthene, pentacene, benzo[ghi]perylene, and coronene. These results demonstrate that PAHs and related molecules, as a class, show the same spectral behaviors as naphthalene when incorporated into H2O-rich matrices. When compared to the spectra of these same molecules isolated in inert matrices (e.g., Ar or N2), the absorption bands produced when they are frozen in H2O matrices are broader (factors of 3-10), show small position shifts in either direction (usually < 4/cm, always < 10/cm), and show variable changes in relative band strengths (typically factors of 1-3). There is no evidence of systematic increases or decreases in the absolute strengths of the bands of these molecules when they are incorporated in H2O matrices. In H2O-rich ices, their absorption bands are relatively insensitive to concentration over the range of 10 < H2O/PAH < 200): The absorption bands of these molecules are also insensitive to temperature over the 10 K < T < 125 K range, although the spectra can show dramatic changes as the ices are warmed through the temperature range in which amorphous H2O ice converts to its cubic and hexagonal crystalline forms (T > 125 Kj. Given the small observed band shifts cause by H2O, the current database of spectra from Ar matrix-isolated neutral PAHs and related molecules should be useful for the search for these species in dense clouds on the basis of observed absorption band positions. Furthermore, these data permit determination of column densities to better than a factor of 3 for PAHs in dense clouds. Column density determination of detected aromatics to better than a factor of 3 will, however, require good knowledge about the nature of the matrix in which the PAH is embedded and laboratory studies of relevant samples.

Profile distribution of polycyclic aromatic hydrocarbons in soils of drained peatlands after wildfires (Moscow region, Russia)

NASA Astrophysics Data System (ADS)

Tsibart, Anna; Gennadiev, Alexander; Koshovskii, Timur; Kovach, Roman

2014-05-01

Polycyclic aromatic compounds (PAHs) are formed in different natural and anthropogenic processes and could be found in many landscape components. These compounds are carcinogenic and belong to the group of persistent organic pollutants. The anthropogenic sources of PAHs are well-studied, but insufficient data are available on the hightemperature production of PAHs in natural processes. For example, natural fires are frequently related to the PAHs sources in landscapes, but very little factual data are on this topic. The soils of drained peatlands affected by catastrophic wildfires of 2010 and 2002 were studied in the Eastern part of Moscow Region (Russia). A total of 14 profiles of histosols and histic podsols were investigated. These series included soils of plots subjected to fires of different intensities and age, as well as soils of the background plots. Soil samples were taken from genetic horizons and from every 10 cm. The samples were analyzed for the contents of 14 prevailing individual compounds: fluorene, naphthalene, phenanthrene, chrysene, pyrene, anthracene, tetraphene, benz[a]pyrene, benzo[ghi]perylene, benzo[e]pyrene, coronene, dibenztiophene, triphenilene, benz(k)fluorantene. Morfological properties of soils after wildfires on drained peatlands were changed dramatically, the horizons of ash and char instead of organic layers were formed. These new horizons differ in the capability of PAHs accumulation. The char horizons have the highest concentrations of PAHs - up to 300 ng/g because of incomplete burning of organic matter in this sites, and the ash horizons, where the complete burning occured, contain only 10 ng/g PAHs. The highest concentrations of PAHs in soil profiles were detected after recent fires, and in cases of thick peat layers. After the combustion of peat chrysene, benz[a]pyrene, benz[e]pyrene, benzo[ghi]perylene, benz(k)fluorantene and tetraphene accumulated in soils. This is mainly the group of 4-6-nuclear compounds. The formation of high-molecular weight compounds is possible during smoldering process under a low oxygen supply. The oxygen deficit acts as a factor of the organic fragments recombination and PAHs production; therefore, relatively large amounts of PAHs are formed in peat fires. Moreover the peat fires occur directly in the soil layer; therefore, larger amounts of the resulting PAHs remain in the soils of the fire sites. The migration of low-molecular weight compounds occures in histic podsols, in histosols PAHs accumalate only in upper organic horizons. The research was conducted with the support of Russian Geographical Society.

Chemical and biological assessment of two offshore drilling sites in the Alaskan Arctic.

PubMed

Trefry, John H; Dunton, Kenneth H; Trocine, Robert P; Schonberg, Susan V; McTigue, Nathan D; Hersh, Eric S; McDonald, Thomas J

2013-05-01

A retrospective chemical and biological study was carried out in Camden Bay, Alaskan Beaufort Sea, where single exploratory oil wells were drilled at two sites more than two decades ago. Barium from discharged drilling mud was present in sediments at concentrations as high as 14%, ~200 times above background, with significantly higher concentrations of Ba, but not other metals, within 250 m of the drilling site versus reference stations. Elevated concentrations of Cr, Cu, Hg and Pb were found only at two stations within 25 m of one drilling site. Concentrations of total polycyclic aromatic hydrocarbons (TPAH) were not significantly different at reference versus drilling-site stations; however, TPAH were elevated in Ba-rich layers from naturally occurring perylene in ancient formation cuttings. Infaunal biomass and species abundance were not significantly different at reference versus drilling-site stations; infauna were less diverse at drilling-site stations. Our assessment showed that discharges from single wells within large areas caused minimal long-term, adverse impacts to the benthic ecosystem. Copyright © 2013 Elsevier Ltd. All rights reserved.

Salt-assisted clean transfer of continuous monolayer MoS2 film for hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Cho, Heung-Yeol; Nguyen, Tri Khoa; Ullah, Farman; Yun, Jong-Won; Nguyen, Cao Khang; Kim, Yong Soo

2018-03-01

The transfer of two-dimensional (2D) materials from one substrate to another is challenging but of great importance for technological applications. Here, we propose a facile etching and residue-free method for transferring a large-area monolayer MoS2 film continuously grown on a SiO2/Si by chemical vapor deposition. Prior to synthesis, the substrate is dropped with water- soluble perylene-3, 4, 9, 10-tetracarboxylic acid tetrapotassium salt (PTAS). The as-grown MoS2 on the substrate is simply dipped in water to quickly dissolve PTAS to yield the MoS2 film floating on the water surface, which is subsequently transferred to the desired substrate. The morphological, optical and X-ray photoelectron spectroscopic results show that our method is useful for fast and clean transfer of the MoS2 film. Specially, we demonstrate that monolayer MoS2 film transferred onto a conducting substrate leads to excellent performance for hydrogen evolution reaction with low overpotential (0.29 V vs the reversible hydrogen electrode) and Tafel slope (85.5 mV/decade).

Study on copper phthalocyanine and perylene-based ambipolar organic light-emitting field-effect transistors produced using neutral beam deposition method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Dae-Kyu; Oh, Jeong-Do; Shin, Eun-Sol

2014-04-28

The neutral cluster beam deposition (NCBD) method has been applied to the production and characterization of ambipolar, heterojunction-based organic light-emitting field-effect transistors (OLEFETs) with a top-contact, multi-digitated, long-channel geometry. Organic thin films of n-type N,N′-ditridecylperylene-3,4,9,10-tetracarboxylic diimide and p-type copper phthalocyanine were successively deposited on the hydroxyl-free polymethyl-methacrylate (PMMA)-coated SiO{sub 2} dielectrics using the NCBD method. Characterization of the morphological and structural properties of the organic active layers was performed using atomic force microscopy and X-ray diffraction. Various device parameters such as hole- and electron-carrier mobilities, threshold voltages, and electroluminescence (EL) were derived from the fits of the observed current-voltage andmore » current-voltage-light emission characteristics of OLEFETs. The OLEFETs demonstrated good field-effect characteristics, well-balanced ambipolarity, and substantial EL under ambient conditions. The device performance, which is strongly correlated with the surface morphology and the structural properties of the organic active layers, is discussed along with the operating conduction mechanism.« less

PAH, PCB, TPH and mercury in surface sediments of the Delaware River Estuary and Delmarva Peninsula, USA.

PubMed

Kim, A W; Vane, C H; Moss-Hayes, V; Engelhart, S E; Kemp, A C

2018-04-01

Surface sediment concentrations of polycyclic aromatic hydrocarbons (PAH) and polychlorinated biphenyls (PCB), total petroleum hydrocarbons (TPH) and mercury, were compared from two areas with contrasting land use history, the industrial Delaware Estuary and the rural Delmarva Peninsula (USA). TPH in the Delaware (38-616mg/kg) and saturate/aromatic fractions suggested petroleum/industrial sources compared to biogenic sources in the Delmarva coastal control (<34-159mg/kg). Within the Delaware the ∑PAH18 ranged from 3749 to 22,324μg/kg with isomeric ratios indicative of petroleum combustion source/s, conversely, those in the Delmarva (5-2139μg/kg) also yielded relatively higher perylene that were consistent with natural background levels derived from vegetation/coal combustion source/s. ∑PCB(tri-hepta) concentrations in the Delmarva (0.6-6.5μg/kg) were less than the threshold effect concentration (TEC), whereas the Delaware had received much higher PCB loading (18.1-136.8μg/kg) as evidenced by a significantly higher amounts in some samples (>TEC). Copyright © 2017 Elsevier Ltd. All rights reserved.

Long-range ordering of composites for organic electronics: TIPS-pentacene single crystals with incorporated nano-fibers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Huanbin; Xue, Guobiao; Wu, Jiake

Multi-component active materials are widely used for organic electronic devices, with every component contributing complementary and synergistic optoelectronic functions. Mixing these components generally leads to lowered crystallinity and weakened charge transport. Therefore, preparing the active materials without substantially disrupting the crystalline lattice is highly desired. In this paper, we show that crystallization of TIPS-pentacene from solutions in the presence of fluorescent nanofibers of a perylene bisimide derivative (PBI) leads to formation of composites with nanofiber guest incorporated in the crystal host. In spite of the binary composite structure, the TIPS-pentacene maintains the single-crystalline nature. As a result, the incorporation ofmore » the PBI guest introduces additional fluorescence function but does not significantly reduce the charge transport property of the TIPS-pentacene host, exhibiting field-effect mobility as high as 3.34 cm 2 V -1 s -1 even though 26.4% of the channel area is taken over by the guest. Finally, as such, this work provides a facile approach toward high-performance multifunctional organic electronic materials.« less

Self-Assembly of Semiconducting-Plasmonic Gold Nanoparticles with Enhanced Optical Property for Photoacoustic Imaging and Photothermal Therapy

PubMed Central

Yang, Zhen; Song, Jibin; Dai, Yunlu; Chen, Jingyi; Wang, Feng; Lin, Lisen; Liu, Yijing; Zhang, Fuwu; Yu, Guocan; Zhou, Zijian; Fan, Wenpei; Huang, Wei; Fan, Quli; Chen, Xiaoyuan

2017-01-01

Although various noble metal and semiconducting molecules have been developed as photoacoustic (PA) agents, the use of semiconducting polymer-metal nanoparticle hybrid materials to enhance PA signal has not been explored. A novel semiconducting-plasmonic nanovesicle was fabricated by self-assembly of semiconducting poly(perylene diimide) (PPDI) and poly(ethylene glycol (PEG) tethered gold nanoparticles (Au@PPDI/PEG). A highly localized and strongly enhanced electromagnetic (EM) field is distributed between adjacent gold nanoparticles in the vesicular shell, where the absorbing collapsed PPDI is present. Significantly, the EM field in turn enhances the light absorption efficiency of PPDI, leading to a much greater photothermal effect and a stronger photoacoustic signal compared to PDI nanoparticle or gold nanovesicle alone. The optical property of the hybrid vesicle can be further tailored by controlling the ratio of PPDI and gold nanoparticle as well as the adjustable interparticle distance of gold nanoparticles localized in the vesicular shell. In vivo imaging and therapeutic evaluation demonstrated that the hybrid vesicle is an excellent probe for cancer theranostics. PMID:28740543

Determination of polycyclic aromatic hydrocarbons in drinking water samples by solid-phase nanoextraction and high-performance liquid chromatography.

PubMed

Wang, Huiyong; Campiglia, Andres D

2008-11-01

A novel alternative is presented for the extraction and preconcentration of polycyclic aromatic hydrocarbons (PAH) from water samples. The new approachwhich we have named solid-phase nanoextraction (SPNE)takes advantage of the strong affinity that exists between PAH and gold nanoparticles. Carefully optimization of experimental parameters has led to a high-performance liquid chromatography method with excellent analytical figures of merit. Its most striking feature correlates to the small volume of water sample (500 microL) for complete PAH analyses. The limits of detection ranged from 0.9 (anthracene) to 58 ng.L (-1) (fluorene). The relative standard deviations at medium calibration concentrations vary from 3.2 (acenaphthene) to 9.1% (naphthalene). The analytical recoveries from tap water samples of the six regulated PAH varied from 83.3 +/- 2.4 (benzo[ k]fluoranthene) to 95.7 +/- 4.1% (benzo[ g,h,i]perylene). The entire extraction procedure consumes less than 100 microL of organic solvents per sample, which makes it environmentally friendly. The small volume of extracting solution makes SPNE a relatively inexpensive extraction approach.

Enhancement in Open-Circuit Voltage in Organic Solar Cells by Using Ladder-Type Nonfullerene Acceptors

DOE PAGES

Cai, Zhengxu; Zhao, Donglin; Sharapov, Valerii; ...

2018-03-28

The open-circuit voltage (V oc) loss has always been a major factor in lowering power conversion efficiencies (PCEs) in bulk heterojunction organic photovoltaic cells (OPVs). A method to improve the V oc is indispensable to achieve high PCEs. Here in this paper, we investigated a series of perylene diimide-based ladder-type molecules as electron acceptors in nonfullerene OPVs. The D-A ladder-type structures described here lock our pi-systems into a planar structure and eliminate bond twisting associated with linear conjugated systems. This enlarges the interface energy gap (ΔE DA), extends electronic delocalization, and hence improves the V oc. More importantly, these devicesmore » showed an increase in V oc without compromising either the J sc or the FF. C5r exhibited a strong intermolecular interaction and a PCE value of 6.1%. Moreover, grazing-incident wide-angle X-ray scattering analysis and atomic force microscopy images suggested that our fused-ring acceptors showed a suitable domain size and uniform blend films, which were not affected by their rigid molecular structures.« less

Self-Assembly of Semiconducting-Plasmonic Gold Nanoparticles with Enhanced Optical Property for Photoacoustic Imaging and Photothermal Therapy.

PubMed

Yang, Zhen; Song, Jibin; Dai, Yunlu; Chen, Jingyi; Wang, Feng; Lin, Lisen; Liu, Yijing; Zhang, Fuwu; Yu, Guocan; Zhou, Zijian; Fan, Wenpei; Huang, Wei; Fan, Quli; Chen, Xiaoyuan

2017-01-01

Although various noble metal and semiconducting molecules have been developed as photoacoustic (PA) agents, the use of semiconducting polymer-metal nanoparticle hybrid materials to enhance PA signal has not been explored. A novel semiconducting-plasmonic nanovesicle was fabricated by self-assembly of semiconducting poly(perylene diimide) (PPDI) and poly(ethylene glycol (PEG) tethered gold nanoparticles (Au@PPDI/PEG). A highly localized and strongly enhanced electromagnetic (EM) field is distributed between adjacent gold nanoparticles in the vesicular shell, where the absorbing collapsed PPDI is present. Significantly, the EM field in turn enhances the light absorption efficiency of PPDI, leading to a much greater photothermal effect and a stronger photoacoustic signal compared to PDI nanoparticle or gold nanovesicle alone. The optical property of the hybrid vesicle can be further tailored by controlling the ratio of PPDI and gold nanoparticle as well as the adjustable interparticle distance of gold nanoparticles localized in the vesicular shell. In vivo imaging and therapeutic evaluation demonstrated that the hybrid vesicle is an excellent probe for cancer theranostics.

Identifying risk sources of air contamination by polycyclic aromatic hydrocarbons.

PubMed

Huzlik, Jiri; Bozek, Frantisek; Pawelczyk, Adam; Licbinsky, Roman; Naplavova, Magdalena; Pondelicek, Michael

2017-09-01

This article is directed to determining concentrations of polycyclic aromatic hydrocarbons (PAHs), which are sorbed to solid particles in the air. Pollution sources were identified on the basis of the ratio of benzo[ghi]perylene (BghiPe) to benzo[a]pyrene (BaP). Because various important information is lost by determining the simple ratio of concentrations, least squares linear regression (classic ordinary least squares regression), reduced major axis, orthogonal regression, and Kendall-Theil robust diagnostics were utilized for identification. Statistical evaluation using all aforementioned methods demonstrated different ratios of the monitored PAHs in the intervals examined during warmer and colder periods. Analogous outputs were provided by comparing gradients of the emission factors acquired from the measured concentrations of BghiPe and BaP in motor vehicle exhaust gases. Based on these outputs, it was possible plausibly to state that the influence of burning organic fuels in heating stoves is prevalent in colder periods whereas in warmer periods transport was the exclusive source because other sources of PAH emissions were not found in the examined locations. Copyright © 2017 Elsevier Ltd. All rights reserved.

Thermal stability and molecular ordering of organic semiconductor monolayers: effect of an anchor group.

PubMed

Jones, Andrew O F; Knauer, Philipp; Resel, Roland; Ringk, Andreas; Strohriegl, Peter; Werzer, Oliver; Sferrazza, Michele

2015-06-08

The thermal stability and molecular order in monolayers of two organic semiconductors, PBI-PA and PBI-alkyl, based on perylene derivatives with an identical molecular structure except for an anchor group for attachment to the substrate in PBI-PA, are reported. In situ X-ray reflectivity measurements are used to follow the stability of these monolayers in terms of order and thickness as temperature is increased. Films have thicknesses corresponding approximately to the length of one molecule; molecules stand upright on the substrate with a defined structure. PBI-PA monolayers have a high degree of order at room temperature and a stable film exists up to 250 °C, but decomposes rapidly above 300 °C. In contrast, stable physisorbed PBI-alkyl monolayers only exist up to 100 °C. Above the bulk melting point at 200 °C no more order exists. The results encourage using anchor groups in monolayers for various applications as it allows enhanced stability at the interface with the substrate. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The spectroscopic characterization of newly developed emissive materials and the effects of environment on their photophysical properties

NASA Astrophysics Data System (ADS)

McNamara, Louis Edward, III

The development of new materials capable of efficient charge transfer and energy storage has become increasingly important in many areas of modern chemical research. This is especially true for the development of emissive optoelectronic devices and in the field of solar to electric energy conversion. The characterization of the photophysical properties of new molecular systems for these applications has become critical in the design and development of these materials. Many molecular building blocks have been developed and understanding the properties of these molecules at a fundamental level is essential for their successful implementation and future engineering. This dissertation focuses on the characterization of some of these newly-developed molecular systems. The spectroscopic studies focus on the characterization of newly-developed molecules based on perylene and indolizine derivatives for solar to electric energy conversion, thienopyrazine derivatives for near infrared (NIR) emissive applications, an SCS pincer complex for blue emissive materials and a fluorescent probe for medical applications. The effects of noncovalent interactions are also investigated on these systems and a benchmark biological molecule trimethylamine N-oxide (TMAO).

Bending nanofibers into nanospirals: coordination chemistry as a tool for shaping hydrophobic assemblies.

PubMed

Kossoy, Elizaveta; Weissman, Haim; Rybtchinski, Boris

2015-01-02

In the current work, we demonstrate how coordination chemistry can be employed to direct self-assembly based on strong hydrophobic interactions. To investigate the influence of coordination sphere geometry on aqueous self-assembly, we synthesized complexes of the amphiphilic perylene diimide terpyridine ligand with the first-row transition-metal centers (zinc, cobalt, and nickel). In aqueous medium, aggregation of these complexes is induced by hydrophobic interactions between the ligands. However, the final shapes of the resulting assemblies depend on the preferred geometry of the coordination spheres typical for the particular metal center. The self-assembly process was characterized by UV/Vis spectroscopy, zeta potential measurements, and cryogenic transmission electron microscopy (cryo-TEM). Coordination of zinc(II) and cobalt(II) leads to the formation of unique nanospiral assemblies, whereas complexation of nickel(II) leads to the formation of straight nanofibers. Notably, coordination bonds are utilized not as connectors between elementary building blocks, but as directing interactions, enabling control over supramolecular geometry. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A new era for homolytic aromatic substitution: replacing Bu3SnH with efficient light-induced chain reactions.

PubMed

Gurry, Michael; Aldabbagh, Fawaz

2016-04-28

Herein is a pertinent review of recent photochemical homolytic aromatic substitution (HAS) literature. Issues with using the reductant Bu3SnH in an oxidative process where the net loss of a hydrogen atom occurs is discussed. Nowadays more efficient light-induced chain reactions are used resulting in HAS becoming a synthetic mechanism of choice rivaling organometallic, transition-metal and electrophilic aromatic substitution protocols. The review includes aromatic substitution as part of a tandem or cascade reaction, Pschorr reaction, as well as HAS facilitated by ipso-substitution, and Smiles rearrangement. Recently visible-light photoredox catalysis, which is carried out at room temperature has become one of the most important means of aromatic substitution. The main photoredox catalysts used are polypyridine complexes of Ru(ii) and Ir(iii), although eosin Y is an alternative allowing metal-free HAS. Other radical initiator-free aromatic substitutions have used 9-mesityl-10-methylacridinium ion and N,N-bis(2,6-diisopropylphenyl)perylene-3,4,9,10-bis(dicarboximide) as the photoredox catalyst, UV-light, photoinduced electron-transfer, zwitterionic semiquinone radical anions, and Barton ester intermediates.

Fabrication of sophisticated two-dimensional organic nanoarchitectures thought hydrogen bond mediated molecular self assembly

NASA Astrophysics Data System (ADS)

Silly, Fabien

2012-02-01

Complex supramolecular two-dimensional (2D) networks are attracting considerable interest as highly ordered functional materials for applications in nanotechnology. The challenge consists in tailoring the ordering of one or more molecular species into specific architectures over an extended length scale with molecular precision. Highly organized supramolecular arrays can be obtained through self-assembly of complementary molecules which can interlock via intermolecular interactions. Molecules forming hydrogen bonds (H-bonds) are especially interesting building blocks for creating sophisticated organic architectures due to high selectivity and directionality of these bindings. We used scanning tunnelling microscopy to investigate at the atomic scale the formation of H-bonded 2D organic nanoarchitectures on surfaces. We mixed perylene derivatives having rectangular shape with melamine and DNA base having triangular and non symmetric shape respectively. We observe that molecule substituents play a key role in formation of the multicomponent H-bonded architectures. We show that the 2D self-assembly of these molecules can be tailored by adjusting the temperature and molecular ratio. We used these stimuli to successfully create numerous close-packed and porous 2D multicomponent structures.

Aromatic hydrocarbons from the Middle Jurassic fossil wood of the Polish Jura

NASA Astrophysics Data System (ADS)

Smolarek, Justyna; Marynowski, Leszek

2013-09-01

Aromatic hydrocarbons are present in the fossil wood samples in relatively small amounts. In almost all of the tested samples the dominating aromatic hydrocarbon is perylene and its methyl and dimethyl derivatives. The most important biomarkers present in the aromatic fraction are dehydroabietane, siomonellite and retene, compounds characteristic for conifers. The distribution of discussed compounds is highly variable due to such early diagenetic processes affecting the wood as oxidation and the activity of microorganisms. MPI1 parameter values (methylphenanthrene index) for the majority of the samples are in the range of 0.1 to 0.5, which results in the highly variable values of Rc (converted value of vitrinite reflectance) ranging from 0.45 to 0.70%. Such values suggest that MPI1 parameter is not useful as maturity parameter in case of Middle Jurassic ore-bearing clays, even if measured strictly on terrestrial organic matter (OM). As a result of weathering processes (oxidation) the distribution of aromatic hydrocarbons changes. In the oxidized samples the amount of aromatic hydrocarbons, both polycyclic as well as aromatic biomarkers decreases.

Enhancement in Open-Circuit Voltage in Organic Solar Cells by Using Ladder-Type Nonfullerene Acceptors.

PubMed

Cai, Zhengxu; Zhao, Donglin; Sharapov, Valerii; Awais, Mohammad A; Zhang, Na; Chen, Wei; Yu, Luping

2018-04-25

The open-circuit voltage ( V oc ) loss has always been a major factor in lowering power conversion efficiencies (PCEs) in bulk heterojunction organic photovoltaic cells (OPVs). A method to improve the V oc is indispensable to achieve high PCEs. In this paper, we investigated a series of perylene diimide-based ladder-type molecules as electron acceptors in nonfullerene OPVs. The D-A ladder-type structures described here lock our π-systems into a planar structure and eliminate bond twisting associated with linear conjugated systems. This enlarges the interface energy gap (Δ E DA ), extends electronic delocalization, and hence improves the V oc . More importantly, these devices showed an increase in V oc without compromising either the J sc or the FF. C5r exhibited a strong intermolecular interaction and a PCE value of 6.1%. Moreover, grazing-incident wide-angle X-ray scattering analysis and atomic force microscopy images suggested that our fused-ring acceptors showed a suitable domain size and uniform blend films, which were not affected by their rigid molecular structures.

Long-range ordering of composites for organic electronics: TIPS-pentacene single crystals with incorporated nano-fibers

DOE PAGES

Li, Huanbin; Xue, Guobiao; Wu, Jiake; ...

2017-08-18

Multi-component active materials are widely used for organic electronic devices, with every component contributing complementary and synergistic optoelectronic functions. Mixing these components generally leads to lowered crystallinity and weakened charge transport. Therefore, preparing the active materials without substantially disrupting the crystalline lattice is highly desired. In this paper, we show that crystallization of TIPS-pentacene from solutions in the presence of fluorescent nanofibers of a perylene bisimide derivative (PBI) leads to formation of composites with nanofiber guest incorporated in the crystal host. In spite of the binary composite structure, the TIPS-pentacene maintains the single-crystalline nature. As a result, the incorporation ofmore » the PBI guest introduces additional fluorescence function but does not significantly reduce the charge transport property of the TIPS-pentacene host, exhibiting field-effect mobility as high as 3.34 cm 2 V -1 s -1 even though 26.4% of the channel area is taken over by the guest. Finally, as such, this work provides a facile approach toward high-performance multifunctional organic electronic materials.« less

Impact of Fluorine Atoms on Perylene Diimide Derivative for Fullerene-Free Organic Photovoltaics.

PubMed

Zhao, Liang; Sun, Hua; Liu, Xiaoyuan; Liu, Changmei; Shan, Haiquan; Xia, Jiuxu; Xu, Zongxiang; Chen, Fei; Chen, Zhi-Kuan; Huang, Wei

2017-08-17

The incorporation of fluorine atoms in organic semiconducting materials has attracted much attention recently due to its unique function to manipulate the molecular packing, film morphology and molecular energy levels. In this work, two perylenediimide (PDI) derivatives FPDI-CDTph and FPDI-CDTph2F were designed and synthesized to investigate the impact of fluorination on non-fullerene acceptors. Both FPDI-CDTph and FPDI-CDTph2F exhibited strong and broad absorption profiles, suitable lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO) energy levels, and good electron transport ability. Compared with FPDI-CDTph, the fluorinated acceptor (FPDI-CDTph2F) afforded an optimal bulk heterojunction morphology with an interconnected and nanoscale phase separated structure that allowed more efficient exciton dissociation and balanced charge transport. Consequently, organic solar cells based on FPDI-CDTph2F showed a much higher power conversion efficiency (PCE) of 6.03 % than that of FPDI-CDTph based devices (4.10 %) without any post-fabrication treatment. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhancement in Open-Circuit Voltage in Organic Solar Cells by Using Ladder-Type Nonfullerene Acceptors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cai, Zhengxu; Zhao, Donglin; Sharapov, Valerii

The open-circuit voltage (V oc) loss has always been a major factor in lowering power conversion efficiencies (PCEs) in bulk heterojunction organic photovoltaic cells (OPVs). A method to improve the V oc is indispensable to achieve high PCEs. Here in this paper, we investigated a series of perylene diimide-based ladder-type molecules as electron acceptors in nonfullerene OPVs. The D-A ladder-type structures described here lock our pi-systems into a planar structure and eliminate bond twisting associated with linear conjugated systems. This enlarges the interface energy gap (ΔE DA), extends electronic delocalization, and hence improves the V oc. More importantly, these devicesmore » showed an increase in V oc without compromising either the J sc or the FF. C5r exhibited a strong intermolecular interaction and a PCE value of 6.1%. Moreover, grazing-incident wide-angle X-ray scattering analysis and atomic force microscopy images suggested that our fused-ring acceptors showed a suitable domain size and uniform blend films, which were not affected by their rigid molecular structures.« less

Self-assembly of electronically abrupt borophene/organic lateral heterostructures

PubMed Central

Liu, Xiaolong; Wei, Zonghui; Balla, Itamar; Mannix, Andrew J.; Guisinger, Nathan P.; Luijten, Erik; Hersam, Mark C.

2017-01-01

Two-dimensional boron sheets (that is, borophene) have recently been realized experimentally and found to have promising electronic properties. Because electronic devices and systems require the integration of multiple materials with well-defined interfaces, it is of high interest to identify chemical methods for forming atomically abrupt heterostructures between borophene and electronically distinct materials. Toward this end, we demonstrate the self-assembly of lateral heterostructures between borophene and perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA). These lateral heterostructures spontaneously form upon deposition of PTCDA onto submonolayer borophene on Ag(111) substrates as a result of the higher adsorption enthalpy of PTCDA on Ag(111) and lateral hydrogen bonding among PTCDA molecules, as demonstrated by molecular dynamics simulations. In situ x-ray photoelectron spectroscopy confirms the weak chemical interaction between borophene and PTCDA, while molecular-resolution ultrahigh-vacuum scanning tunneling microscopy and spectroscopy reveal an electronically abrupt interface at the borophene/PTCDA lateral heterostructure interface. As the first demonstration of a borophene-based heterostructure, this work will inform emerging efforts to integrate borophene into nanoelectronic applications. PMID:28261662

Mutagenicity and polycyclic aromatic hydrocarbons associated with extractable organic matter from airborne particles ⩽10 μm in southwest Mexico City

NASA Astrophysics Data System (ADS)

Villalobos-Pietrini, Rafael; Amador-Muñoz, Omar; Waliszewski, Stefan; Hernández-Mena, Leonel; Munive-Colín, Zenaida; Gómez-Arroyo, Sandra; Bravo-Cabrera, José Luis; Frías-Villegas, Alejandro

A year-long sampling and analysis of 24 h airborne particles equal to or less than 10 μm (PM 10) was conducted in Southwest (SW) Mexico City in 1998. The amount of airborne PM 10 and its extractable organic matter (EOM) were highly correlated. The year 1998 was particularly dry with many fires, and higher values of PM 10 and EOM were obtained in the fire period (February-May) compared to the without fire period (January, June-December). The indirect-acting mutagenicity ( Salmonella typhimurium strain TA98 with mammalian metabolic activation, S9) did not correlate with the monthly concentrations of PM 10 and EOM, while the direct-acting mutagenicity (strains TA98 and YG1021, without mammalian metabolic activation) did correlate. The highest monthly mutagenic potency of TA98+S9 and of TA98-S9 were registered in May which correspond to the fire period, while for YG1021 the highest was in December, a without fire month. The highest TA98+S9/TA98-S9 ratios appeared from April to September (with the exception of June), indicating that emission of the direct mutagens occurred in the rest of the year (the coldest months), and December showed the highest mutagenicity of YG1021. The correlation of this mutagenicity with the number of ground-based inversions indicated a greater emissions of nitroarenes in the coldest months emitted mainly by vehicular traffic as shown by the correlation between YG1021 with CO and with NO 2. We did not find a correlation in the EOM of the complex mixtures between TA98+S9 and the total concentration of polycyclic aromatic hydrocarbons (PAH) nor between TA98+S9 and specific PAH. The analysis by gas chromatography/mass spectrometry indicated the presence of retene, a PAH found in the fire period and considered a softwood burning marker. The concentrations of fluoranthene and benz[ a]anthracene correlated with that of retene and with the burned area; they were the only PAH that presented significant differences between the periods with fire and without fire, showing that these compounds could have a similar origin. Benzo[ ghi]perylene, coronene and indeno[1,2,3 -cd]pyrene were the most abundant PAH of the 17 analyzed in SW Mexico City, indicating that the main emission source for PAH in the airborne particle phase in this zone were vehicles with the combustion of gasoline and diesel rather than wood burning. The mean concentrations for most PAH were higher during the fire period, except for perylene and coronene, suggesting that the fires were not the emission source for these two last PAH.

Coherent random lasing controlled by Brownian motion of the active scatterer

NASA Astrophysics Data System (ADS)

Liang, Shuofeng; Yin, Leicheng; Zhang, ZhenZhen; Xia, Jiangying; Xie, Kang; Zou, Gang; Hu, Zhijia; Zhang, Qijin

2018-05-01

The stability of the scattering loop is fundamental for coherent random lasing in a dynamic scattering system. In this work, fluorescence of DPP (N, N-di [3-(isobutyl polyhedral oligomeric silsesquioxanes) propyl] perylene diimide) is scattered to produce RL and we realize the transition from incoherent RL to coherent RL by controlling the Brownian motion of the scatterers (dimer aggregates of DPP) and the stability of scattering loop. To produce coherent random lasers, the loop needs to maintain a stable state within the loop-stable time, which can be determined through controlled Brownian motion of scatterers in the scattering system. The result shows that the loop-stable time is within 5.83 × 10‑5 s to 1.61 × 10‑4 s based on the transition from coherent to incoherent random lasing. The time range could be tuned by finely controlling the viscosity of the solution. This work not only develops a method to predict the loop-stable time, but also develops the study between Brownian motion and random lasers, which opens the road to a variety of novel interdisciplinary investigations involving modern statistical mechanics and disordered photonics.

Automobile tires--a potential source of highly carcinogenic dibenzopyrenes to the environment.

PubMed

Sadiktsis, Ioannis; Bergvall, Christoffer; Johansson, Christer; Westerholm, Roger

2012-03-20

Eight tires were analyzed for 15 high molecular weight (HMW) polycyclic aromatic hydrocarbons (PAH), using pressurized fluid extraction. The variability of the PAH concentrations determined between different tires was large; a factor of 22.6 between the lowest and the highest. The relative abundance of the analytes was quite similar regardless of tire. Almost all (92.3%) of the total extractable PAH content was attributed to five PAHs: benzo[ghi]perylene, coronene, indeno[1,2,3-cd]pyrene, benzo[e]pyrene, and benzo[a]pyrene. The difference in the measured PAH content between summer and winter tires varied substantially across manufacturers, making estimates of total vehicle fleet emissions very uncertain. However, when comparing different types of tires from the same manufacturer they had significantly (p = 0.05) different PAH content. Previously, there have been no data available for carcinogenic dibenzopyrene isomers in automobile tires. In this study, the four dibenzopyrene isomers dibenzo[a,l]pyrene, dibenzo[a,e]pyrene, dibenzo[a,i]pyrene, and dibenzo[a,h]pyrene constituted <2% of the sum of the 15 analyzed HMW PAHs. These findings show that automobile tires may be a potential previously unknown source of carcinogenic dibenzopyrenes to the environment.

Adsorption heights and bonding strength of organic molecules on a Pb-Ag surface alloy

NASA Astrophysics Data System (ADS)

Stadtmüller, Benjamin; Haag, Norman; Seidel, Johannes; van Straaten, Gerben; Franke, Markus; Kumpf, Christian; Cinchetti, Mirko; Aeschlimann, Martin

2016-12-01

The understanding of the fundamental geometric and electronic properties of metal-organic hybrid interfaces is a key issue on the way to improving the performance of organic electronic and spintronic devices. Here, we studied the adsorption heights of copper-II-phthalocyanine (CuPc) and 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) on a Pb1Ag2 surface alloy on Ag(111) using the normal-incidence x-ray standing waves technique. We find a significantly larger adsorption height of both molecules on the Pb-Ag surface alloy compared to the bare Ag(111) surface which is caused by the larger size of Pb. This increased adsorption height suppresses the partial chemical interaction of both molecules with Ag surface atoms. Instead, CuPc and PTCDA molecules bond only to the Pb atoms with different interaction strength ranging from a van der Waals-like interaction for CuPc to a weak chemical interaction with additional local bonds for PTCDA. The different adsorption heights for CuPc and PTCDA on Pb1Ag2 are the result of local site-specific molecule-surface bonds mediated by functional molecular groups and the different charge donating and accepting character of CuPc and PTCDA.

Nondispersive hole transport in a spin-coated dendrimer film measured by the charge-generation-layer time-of-flight method

NASA Astrophysics Data System (ADS)

Markham, Jonathan P. J.; Anthopoulos, Thomas D.; Samuel, Ifor D. W.; Richards, Gary J.; Burn, Paul L.; Im, Chan; Bassler, Heinz

2002-10-01

Measurements of the mobility of a first-generation (G1) bis-fluorene cored dendrimer have been performed on spin-coated samples of 500 nm thickness using the charge-generation-layer time-of-flight (TOF) technique. A 10 nm perylene charge generation layer was excited by the 532 nm line of a Q-switched Nd:YAG laser and the generated carriers swept through the dendrimer film under an applied field. We observe nondispersive hole transport in the dendrimer layer with a room-temperature mobility mu=2.0 x10-4 cm2/V s at a field of 0.55 MV/cm. There is a weak field dependence of the mobility and it increases from mu=1.6 x10-4 cm2/V s at 0.2 MV/cm to mu=3.0 x10-4 cm2/V s at 1.4 MV/cm. These results suggest that the measurement of mobility by TOF in spin-coated samples on thickness scales relevant to organic light-emitting diodes can yield valuable information, and that dendrimers are promising materials for device applications.

Input and behavior of polycyclic aromatic hydrocarbons in arable, fallow, and forest soils of the taiga zone (Tver oblast)

NASA Astrophysics Data System (ADS)

Zhidkin, A. P.; Gennadiev, A. N.; Koshovskii, T. S.

2017-03-01

Contents of 11 most prevalent polycyclic aromatic hydrocarbons (PAHs) in snow and soils of arable, fallow, and forest areas significantly remote from impact technogenic sources of polyarenes have been examined in the Torzhok district of Tver oblast. From the analysis of snow samples, the volumes and composition of PAHs coming from the atmosphere onto the areas of different land use have been determined. Light hydrocarbons prevail in PAHs. They make up 65-70% of total PAHs; their share in soils reaches almost 95%. An increase in the content of PAHs is revealed in fallow soils compared to arable and afforested areas. A direct relationship is revealed between the lateral distribution of total PAHs and the content of organic carbon. The distribution of total PAHs is surface-accumulative in forest soils, mainly uniform in arable soils, and deepaccumulative in fallow soils. PAH groups characterized by similar radial distributions and ratios between their reserves in snow and soils are distinguished: (1) fluorene and phenanthrene, (2) biphenyl and naphthalene, (3) benzo(a)anthracene, chrysene, perylene, and benzo[ a]pyrene, and (4) anthracene and benzo[ ghi]pyrene.

Singlet oxygen production in Chlamydomonas reinhardtii under heat stress.

PubMed

Prasad, Ankush; Ferretti, Ursula; Sedlářová, Michaela; Pospíšil, Pavel

2016-02-01

In the current study, singlet oxygen formation by lipid peroxidation induced by heat stress (40 °C) was studied in vivo in unicellular green alga Chlamydomonas reinhardtii. Primary and secondary oxidation products of lipid peroxidation, hydroperoxide and malondialdehyde, were generated under heat stress as detected using swallow-tailed perylene derivative fluorescence monitored by confocal laser scanning microscopy and high performance liquid chromatography, respectively. Lipid peroxidation was initiated by enzymatic reaction as inhibition of lipoxygenase by catechol and caffeic acid prevented hydroperoxide formation. Ultra-weak photon emission showed formation of electronically excited species such as triplet excited carbonyl, which, upon transfer of excitation energy, leads to the formation of either singlet excited chlorophyll or singlet oxygen. Alternatively, singlet oxygen is formed by direct decomposition of hydroperoxide via Russell mechanisms. Formation of singlet oxygen was evidenced by the nitroxyl radical 2,2,6,6-tetramethylpiperidine-1-oxyl detected by electron paramagnetic resonance spin-trapping spectroscopy and the imaging of green fluorescence of singlet oxygen sensor green detected by confocal laser scanning microscopy. Suppression of singlet oxygen formation by lipoxygenase inhibitors indicates that singlet oxygen may be formed via enzymatic lipid peroxidation initiated by lipoxygenase.

Effects of polycyclic aromatic compounds in fine particulate matter generated from household coal combustion on response to EGFR mutations in vitro.

PubMed

Ho, Kin-Fai; Chang, Chih-Cheng; Tian, Linwei; Chan, Chi-Sing; Musa Bandowe, Benjamin A; Lui, Ka-Hei; Lee, Kang-Yun; Chuang, Kai-Jen; Liu, Chien-Ying; Ning, Zhi; Chuang, Hsiao-Chi

2016-11-01

Induction of PM 2.5 -associated lung cancer in response to EGFR-tyrosine kinase inhibitors (EGFR-TKI) remains unclear. Polycyclic aromatic hydrocarbons (PAHs) and their polar derivatives (oxygenated PAHs: OPAHs and azaarenes: AZAs) were characterized in fine particulates (PM 2.5 ) emitted from indoor coal combustion. Samples were collected in Xuanwei (Yunnan Province), a region in China with a high rate of lung cancer. Human lung adenocarcinoma cells A549 (with wild-type EGFR) and HCC827 (with EGFR mutation) were exposed to the PM 2.5 , followed by treatment with EGFR-TKI. Two samples showed significant and dose-dependent reduction in the cell viability in A549. EGFR-TKI further demonstrated significantly decreased in cell viability in A549 after exposure to the coal emissions. Chrysene and triphenylene, dibenzo[a,h]anthracene, benzo[ghi]perylene, azaarenes and oxygenated polycyclic aromatic hydrocarbons (carbonyl-OPAHs) were all associated with EGFR-TKI-dependent reduced cell viability after 72-h exposure to the PM 2.5 . The findings suggest the coal emissions could influence the response of EGFR-TKI in lung cancer cells in Xuanwei. Copyright © 2016 Elsevier Ltd. All rights reserved.

Characterization of particulate polycyclic aromatic hydrocarbons in an urban atmosphere of central-southern Spain.

PubMed

Villanueva, Florentina; Tapia, Araceli; Cabañas, Beatriz; Martínez, Ernesto; Albaladejo, José

2015-12-01

Over 1-year period, 13 polycyclic aromatic hydrocarbons (PAHs) associated with particulate matter PM10 have been monitored for the first time in the atmosphere of Ciudad Real, situated at the central-southern Spain. PM10-bound PAHs were collected using a high-volume sampler from autumn 2012 to summer 2013 and were analyzed by HPLC with fluorescence detector. The most abundant PAHs were pyrene, chrysene, benzo[b]fluoranthene, dibenzo[a,h]anthracene and benzo[g,h,i]perylene. The ∑PAH concentrations in Ciudad Real were 888, 368, 259 and 382 pg m(-3) for winter, spring, summer and autumn seasons, respectively. The diurnal variation of PAH was also investigated presenting the highest concentrations during the evening (19:00-23:00). Benzo[a]pyrene concentrations ranged from 2.4 to 110 pg m(-3), these values are lower than the target value proposed by the European legislation, 1 ng m(-3). Diagnostic ratios were used to identify potential sources of PAHs. Results suggest that vehicle emissions are the major source of identified PAHs, with a higher contribution of diesel engines although other anthropogenic sources could also have an impact on the PAH levels.

Determination of polycyclic aromatic hydrocarbons in fractions in asphalt mixtures using liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization.

PubMed

Nascimento, Paulo Cicero; Gobo, Luciana Assis; Bohrer, Denise; Carvalho, Leandro Machado; Cravo, Margareth Coutinho; Leite, Leni Figueiredo Mathias

2015-07-01

An analytical method using liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization for the determination of polycyclic aromatic hydrocarbons in asphalt fractions has been developed. The 14 compounds determined, characterized by having two or more condensed aromatic rings, are expected to be present in asphalt and are considered carcinogenic and mutagenic. The parameters of the atmospheric pressure chemical ionization interface were optimized to obtain the highest possible sensitivity for all of the compounds. The limits of detection ranged from 0.5 to 346.5 μg/L and the limits of quantification ranged from 1.7 to 1550 μg/L. The method was validated against a diesel particulate extract standard reference material (NIST SRM 1975), and the obtained concentrations agreed with the certified values. The method was applied to asphalt samples after its fractionation according to ASTM D4124 and the method of Green. The concentrations of the seven polycyclic aromatic hydrocarbons quantified in the sample ranged from 0.86 mg/kg for benzo[ghi]perylene to 98.32 mg/kg for fluorene. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Charge-transfer dynamics and nonlocal dielectric permittivity tuned with metamaterial structures as solvent analogues

NASA Astrophysics Data System (ADS)

Lee, Kwang Jin; Xiao, Yiming; Woo, Jae Heun; Kim, Eunsun; Kreher, David; Attias, André-Jean; Mathevet, Fabrice; Ribierre, Jean-Charles; Wu, Jeong Weon; André, Pascal

2017-07-01

Charge transfer (CT) is a fundamental and ubiquitous mechanism in biology, physics and chemistry. Here, we evidence that CT dynamics can be altered by multi-layered hyperbolic metamaterial (HMM) substrates. Taking triphenylene:perylene diimide dyad supramolecular self-assemblies as a model system, we reveal longer-lived CT states in the presence of HMM structures, with both charge separation and recombination characteristic times increased by factors of 2.4 and 1.7--that is, relative variations of 140 and 73%, respectively. To rationalize these experimental results in terms of driving force, we successfully introduce image dipole interactions in Marcus theory. The non-local effect herein demonstrated is directly linked to the number of metal-dielectric pairs, can be formalized in the dielectric permittivity, and is presented as a solid analogue to local solvent polarity effects. This model and extra PH3T:PC60BM results show the generality of this non-local phenomenon and that a wide range of kinetic tailoring opportunities can arise from substrate engineering. This work paves the way toward the design of artificial substrates to control CT dynamics of interest for applications in optoelectronics and chemistry.

Optochemical sensor based on screenprinted fluorescent sensorspots surrounded by organic photodiodes for multianalyte detection

NASA Astrophysics Data System (ADS)

Kraker, E.; Lamprecht, B.; Haase, A.; Jakopic, G.; Abel, T.; Konrad, C.; Köstler, S.; Tscherner, M.; Stadlober, B.; Mayr, T.

2010-08-01

A compact, integrated photoluminescence based oxygen sensor, utilizing an organic light emitting device (OLED) as the light source and an organic photodiode (OPD) as the detection unit, is described. The detection system of the sensor array consists of an array of circular screen-printed fluorescent sensor spots surrounded by organic photodiodes as integrated fluorescence detectors. The OPD originates from the well-known Tang photodiode, consisting of a stacked layer of copper phthalocyanine (CuPc, p-type material) and perylene tetracarboxylic bisbenzimidazole (PTCBi, n-type material). An additional layer of tris-8-hydroxyquinolinatoaluminium (Alq3, n-type material) was inserted between the PTCBi layer and cathode. An ORMOCERR layer was used as encapsulation layer. For excitation an organic light emitting diode is used. The sensor spot and the detector are processed on the same flexible substrate. This approach not only simplifies the detection system by minimizing the numbers of required optical components - no optical filters have to be used for separating the excitation light and the luminescent emission-, but also has a large potential for low-cost sensor applications. The feasibility of the concept is demonstrated by an integrated oxygen sensor, indicating good performance. Sensor schemes for other chemical parameters are proposed.

Chemical and Morphological Control of Interfacial Self-Doping for Efficient Organic Electronics.

PubMed

Liu, Yao; Cole, Marcus D; Jiang, Yufeng; Kim, Paul Y; Nordlund, Dennis; Emrick, Todd; Russell, Thomas P

2018-04-01

Solution-based processing of materials for electrical doping of organic semiconductor interfaces is attractive for boosting the efficiency of organic electronic devices with multilayer structures. To simplify this process, self-doping perylene diimide (PDI)-based ionene polymers are synthesized, in which the semiconductor PDI components are embedded together with electrolyte dopants in the polymer backbone. Functionality contained within the PDI monomers suppresses their aggregation, affording self-doping interlayers with controllable thickness when processed from solution into organic photovoltaic devices (OPVs). Optimal results for interfacial self-doping lead to increased power conversion efficiencies (PCEs) of the fullerene-based OPVs, from 2.62% to 10.64%, and of the nonfullerene-based OPVs, from 3.34% to 10.59%. These PDI-ionene interlayers enable chemical and morphological control of interfacial doping and conductivity, demonstrating that the conductive channels are crucial for charge transport in doped organic semiconductor films. Using these novel interlayers with efficient doping and high conductivity, both fullerene- and nonfullerene-based OPVs are achieved with PCEs exceeding 9% over interlayer thicknesses ranging from ≈3 to 40 nm. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly Soluble Benzo[ghi]perylenetriimide Derivatives: Stable and Air-Insensitive Electron Acceptors for Artificial Photosynthesis.

PubMed

Chen, Hung-Cheng; Hsu, Chao-Ping; Reek, Joost N H; Williams, René M; Brouwer, Albert M

2015-11-01

A series of new benzo[ghi]perylenetriimide (BPTI) derivatives has been synthesized and characterized. These remarkably soluble BPTI derivatives show strong optical absorption in the range of λ=300-500 nm and have a high triplet-state energy of 1.67 eV. A cyanophenyl substituent renders BPTI such a strong electron acceptor (Ered =-0.11 V vs. the normal hydrogen electrode) that electron-trapping reactions with O2 and H2 O do not occur. The BPTI radical anion on a fluorine-doped tin oxide|TiO2 electrode is persistent up to tens of seconds (t1/2 =39 s) in air-saturated buffer solution. As a result of favorable packing, theoretical electron mobilities (10(-2) ∼10(-1) cm(2) V(-1) s(-1)) are high and similar to the experimental values observed for perylene diimide and C60 derivatives. Our studies show the potential of the cyanophenyl-modified BPTI compounds as electron acceptors in devices for artificial photosynthesis in water splitting that are also very promising nonfullerene electron-transport materials for organic solar cells. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

BODIPY-Based Donor-Acceptor Pi-Conjugated Alternating Copolymers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Popere, Bhooshan C.; Della Pelle, Andrea M.; Thayumanavan, S.

2011-06-28

Four novel π-conjugated copolymers incorporating 4,4-difluoro-4-borata-3a-azonia-4a-aza-s-indacene (BODIPY) core as the “donor” and quinoxaline (Qx), 2,1,3-benzothiadiazole (BzT), N,N'-di(2'-ethyl)hexyl-3,4,7,8-naphthalenetetracarboxylic diimide (NDI), and N,N'-di(2'-ethyl)hexyl-3,4,9,10-perylene tetracarboxylic diimide (PDI) as acceptors were designed and synthesized via Sonogashira polymerization. The polymers were characterized by ¹H NMR spectroscopy, gel permeation chromatography (GPC), UV–vis absorption spectroscopy, and cyclic voltammetry. Density functional theory (DFT) calculations were performed on polymer repeat units, and the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energy levels were estimated from the optimized geometry using B3LYP functional and 6-311g(d,p) basis set. Copolymers with Qx and BzT possessed HOMO and LUMOmore » energy levels comparable to those of BODIPY homopolymer, while PDI stabilized both HOMO and LUMO levels. Semiconductor behavior of these polymers was estimated in organic thin-film transistors (OTFT). While the homopolymer, Qx, and BzT-based copolymers showed only p-type semiconductor behavior, copolymers with PDI and NDI showed only n-type behavior.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Serkovic Loli, L. N.; Sanchez, E. A.; Grizzi, O.

A combined experimental and theoretical study of the energy loss of protons in fluorides and organic films is presented. The measurements were performed in fresh AlF{sub 3}, LiF, and N,N{sup '}-bis(1-ethylpropyl)-perylene-3,4,9,10-tetracarboxdiimide (EP-PTCDI) evaporated in situ on self-supported C or Ag foils, covering the very low energy range from 25 keV down to 0.7 keV. The transmission method is used in combination with time-of-flight (TOF) spectrometry. In the case of fluorides with large band gap energies (AlF{sub 3} and LiF), the experimental stopping power increases almost linearly with the mean projectile velocity showing a velocity threshold at about 0.1 a.u. Thesemore » features are well reproduced by a model based on quantum scattering theory that takes into account the velocity distribution and the excitation of the active 2p electrons in the F{sup -} anions, and the properties of the electronic bands of the insulators. In the case of the semiconductor organic film with a lower gap, the experimental stopping power increases linearly with the mean projectile velocity without presenting a clear threshold. This trend is also reproduced by the proposed model.« less

Synthesis and Exploration of Ladder-Structured Large Aromatic Dianhydrides as Organic Cathodes for Rechargeable Lithium-Ion Batteries.

PubMed

Xie, Jian; Chen, Wangqiao; Wang, Zilong; Jie, Kenneth Choo Wei; Liu, Ming; Zhang, Qichun

2017-04-18

Compared to anode materials in Li-ion batteries, the research on cathode materials is far behind, and their capacities are much smaller. Thus, in order to address these issues, we believe that organic conjugated materials could be a solution. In this study, we synthesized two non-polymeric dianhydrides with large aromatic structures: NDA-4N (naphthalenetetracarboxylic dianhydride with four nitrogen atoms) and PDA-4N (perylenetetracarboxylic dianhydride with four nitrogen atoms). Their electrochemical properties have been investigated between 2.0 and 3.9 V (vs. Li + /Li). Benefiting from multi-electron reactions, NDA-4N and PDA-4N could reversibly achieve 79.7 % and 92.3 %, respectively, of their theoretical capacity. Further cycling reveals that the organic compound with a relatively larger aromatic building block could achieve a better stability, as an obvious 36.5 % improvement of the capacity retention was obtained when the backbone was switched from naphthalene to perylene. This study proposes an opportunity to attain promising small-molecule-based cathode materials through tailoring organic structures. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molecular dynamics studies of the 3D structure and planar ligand binding of a quadruplex dimer.

PubMed

Li, Ming-Hui; Luo, Quan; Xue, Xiang-Gui; Li, Ze-Sheng

2011-03-01

G-rich sequences can fold into a four-stranded structure called a G-quadruplex, and sequences with short loops are able to aggregate to form stable quadruplex multimers. Few studies have characterized the properties of this variety of quadruplex multimers. Using molecular modeling and molecular dynamics simulations, the present study investigated a dimeric G-quadruplex structure formed from a simple sequence of d(GGGTGGGTGGGTGGGT) (G1), and its interactions with a planar ligand of a perylene derivative (Tel03). A series of analytical methods, including free energy calculations and principal components analysis (PCA), was used. The results show that a dimer structure with stacked parallel monomer structures is maintained well during the entire simulation. Tel03 can bind to the dimer efficiently through end stacking, and the binding mode of the ligand stacked with the 3'-terminal thymine base is most favorable. PCA showed that the dominant motions in the free dimer occur on the loop regions, and the presence of the ligand reduces the flexibility of the loops. Our investigation will assist in understanding the geometric structure of stacked G-quadruplex multimers and may be helpful as a platform for rational drug design.

Quantification of polycyclic aromatic hydrocarbons (PAHs) in human hair by HPLC with fluorescence detection: a biological monitoring method to evaluate the exposure to PAHs.

PubMed

Toriba, Akira; Kuramae, Yayoi; Chetiyanukornkul, Thaneeya; Kizu, Ryoichi; Makino, Tsunehisa; Nakazawa, Hiroyuki; Hayakawa, Kazuichi

2003-01-01

A high-performance liquid chromatographic (HPLC) method with fluorescence detection was developed for the quantification of polycyclic aromatic hydrocarbons (PAHs) in human hair. Fifteen kinds of PAHs classified as priority pollutants by the US EPA were quantified with four perdeuterated PAHs as internal standards. After 50 mg hair samples were washed with n-hexane to remove external contamination of PAHs, the samples were digested in 2.5 M sodium hydroxide. The digests were extracted with n-hexane and then analyzed by HPLC. Eleven kinds of PAHs were identified in hair samples of 20 subjects, and 10 kinds of PAHs were eventually quantified using the internal standards. For anthracene, chrysene and benzo[k]fluoranthene, significant differences were observed between smokers and non-smokers. Although benzo[b]fluoranthene, dibenz[a,h]anthracene, benzo[ghi]perylene and indeno[1,2,3-cd]pyrene were observed in the particulates of indoor and outdoor air, they were not detected in all hair samples. The analysis of PAHs in human hair should be useful as a new biomarker to evaluate the exposure to PAHs.

On-line and in-situ detection of polycyclic aromatic hydrocarbons (PAH) on aerosols via thermodesorption and laser-induced fluorescence spectroscopy.

PubMed

Panne, U; Knöller, A; Kotzick, R; Niessner, R

2000-02-01

A fiber optical sensor system for the determination of polycyclic aromatic hydrocarbons (PAH) on aerosols by laser-induced, time-resolved fluorescence is combined with a thermodesorption device. The sensor system is based on an aerosol flow cell, which is fibre-optically coupled to a pulsed nitrogen laser for excitation and the detection system. Time-resolved fluorescence emission spectra are detected by a monochromator equipped with a photomultiplier and a fast digital storage oscilloscope. The analytical figures of merit of the thermodenuder are reported for benzo[a]pyrene, benzo[b]fluoranthene, and benzo[ghi]-perylene on ultrafine soot and NaCl aerosols. By thermodesorption of the PAH, problems due to quenching of the PAH fluorescence by the bulk aerosol material or excimer formation on the aerosol surface were avoided. For the PAH under study, the sensitivity was improved considerably and detection limits between 110 and 850 ng m(-3) were attained, while a response time of 2-3 min was achieved with the thermodenuder. A calibration for PAH on ultrafine soot and NaCl aerosols was established independent of the aerosol substrate.

Polycyclic aromatic hydrocarbons, elemental and organic carbon emissions from tire-wear.

PubMed

Aatmeeyata; Sharma, Mukesh

2010-09-15

Tire-wear is an important source of PAHs, elemental carbon (EC) and organic carbon (OC). The emissions of these pollutants have been studied in an experimental set-up, simulating a realistic road-tire interaction (summer tire-concrete road). The large particle non-exhaust emissions (LPNE; diameter greater than 10 microm) have been evaluated over 14,500 km run of the tire. An increasing linear trend with cumulative km run was observed for emissions of PAHs and carbon. Amongst PAHs in LPNE, pyrene has been observed to be the highest (30+/-4 mg kg(-1)) followed by benzo[ghi]perylene (17+/-2 mg kg(-1)). Different fractions of EC-OC for tire-wear have been analyzed, and unlike exhaust emissions, EC1 was observed to be 99% of EC whereas more than 70% of the OC was the high temperature carbon (OC3 and OC4). The overall emission factors (mass tire(-1) km(-1)) for PAHs, EC and OC from tire-wear are 378 ng tire(-1) km(-1), 1.46 mg tire(-1) km(-1) and 2.37 mg tire(-1) km(-1) for small cars. Copyright 2010 Elsevier B.V. All rights reserved.

Photochemistry of coronene in cosmic water ice analogs at different concentrations.

PubMed

de Barros, A L F; Mattioda, A L; Ricca, A; Cruz, G; Allamandola, L J

2017-10-20

This work presents the photochemistry of ultraviolet (UV) irradiated coronene in water ices at 15 K, studied using mid-infrared Fourier transform (FTIR) spectroscopy for C 24 H 12 :H 2 O at concentrations of (1:50), (1:150), (1:200), (1:300) and (1:400). Previous UV irradiation studies of anthracene:H 2 O, pyrene:H 2 O and benzo[ghi]perylene:H 2 O ices at 15 K have shown that aromatic alcohols and ketones, as well as CO 2 and H 2 CO are formed at very low temperatures. Like-wise, here, in addition to the coronene cation, hydroxy-, keto-, and protonated coronene (coronene-H + ) are formed. The rate constants for the decay of neutral coronene and for the formation of photoproducts have been derived. It is shown that PAHs and their UV-induced PAH:H 2 O photoproducts have mid-infrared spectroscopic signatures in the 5-8 μ m region that can contribute to the interstellar ice components described by Boogert et al. (2008) as C1-C5. Our results suggest that oxygenated and hydrogenated PAHs could be in UV-irradiated regions of the ISM where water-rich ices are important.

Polycyclic aromatic hydrocarbon analysis with the Mars organic analyzer microchip capillary electrophoresis system.

PubMed

Stockton, Amanda M; Chiesl, Thomas N; Scherer, James R; Mathies, Richard A

2009-01-15

The Mars Organic Analyzer (MOA), a portable microchip capillary electrophoresis (CE) instrument developed for sensitive amino acid analysis on Mars, is used to analyze laboratory standards and real-world samples for polycyclic aromatic hydrocarbons (PAHs). The microfabricated CE separation and analysis method for these hydrophobic analytes is optimized, resulting in a separation buffer consisting of 10 mM sulfobutylether-beta-cyclodextrin, 40 mM methyl-beta-cyclodextrin, 5 mM carbonate buffer at pH 10, 5 degrees C. A PAH standard consisting of seven PAHs found in extraterrestrial matter and two terrestrial PAHs is successfully baseline separated. Limits of detection for the components of the standard ranged from 2000 ppm to 6 ppb. Analysis of an environmental contamination standard from Lake Erie and of a hydrothermal vent chimney sample from the Guaymas Basin agreed with published composition. A Martian analogue sample from the Yungay Hills region of the Atacama Desert was analyzed and found to contain 9,10-diphenylanthracene, anthracene, anthanthrene, fluoranthene, perylene, and benzo[ghi]fluoranthene at ppm levels. This work establishes the viability of the MOA for detecting and analyzing PAHs in in situ planetary exploration.

Photochemistry of Coronene in Cosmic Water Ice Analogs at Different Concentrations

NASA Astrophysics Data System (ADS)

de Barros, A. L. F.; Mattioda, A. L.; Ricca, A.; Cruz-Diaz, G. A.; Allamandola, L. J.

2017-10-01

This work presents the photochemistry of ultraviolet (UV) irradiated coronene in water ices at 15 K studied using mid-infrared Fourier transform (FTIR) spectroscopy for C24H12:H2O at concentrations of (1:50), (1:150), (1:200), (1:300), and (1:400). Previous UV irradiation studies of anthracene:H2O, pyrene:H2O, and benzo[ghi]perylene:H2O ices at 15 K have shown that aromatic alcohols and ketones, as well as CO2 and H2CO, are formed at very low temperatures. Likewise, here, in addition to the coronene cation, hydroxy-, keto-, and protonated coronene (coronene H+) are formed. The rate constants for the decay of neutral coronene and for the formation of photoproducts have been derived. It is shown that Polycyclic Aromatic Hydrocarbons (PAHs) and their UV induced PAH:H2O photoproducts have mid-infrared spectroscopic signatures in the 5-8 μm region that can contribute to the interstellar ice components described by Boogert et al. as C1-C5. Our results suggest that oxygenated and hydrogenated PAHs could be in UV-irradiated regions of the interstellar medium where water-rich ices are important.

Remarkably constant PAH concentrations in Swiss soils over the last 30 years.

PubMed

Gubler, Andreas; Wächter, Daniel; Blum, Franziska; Bucheli, Thomas D

2015-10-01

Although polycyclic aromatic hydrocarbons (PAH) are of concern due to their carcinogenic, mutagenic, and teratogenic properties and their ubiquitous occurrence in environmental compartments, only few studies assessed the temporal evolutions of PAH contents of soils over extended time periods. The Swiss Soil Monitoring Network NABO runs long-term monitoring sites resampled every five years since the 1980s. In the present study, soil (0-20 cm) samples collected from 1985 through 2013 at 25 selected monitoring sites were analysed for the 16 priority PAH according to the U.S. EPA and five PAH marker substances. We observed divergent trends for light PAH, such as naphthalene and phenanthrene, compared with heavy PAH, such as benzo[a]pyrene and benzo[ghi]perylene. Whereas the former showed decreasing concentrations since the late 1980s, no significant trends were found for the latter. Furthermore, the analyses showed that naphthalene contents decreased most strongly at rural sites featuring low population densities, while phenanthrene contents generally decreased most strongly at semi-rural sites. The deviating evolutions of light and heavy PAH were mainly attributed to their differing physico-chemical properties. Temporal evolutions in soils contradict emission inventory data suggesting PAH emissions to decline since the 1980s.

Self-assembled supramolecular system PDINH on TiO2 surface enhances hydrogen production.

PubMed

Li, Xin; Lv, Xingshuai; Zhang, Qianqian; Huang, Baibiao; Wang, Peng; Qin, Xiaoyan; Zhang, Xiaoyang; Dai, Ying

2018-09-01

Constructing organic-inorganic hybrids is one of the hopeful strategies to improve photocatalyst performance. In this study, perylene-3,4,9,10-tetracarboxylic diimide (PDINH) and commercial TiO 2 P25 are chosen as raw materials to construct a PDINH/TiO 2 organic-inorganic hybrid, which has higher photocatalytic H 2 production activity and photocurrent intensity than pure PDINH and TiO 2 , respectively. The apparent quantum efficiency for H 2 production over 0.5%PDINH/TiO 2 reaches as high as 70.69% using irradiation at 365 nm. Moreover, XRD, DRS, HRTEM, FT-IR, and XPS are used to characterize the crystal structure, optical absorption, morphology, molecular structure, and chemical bonds, as well as the elemental and chemical states of PDINH/TiO 2 organic-inorganic hybrid. The interfaces between PDINH and TiO 2 , which largely determine photocatalytic performance, is also analyzed systematically. Furthermore, charge density difference (Δρ) is used to analyze the electron-ion interactions of PDINH and TiO 2 , and reveals that substantial charge transfer occurs from PDINH to TiO 2 . Copyright © 2018. Published by Elsevier Inc.

Facile fabrication of organic/inorganic nanotube heterojunction arrays for enhanced photoelectrochemical water splitting

NASA Astrophysics Data System (ADS)

Chen, Yingzhi; Li, Aoxiang; Yue, Xiaoqi; Wang, Lu-Ning; Huang, Zheng-Hong; Kang, Feiyu; Volinsky, Alex A.

2016-07-01

Organic/inorganic heterojunction photoanodes are appealing for making concurrent use of the highly photoactive organic semiconductors, and the efficient dielectric screening provided by their inorganic counterparts. In the present work, organic/inorganic nanotube heterojunction arrays composed of TiO2 nanotube arrays and a semiconducting N,N-(dicyclohexyl) perylene-3,4,9,10-tetracarboxylic diimide (PDi) layer were fabricated for photoelectrochemical water splitting. In this arrayed architecture, a PDi layer with a tunable thickness was coated on anodic TiO2 nanotube arrays by physical vapor deposition, which is advantageous for the formation of a uniform layer and an adequate interface contact between PDi and TiO2. The obtained PDi/TiO2 junction exhibited broadened visible light absorption, and an effective interface for enhanced photogenerated electron-hole separation, which is supported by the reduced charge transfer resistance and prolonged excitation lifetime via impedance spectroscopy analysis and fluorescence emission decay investigations. Consequently, such a heterojunction photoanode was photoresponsive to a wide visible light region of 400-600 nm, and thus demonstrated a highly enhanced photocurrent density at 1.23 V vs. a reversible hydrogen electrode. Additionally, the durability of such a photoanode can be guaranteed after long-time illumination because of the geometrical restraint imposed by the PDi aggregates. These results pave the way to discover new organic/inorganic assemblies for high-performance photoelectric applications and device integration.Organic/inorganic heterojunction photoanodes are appealing for making concurrent use of the highly photoactive organic semiconductors, and the efficient dielectric screening provided by their inorganic counterparts. In the present work, organic/inorganic nanotube heterojunction arrays composed of TiO2 nanotube arrays and a semiconducting N,N-(dicyclohexyl) perylene-3,4,9,10-tetracarboxylic diimide (PDi) layer were fabricated for photoelectrochemical water splitting. In this arrayed architecture, a PDi layer with a tunable thickness was coated on anodic TiO2 nanotube arrays by physical vapor deposition, which is advantageous for the formation of a uniform layer and an adequate interface contact between PDi and TiO2. The obtained PDi/TiO2 junction exhibited broadened visible light absorption, and an effective interface for enhanced photogenerated electron-hole separation, which is supported by the reduced charge transfer resistance and prolonged excitation lifetime via impedance spectroscopy analysis and fluorescence emission decay investigations. Consequently, such a heterojunction photoanode was photoresponsive to a wide visible light region of 400-600 nm, and thus demonstrated a highly enhanced photocurrent density at 1.23 V vs. a reversible hydrogen electrode. Additionally, the durability of such a photoanode can be guaranteed after long-time illumination because of the geometrical restraint imposed by the PDi aggregates. These results pave the way to discover new organic/inorganic assemblies for high-performance photoelectric applications and device integration. Electronic supplementary information (ESI) available: Additional structural characterization. See DOI: 10.1039/c5nr07893h

Bioaccumulation of Stentorin, the Probable Causative Agent for Discolored ("Purple") Eggs and Ovaries in Blue Catfish (Ictalurus furcatus) from Eufaula Lake, Oklahoma, USA.

PubMed

Gale, Robert W; Papoulias, Diana M; Schmitt, Christopher J

2015-08-18

Observations of reddish to "purple" discolored eggs in the ovaries of adult female blue catfish (Ictalurus furcatus) from the northern arm of Eufaula Lake, a eutrophic multiuse impoundment in east-central Oklahoma, were first reported in 2006. Blue catfish eggs are normally cream to light yellow. Reports peaked in 2007-2008 and declined through 2009-2010; purple eggs have not been reported between 2010 and 2014. In the laboratory, all tissues and fluids of affected fish were strongly orange-red fluorescent under UV illumination, with the fluorescence most apparent in the lipid-rich ovaries and eggs. The causative agent was isolated chromatographically and confirmed by mass spectrometry as stentorin (1,3,4,6,8,10,11,13-octahydroxy-2,5-diisopropyl-phenanthro[1,10,9,8,o,p,q,r,a]perylene-7,14-dione), the fluorescent, lipophilic pigment associated with the photoreceptor protein of the ciliated protozoan Stentor coeruleus (Heterotrichea; Stentoridae). Larval medaka (Orizias latipes) readily consumed S. coeruleus in the laboratory and were observed to fluoresce in the same manner as the affected blue catfish. Potential deleterious effects of stentorin bioaccumulation remain to be determined, as do the geographic extent and the identities of other fluorescent compounds isolated from catfish eggs and ovaries.

Comparison of various extraction techniques for the determination of polycyclic aromatic hydrocarbons in worms.

PubMed

Mooibroek, D; Hoogerbrugge, R; Stoffelsen, B H G; Dijkman, E; Berkhoff, C J; Hogendoorn, E A

2002-10-25

Two less laborious extraction methods, viz. (i) a simplified liquid extraction using light petroleum or (ii) microwave-assisted solvent extraction (MASE), for the analysis of polycyclic aromatic hydrocarbons (PAHs) in samples of the compost worm Eisenia andrei, were compared with a reference method. After extraction and concentration, analytical methodology consisted of a cleanup of (part) of the extract with high-performance gel permeation chromatography (HPGPC) and instrumental analysis of 15 PAHs with reversed-phase liquid chromatography with fluorescence detection (RPLC-FLD). Comparison of the methods was done by analysing samples with incurred residues (n=15, each method) originating from an experiment in which worms were exposed to a soil contaminated with PAHs. Simultaneously, the performance of the total lipid determination of each method was established. Evaluation of the data by means of principal component analysis (PCA) and analysis of variance (ANOVA) revealed that the performance of the light petroleum method for both the extraction of PAHs (concentration range 1-30 ng/g) and lipid content corresponds very well with the reference method. Compared to the reference method, the MASE method yielded somewhat lower concentrations for the less volatile PAHs, e.g., dibenzo[ah]anthracene and benzo[ghi]perylene and provided a significant higher amount of co-extracted material.

Extended wavelength anisotropy resolved multidimensional emission spectroscopy (ARMES) measurements: better filters, validation standards, and Rayleigh scatter removal methods

NASA Astrophysics Data System (ADS)

Casamayou-Boucau, Yannick; Ryder, Alan G.

2017-09-01

Anisotropy resolved multidimensional emission spectroscopy (ARMES) provides valuable insights into multi-fluorophore proteins (Groza et al 2015 Anal. Chim. Acta 886 133-42). Fluorescence anisotropy adds to the multidimensional fluorescence dataset information about the physical size of the fluorophores and/or the rigidity of the surrounding micro-environment. The first ARMES studies used standard thin film polarizers (TFP) that had negligible transmission between 250 and 290 nm, preventing accurate measurement of intrinsic protein fluorescence from tyrosine and tryptophan. Replacing TFP with pairs of broadband wire grid polarizers enabled standard fluorescence spectrometers to accurately measure anisotropies between 250 and 300 nm, which was validated with solutions of perylene in the UV and Erythrosin B and Phloxine B in the visible. In all cases, anisotropies were accurate to better than ±1% when compared to literature measurements made with Glan Thompson or TFP polarizers. Better dual wire grid polarizer UV transmittance and the use of excitation-emission matrix measurements for ARMES required complete Rayleigh scatter elimination. This was achieved by chemometric modelling rather than classical interpolation, which enabled the acquisition of pure anisotropy patterns over wider spectral ranges. In combination, these three improvements permit the accurate implementation of ARMES for studying intrinsic protein fluorescence.

Sample preparation of sewage sludge and soil samples for the determination of polycyclic aromatic hydrocarbons based on one-pot microwave-assisted saponification and extraction.

PubMed

Pena, M Teresa; Pensado, Luis; Casais, M Carmen; Mejuto, M Carmen; Cela, Rafael

2007-04-01

A microwave-assisted sample preparation (MASP) procedure was developed for the analysis of polycyclic aromatic hydrocarbons (PAHs) in sewage sludge and soil samples. The procedure involved the simultaneous microwave-assisted extraction of PAHs with n-hexane and the hydrolysis of samples with methanolic potassium hydroxide. Because of the complex nature of the samples, the extracts were submitted to further cleaning with silica and Florisil solid-phase extraction cartridges connected in series. Naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[e]pyrene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenz[a,h]anthracene, benzo[g,h,i]perylene, and indeno[1,2,3-cd]pyrene, were considered in the study. Quantification limits obtained for all of these compounds (between 0.4 and 14.8 microg kg(-1) dry mass) were well below of the limits recommended in the USA and EU. Overall recovery values ranged from 60 to 100%, with most losses being due to evaporation in the solvent exchange stages of the procedure, although excellent extraction recoveries were obtained. Validation of the accuracy was carried out with BCR-088 (sewage sludge) and BCR-524 (contaminated industrial soil) reference materials.

[Effect of annealing temperature on the crystallization and spectroscopic response of a small-molecule semiconductor doped in polymer film].

PubMed

Yin, Ming; Zhang, Xin-Ping; Liu, Hong-Mei

2012-11-01

The crystallization properties of the perylene (EPPTC) molecules doped in the solid film of the derivative of polyfluorene (F8BT) at different annealing temperatures, as well as the consequently induced spectroscopic response of the exciplex emission in the heterojunction structures, were studied in the present paper. Experimental results showed that the phase separation between the small and the polymer molecules in the blend film is enhanced with increasing the annealing temperature, which leads to the crystallization of the EPPTC molecules due to the strong pi-pi stacking. The size of the crystal phase increases with increasing the annealing temperature. However, this process weakens the mechanisms of the heterojunction configuration, thus, the total interfacial area between the small and the polymer molecules and the amount of exciplex are reduced significantly in the blend film. Meanwhile, the energy transfer from the polymer to the small molecules is also reduced. As a result, the emission from the exciplex becomes weaker with increasing the annealing temperature, whereas the stronger emission from the polymer molecules and from the crystal phase of the small molecules can be observed. These experimental results are very important for understanding and tailoring the organic heterojunction structures. Furthermore, this provides photophysics for improving the performance of photovoltaic or solar cell devices.

Avoiding bias effects in NMR experiments for heteronuclear dipole-dipole coupling determinations: principles and application to organic semiconductor materials.

PubMed

Kurz, Ricardo; Cobo, Marcio Fernando; de Azevedo, Eduardo Ribeiro; Sommer, Michael; Wicklein, André; Thelakkat, Mukundan; Hempel, Günter; Saalwächter, Kay

2013-09-16

Carbon-proton dipole-dipole couplings between bonded atoms represent a popular probe of molecular dynamics in soft materials or biomolecules. Their site-resolved determination, for example, by using the popular DIPSHIFT experiment, can be challenged by spectral overlap with nonbonded carbon atoms. The problem can be solved by using very short cross-polarization (CP) contact times, however, the measured modulation curves then deviate strongly from the theoretically predicted shape, which is caused by the dependence of the CP efficiency on the orientation of the CH vector, leading to an anisotropic magnetization distribution even for isotropic samples. Herein, we present a detailed demonstration and explanation of this problem, as well as providing a solution. We combine DIPSHIFT experiments with the rotor-directed exchange of orientations (RODEO) method, and modifications of it, to redistribute the magnetization and obtain undistorted modulation curves. Our strategy is general in that it can also be applied to other types of experiments for heteronuclear dipole-dipole coupling determinations that rely on dipolar polarization transfer. It is demonstrated with perylene-bisimide-based organic semiconductor materials, as an example, in which measurements of dynamic order parameters reveal correlations of the molecular dynamics with the phase structure and functional properties. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrocarbons derived from petroleum in bottled drinking water from Mexico City.

PubMed

Vega, Salvador; Gutiérrez, Rey; Ortiz, Rutilio; Schettino, Beatriz; Ramírez, Maria de Lourdes; Pérez, José Jesus

2011-06-01

This paper describes the concentrations of polycyclic aromatic hydrocarbons (PAHs) and aliphatic hydrocarbons (AHs) derived from petroleum in bottled drinking water samples that were collected over 1 year from Mexico City in two bottle sizes (1.5 and 19 L), all brought in supermarkets. The analysis was by gas chromatography with flame ionization detection. -Concentrations of AHs (9.26-1.74 μg/L) were greater than PAHs (20.15-12.78 ng/L). Individual concentrations of PAHs such as fluoranthene, benzo(b)fluoranthene, benzo(k)fluoranthene, indeno(1,2,3-cd)pyrene and benzo(ghi)perylene were comparable with data reported by the World Health Organization (WHO). Total concentrations of PAHs for all samples (BDW1: 12.78 μg/L, BDW2: 16.72 μg/L, BDW3: 14.62 μg/L, BDW4: 20.15 μg/L and BDW5: 13.23 ng/L) were below the maximum permissible European level of 100 ng/L; no regulations exist for AHs although their values were greater than PAHs (BDW1: 3.11 μg/L, BDW2: 8.45 μg/L, BDW3: 1.74 μg/L, BDW4: 4.75 μg/L and BDW5: 9.26 μg/L).

Surface tuning laser desorption/ionization mass spectrometry (STLDI-MS) for the analysis of small molecules using quantum dots.

PubMed

Abdelhamid, Hani Nasser; Chen, Zhen-Yu; Wu, Hui-Fen

2017-08-01

In most applications of quantum dots (QDs) for surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS), one side of QDs is supported by a solid substrate (stainless - steel plate), whereas the other side is in contact with the target analytes. Therefore, the surface capping agent of QDs is a key parameter for laser desorption/ionization mass spectrometry (LDI-MS). Cadmium telluride quantum dots (CdTe QDs) modified with different capping agents are synthesized, characterized, and applied for surface tuning laser desorption/ionization mass spectrometry (STLDI-MS). Data shows that CdTe quantum dot modified cysteine (cys@CdTe QDs) has an absorption that matches with the wavelength of the N 2 laser (337 nm). The synergistic effect of large surface area and absorption of the laser irradiation of cys@CdTe QDs enhances the LDI-MS process for small - molecule analysis, including α-, β-, and γ-cyclodextrin, gramicidin D, perylene, pyrene, and triphenylphosphine. Cys@CdTe QDs are also applied using Al foils as substrates. Aluminum foil combined with cys@CdTe QDs enhances the ionization efficiency and is cheap compared to traditional matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) with a stainless - steel plate.

Effects of electrolytes on redox potentials through ion pairing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bird, Matthew J.; Iyoda, Tomokazu; Bonura, Nicholas

Here, reduction potentials have been determined for two molecules, benzophenone (BzPh) and perylene (Per), effectively in the complete absence of electrolyte as well as in the presence of three different supporting electrolytes in the moderately polar solvent THF. A description of how this can be so, and qualifications, are described in the discussion section. The primary tool in this work, pulse radiolysis, measures electron transfer (ET) equilibria in solution to obtain differences in redox potentials. Voltammetry measures redox potentials by establishing ET equilibria at electrodes, but electrolytes are needed for current flow. Results here show that without electrolyte the redoxmore » potentials were 100–451 mV more negative than those with 100 mM electrolyte. These changes depended both on the molecule and the electrolyte. In THF the dominant contributor to stabilization of radical anions by electrolyte was ion pairing. An equation was derived to give changes in redox potentials when electrolyte is added in terms of ion pair dissociation constants and activity coefficients. Definite values were determined for energetics, ΔG d°, of ion pairing. Values of ΔG d° for pairs with TBA + give some doubt that it is a “weakly-coordinating cation.” Computations with DFT methods were moderately successful at describing the ion paring energies.« less

Molecular Packing of Amphiphilic Nanosheets Resolved by X-ray Scattering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harutyunyan, Boris; Dannenhoffer, Adam; Kewalramani, Sumit

2016-12-29

Molecular packing in light harvesting 2D assemblies of photocatalytic materials is a critical factor for solar-to-fuel conversion efficiency. However, structure–function correlations have yet to be fully established. This is partly due to the difficulties in extracting the molecular arrangements from the complex 3D powder averaged diffraction patterns of 2D lattices, obtained via in situ wide-angle X-ray scattering. Here, we develop a scattering theory formalism and couple it with a simple geometrical model for the molecular shape of chromophore 9-methoxy-N-(sodium hexanoate)perylene-3,4-dicarboximide (MeO-PMI) used in our study. This generally applicable method fully reproduces the measured diffraction pattern including the asymmetric line shapesmore » for the Bragg reflections and yields the molecular packing arrangement within a 2D crystal structure with a remarkable degree of detail. We find an approximate edge-centered herringbone structure for the PMI fused aromatic rings and ordering of the carboxypentyl chains above and below the nanosheets. Such a packing arrangement differs from the more symmetric face-to-face orientation of the unsubstituted PMI rings. This structural difference is correlated to our measurement of the reduced catalytic performance of MeO-PMI nanosheets as compared to the mesoscopically similar unsubstituted PMI assemblies.« less

Facile fabrication of palladium-ionic liquids-nitrogen-doped graphene nanocomposites as enhanced electro-catalyst for ethanol oxidation

NASA Astrophysics Data System (ADS)

Li, Shuwen; Yang, Honglei; Ren, Ren; Ma, Jianxin; Jin, Jun; Ma, Jiantai

2015-10-01

The palladium-ionic liquids-nitrogen-doped graphene nanocomposites are facile fabricated as enhanced electro-catalyst for ethanol oxidation. First, the ionic liquids functionalized nitrogen-doping graphene nanosheets (PDIL-NGS) with few layers is synthesized through a facile and effective one-pot hydrothermal method with graphene oxide as raw material, urea as reducing-doping agents and ionic liquids (ILs) derived from 3,4,9,10-perylene tetracarboxylic acid as functional molecules. The results of systematic characterization reveal that the PDIL molecules not only can functionalize NGS by π-π stacking with no affecting the nitrogen doping but also prevent the agglomeration of NGS. More importantly, the processing performance and the property of electron transfer are remarkably enhanced duo to introducing a large number of ILs groups. Then, the enhanced electrocatalytic Pd nanoparticles are successfully anchored on PDIL-NGS by a facile and surfactant-free synthetic technique. As an anode catalyst, the novel catalyst exhibits better kinetics, more superior electrocatalytic performance, higher tolerance and electrochemical stability than the other catalysts toward ethanol electrooxidation, owing to the role of PDIL molecules. Therefore, the new catalyst is believed to have the potential use for direct alcohol fuel cells in the future and the functionalized NGS is promising useful materials applied in other fields.

Presence of aliphatic and polycyclic aromatic hydrocarbons in near-surface sediments of an oil spill area in Bohai Sea.

PubMed

Li, Shuanglin; Zhang, Shengyin; Dong, Heping; Zhao, Qingfang; Cao, Chunhui

2015-11-15

In order to determine the source of organic matter and the fingerprint of the oil components, 50 samples collected from the near-surface sediments of the oil spill area in Bohai Sea, China, were analyzed for grain size, total organic carbon, aliphatic hydrocarbons (AHs), and polycyclic aromatic hydrocarbons (PAHs). The concentrations of C15-35 n-alkanes and 16 United States Environmental Protection Agency (US EPA) priority pollutant PAHs were found in the ranges of 0.88-3.48μg g(-1) and 9.97-490.13ng/g, respectively. The terrestrial organic matters characterized by C27-C35 n-alkanes and PAHs, resulting from the combustion of higher plants, are dominantly contributed from the transportation of these plants by rivers. Marine organic matters produced from plankton and aquatic plants were represented by C17-C26 n-alkanes in AHs. Crude oil, characterized by C17-C21 n-alkanes, unresolved complex mixture (UCM) with a mean response factor of C19 n-alkanes, low levels of perylene, and a high InP/(InP+BghiP) ratio, seeped into the oceans from deep hydrocarbon reservoirs, as a result of geological faults. Copyright © 2015 Elsevier Ltd. All rights reserved.

Concentration of isoprene in artificial and thylakoid membranes.

PubMed

Harvey, Christopher M; Li, Ziru; Tjellström, Henrik; Blanchard, Gary J; Sharkey, Thomas D

2015-10-01

Isoprene emission protects plants from a variety of abiotic stresses. It has been hypothesized to do so by partitioning into cellular membranes, particularly the thylakoid membrane. At sufficiently high concentrations, this partitioning may alter the physical properties of membranes. As much as several per cent of carbon taken up in photosynthesis is re-emitted as isoprene but the concentration of isoprene in the thylakoid membrane of rapidly emitting plants has seldom been considered. In this study, the intramembrane concentration of isoprene in phosphatidylcholine liposomes equilibrated to a physiologically relevant gas phase concentration of 20 μL L(-1) isoprene was less than predicted by ab initio calculations based on the octanol-water partitioning coefficient of isoprene while the concentration in thylakoid membranes was more. However, the concentration in both systems was roughly two orders of magnitude lower than previously assumed. High concentrations of isoprene (2000 μL L(-1) gas phase) failed to alter the viscosity of phosphatidylcholine liposomes as measured with perylene, a molecular probe of membrane structure. These results strongly suggest that the physiological concentration of isoprene within the leaves of highly emitting plants is too low to affect the dynamics of thylakoid membrane acyl lipids. It is speculated that isoprene may bind to and modulate the dynamics of thylakoid embedded proteins.

Förster-Induced Energy Transfer in Functionalized Graphene

PubMed Central

2014-01-01

Carbon nanostructures are ideal substrates for functionalization with molecules since they consist of a single atomic layer giving rise to an extraordinary sensitivity to changes in their surrounding. The functionalization opens a new research field of hybrid nanostructures with tailored properties. Here, we present a microscopic view on the substrate–molecule interaction in the exemplary hybrid material consisting of graphene functionalized with perylene molecules. First experiments on similar systems have been recently realized illustrating an extremely efficient transfer of excitation energy from adsorbed molecules to the carbon substrate, a process with a large application potential for high-efficiency photovoltaic devices and biomedical imaging and sensing. So far, there has been no microscopically founded explanation for the observed energy transfer. Based on first-principle calculations, we have explicitly investigated the different transfer mechanisms revealing the crucial importance of Förster coupling. Due to the efficient Coulomb interaction in graphene, we obtain strong Förster rates in the range of 1/fs. We investigate its dependence on the substrate–molecule distance R and describe the impact of the momentum transfer q for an efficient energy transfer. Furthermore, we find that the Dexter transfer mechanism is negligibly small due to the vanishing overlap between the involved strongly localized orbital functions. The gained insights are applicable to a variety of carbon-based hybrid nanostructures. PMID:24808936

Influence of Cadmium and Mercury on Activities of Ligninolytic Enzymes and Degradation of Polycyclic Aromatic Hydrocarbons by Pleurotus ostreatus in Soil

PubMed Central

Baldrian, Petr; in der Wiesche, Carsten; Gabriel, Jiří; Nerud, František; Zadražil, František

2000-01-01

The white-rot fungus Pleurotus ostreatus was able to degrade the polycyclic aromatic hydrocarbons (PAHs) benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenzo[a,h]anthracene, and benzo[ghi]perylene in nonsterile soil both in the presence and in the absence of cadmium and mercury. During 15 weeks of incubation, recovery of individual compounds was 16 to 69% in soil without additional metal. While soil microflora contributed mostly to degradation of pyrene (82%) and benzo[a]anthracene (41%), the fungus enhanced the disappearance of less-soluble polycyclic aromatic compounds containing five or six aromatic rings. Although the heavy metals in the soil affected the activity of ligninolytic enzymes produced by the fungus (laccase and Mn-dependent peroxidase), no decrease in PAH degradation was found in soil containing Cd or Hg at 10 to 100 ppm. In the presence of cadmium at 500 ppm in soil, degradation of PAHs by soil microflora was not affected whereas the contribution of fungus was negligible, probably due to the absence of Mn-dependent peroxidase activity. In the presence of Hg at 50 to 100 ppm or Cd at 100 to 500 ppm, the extent of soil colonization by the fungus was limited. PMID:10831426

Effects of electrolytes on redox potentials through ion pairing

DOE PAGES

Bird, Matthew J.; Iyoda, Tomokazu; Bonura, Nicholas; ...

2017-09-21

Here, reduction potentials have been determined for two molecules, benzophenone (BzPh) and perylene (Per), effectively in the complete absence of electrolyte as well as in the presence of three different supporting electrolytes in the moderately polar solvent THF. A description of how this can be so, and qualifications, are described in the discussion section. The primary tool in this work, pulse radiolysis, measures electron transfer (ET) equilibria in solution to obtain differences in redox potentials. Voltammetry measures redox potentials by establishing ET equilibria at electrodes, but electrolytes are needed for current flow. Results here show that without electrolyte the redoxmore » potentials were 100–451 mV more negative than those with 100 mM electrolyte. These changes depended both on the molecule and the electrolyte. In THF the dominant contributor to stabilization of radical anions by electrolyte was ion pairing. An equation was derived to give changes in redox potentials when electrolyte is added in terms of ion pair dissociation constants and activity coefficients. Definite values were determined for energetics, ΔG d°, of ion pairing. Values of ΔG d° for pairs with TBA + give some doubt that it is a “weakly-coordinating cation.” Computations with DFT methods were moderately successful at describing the ion paring energies.« less

Lateral ordering of PTCDA on the clean and the oxygen pre-covered Cu(100) surface investigated by scanning tunneling microscopy and low energy electron diffraction.

PubMed

Gärtner, Stefan; Fiedler, Benjamin; Bauer, Oliver; Marele, Antonela; Sokolowski, Moritz M

2014-01-01

We have investigated the adsorption of perylene-3,4,9,10-tetracarboxylic acid dianhydride (PTCDA) on the clean and on the oxygen pre-covered Cu(100) surface [referred to as (√2 × 2√2)R45° - 2O/Cu(100)] by scanning tunneling microscopy (STM) and low energy electron diffraction (LEED). Our results confirm the (4√2 × 5√2)R45° superstructure of PTCDA/Cu(100) reported by A. Schmidt et al. [J. Phys. Chem. 1995, 99,11770-11779]. However, contrary to Schmidt et al., we have no indication for a dissociation of the PTCDA upon adsorption, and we propose a detailed structure model with two intact PTCDA molecules within the unit cell. Domains of high lateral order are obtained, if the deposition is performed at 400 K. For deposition at room temperature, a significant density of nucleation defects is found pointing to a strong interaction of PTCDA with Cu(100). Quite differently, after preadsorption of oxygen and formation of the (√2 × 2√2)R45° - 2O/Cu(100) superstructure on Cu(100), PTCDA forms an incommensurate monolayer with a structure that corresponds well to that of PTCDA bulk lattice planes.

Photochemistry of Coronene in Cosmic Water Ice Analogs at Different Concentrations

DOE Office of Scientific and Technical Information (OSTI.GOV)

De Barros, A. L. F.; Mattioda, A. L.; Ricca, A.

This work presents the photochemistry of ultraviolet (UV) irradiated coronene in water ices at 15 K studied using mid-infrared Fourier transform (FTIR) spectroscopy for C{sub 24}H{sub 12}:H{sub 2}O at concentrations of (1:50), (1:150), (1:200), (1:300), and (1:400). Previous UV irradiation studies of anthracene:H{sub 2}O, pyrene:H{sub 2}O, and benzo[ghi]perylene:H{sub 2}O ices at 15 K have shown that aromatic alcohols and ketones, as well as CO{sub 2} and H{sub 2}CO, are formed at very low temperatures. Likewise, here, in addition to the coronene cation, hydroxy-, keto-, and protonated coronene (coronene H{sup +}) are formed. The rate constants for the decay of neutralmore » coronene and for the formation of photoproducts have been derived. It is shown that Polycyclic Aromatic Hydrocarbons (PAHs) and their UV induced PAH:H{sub 2}O photoproducts have mid-infrared spectroscopic signatures in the 5–8 μ m region that can contribute to the interstellar ice components described by Boogert et al. as C1–C5. Our results suggest that oxygenated and hydrogenated PAHs could be in UV-irradiated regions of the interstellar medium where water-rich ices are important.« less

Sediment-deposition rates and organic compounds in bottom sediment at four sites in Lake Mead, Nevada, May 1998

USGS Publications Warehouse

Covay, K.J.; Beck, D.A.

2001-01-01

In May 1998 the U.S. Geological Survey, in cooperation with the University of Nevada, Las Vegas, investigated rates of sediment deposition and concentrations of selected synthetic organic compounds at four sites in Lake Mead. Sediment cores were extracted from two sites (one shallow and one deep) in Las Vegas Bay, from one site in the Overton Arm, and from one site near the historic confluence of the Colorado and Virgin Rivers. The sediment cores were age-dated using cesium-137 and were analyzed for the presence of organochlorine compounds (pesticides and degradation products, polychlorinated biphenyls, dioxins, and furans) and for semivolatile organic compounds (polycyclic aromatic hydrocarbons and phenols). Sediment-deposition rates after impoundment of the Colorado River by Hoover Dam were determined by measuring the accumulation of mass during three different periods: (1) from the approximate impoundment date for each site (1935-37) to the initial occurrence of cesium-137 in the atmosphere (1952); (2) from 1952 to the maximum concentration of cesium-137 in the atmosphere (1964); and (3) from 1964 to the collection date of the sample (1998). Sediment-deposition rates for the entire post-impoundment period (1935-98) averaged 1.45 (g/cm2)/yr (grams per square centimeter per year) at the Las Vegas Bay shallow site, 1.25 (g/cm2)/yr at the Las Vegas Bay deep site, 0.80 (g/cm2)/yr at the Overton Arm site, and 0.65 (g/cm2)/yr at the Colorado and Virgin Rivers confluence site. Sediment-deposition rates after impoundment of the Colorado River by Hoover Dam were determined by measuring the accumulation of mass during three different periods: (1) from the approximate impoundment date for each site (1935-37) to the initial occurrence of cesium-137 in the atmosphere (1952); (2) from 1952 to the maximum concentration of cesium-137 in the atmosphere (1964); and (3) from 1964 to the collection date of the sample (1998). Sediment-deposition rates for the entire post-impoundment period (1935-98) averaged 1.45 (g/cm2)/yr (grams per square centimeter per year) at the Las Vegas Bay shallow site, 1.25 (g/cm2)/yr at the Las Vegas Bay deep site, 0.80 (g/cm2)/yr at the Overton Arm site, and 0.65 (g/cm2)/yr at the Colorado and Virgin Rivers confluence site. Total numbers of synthetic organic compounds detected in sediment samples were 48 at the Las Vegas Bay shallow site, 57 at the Las Vegas Bay deep site, 26 at the Overton Arm site, and 31 at the Colorado and Virgin Rivers confluence site. The most commonly detected organochlorine pesticide and polychlorinated biphenyl compounds were dichlorodiphenyldichloroethane and dichlorodiphenyldichloroethylene. The most commonly detected dioxin compounds were tetrachlorodibenzo-p-dioxin and octochlorodibenzo-p-dioxin. The most commonly detected furan compounds were tetrachlorodibenzofuran and octochlorodibenzofuran. The most commonly detected polycyclic aromatic hydrocarbons included perylene, benzo[g,h,i]perylene, 2,6-dimethylnaphthalene, and indeno[1,2,3-c,d]pyrene. The most commonly detected phenol compound was phenol.

A survey on polycyclic aromatic hydrocarbon concentrations in soil in Chiang-Mai, Thailand

DOE Office of Scientific and Technical Information (OSTI.GOV)

Amagai, Takashi; Takahashi, Yukari; Matsushita, Hidetsuru

Soil samples were collected at 30 sampling sites along roadsides in the city of Chiang-Mai, Thailand, in February 1996, and concentrations of 16 polycyclic aromatic hydrocarbons (PAHs) were determined. The distribution of PAH concentration in the soil samples was almost log-normal for all PAHs. Concentrations of pyrene (Py) and fluoranthene (Fluor) were the highest, followed by those of benzo[ghi]perylene and coronene (Cor). Since PAH concentrations were highest on the roadside where the traffic density was high, vehicles were the main determinants of PAH concentration in soil in Chiang-Mai. Significant correlations among PAH concentrations were found for almost all PAHs. PAHmore » profiles in the air were different from those in the soil. For example, relative benzo[a]pyrene (BaP) concentration in the soil was significantly lower than that in the air. Relative concentrations of Fluor, Py, chrysene, and Cor in the soil were considerably higher than those in the air, due presumably to their difference in photochemical reactivities and in sources. The sampling of soil has advantages relative to that of air: (1) collection of soil is easy; (2) it needs no special equipment and electricity; (3) it takes little time; and (4) it can be collected anywhere. Therefore PAH analysis in soil was useful as a proxy-screening tool for air pollution levels with consideration of compositional differences between soil and air samples.« less

Quantitative resonant soft x-ray reflectivity of ultrathin anisotropic organic layers: Simulation and experiment of PTCDA on Au.

PubMed

Capelli, R; Mahne, N; Koshmak, K; Giglia, A; Doyle, B P; Mukherjee, S; Nannarone, S; Pasquali, L

2016-07-14

Resonant soft X-ray reflectivity at the carbon K edge, with linearly polarized light, was used to derive quantitative information of film morphology, molecular arrangement, and electronic orbital anisotropies of an ultrathin 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) film on Au(111). The experimental spectra were simulated by computing the propagation of the electromagnetic field in a trilayer system (vacuum/PTCDA/Au), where the organic film was treated as an anisotropic medium. Optical constants were derived from the calculated (through density functional theory) absorption cross sections of the single molecule along the three principal molecular axes. These were used to construct the dielectric tensor of the film, assuming the molecules to be lying flat with respect to the substrate and with a herringbone arrangement parallel to the substrate plane. Resonant soft X-ray reflectivity proved to be extremely sensitive to film thickness, down to the single molecular layer. The best agreement between simulation and experiment was found for a film of 1.6 nm, with flat laying configuration of the molecules. The high sensitivity to experimental geometries in terms of beam incidence and light polarization was also clarified through simulations. The optical anisotropies of the organic film were experimentally determined and through the comparison with calculations, it was possible to relate them to the orbital symmetry of the empty electronic states.

Morphology of the D/A interface in vapor deposited bilayer organic photovoltaics

NASA Astrophysics Data System (ADS)

Erwin, Patrick; Dimitriou, Michael; Thompson, Mark E.

2017-08-01

A series of bilayer films were prepared by vacuum deposition onto Silicon substrates. These films consisted of either Si/SiO2/donor/C60 or Si/SiO2/C60/donor, where the organic films were in the 20-40 nm thick range and the donors were 7,7-difluoro-14-phenyl-7H-6l4,7l4-[1,3,2]diazaborinino[4,3-a:6,1-a']diisoindole (bDIP), copper phthalocyanine (CuPC), 3,6,11,14-tetraphenyldiindeno[1,2,3-cd:1',2',3'-lm]perylene (DBP) and 2-(4-(diphenylamino)-2,6- dihydroxyphenyl)-4-(4-(diphenyliminio)-2,6-dihydroxycyclohexa-2,5-dien-1-ylidene)-3-oxocyclobut-1-en-1-olate (DPSQ). The donors chosen here have been reported to give good power efficiencies when incorporated into bilayer photovoltaic cells with a C60 acceptor. These bilayer films were examined by neutron reflectometry to characterize the interface between the donor and C60. In the SiO2/donor/C60 films, DPSQ, CuPC, and DBP show a discrete interface with C60 while bDIP shows substantial spontaneous mixing at the interface, consistent with a donor/(donor + C60)/C60 structure, where the mixed layer is 14 nm.. In the SiO2/C60/donor films, all four donors show negligible mixing at the D/A interface consistent with a discrete D/A junction.

Optimization, validation and comparison of various extraction techniques for the trace determination of polycyclic aromatic hydrocarbons in sewage sludges by liquid chromatography coupled to diode-array and fluorescence detection.

PubMed

Miège, C; Dugay, J; Hennion, M C

2003-05-02

There is a need for a better characterization of sludges from wastewater treatment plants which are destined to be spread on agricultural lands. Inorganic pollutants are regularly controlled but organic pollutants have received few attention up to now. On this paper, we have been interested on the analysis of the 16 polycyclic aromatic hydrocarbons (PAHs) listed in the US Environmental Protection Agency (US EPA) priority list and more particularly of the six PAHs listed in the European community list (fluoranthene, benzo[b and k]fluoranthene, benzo[a]pyrene, benzo[ghi]perylene, indeno[1,2,3-cd]pyrene). The analysis step consists on liquid chromatography with both fluorescence and UV detections as described in the EPA Method 8310. As for the extraction step, several techniques such as supercritical fluid extraction, pressurized liquid extraction, focused microwave extraction in open vessels, Soxhlet and ultrasonic extractions are compared after optimization of the experimental conditions (solvent nature and quantity, temperature, pressure, duration, ... ) and validation with certified sludges. When optimized, these five extraction techniques are as much efficient with similar relative standard deviation. Whatever the extraction techniques used, the whole analysis protocol permits to quantify PAHs in the range of 0.09 to 0.9 mg/kg of dried sludges.

Molecular dewetting on insulators.

PubMed

Burke, S A; Topple, J M; Grütter, P

2009-10-21

Recent attention given to the growth and morphology of organic thin films with regard to organic electronics has led to the observation of dewetting (a transition from layer(s) to islands) of molecular deposits in many of these systems. Dewetting is a much studied phenomenon in the formation of polymer and liquid films, but its observation in thin films of the 'small' molecules typical of organic electronics requires additional consideration of the structure of the interface between the molecular film and the substrate. This review covers some key concepts related to dewetting and molecular film growth. In particular, the origins of different growth modes and the thickness dependent interactions which give rise to dewetting are discussed in terms of surface energies and the disjoining pressure. Characteristics of molecular systems which may lead to these conditions, including the formation of metastable interface structures and commensurate-incommensurate phase transitions, are also discussed. Brief descriptions of some experimental techniques which have been used to study molecular dewetting are given as well. Examples of molecule-on-insulator systems which undergo dewetting are described in some detail, specifically perylene derivatives on alkali halides, C(60) on alkali halides, and the technologically important system of pentacene on SiO(2). These examples point to some possible predicting factors for the occurrence of dewetting, most importantly the formation of an interface layer which differs from the bulk crystal structure.

Impact of pyrolysis conditions on polycyclic aromatic hydrocarbons (PAHs) formation in particulate matter (PM) during sewage sludge pyrolysis.

PubMed

Ko, Jae Hac; Wang, Jingchen; Xu, Qiyong

2018-05-21

Polycyclic aromatic hydrocarbons (PAHs) not only present a risk to human health when released into the air, but also can be precursors to form particulate matter (PM) during sewage sludge pyrolysis. In this study, 16 EPA PAHs in PM (ΣPAH PM ) during sewage sludge pyrolysis were investigated with increasing temperature (200 o C-1000 °C) and holding time under different operation conditions [inert gas flow rate (IGFR) (200-800 mL/min) and heating rate (5-20 °C/min)]. ΣPAH PM varied with temperature, IGFR, and heating rate, and ranged from 597 (±41) μg/g to 3240 (±868) μg/g. ΣPAH PM decreased with increasing IGFR but increased with rapid heating rate. Among PAHs species in PM, naphthalene (Nap) was commonly detected at low temperature ranges in all tested conditions. Chrysene (CHR), benzo[b]fluoranthene (BbF), benzo[k]fluoranthene (BkF), benzo[a]pyrene (BaP), indeno[1,2,3-cd] pyrene (IND), and benzo[g,h,i]perylene (BghiP) in PM became abundant at high temperature with a low IGFR. At high temperature ranges with high volatile conditions (rapid heating rate and low IGFR), PAH formation and growth reactions were considerable, resulting in the formation of heavy PAHs in PM. Copyright © 2018 Elsevier Ltd. All rights reserved.

Contamination from polycyclic aromatic hydrocarbons (PAHs) in the soil of a botanic garden localized next to a former manufacturing gas plant in Palermo (Italy).

PubMed

Orecchio, Santino

2010-08-15

The Botanical Garden lies within the city of Palermo, a few meters away from one of the largest unused Manufacturing Gas Plant in Sicily. The total concentrations of PAHs (23 compounds) in the soil of Botanical Garden ranged from 947 to 18,072 microg/kg. The wide range of PAH concentrations (RSD=84%) found in the soil samples indicates heterogeneous levels of contamination in the area and this can be explained by considering the different tree distributions which prevents the homogeneous deposition of pollutants on the soil. Soils collected in the Botanical Garden generally showed the highest PAH concentrations, being almost 2-3 times higher than the concentration samples obtained in the urban reference sites and about 20 times higher than those in the rural stations. The total PAH concentrations, in the Botanical Garden soil, resulted higher than the maximum concentrations allowed by the Italian legislation for the green areas. Perylene, was found in all the stations. From a careful study of the isomeric ratios, we can hypothesize that the soils of the Botanical Garden are mainly affected by localized MGP particulate deposition, suggesting that the partitioning between organic matter and PAHs is not the dominant process in the soils with higher organic matter content. Copyright 2010 Elsevier B.V. All rights reserved.

Impact of Alkyl Spacer Length on Aggregation Pathways in Kinetically Controlled Supramolecular Polymerization.

PubMed

Ogi, Soichiro; Stepanenko, Vladimir; Thein, Johannes; Würthner, Frank

2016-01-20

We have investigated the kinetic and thermodynamic supramolecular polymerizations of a series of amide-functionalized perylene bisimide (PBI) organogelator molecules bearing alkyl spacers of varied lengths (ethylene to pentylene chains, PBI-1-C2 to PBI-1-C5) between the amide and PBI imide groups. These amide-functionalized PBIs form one-dimensional fibrous nanostructures as the thermodynamically favored states in solvents of low polarity. Our in-depth studies revealed, however, that the kinetic behavior of their supramolecular polymerization is dependent on the spacer length. Propylene- and pentylene-tethered PBIs follow a similar polymerization process as previously observed for the ethylene-tethered PBI. Thus, the monomers of these PBIs are kinetically trapped in conformationally restricted states through intramolecular hydrogen bonding between the amide and imide groups. In contrast, the intramolecularly hydrogen-bonded monomers of butylene-tethered PBI spontaneously self-assemble into nanoparticles, which constitute an off-pathway aggregate state with regard to the thermodynamically stable fibrous supramolecular polymers obtained. Thus, for this class of π-conjugated system, an unprecedented off-pathway aggregate with high kinetic stability could be realized for the first time by introducing an alkyl linker of optimum length (C4 chain) between the amide and imide groups. Our current system with an energy landscape of two competing nucleated aggregation pathways is applicable to the kinetic control over the supramolecular polymerization by the seeding approach.

Many-body dispersion effects in the binding of adsorbates on metal surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maurer, Reinhard J.; Ruiz, Victor G.; Tkatchenko, Alexandre

2015-09-14

A correct description of electronic exchange and correlation effects for molecules in contact with extended (metal) surfaces is a challenging task for first-principles modeling. In this work, we demonstrate the importance of collective van der Waals dispersion effects beyond the pairwise approximation for organic–inorganic systems on the example of atoms, molecules, and nanostructures adsorbed on metals. We use the recently developed many-body dispersion (MBD) approach in the context of density-functional theory [Tkatchenko et al., Phys. Rev. Lett. 108, 236402 (2012) and Ambrosetti et al., J. Chem. Phys. 140, 18A508 (2014)] and assess its ability to correctly describe the binding ofmore » adsorbates on metal surfaces. We briefly review the MBD method and highlight its similarities to quantum-chemical approaches to electron correlation in a quasiparticle picture. In particular, we study the binding properties of xenon, 3,4,9,10-perylene-tetracarboxylic acid, and a graphene sheet adsorbed on the Ag(111) surface. Accounting for MBD effects, we are able to describe changes in the anisotropic polarizability tensor, improve the description of adsorbate vibrations, and correctly capture the adsorbate–surface interaction screening. Comparison to other methods and experiment reveals that inclusion of MBD effects improves adsorption energies and geometries, by reducing the overbinding typically found in pairwise additive dispersion-correction approaches.« less

Analysis of particle and vapour phase PAHs from the personal air samples of bus garage workers exposed to diesel exhaust.

PubMed

Kuusimaki, Leea; Peltonen, Kimmo; Mutanen, Pertti; Savela, Kirsti

2003-07-01

The levels of particle and vapour phase polycyclic aromatic hydrocarbons (PAHs) derived from the diesel exhaust compounds in bus garage work were measured in winter and in summer. Five personal air samples were collected from the breathing zones of 22 garage workers every other day of consecutive weeks. Control samples (n = 22) were collected from office workers in Helsinki. Fifteen PAHs in the air samples were analysed by HPLC using a fluorescence detector. Statistically significant differences were observed between total PAH levels of the exposed workers (2241 and 1245 ng/m(3)) and the control group (254 and 275 ng/m(3)) in both winter (P < 0.001) and summer (P < 0.001). Phenanthrene, pyrene, benzo[ghi]perylene and fluoranthene were the major compounds in the particle phase, and naphthalene, phenanthrene and fluorene in the vapour phase. About 98% of PAHs measured were related to the vapour phase compounds, whereas the high molecular weight PAH compounds were detected only in the particle phase. The PAH levels in the garages were twice as high (P < 0.001) in winter as in summer. Even though the exposure levels were low in the bus garages, the low level does not allow conclusions to be drawn about the possible adverse health effects due to exposure to diesel exhaust.

Electrochemical immunosensor with nanocellulose-Au composite assisted multiple signal amplification for detection of avian leukosis virus subgroup J.

PubMed

Liu, Chao; Dong, Jing; Waterhouse, Geoffrey I N; Cheng, Ziqiang; Ai, Shiyun

2018-03-15

A sensitive sandwich-type electrochemical immunosensor was developed for the detection of avian leukosis virus subgroup J (ALV-J), which benefitted from multiple signal amplification involving graphene-perylene-3,4,9,10-tetracarboxylic acid nanocomposites (GR-PTCA), nanocellulose-Au NP composites (NC-Au) and the alkaline phosphatase (ALP) catalytic reaction. GR-PTCA nanocomposites on glassy carbon electrodes served as the immunosensor platform. Due to their excellent electrical conductivity and abundant polycarboxylic sites, the GR-PTCA nanocomposites allowed fast electron transfer and good immobilization of primary antibodies, thereby affording a strong immunosensor signal in the presence of ALV-J. The detected signal could be further amplified by the introduction of NC-Au composites as a carrier of secondary antibodies (Ab 2 ) and by harnessing the catalytic properties of Au and ALP. Under optimized testing conditions, the electrochemical immunosensor displayed excellent analytical performance for the detection of ALV-J, showing a linear current response from 10 2.08 to 10 4.0 TCID 50 /mL (TCID 50 : 50% tissue culture infective dose) with a low detection limit of 10 1.98 TCID 50 /mL (S/N = 3). In addition to high sensitivity, the immunosensor showed very good selectivity, reproducibility and operational stability, demonstrating potential application for the quantitative detection of ALV-J in clinical diagnosis. Copyright © 2017 Elsevier B.V. All rights reserved.

Bioaccumulation of stentorin, the probable causative agent for discolored (“purple”) eggs and ovaries in blue catfish (Ictalurus furcatus) from Eufaula Lake, Oklahoma, USA

USGS Publications Warehouse

Gale, Robert W.; Papoulias, Diana M.; Schmitt, Christopher J.

2015-01-01

Observations of reddish to “purple” discolored eggs in the ovaries of adult female blue catfish (Ictalurus furcatus) from the northern arm of Eufaula Lake, a eutrophic multiuse impoundment in east-central Oklahoma, were first reported in 2006. Blue catfish eggs are normally cream to light yellow. Reports peaked in 2007–2008 and declined through 2009–2010; purple eggs have not been reported between 2010 and 2014. In the laboratory, all tissues and fluids of affected fish were strongly orange-red fluorescent under UV illumination, with the fluorescence most apparent in the lipid-rich ovaries and eggs. The causative agent was isolated chromatographically and confirmed by mass spectrometry as stentorin (1,3,4,6,8,10,11,13-octahydroxy-2,5-diisopropyl-phenanthro[1,10,9,8,o,p,q,r,a]perylene-7,14-dione), the fluorescent, lipophilic pigment associated with the photoreceptor protein of the ciliated protozoan Stentor coeruleus (Heterotrichea; Stentoridae). Larval medaka (Orizias latipes) readily consumed S. coeruleus in the laboratory and were observed to fluoresce in the same manner as the affected blue catfish. Potential deleterious effects of stentorin bioaccumulation remain to be determined, as do the geographic extent and the identities of other fluorescent compounds isolated from catfish eggs and ovaries.

Distribution and Sources of Petroleum Hydrocarbons in Recent Sediments of the Imo River, SE Nigeria.

PubMed

Oyo-Ita, Inyang O; Oyo-Ita, Orok E; Dosunmu, Miranda I; Domínguez, Carmen; Bayona, Josep M; Albaigés, Joan

2016-02-01

The distribution of aliphatic and aromatic hydrocarbons in surface sediments of the lower course of the Imo River (Nigeria) was investigated to determine the sources and fate of these compounds. The aliphatic fraction is characterized by a widespread contribution of highly weathered/biodegraded hydrocarbon residues (reflected in the absence of prominent n-alkane peaks coupled with the presence of 17α(H),21β(H)-25-norhopane, an indicator of heavy hydrocarbon biodegradation) of Nigerian crude oils (confirmed by the occurrence of 18α(H)-oleanane, a compound characteristic of oils of deltaic origin). The concentrations of polycyclic aromatic hydrocarbons (PAHs) ranging from 48 to 117 ng/g dry weight (dw; ∑13PAHs) indicate a moderate pollution, possibly lowered by the sandy lithology and low organic carbon (OC) content of the sediments. Concentrations slightly decrease towards the estuary of the river, probably due to the fact that these stations are affected by tidal flushing of pollutants adsorbed on sediment particles and carried away by occasional storm to the Atlantic Ocean. A number of PAH ratios, including parent/alkylated and isomeric compounds, indicates a predominance of petrogenic sources, with a low contribution of pyrolytic inputs, particularly of fossil fuel combustion. On the basis of OC/ON (>10) and Per/ΣPAHpenta- (>10) values, a diagenetic terrigenous OC was proposed as a source of perylene to the river.

Determination of heavy polycyclic aromatic hydrocarbons of concern in edible oils via excitation-emission fluorescence spectroscopy on nylon membranes coupled to unfolded partial least-squares/residual bilinearization.

PubMed

Vásquez, Valeria; Báez, María E; Bravo, Manuel; Fuentes, Edwar

2013-09-01

Seven heavy polycyclic aromatic hydrocarbons (PAHs) of concern on the US Environmental Protection Agency priority pollutant list (benzo[a]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenz[a,h]anthracene, benzo[g,h,i]perylene, and indeno[1,2,3-c,d]-pyrene) were simultaneously analyzed in extra virgin olive oil. The analysis is based on the measurement of excitation-emission matrices on nylon membrane and processing of data using unfolded partial least-squares regression with residual bilinearization (U-PLS/RBL). The conditions needed to retain the PAHs present in the oil matrix on the nylon membrane were evaluated. The limit of detection for the proposed method ranged from 0.29 to 1.0 μg kg(-1), with recoveries between 64 and 78 %. The predicted U-PLS/RBL concentrations compared favorably with those measured using high-performance liquid chromatography with fluorescence detection. The proposed method was applied to ten samples of edible oil, two of which presented PAHs ranging from 0.35 to 0.63 μg kg(-1). The principal advantages of the proposed analytical method are that it provides a significant reduction in time and solvent consumption with a similar limit of detection as compared with chromatography.

Feasibility of the determination of polycyclic aromatic hydrocarbons in edible oils via unfolded partial least-squares/residual bilinearization and parallel factor analysis of fluorescence excitation emission matrices.

PubMed

Alarcón, Francis; Báez, María E; Bravo, Manuel; Richter, Pablo; Escandar, Graciela M; Olivieri, Alejandro C; Fuentes, Edwar

2013-01-15

The possibility of simultaneously determining seven concerned heavy polycyclic aromatic hydrocarbons (PAHs) of the US-EPA priority pollutant list, in extra virgin olive and sunflower oils was examined using unfolded partial least-squares with residual bilinearization (U-PLS/RBL) and parallel factor analysis (PARAFAC). Both of these methods were applied to fluorescence excitation emission matrices. The compounds studied were benzo[a]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenz[a,h]anthracene, benzo[g,h,i]perylene and indeno[1,2,3-c,d]-pyrene. The analysis was performed using fluorescence spectroscopy after a microwave assisted liquid-liquid extraction and solid-phase extraction on silica. The U-PLS/RBL algorithm exhibited the best performance for resolving the heavy PAH mixture in the presence of both the highly complex oil matrix and other unpredicted PAHs of the US-EPA list. The obtained limit of detection for the proposed method ranged from 0.07 to 2 μg kg(-1). The predicted U-PLS/RBL concentrations were satisfactorily compared with those obtained using high-performance liquid chromatography with fluorescence detection. A simple analysis with a considerable reduction in time and solvent consumption in comparison with chromatography are the principal advantages of the proposed method. Copyright © 2012 Elsevier B.V. All rights reserved.

Manganese porphyrin decorated on DNA networks as quencher and mimicking enzyme for construction of ultrasensitive photoelectrochemistry aptasensor.

PubMed

Huang, Liaojing; Zhang, Li; Yang, Liu; Yuan, Ruo; Yuan, Yali

2018-05-01

In this work, the manganese porphyrin (MnPP) decorated on DNA networks could serve as quencher and mimicking enzyme to efficiently reduce the photocurrent of photoactive material 3,4,9,10-perylene tetracarboxylic acid (PTCA), which was elaborately used to construct a novel label-free aptasensor for ultrasensitive detection of thrombin (TB) in a signal-off manner. The Au-doped PTCA (PTCA-PEI-Au) with outstanding membrane-forming and photoelectric property was modified on electrode to acquire a strong initial photoelectrochemistry (PEC) signal. Afterward, target binding aptamer Ι (TBAΙ) was modified on electrode to specially recognize target TB, which could further combine with TBAII and single-stranded DNA P1-modified platinum nanoparticles (TBAII-PtNPs-P1) for immobilizing DNA networks with abundant MnPP. Ingeniously, the MnPP could not only directly quench the photocurrent of PTCA, but also acted as hydrogen peroxide (HRP) mimicking enzyme to remarkably stimulate the deposition of benzo-4-chlorhexidine (4-CD) on electrode for further decreasing the photocurrent of PTCA, thereby obtaining a definitely low photocurrent for detection of TB. As a result, the proposed PEC aptasensor illustrated excellent sensitivity with a low detection limit down to 3 fM, exploiting a new avenue about intergrating two functions in one substance for ultrasensitive biological monitoring. Copyright © 2017 Elsevier B.V. All rights reserved.

Assessment of hydrocarbons concentration in marine fauna due to Tasman Spirit oil spill along the Clifton beach at Karachi coast.

PubMed

Siddiqi, Hina A; Ansari, Fayyaz A; Munshi, Alia B

2009-01-01

On 27 July 2003, Tasman Spirit spilled 31,000 tonnes of crude oil into the sea at the Karachi coast. This disaster badly affected the marine life (Flora and Fauna.) Present research has been proposed to ascertain the level of Polycyclic Aromatic hydrocarbons (PAHs) contamination in different fisheries including Fishes, Crustaceans; Crabs and Shrimps, Mollusks and Echinoderms along with passing time. Heavier components of crude oil such as Polycyclic Aromatic Hydrocarbons (PAHs) appear to cause most damages as these are relatively unreactive and persist in water. High concentrations of toxic PAHs were observed in all the fisheries and shellfishes caught form oil-impacted area. In this study fishes were found most contaminated than shellfishes i.e. summation operator 16 PAH = 1821.24 microg/g and summation operator 1164.34 microg/g, respectively. Naphthalene was found in the range of 0.042-602.23 microg/g. Acenaphthylene, acenaphthene, fluorene, phenanthrene and anthracene were detected in the range 0.008-80.03 microg/g, fluoranthene, pyrene, benzo(a)anthracene and chrysene 0.0008-221.32 microg/g, benzo(b) fluoranthene, benzo(k)fluoranthene and benzo(a) pyrene 0.0005-7.71 microg/g, benzo(g,h,i)perylene and indeno(1,2,3-c,d)pyrene 0.02-503.7 microg/g. Dibenzo(a,h)anthracenre was not detected in any specie.

Lead Halide Perovskites as Charge Generation Layers for Electron Mobility Measurement in Organic Semiconductors.

PubMed

Love, John A; Feuerstein, Markus; Wolff, Christian M; Facchetti, Antonio; Neher, Dieter

2017-12-06

Hybrid lead halide perovskites are introduced as charge generation layers (CGLs) for the accurate determination of electron mobilities in thin organic semiconductors. Such hybrid perovskites have become a widely studied photovoltaic material in their own right, for their high efficiencies, ease of processing from solution, strong absorption, and efficient photogeneration of charge. Time-of-flight (ToF) measurements on bilayer samples consisting of the perovskite CGL and an organic semiconductor layer of different thickness are shown to be determined by the carrier motion through the organic material, consistent with the much higher charge carrier mobility in the perovskite. Together with the efficient photon-to-electron conversion in the perovskite, this high mobility imbalance enables electron-only mobility measurement on relatively thin application-relevant organic films, which would not be possible with traditional ToF measurements. This architecture enables electron-selective mobility measurements in single components as well as bulk-heterojunction films as demonstrated in the prototypical polymer/fullerene blends. To further demonstrate the potential of this approach, electron mobilities were measured as a function of electric field and temperature in an only 127 nm thick layer of a prototypical electron-transporting perylene diimide-based polymer, and found to be consistent with an exponential trap distribution of ca. 60 meV. Our study furthermore highlights the importance of high mobility charge transporting layers when designing perovskite solar cells.

Quantitative resonant soft x-ray reflectivity of ultrathin anisotropic organic layers: Simulation and experiment of PTCDA on Au

DOE Office of Scientific and Technical Information (OSTI.GOV)

Capelli, R.; Koshmak, K.; Giglia, A.

Resonant soft X-ray reflectivity at the carbon K edge, with linearly polarized light, was used to derive quantitative information of film morphology, molecular arrangement, and electronic orbital anisotropies of an ultrathin 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) film on Au(111). The experimental spectra were simulated by computing the propagation of the electromagnetic field in a trilayer system (vacuum/PTCDA/Au), where the organic film was treated as an anisotropic medium. Optical constants were derived from the calculated (through density functional theory) absorption cross sections of the single molecule along the three principal molecular axes. These were used to construct the dielectric tensor of themore » film, assuming the molecules to be lying flat with respect to the substrate and with a herringbone arrangement parallel to the substrate plane. Resonant soft X-ray reflectivity proved to be extremely sensitive to film thickness, down to the single molecular layer. The best agreement between simulation and experiment was found for a film of 1.6 nm, with flat laying configuration of the molecules. The high sensitivity to experimental geometries in terms of beam incidence and light polarization was also clarified through simulations. The optical anisotropies of the organic film were experimentally determined and through the comparison with calculations, it was possible to relate them to the orbital symmetry of the empty electronic states.« less

Charge transport in fibre-based perylene-diimide transistors: effect of the alkyl substitution and processing technique.

PubMed

Savage, Rebecca C; Orgiu, Emanuele; Mativetsky, Jeffrey M; Pisula, Wojciech; Schnitzler, Tobias; Eversloh, Christian Lütke; Li, Chen; Müllen, Klaus; Samorì, Paolo

2012-04-07

We report a comparative study on the self-assembly from solution and electrical characterization of n-type semiconducting fibres obtained from five different perylenebis(dicarboximide) (PDI) derivatives. In particular we investigated the role of the nature of the alkyl chain covalently linked to the N,N' sites of the PDI in modulating the molecular solubility and aggregation capacity. We explored the morphologies of the self-assembled architectures physisorbed on dielectric surfaces and in particular how they can be modified by tuning the deposition and post-deposition procedures, i.e. by modulating the kinetics of the self-assembly process. To this end, alongside the conventional spin-coating, solvent vapour annealing (SVA) and solvent induced precipitation (SIP) have been employed. Both approaches led to fibres having widths of several hundred nanometres and lengths up to tens of micrometres. SVA formed isolated fibres which were tens of nanometres high, flat, and tapered at the ends. Conversely, SIP fibres exhibited nearly matching heights and widths, but organized into bundles. Despite these morphological differences, the same intermolecular packing is found by XRD in each type of structure, albeit with differing degrees of long-range order. The study of the electrical characteristics of the obtained low dimensional nano-assemblies has been accomplished by fabricating and characterizing organic field-effect transistors. This journal is © The Royal Society of Chemistry 2012

High-Performance Phototransistors Based on PDIF-CN2 Solution-Processed Single Fiber and Multifiber Assembly.

PubMed

Rekab, Wassima; Stoeckel, Marc-Antoine; El Gemayel, Mirella; Gobbi, Marco; Orgiu, Emanuele; Samorì, Paolo

2016-04-20

Here we describe the fabrication of organic phototransistors based on either single or multifibers integrated in three-terminal devices. These self-assembled fibers have been produced by solvent-induced precipitation of an air stable and solution-processable perylene di-imide derivative, i.e., PDIF-CN2. The optoelectronic properties of these devices were compared to devices incorporating more disordered spin-coated PDIF-CN2 thin-films. The single-fiber devices revealed significantly higher field-effect mobilities, compared to multifiber and thin-films, exceeding 2 cm(2) V(-1) s(-1). Such an efficient charge transport is the result of strong intermolecular coupling between closely packed PDIF-CN2 molecules and of a low density of structural defects. The improved crystallinity allows efficient collection of photogenerated Frenkel excitons, which results in the highest reported responsivity (R) for single-fiber PDI-based phototransistors, and photosensitivity (P) exceeding 2 × 10(3) AW(-1), and 5 × 10(3), respectively. These findings provide unambiguous evidence for the key role played by the high degree of order at the supramolecular level to leverage the material's properties toward the fabrication of light-sensitive organic field-effect transistors combining a good operational stability, high responsivity and photosensitivity. Our results show also that the air-stability performances are superior in devices where highly crystalline supramolecularly engineered architectures serve as the active layer.

Polyfluorophore Labels on DNA: Dramatic Sequence Dependence of Quenching

PubMed Central

Teo, Yin Nah; Wilson, James N.

2010-01-01

We describe studies carried out in the DNA context to test how a common fluorescence quencher, dabcyl, interacts with oligodeoxynu-cleoside fluorophores (ODFs)—a system of stacked, electronically interacting fluorophores built on a DNA scaffold. We tested twenty different tetrameric ODF sequences containing varied combinations and orderings of pyrene (Y), benzopyrene (B), perylene (E), dimethylaminostilbene (D), and spacer (S) monomers conjugated to the 3′ end of a DNA oligomer. Hybridization of this probe sequence to a dabcyl-labeled complementary strand resulted in strong quenching of fluorescence in 85% of the twenty ODF sequences. The high efficiency of quenching was also established by their large Stern–Volmer constants (KSV) of between 2.1 × 104 and 4.3 × 105M−1, measured with a free dabcyl quencher. Interestingly, quenching of ODFs displayed strong sequence dependence. This was particularly evident in anagrams of ODF sequences; for example, the sequence BYDS had a KSV that was approximately two orders of magnitude greater than that of BSDY, which has the same dye composition. Other anagrams, for example EDSY and ESYD, also displayed different responses upon quenching by dabcyl. Analysis of spectra showed that apparent excimer and exciplex emission bands were quenched with much greater efficiency compared to monomer emission bands by at least an order of magnitude. This suggests an important role played by delocalized excited states of the π stack of fluorophores in the amplified quenching of fluorescence. PMID:19780115

Synthetic organic pigments of the 20th and 21st century relevant to artist's paints: Raman spectra reference collection

NASA Astrophysics Data System (ADS)

Scherrer, Nadim C.; Stefan, Zumbuehl; Francoise, Delavy; Annette, Fritsch; Renate, Kuehnen

2009-08-01

Some 170 organic pigments relevant to artist's paints have been collected from historic collections and modern manufacturers. The number includes multiples of the same pigment from different sources and comprises 118 different color indices (C.I.). All of them have been analysed with FTIR spectroscopy and 125 pigments (93 different C.I. No.s) of particular relevance to artist's paints have been characterised with Raman spectroscopy so far. The pigment collection encompasses the following pigment classes and subgroups: monoazo pigments represented by acetoacetic arylide yellow (hansa yellow), β-naphthol, BON, naphthol AS and benzimidazolone; disazo pigments with disazo condensation, diarylide, bisacetoacetarylide, pyrazolone; azo-azomethin metal complex pigments; non-azo, polycyclic pigments such as phthalocyanines, diketopyrrolo-pyrroles (DPP), perylenes and perinones, quinacridones, isoindolinones, polycarbocyclic anthraquinones and dioxanines. The selection of references was based on availability (historic collections) and current use in 16 acrylic, alkyd and oil-based artist's paints, and it covers pigment colors PY yellow (27 C.I. No.s), PR red (38), PO orange (9), PB blue (8), PV violet (6), PG green (3) and PBr brown (2). Besides peak tables and spectra patterns, flow charts based on color, pigment class, group and individual color index are presented to help identification of unknowns and mixed paint samples. While Raman could isolate all different C.I. numbers, multiple references of the same C.I. from different sources could not be distinguished.

16S metagenomic analysis reveals adaptability of a mixed-PAH-degrading consortium isolated from crude oil-contaminated seawater to changing environmental conditions.

PubMed

Muangchinda, Chanokporn; Rungsihiranrut, Adisan; Prombutara, Pinidphon; Soonglerdsongpha, Suwat; Pinyakong, Onruthai

2018-05-29

A bacterial consortium, named SWO, was enriched from crude oil-contaminated seawater from Phrao Bay in Rayong Province, Thailand, after a large oil spill in 2013. The bacterial consortium degraded a polycyclic aromatic hydrocarbon (PAH) mixture consisting of phenanthrene, anthracene, fluoranthene, and pyrene (50 mg L -1 each) by approximately 73%, 69%, 52%, and 48%, respectively, within 21 days. This consortium exhibited excellent adaptation to a wide range of environmental conditions. It could degrade a mixture of four PAHs under a range of pH values (4.0-9.0), temperatures (25 °C-37 °C), and salinities (0-10 g L -1 with NaCl). In addition, this consortium degraded 20-30% of benzo[a]pyrene and perylene (10 mg L -1 each), high molecular weight PAHs, in the presence of other PAHs within 35 days, and degraded 40% of 2% (v/v) crude oil within 20 days. The 16S rRNA gene amplicon sequencing analysis demonstrated that Pseudomonas and Methylophaga were the dominant genera of consortium SWO in almost all treatments, while Pseudidiomarina, Thalassospira and Alcanivorax were predominant under higher salt concentrations. Moreover, Pseudomonas and Alcanivorax were dominant in the crude oil-degradation treatment. Our results suggest that the consortium SWO maintained its biodegradation ability by altering the bacterial community profile upon encountering changes in the environmental conditions. Copyright © 2018 Elsevier B.V. All rights reserved.

High-Resolution IR Absorption Spectroscopy of Polycyclic Aromatic Hydrocarbons in the 3-micrometers Region: Role of Periphery

NASA Technical Reports Server (NTRS)

Maltseva, Elena; Petrignani, Annemieke; Candian, Alessandra; Mackie, Cameron J.; Huang, Xinchuan; Lee, Timothy J.; Tielens, Alexander G. G. M.; Oomens, Jos; Buma, Wybren Jan

2017-01-01

In this work we report on high-resolution IR absorption studies that provide a detailed view on how the peripheral structure of irregular polycyclic aromatic hydrocarbons (PAHs) affects the shape and position of their 3-micrometers absorption band. To this purpose we present mass-selected, high-resolution absorption spectra of cold and isolated phenanthrene, pyrene, benz[a]antracene, chrysene, triphenylene, and perylene molecules in the 2950-3150 per cm range. The experimental spectra are compared with standard harmonic calculations, and anharmonic calculations using a modified version of the SPECTRO program that incorporates a Fermi resonance treatment utilizing intensity redistribution. We show that the 3-micrometers region is dominated by the effects of anharmonicity, resulting in many more bands than would have been expected in a purely harmonic approximation. Importantly, we find that anharmonic spectra as calculated by SPECTRO are in good agreement with the experimental spectra. Together with previously reported high-resolution spectra of linear acenes, the present spectra provide us with an extensive dataset of spectra of PAHs with a varying number of aromatic rings, with geometries that range from open to highly-condensed structures, and featuring CH groups in all possible edge configurations. We discuss the astrophysical implications of the comparison of these spectra on the interpretation of the appearance of the aromatic infrared 3-micrometers band, and on features such as the two-component emission character of this band and the 3-micrometers emission plateau.

Reliable energy level alignment at physisorbed molecule-metal interfaces from density functional theory.

PubMed

Egger, David A; Liu, Zhen-Fei; Neaton, Jeffrey B; Kronik, Leeor

2015-04-08

A key quantity for molecule-metal interfaces is the energy level alignment of molecular electronic states with the metallic Fermi level. We develop and apply an efficient theoretical method, based on density functional theory (DFT) that can yield quantitatively accurate energy level alignment information for physisorbed metal-molecule interfaces. The method builds on the "DFT+Σ" approach, grounded in many-body perturbation theory, which introduces an approximate electron self-energy that corrects the level alignment obtained from conventional DFT for missing exchange and correlation effects associated with the gas-phase molecule and substrate polarization. Here, we extend the DFT+Σ approach in two important ways: first, we employ optimally tuned range-separated hybrid functionals to compute the gas-phase term, rather than rely on GW or total energy differences as in prior work; second, we use a nonclassical DFT-determined image-charge plane of the metallic surface to compute the substrate polarization term, rather than the classical DFT-derived image plane used previously. We validate this new approach by a detailed comparison with experimental and theoretical reference data for several prototypical molecule-metal interfaces, where excellent agreement with experiment is achieved: benzene on graphite (0001), and 1,4-benzenediamine, Cu-phthalocyanine, and 3,4,9,10-perylene-tetracarboxylic-dianhydride on Au(111). In particular, we show that the method correctly captures level alignment trends across chemical systems and that it retains its accuracy even for molecules for which conventional DFT suffers from severe self-interaction errors.

[Simultaneous determination of 15 polycyclic aromatic hydrocarbons in cigarette filter by gas chromatography-tandem mass spectrometry].

PubMed

Zhang, Xiaotao; Zhang, Li; Ruan, Yibin; Wang, Weiwei; Ji, Houwei; Wan, Qiang; Lin, Fucheng; Liu, Jian

2017-10-08

A method for the simultaneous determination of 15 polycyclic aromatic hydrocarbons in cigarette filter was developed by isotope internal standard combined with gas chromatography-tandem mass spectrometry. The cigarette filters were extracted with dichloromethane, and the extract was filtered with 0.22 μm organic phase membrane. The samples were isolated by DB-5MS column (30 m×0.25 mm, 0.25 μm) and detected using multiple reaction monitoring mode of electron impact source under positive ion mode. The linearities of the 15 polycyclic aromatic hydrocarbons (acenapthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, ben[ a ]anthracene, chrysene, benzo[ b ]fluoranthene, benzo[ k ]fluoranthene, benzo[ a ]pyrene, dibenzo[ a,h ]anthracene, benzo[ g,h,i ]perylene and indeno[1,2,3- c,d ]pyrene) were good, and the correlation coefficients ( R 2 ) ranged from 0.9914 to 0.9999. The average recoveries of the 15 polycyclic aromatic hydrocarbons were 81.6%-109.6% at low, middle and high spiked levels, and the relative standard deviations were less than 16%, except that the relative standard deviation of fluorene at the low spiked level was 19.2%. The limits of detection of the 15 polycyclic aromatic hydrocarbons were 0.02 to 0.24 ng/filter, and the limits of quantification were 0.04 to 0.80 ng/filter. The method is simple, rapid, accurate, sensitive and reproducible. It is suitable for the quantitative analysis of the 15 polycyclic aromatic hydrocarbons in cigarette filters.

Enhanced sorption of PAHs in natural-fire-impacted sediments from Oriole Lake, California.

PubMed

Sullivan, Julia; Bollinger, Kevyn; Caprio, Anthony; Cantwell, Mark; Appleby, Peter; King, John; Ligouis, Bertrand; Lohmann, Rainer

2011-04-01

Surface sediment cores from Oriole Lake (CA) were analyzed for organic carbon (OC), black carbon (BC), and their δ(13)C isotope ratios. Sediments displayed high OC (20-25%) and increasing BC concentrations from ∼0.40% (in 1800 C.E.) to ∼0.60% dry weight (in 2000 C.E.). Petrographic analysis confirmed the presence of fire-derived carbonaceous particles/BC at ∼2% of total OC. Natural fires were the most likely cause of both elevated polycyclic aromatic hydrocarbon (PAH) concentrations and enhanced sorption in Oriole Lake sediments prior to 1850, consistent with their tree-ring-based fire history. In contrast to other PAHs, retene and perylene displayed decreasing concentrations during periods with natural fires, questioning their use as fire tracers. The occurrence of natural fires, however, did not result in elevated concentrations of black carbon or chars in the sediments. Only the 1912-2007 sediment layer contained anthropogenic particles, such as soot BC. In this layer, combining OC absorption with adsorption to soot BC (using a Freundlich coefficient n = 0.7) explained the observed sorption well. In the older layers, n needed to be 0.3 and 0.5 to explain the enhanced sorption to the sediments, indicating the importance of natural chars/inertinites in sorbing PAHs. For phenanthrene, values of n differed significantly between sorption to natural chars (0.1-0.4) and sorption to anthropogenic black carbon (>0.5), suggesting it could serve as an in situ probe of sorbents.

Impact of molecular flexibility on binding strength and self-sorting of chiral π-surfaces.

PubMed

Safont-Sempere, Marina M; Osswald, Peter; Stolte, Matthias; Grüne, Matthias; Renz, Manuel; Kaupp, Martin; Radacki, Krzysztof; Braunschweig, Holger; Würthner, Frank

2011-06-22

In this work, we have explored for the first time the influence of conformational flexibility of π-core on chiral self-sorting properties of perylene bisimides (PBIs) that are currently one of the most prominent classes of functional dyes. For this purpose, two series of chiral macrocyclic PBIs 3a-c and 4a-c comprising oligoethylene glycol bridges of different lengths at the 1,7 bay positions were synthesized and their atropo-enantiomers (P and M enantiomers) were resolved. Single crystal analysis of atropo-enantiomerically pure (P)-3a not only confirmed the structural integrity of the ethylene glycol bridged macrocycle but also illustrated the formation of π-stacked dimers with left-handed supramolecular helicity. Our detailed studies with the series of highly soluble chiral PBIs 4a-c by 1- and 2-D (1)H NMR techniques, and temperature- and concentration-dependent UV/vis absorption and circular dichroism (CD) spectroscopy revealed that in π-π-stacking dimerization of these PBIs chiral self-recognition (i.e., PP and MM homodimer formation) prevails over self-discrimination (i.e., PM heterodimer formation). Our studies clearly showed that with increasing conformational flexibility of PBI cores imparted by longer bridging units, the binding strength for the dimerization process increases, however, the efficiency for chiral self-recognition decreases. These results are rationalized in terms of an induced-fit mechanism facilitating more planarized π-scaffolds of PBIs containing longer bridging units upon π-π-stacking.

"Double-Cable" Conjugated Polymers with Linear Backbone toward High Quantum Efficiencies in Single-Component Polymer Solar Cells.

PubMed

Feng, Guitao; Li, Junyu; Colberts, Fallon J M; Li, Mengmeng; Zhang, Jianqi; Yang, Fan; Jin, Yingzhi; Zhang, Fengling; Janssen, René A J; Li, Cheng; Li, Weiwei

2017-12-27

A series of "double-cable" conjugated polymers were developed for application in efficient single-component polymer solar cells, in which high quantum efficiencies could be achieved due to the optimized nanophase separation between donor and acceptor parts. The new double-cable polymers contain electron-donating poly(benzodithiophene) (BDT) as linear conjugated backbone for hole transport and pendant electron-deficient perylene bisimide (PBI) units for electron transport, connected via a dodecyl linker. Sulfur and fluorine substituents were introduced to tune the energy levels and crystallinity of the conjugated polymers. The double-cable polymers adopt a "face-on" orientation in which the conjugated BDT backbone and the pendant PBI units have a preferential π-π stacking direction perpendicular to the substrate, favorable for interchain charge transport normal to the plane. The linear conjugated backbone acts as a scaffold for the crystallization of the PBI groups, to provide a double-cable nanophase separation of donor and acceptor phases. The optimized nanophase separation enables efficient exciton dissociation as well as charge transport as evidenced from the high-up to 80%-internal quantum efficiency for photon-to-electron conversion. In single-component organic solar cells, the double-cable polymers provide power conversion efficiency up to 4.18%. This is one of the highest performances in single-component organic solar cells. The nanophase-separated design can likely be used to achieve high-performance single-component organic solar cells.

Reliable Energy Level Alignment at Physisorbed Molecule–Metal Interfaces from Density Functional Theory

PubMed Central

2015-01-01

A key quantity for molecule–metal interfaces is the energy level alignment of molecular electronic states with the metallic Fermi level. We develop and apply an efficient theoretical method, based on density functional theory (DFT) that can yield quantitatively accurate energy level alignment information for physisorbed metal–molecule interfaces. The method builds on the “DFT+Σ” approach, grounded in many-body perturbation theory, which introduces an approximate electron self-energy that corrects the level alignment obtained from conventional DFT for missing exchange and correlation effects associated with the gas-phase molecule and substrate polarization. Here, we extend the DFT+Σ approach in two important ways: first, we employ optimally tuned range-separated hybrid functionals to compute the gas-phase term, rather than rely on GW or total energy differences as in prior work; second, we use a nonclassical DFT-determined image-charge plane of the metallic surface to compute the substrate polarization term, rather than the classical DFT-derived image plane used previously. We validate this new approach by a detailed comparison with experimental and theoretical reference data for several prototypical molecule–metal interfaces, where excellent agreement with experiment is achieved: benzene on graphite (0001), and 1,4-benzenediamine, Cu-phthalocyanine, and 3,4,9,10-perylene-tetracarboxylic-dianhydride on Au(111). In particular, we show that the method correctly captures level alignment trends across chemical systems and that it retains its accuracy even for molecules for which conventional DFT suffers from severe self-interaction errors. PMID:25741626

Polycyclic aromatic hydrocarbons in post-fire soils of drained peatlands in western Meshchera (Moscow region, Russia)

NASA Astrophysics Data System (ADS)

Tsibart, A.; Gennadiev, A.; Koshovskii, T.; Watts, A.

2014-12-01

Polycyclic aromatic hydrocarbons (PAHs) are priority pollutants that arrive in the environment from numerous anthropogenic and natural sources, but the data on their natural sources including wildfires remain insufficient. The level of contamination and the composition of PAHs in soils of the areas affected by wildfires were studied in this work. The study was conducted in the Moscow region (Russia) in areas occupied by drained peatland and strongly damaged by fires in 2002, 2010 and 2012. The features of PAH accumulation and the profile distributions in histosols and histic podzols after the fires of different times were analyzed. It was shown that new soil horizons formed after the fires - Cpir, Hpir and incipient O horizons - and that these horizons differ in PAH accumulation rate. Maximal total concentrations of 14 PAHs were detected in charred peat horizons Hpir (up to 330 ng g-1) and in post-fire incipient O horizons (up to 180 ng g-1), but the high-molecular-weight PAHs (benz(ghi)perylene, benz(a)pyrene, benz(k)fluoranthene) were revealed only in charry peat horizons. The trends of higher PAH concentrations were found in cases when smoldering combustion resulted in rather thick residual peat horizons. In cases of almost complete pyrogenic destruction of He horizons, total PAH concentrations were no more than 50 ng g-1. Also, PAH accumulation in upper horizons of soils near the sites of the latest fires was observed.

High-resolution IR Absorption Spectroscopy of Polycyclic Aromatic Hydrocarbons in the 3 μm Region: Role of Periphery

NASA Astrophysics Data System (ADS)

Maltseva, Elena; Petrignani, Annemieke; Candian, Alessandra; Mackie, Cameron J.; Huang, Xinchuan; Lee, Timothy J.; Tielens, Alexander G. G. M.; Oomens, Jos; Buma, Wybren Jan

2016-11-01

In this work we report on high-resolution IR absorption studies that provide a detailed view on how the peripheral structure of irregular polycyclic aromatic hydrocarbons (PAHs) affects the shape and position of their 3 μm absorption band. For this purpose, we present mass-selected, high-resolution absorption spectra of cold and isolated phenanthrene, pyrene, benz[a]antracene, chrysene, triphenylene, and perylene molecules in the 2950-3150 cm-1 range. The experimental spectra are compared with standard harmonic calculations and anharmonic calculations using a modified version of the SPECTRO program that incorporates a Fermi resonance treatment utilizing intensity redistribution. We show that the 3 μm region is dominated by the effects of anharmonicity, resulting in many more bands than would have been expected in a purely harmonic approximation. Importantly, we find that anharmonic spectra as calculated by SPECTRO are in good agreement with the experimental spectra. Together with previously reported high-resolution spectra of linear acenes, the present spectra provide us with an extensive data set of spectra of PAHs with a varying number of aromatic rings, with geometries that range from open to highly condensed structures, and featuring CH groups in all possible edge configurations. We discuss the astrophysical implications of the comparison of these spectra on the interpretation of the appearance of the aromatic infrared 3 μm band, and on features such as the two-component emission character of this band and the 3 μm emission plateau.

Polycyclic aromatic hydrocarbons in post-pyrogenic soils of drained peatlands in West Meshchera (Moscow Region, Russia)

NASA Astrophysics Data System (ADS)

Tsibart, A. S.; Gennadiev, A. N.; Koshovskii, T. S.

2014-05-01

Polycyclic aromatic hydrocarbons (PAHs) are priority pollutants and they arrive to the environment from numerous anthropogenic and natural sources, but the data on their natural sources which include wildfires remains insufficient. The level of contamination and the composition of PAHs in soils of the areas affected by wildfires were studied in this work. The study was conducted in Moscow Region (Russia) on the territories occupied with drained peatland and strongly damaged by fires of 2002, 2010 and 2012. The features of PAHs accumulation and profile distribution in histosols and histic podzols after the fires of different time were analyzed. It was shown that new soil horizon form after the fires - Cpir, Hpir and incipient O horizons, and these horizons differ in PAHs accumulation rate. Maximal total concentrations of 14 PAHs were detected in charry peat horizons Hpir (up to 330 ng g-1) and in post-pyrogenic incipient O horizons (up to 180 ng g-1), but the high-molecular weight PAHs (benz(ghi)perylene, benz(a)pyrene, benz(k)fluoranthene) were revealed only in charry peat horizons. The trends to higher PAHs concentrations were found in cases of incomplete burning out of peat horizons while in cases of almost complete pyrogenic destruction of He horizons total PAHs concentration were no more than 50 ng g-1. Also the PAHs accumulation in upper horizons of soils near the sites of latest fires was observed.

Supramolecular Packing Controls H 2 Photocatalysis in Chromophore Amphiphile Hydrogels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weingarten, Adam S.; Kazantsev, Roman V.; Palmer, Liam C.

2015-11-21

Light harvesting supramolecular assemblies are potentially useful structures as components of solar-to-fuel conversion materials. The development of these functional constructs requires an understanding of optimal packing modes for chromophores. We investigated here assembly in water and the photocatalytic function of perylene monoimide chromophore amphiphiles with different alkyl linker lengths separating their hydrophobic core and the hydrophilic carboxylate headgroup. We found that these chromophore amphiphiles (CAs) self-assemble into charged nanostructures of increasing aspect ratio as the linker length is increased. The addition of salt to screen the charged nanostructures induced the formation of hydrogels and led to internal crystallization within somemore » of the nanostructures. For linker lengths up to seven methylenes, the CAs were found to pack into 2D crystalline unit cells within ribbon-shaped nanostructures, whereas the nine methylene CAs assembled into long nanofibers without crystalline molecular packing. At the same time, the different molecular packing arrangements after charge screening led to different absorbance spectra, despite the identical electronic properties of all PMI amphiphiles. While the crystalline CAs formed electronically coupled H-aggregates, only CAs with intermediate linker lengths showed evidence of high intermolecular orbital overlap. Photocatalytic hydrogen production using a nickel-based catalyst was observed in all hydrogels, with the highest turnovers observed for CA gels having intermediate linker lengths. We conclude that the improved photocatalytic performance of the hydrogels formed by supramolecular assemblies of the intermediate linker CA molecules likely arises from improved exciton splitting efficiencies due to their higher orbital overlap.« less

High-resolution record of pyrogenic polycyclic aromatic hydrocarbon deposition during the 20th century.

PubMed

Lima, Ana Lúcia C; Eglinton, Timothy I; Reddy, Christopher M

2003-01-01

A high-resolution record of polycyclic aromatic hydrocarbon (PAH) deposition in Rhode Island over the past approximately 180 years was constructed using a sediment core from the anoxic Pettaquamscutt River basin. The record showed significantly more structure than has hitherto been reported and revealed four distinct maxima in PAH flux. The characteristic increase in PAH flux at the turn of the 20th century was captured in detail, leading to an initial maximum prior to the Great Depression. The overall peak in PAH flux in the 1950s was followed by a maximum that immediately preceded the 1973 Organization of Petroleum Exporting Countries (OPEC) oil embargo. During the most recent portion of the record, an abrupt increase in PAH flux between 1996 and 1999 has been found to follow a period of near constant fluxes. Because source-diagnostic ratios indicate that petrogenic inputs are minor throughout the record, these trends are interpreted in terms of past variations in the magnitude and type of combustion processes. For the most recent PAH maximum, energy consumption data suggest that diesel fuel combustion, and hence traffic of heavier vehicles, is the most probable cause for the increase in PAH flux. Systematic variations in the relative abundance of individual PAHs in conjunction with the above changes in flux are interpreted in relation to the evolution of combustion processes. Coronene, retene, and perylene are notable exceptions, exhibiting unique down-core profiles.

Microwave-assisted extraction and ultrasonic extraction to determine polycyclic aromatic hydrocarbons in needles and bark of Pinus pinaster Ait. and Pinus pinea L. by GC-MS.

PubMed

Ratola, Nuno; Lacorte, Sílvia; Barceló, Damià; Alves, Arminda

2009-01-15

Two different extraction strategies (microwave-assisted extraction (MAE) and ultrasonic extraction (USE)) were tested in the extraction of the 16 US Environmental Protection Agency (EPA) polycyclic aromatic hydrocarbons (PAHs) from pine trees. Extraction of needles and bark from two pine species common in the Iberian Peninsula (Pinus pinaster Ait. and Pinus pinea L.) was optimized using two amounts of sample (1g and 5 g) and two PAHs spiking levels (20 ng/g and 100 ng/g). In all cases, the clean-up procedure following extraction consisted in solid-phase extraction (SPE) with alumina cartridges. Quantification was done by gas chromatography (GC) with mass spectrometry (MS), using five deuterated PAH surrogate standards as internal standards. Limits of detection were globally below 0.2 ng/g. The method was robust for the matrices studied regardless of the extraction procedures. Recovery values between 70 and 130% were reached in most cases, except for high molecular weight PAHs (indeno[1,2,3-cd]pyrene, dibenzo[a,h]anthracene and benzo[ghi]perylene). A field study with naturally contaminated samples from eight sites (four in Portugal and four in Catalonia, Spain) showed that needles are more suitable biomonitors for PAHs, yielding concentrations from 2 to 17 times higher than those found in bark. The levels varied according to the sampling site, with the sum of the individual PAH concentrations between 213 and 1773 ng/g (dry weight). Phenanthrene was the most abundant PAH, followed by fluoranthene, naphthalene and pyrene.

PAHs and PCBs deposited in surficial sediments along a rural to urban transect in a mid-Atlantic coastal river basin (USA).

PubMed

Foster, Gregory D; Cui, Vickie

2008-10-01

PAHs and PCBs were measured in river sediments along a 226 km longitudinal transect that spanned rural to urban land use settings through Valley and Ridge, Piedmont Plateau and Coastal Plain physiographic provinces in the Potomac River basin (mid-Atlantic USA). A gradient in PAH concentrations was found in river bed sediments along the upstream transect in the Potomac and Shenandoah Rivers that correlated with population densities in the nearby sub-basins. Sediment PAH concentrations halved per each approximately 40 km of transect distance upstream (i.e., the half-concentration distance) from the urban center (Washington, DC) of the Potomac River basin in direct proportion to population density. The PAH molecular composition was consistent across all geologic provinces, revealing a dominant pyrogenic source. Fluoranthene to perylene ratios served as useful markers for urban inputs, with a ratio > 2.4 observed in sediments near urban structures such as roadways, bridges and sewer outfalls. PCBs in sediments were not well correlated with population densities along the river basin transect, but the highest concentrations were found in the urban Coastal Plain region near Washington, DC and in the Shenandoah River near a known industrial Superfund site. PAHs were moderately correlated with sediment total organic carbon (TOC) in the Shenandoah River and Coastal Plain Potomac River regions, but TOC was poorly correlated with PCB concentrations throughout the entire basin. Although both PAHs and PCBs are widely recognized as urban-derived contaminants, their concentration profiles and geochemistry in river sediments were uniquely different throughout the upper Potomac River basin.

Smart SERS Hot Spots: Single Molecules Can Be Positioned in a Plasmonic Nanojunction Using Host-Guest Chemistry.

PubMed

Kim, Nam Hoon; Hwang, Wooseup; Baek, Kangkyun; Rohman, Md Rumum; Kim, Jeehong; Kim, Hyun Woo; Mun, Jungho; Lee, So Young; Yun, Gyeongwon; Murray, James; Ha, Ji Won; Rho, Junsuk; Moskovits, Martin; Kim, Kimoon

2018-04-04

Single-molecule surface-enhanced Raman spectroscopy (SERS) offers new opportunities for exploring the complex chemical and biological processes that cannot be easily probed using ensemble techniques. However, the ability to place the single molecule of interest reliably within a hot spot, to enable its analysis at the single-molecule level, remains challenging. Here we describe a novel strategy for locating and securing a single target analyte in a SERS hot spot at a plasmonic nanojunction. The "smart" hot spot was generated by employing a thiol-functionalized cucurbit[6]uril (CB[6]) as a molecular spacer linking a silver nanoparticle to a metal substrate. This approach also permits one to study molecules chemically reluctant to enter the hot spot, by conjugating them to a moiety, such as spermine, that has a high affinity for CB[6]. The hot spot can accommodate at most a few, and often only a single, analyte molecule. Bianalyte experiments revealed that one can reproducibly treat the SERS substrate such that 96% of the hot spots contain a single analyte molecule. Furthermore, by utilizing a series of molecules each consisting of spermine bound to perylene bisimide, a bright SERS molecule, with polymethylene linkers of varying lengths, the SERS intensity as a function of distance from the center of the hot spot could be measured. The SERS enhancement was found to decrease as 1 over the square of the distance from the center of the hot spot, and the single-molecule SERS cross sections were found to increase with AgNP diameter.

Screening Libraries of Semifluorinated Arylene Bisimides to Discover and Predict Thermodynamically Controlled Helical Crystallization.

PubMed

Ho, Ming-Shou; Partridge, Benjamin E; Sun, Hao-Jan; Sahoo, Dipankar; Leowanawat, Pawaret; Peterca, Mihai; Graf, Robert; Spiess, Hans W; Zeng, Xiangbing; Ungar, Goran; Heiney, Paul A; Hsu, Chain-Shu; Percec, Virgil

2016-12-12

Synthesis, structural, and retrostructural analysis of a library containing 16 self-assembling perylene (PBI), 1,6,7,12-tetrachloroperylene (Cl 4 PBI), naphthalene (NBI), and pyromellitic (PMBI) bisimides functionalized with environmentally friendly AB 3 chiral racemic semifluorinated minidendrons at their imide groups via m = 0, 1, 2, and 3 methylene units is reported. These semifluorinated compounds melt at lower temperatures than homologous hydrogenated compounds, permitting screening of all their thermotropic phases via structural analysis to discover thermodynamically controlled helical crystallization from propeller-like, cogwheel, and tilted molecules as well as lamellar-like structures. Thermodynamically controlled helical crystallization was discovered for propeller-like PBI, Cl 4 PBI and NBI with m = 0. Unexpectedly, assemblies of twisted Cl 4 PBIs exhibit higher order than those of planar PBIs. PBI with m = 1, 2, and 3 form a thermodynamically controlled columnar hexagonal 2D lattice of tilted helical columns with intracolumnar order. PBI and Cl 4 PBI with m = 1 crystallize via a recently discovered helical cogwheel mechanism, while NBI and PMBI with m = 1 form tilted helical columns. PBI, NBI and PMBI with m = 2 generate lamellar-like structures. 3D and 2D assemblies of PBI with m = 1, 2, and 3, NBI with m = 1 and PMBI with m = 2 exhibit 3.4 Å π-π stacking. The library approach applied here and in previous work enabled the discovery of six assemblies which self-organize via thermodynamic control into 3D and 2D periodic arrays, and provides molecular principles to predict the supramolecular structure of electronically active components.

Hyperbolic metamaterial nanostructures to tune charge-transfer dynamics (Conference Presentation)

NASA Astrophysics Data System (ADS)

Lee, Kwang Jin; Xiao, Yiming; Woo, Jae Heun; Kim, Eun Sun; Kreher, David; Attias, André-Jean; Mathevet, Fabrice; Ribierre, Jean-Charles; Wu, Jeong Weon; André, Pascal

2016-09-01

Charge transfer (CT) is an essential phenomenon relevant to numerous fields including biology, physics and chemistry.1-5 Here, we demonstrate that multi-layered hyperbolic metamaterial (HMM) substrates alter organic semiconductor CT dynamics.6 With triphenylene:perylene diimide dyad supramolecular self-assemblies prepared on HMM substrates, we show that both charge separation (CS) and charge recombination (CR) characteristic times are increased by factors of 2.5 and 1.6, respectively, resulting in longer-lived CT states. We successfully rationalize the experimental data by extending Marcus theory framework with dipole image interactions tuning the driving force. The number of metal-dielectric pairs alters the HMM interfacial effective dielectric constant and becomes a solid analogue to solvent polarizability. Based on the experimental results and extended Marcus theory framework, we find that CS and CR processes are located in normal and inverted regions on Marcus parabola diagram, respectively. The model and further PH3T:PCBM data show that the phenomenon is general and that molecular and substrate engineering offer a wide range of kinetic tailoring opportunities. This work opens the path toward novel artificial substrates designed to control CT dynamics with potential applications in fields including optoelectronics, organic solar cells and chemistry. 1. Marcus, Rev. Mod. Phys., 1993, 65, 599. 2. Marcus, Phys. Chem. Chem. Phys., 2012, 14, 13729. 3. Lambert, et al., Nat. Phys., 2012, 9, 10. 4. C. Clavero, Nat. Photon., 2014, 8, 95. 5. A. Canaguier-Durand, et al., Angew. Chem. Int. Ed., 2013, 52, 10533. 6. K. J. Lee, et al., Submitted, 2015, arxiv.org/abs/1510.08574.

Analysis of transformations of the ultrafast electron transfer photoreaction mechanism in liquid solutions by the rate distribution approach.

PubMed

Kuzmin, Michael G; Soboleva, Irina V

2014-05-01

Representation of the experimental reaction kinetics in the form of rate distribution is shown to be an effective method for the analysis of the mechanisms of these reactions and for comparisons of the kinetics with QC calculations, as well as with the experimental data on the medium mobility. The rate constant distribution function P(k) can be obtained directly from the experimental kinetics N(t) by an inverse Laplace transform. The application of this approach to kinetic data for several excited-state electron transfer reactions reveals the transformations of their rate control factors in the time domain of 1-1000 ps. In neat electron donating solvents two components are observed. The fastest component (k > 1 ps(-1)) was found to be controlled by the fluctuations of the overall electronic coupling matrix element, involving all the reactant molecules, located inside the interior of the solvent shell, rather than for specific pairs of reactant molecules. The slower component (1 > k > 0.1 ps(-1)) is controlled by the medium reorganization (longitudinal relaxation times, τL). A substantial contribution from the non-stationary diffusion controlled reaction is observed in diluted solutions ([Q] < 1 M). No contribution from the long-distance electron transfer (electron tunneling) proposed earlier for the excited-state electron transfer between perylene and tetracyanoethylene in acetonitrile is observed. The rate distribution approach provides a simple and efficient method for the quantitative analysis of the reaction mechanism and transformation of the rate control factors in the course of the reactions.

High-Performance All-Polymer Solar Cells Achieved by Fused Perylenediimide-Based Conjugated Polymer Acceptors.

PubMed

Yin, Yuli; Yang, Jing; Guo, Fengyun; Zhou, Erjun; Zhao, Liancheng; Zhang, Yong

2018-05-09

We report three n-type polymeric electron acceptors (PFPDI-TT, PFPDI-T, and PFPDI-Se) based on the fused perylene diimide (FPDI) and thieno[3,2- b]thiophene, thiophene, or selenophene units for all-polymer solar cells (all-PSCs). These FPDI-based polymer acceptors exhibit strong absorption between 350 and 650 nm with wide optical bandgap of 1.86-1.91 eV, showing good absorption compensation with the narrow bandgap polymer donor. The lowest unoccupied molecular orbital (LUMO) energy levels were located at around -4.11 eV, which are comparable with those of the fullerene derivatives and other small molecular electron acceptors. The conventional all-PSCs based on the three polymer acceptors and PTB7-Th as polymer donor gave remarkable power conversion efficiencies (PCEs) of >6%, and the PFPDI-Se-based all-PSC achieved the highest PCE of 6.58% with a short-circuit current density ( J sc ) of 13.96 mA/cm 2 , an open-circuit voltage ( V oc ) of 0.76 V, and a fill factor (FF) of 62.0%. More interestingly, our results indicate that the photovoltaic performances of the FPDI-based polymer acceptors are mainly determined by the FPDI unit with a small effect from the comonomers, which is quite different from the others reported rylenediimide-based polymer acceptors. This intriguing phenomenon is speculated as the huge geometry configuration of the FPDI unit, which minimizes the effect of the comonomer. These results highlight a promising future for the application of the FPDI-based polymer acceptors in the highly efficient all-PSCs.

Transport of terrigenous polycyclic aromatic hydrocarbons affected by the coastal upwelling in the northwestern coast of South China Sea.

PubMed

Ya, Miaolei; Wu, Yuling; Li, Yongyu; Wang, Xinhong

2017-10-01

Coastal upwelling prevails in the coast of Hainan Island, the northern South China Sea (SCS) during summer. We studied the influences of the upwelling on the horizontal and vertical transport of terrigenous polycyclic aromatic hydrocarbons (PAHs). PAHs in dissolved and suspended particulate phase of water samples were determined in the upper (depth < 1 m) and water column (depth > 10 m). PAH levels decreased sharply from inshore to offshore to open sea. The results showed that terrestrial input was the main source of coastal PAHs. Perylene, an important indicator of land plant-derived PAH, showed the significant correlation with PAHs (p < 0.005). This implied that fluvial transport was the primary pathway of terrigenous PAHs into the coast of northern SCS. Variations of the concentrations, compositions and diagnostic ratios of PAHs, accompanied the partition equilibrium in the water column, could indicate the selective degradation of PAHs by the plankton affected by upwelling. Different from the "traditional" transport pathway of PAHs in the water column (surface enrichment-depth depletion distribution), the upwelling could provide the original driver to elevate the upward diffusion of sediment entrained contaminants towards the intermediate even the upper waters. It could also enhance the outward diffusion of terrigenous PAHs accompanied by the offshore transport of the upper waters. Therefore, the transport pathway of PAHs can be summarized by the coastal upwelling rising PAHs with their subsequent transport offshore and settling in the adjacent open sea. Copyright © 2017 Elsevier Ltd. All rights reserved.

Optimization of ultrasonic-assisted extraction for determination of polycyclic aromatic hydrocarbons in biochar-based fertilizer by gas chromatography-mass spectrometry.

PubMed

Chen, Ping; Sun, Mingxing; Zhu, Zhixiu; Zhang, Jidong; Shen, Guoqing

2015-08-01

Application of biochar-based fertilizers is increasingly being considered for its potential agronomic and environmental benefits. However, biochar may contain residues of polycyclic aromatic hydrocarbons (PAHs) as a result of its production by pyrolysis. The strong adsorption of PAHs to biochar makes extraction and analysis of biochar-based fertilizers difficult. This study optimizes the extraction of PAHs in biochar-based fertilizer samples by using an ultrasonic bath for quantification by gas chromatography-mass spectrometry. Among 12 solvents, acetone-cyclohexane (1:1) mixture was selected as the optimum solvent for extraction. Three variables affecting the extraction were studied by Box-Behnken design. The optimum conditions were 57 °C extraction temperature, 81 min extraction time, and two extraction cycles, which were validated by assessing the linearity of analysis, LOD, LOQ, recovery, and levels of PAHs in real biochar-based fertilizer samples. Results revealed that the 16 U.S. EPA PAHs had good linearity, with squared correlation coefficients greater than 0.99. LODs were low, ranging from 2.2 ng g(-1) (acenaphthene) to 23.55 ng g(-1) (indeno[1,2,3-cd]perylene), and LOQs varied from 7.51 ng g(-1) to 78.49 ng g(-1). The recoveries of 16 individual PAHs from the three biochar-based fertilizer samples were 81.8-109.4 %. Graphical Abstract Use of RSM to optimize UAE for extraction of the PAHs in biochar-based fertilizer.

A surface science compatible epifluorescence microscope for inspection of samples under ultra high vacuum and cryogenic conditions.

PubMed

Marquardt, Christian; Paulheim, Alexander; Rohbohm, Nils; Merkel, Rudolf; Sokolowski, Moritz

2017-08-01

We modified an epi-illumination light microscope and mounted it on an ultra high vacuum chamber for investigating samples used in a surface science experiment. For easy access and bake out, all optical components are placed outside the vacuum and the sample is imaged through a glass window. The microscope can be operated in reflection brightfield or epifluorescence mode to image the sample surface or fluorescent dye molecules adsorbed on it. The homemade sample mounting was made compatible for the use under the microscope; sample temperatures as low as 6 K can be achieved. The performance of the microscope is demonstrated on two model samples: Brightfield-images of a well-prepared Ag(100) surface show a macroscopic corrugation of the surface, although low energy electron diffraction data indicate a highly ordered crystalline surface. The surface shows macroscopic protrusions with flat regions, about 20-200 μm in diameter, in between. Fluorescence images of diluted 3,4,9,10-perylene tetracarboxylicacid dianhydride (PTCDA) molecules adsorbed on an ultrathin epitaxial KCl film on the Ag(100) surface show a shading effect at surface protrusions due to an inclined angle of incidence of the PTCDA beam during deposition. For some preparations, the distribution of the fluorescence intensity is inhomogeneous and shows a dense network of bright patches about 5 μm in diameter related to the macroscopic corrugation of the surface. We propose that such a light microscope can aid many surface science experiments, especially those dealing with epitaxial growth or fluorescent materials.

Polycyclic aromatic hydrocarbons (PAHs) and their derivatives (oxygenated-PAHs, nitrated-PAHs and azaarenes) in size-fractionated particles emitted in an urban road tunnel

NASA Astrophysics Data System (ADS)

Alves, C. A.; Vicente, A. M. P.; Gomes, J.; Nunes, T.; Duarte, M.; Bandowe, B. A. M.

2016-11-01

A sampling campaign of size segregated particulate matter (PM0.5, PM0.5-1, PM1-2.5 and PM2.5-10) was carried out at two sites, one in a road tunnel (Braga, Portugal) and another at an urban background location in the neighbourhood. Particle-bound polycyclic aromatic compounds were extracted with organic solvents and analysed by gas chromatography-mass spectrometry. Twenty six parent and alkyl-polycyclic aromatic hydrocarbons (PAHs), 4 azaarenes (AZAs), 15 nitrated and 15 oxygenated derivatives (NPAHs and OPAHs) were analysed. On average, submicron particles (PM1) in the tunnel comprised 93, 91, 96 and 71% of the total PAHs, OPAHs, NPAHs and AZAs mass in PM10, respectively. Tunnel to outdoor PAH concentration ratios between 10 and 14 reveal the strong contribution of fresh exhaust emissions to the PM loads. The dominant PAHs in the tunnel were pyrene, retene and benzo[ghi]perylene, accounting for 20, 17 and 8% of the total PAH levels in PM10, respectively. Isomer ratios indicated the importance of unburnt fuel as a significant PAH source. The only NPAH consistently present in all samples was 5-nitroacenaphthene. Indanone and 1,8-naphthalic anhydride were the most abundant OPAHs, accounting for 25 and 17% of the total concentrations of this organic class, respectively. Other abundant OPAHs were 1,4-naphthoquinone, 9-fluorenone, 1,2-acenaphthylenequinone and 7H-benz[de]anthracene-7-one. Individual emission factors (μg veh- 1 km- 1) were estimated and compared with those obtained in other tunnel studies.

Atmospheric behaviors of polycyclic aromatic hydrocarbons at a Japanese remote background site, Noto peninsula, from 2004 to 2014

NASA Astrophysics Data System (ADS)

Tang, Ning; Hakamata, Mariko; Sato, Kousuke; Okada, Yumi; Yang, Xiaoyang; Tatematsu, Michiya; Toriba, Akira; Kameda, Takayuki; Hayakawa, Kazuichi

2015-11-01

Total suspended particulates were collected at a Japanese remote background site (Noto Air Monitoring Station; NAMS) on the Noto Peninsula from September 2004 to June 2014. Nine polycyclic aromatic hydrocarbons (PAHs) in the particulates (fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, benzo[ghi]perylene and indeno[1,2,3-cd]pyrene) were determined by HPLC with fluorescence detection. The mean total concentrations of the nine PAHs in the cold season (November to May for the years 2004-2014) was 670 pg m-3 (range 37-4100 pg m-3). The mean total concentration in the warm season (June to October for the same period) was 170 pg m-3 (range 31-960 pg m-3). The atmospheric PAH level at NAMS decreased in recent years, although no significant change was found in the warm season. An analysis of meteorological conditions showed that the atmospheric PAHs at NAMS were long range transported from Northeast China in the cold seasons and were contributed to by Japanese domestic sources in the warm seasons. Lower concentration ratios of reactive PAHs to their isomers at NAMS also supported these results. Activities associated with the Beijing Olympic and Paralympic Games in 2008 and reconstruction after the 2007 Noto Hanto earthquake may have contributed to the yearly variations of atmospheric PAH levels at NAMS during the period 2007-2009. Source control measures implemented by the Chinese and Japanese governments appear to have been effective in decreasing the atmospheric PAH levels at NAMS in recent years.

Characteristics of particulate-bound polycyclic aromatic hydrocarbons emitted from industrial grade biomass boilers.

PubMed

Yang, Xiaoyang; Geng, Chunmei; Sun, Xuesong; Yang, Wen; Wang, Xinhua; Chen, Jianhua

2016-02-01

Polycyclic aromatic hydrocarbons (PAHs) are carcinogenic or mutagenic and are important toxic pollutants in the flue gas of boilers. Two industrial grade biomass boilers were selected to investigate the characteristics of particulate-bound PAHs: one biomass boiler retro-fitted from an oil boiler (BB1) and one specially designed (BB2) biomass boiler. One coal-fired boiler was also selected for comparison. By using a dilution tunnel system, particulate samples from boilers were collected and 10 PAH species were analyzed by gas chromatography-mass spectrometry (GC-MS). The total emission factors (EFs) of PAHs ranged from 0.0064 to 0.0380 mg/kg, with an average of 0.0225 mg/kg, for the biomass boiler emission samples. The total PAH EFs for the tested coal-fired boiler were 1.8 times lower than the average value of the biomass boilers. The PAH diagnostic ratios for wood pellets and straw pellets were similar. The ratio of indeno(1,2,3-cd)pyrene/[indeno(1,2,3-cd)pyrene+benzo(g,h,i)perylene] for the two biomass boilers was lower than those of the reference data for other burning devices, which can probably be used as an indicator to distinguish the emission of biomass boilers from that of industrial coal-fired boilers and residential stoves. The toxic potential of the emission from wood pellet burning was higher than that from straw pellet burning, however both of them were much lower than residential stove exhausts. Copyright © 2015. Published by Elsevier B.V.

Selective excitation of exciton transitions in PTCDA crystals and films

NASA Astrophysics Data System (ADS)

Gangilenka, V. R.; Titova, L. V.; Smith, L. M.; Wagner, H. P.; Desilva, L. A. A.; Gisslén, L.; Scholz, R.

2010-04-01

Photoluminescence excitation studies on 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) single crystals and polycrystalline PTCDA films are compared to the calculated excitonic dispersion deduced from an exciton model including the coupling between Frenkel and charge transfer (CT) excitons along the stacking direction. For excitation energies below the 0-0 Frenkel exciton absorption band at 5 K these measurements enable the selective excitation of several CT states. The CT2 state involving stacked PTCDA molecules reveals two excitation resonances originating from different vibronic sublevels. Moreover, the fundamental transition of the CT1 exciton state delocalized over both basis molecules in the crystal unit cell has been identified from the corresponding excitation resonance. From the excitation energy dependence the fundamental transition energies of the CT2 and CT1 excitons have been deduced to occur at 1.95 and 1.98 eV, respectively. When the excitation energy exceeds ˜2.08eV , we observe a strong emission channel which is related to the indirect minimum of the lowest dispersion branch dominated by Frenkel excitons. Photoluminescence excitation spectroscopy measurements on polycrystalline PTCDA films reveal a strong CT2 signal intensity which is attributed to an increased density of defect-related CT2 states that are preferentially formed by slightly deformed or compressed stacked PTCDA molecules in the vicinity of defects or at grain boundaries. Temperature-dependent PL measurements in polycrystalline PTCDA films between 10 and 300 K at an excitation of 1.88 eV further allow a detailed investigation of the CT2 transition and its vibronic subband.

Semi-volatile organic compounds in the particulate phase in dwellings: A nationwide survey in France

NASA Astrophysics Data System (ADS)

Mandin, Corinne; Mercier, Fabien; Ramalho, Olivier; Lucas, Jean-Paul; Gilles, Erwann; Blanchard, Olivier; Bonvallot, Nathalie; Glorennec, Philippe; Le Bot, Barbara

2016-07-01

Sixty-six semi-volatile organic compounds (SVOCs)-phthalates, polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), one pyrethroid, organochlorine and organophosphorous pesticides, alkylphenols, synthetic musks, tri-n-butylphosphate and triclosan-were measured on PM10 filters collected over 7 days during a nationwide survey of 285 French dwellings, representative of nearly 25 million housing units. Thirty-five compounds were detected in more than half of the dwellings. PAHs, phthalates and triclosan were the major particle-bound SVOCs, with a median concentration greater than 1 ng m-3 for butylbenzyl phthalate (BBP) (median: 1.6 ng m-3), di(2-ethylhexyl) phthalate (DEHP) (46 ng m-3) and di-iso-nonyl phthalate (DiNP) (7.9 ng m-3), and greater than 0.1 ng m-3 for triclosan (114 pg m-3), benzo(a)pyrene (138 pg m-3), benzo(b)fluoranthene (306 pg m-3), benzo(g,h,i)perylene (229 pg m-3), and indeno(1,2,3-c,d)pyrene (178 pg m-3). For most of the SVOCs, higher concentrations were found in the dwellings of smokers and during the heating season. The concentrations of banned SVOCs-namely, PCBs and organochlorine pesticides-were correlated. Permethrin, 4-tert-butylphenol and bisphenol-A showed no correlation with the other SVOCs and seemed to have their own specific sources. Most SVOCs were positively associated with PM10 concentration, suggesting that any factor that raises the mass of indoor airborne particles also increases the exposure to SVOCs through inhalation.

Supramolecular Packing Controls H 2 Photocatalysis in Chromophore Amphiphile Hydrogels

DOE PAGES

Weingarten, Adam S.; Kazantsev, Roman V.; Palmer, Liam C.; ...

2015-11-21

Light harvesting supramolecular assemblies are potentially useful structures as components of solar-to-fuel conversion materials. The development of these functional constructs requires an understanding of optimal packing modes for chromophores. Here, we investigated assembly in water and the photocatalytic function of perylene monoimide chromophore amphiphiles with different alkyl linker lengths separating their hydrophobic core and the hydrophilic carboxylate headgroup. We found that these chromophore amphiphiles (CAs) self-assemble into charged nanostructures of increasing aspect ratio as the linker length is increased. The addition of salt to screen the charged nanostructures induced the formation of hydrogels and led to internal crystallization within somemore » of the nanostructures. For linker lengths up to seven methylenes, the CAs were found to pack into 2D crystalline unit cells within ribbon-shaped nanostructures, whereas the nine methylene CAs assembled into long nanofibers without crystalline molecular packing. At the same time, the different molecular packing arrangements after charge screening led to different absorbance spectra, despite the identical electronic properties of all PMI amphiphiles. While the crystalline CAs formed electronically coupled H-aggregates, only CAs with intermediate linker lengths showed evidence of high intermolecular orbital overlap. Photocatalytic hydrogen production using a nickel-based catalyst was observed in all hydrogels, with the highest turnovers observed for CA gels having intermediate linker lengths. Lastly, we conclude that the improved photocatalytic performance of the hydrogels formed by supramolecular assemblies of the intermediate linker CA molecules likely arises from improved exciton splitting efficiencies due to their higher orbital overlap.« less

HIGH-RESOLUTION IR ABSORPTION SPECTROSCOPY OF POLYCYCLIC AROMATIC HYDROCARBONS IN THE 3 μ m REGION: ROLE OF PERIPHERY

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maltseva, Elena; Petrignani, Annemieke; Buma, Wybren Jan

2016-11-01

In this work we report on high-resolution IR absorption studies that provide a detailed view on how the peripheral structure of irregular polycyclic aromatic hydrocarbons (PAHs) affects the shape and position of their 3 μ m absorption band. For this purpose, we present mass-selected, high-resolution absorption spectra of cold and isolated phenanthrene, pyrene, benz[a]antracene, chrysene, triphenylene, and perylene molecules in the 2950–3150 cm{sup −1} range. The experimental spectra are compared with standard harmonic calculations and anharmonic calculations using a modified version of the SPECTRO program that incorporates a Fermi resonance treatment utilizing intensity redistribution. We show that the 3 μmore » m region is dominated by the effects of anharmonicity, resulting in many more bands than would have been expected in a purely harmonic approximation. Importantly, we find that anharmonic spectra as calculated by SPECTRO are in good agreement with the experimental spectra. Together with previously reported high-resolution spectra of linear acenes, the present spectra provide us with an extensive data set of spectra of PAHs with a varying number of aromatic rings, with geometries that range from open to highly condensed structures, and featuring CH groups in all possible edge configurations. We discuss the astrophysical implications of the comparison of these spectra on the interpretation of the appearance of the aromatic infrared 3 μ m band, and on features such as the two-component emission character of this band and the 3 μ m emission plateau.« less

Experimental determination of photostability and fluorescence-based detection of PAHs on the Martian surface

NASA Astrophysics Data System (ADS)

Dartnell, Lewis R.; Patel, Manish R.; Storrie-Lombardi, Michael C.; Ward, John M.; Muller, Jan-Peter

2012-05-01

Even in the absence of any biosphere on Mars, organic molecules, including polycyclic aromatic hydrocarbons (PAHs), are expected on its surface due to delivery by comets and meteorites of extraterrestrial organics synthesized by astrochemistry, or perhaps in situ synthesis in ancient prebiotic chemistry. Any organic compounds exposed to the unfiltered solar ultraviolet spectrum or oxidizing surface conditions would have been readily destroyed, but discoverable caches of Martian organics may remain shielded in the subsurface or within surface rocks. We have studied the stability of three representative polycyclic aromatic hydrocarbons (PAHs) in a Mars chamber, emulating the ultraviolet spectrum of unfiltered sunlight under temperature and pressure conditions of the Martian surface. Fluorescence spectroscopy is used as a sensitive indicator of remaining PAH concentration for laboratory quantification of molecular degradation rates once exposed on the Martian surface. Fluorescence-based instrumentation has also been proposed as an effective surveying method for prebiotic organics on the Martian surface. We find the representative PAHs, anthracene, pyrene, and perylene, to have persistence half-lives once exposed on the Martian surface of between 25 and 60 h of noontime summer UV irradiation, as measured by fluorescence at their peak excitation wavelength. This equates to between 4 and 9.6 sols when the diurnal cycle of UV light intensity on the Martian surface is taken into account, giving a substantial window of opportunity for detection of organic fluorescence before photodegradation. This study thus supports the use of fluorescence-based instrumentation for surveying recently exposed material (such as from cores or drill tailings) for native Martian organic molecules in rover missions.

Reliable Energy Level Alignment at Physisorbed Molecule–Metal Interfaces from Density Functional Theory

DOE PAGES

Egger, David A.; Liu, Zhen-Fei; Neaton, Jeffrey B.; ...

2015-03-05

We report a key quantity for molecule–metal interfaces is the energy level alignment of molecular electronic states with the metallic Fermi level. We develop and apply an efficient theoretical method, based on density functional theory (DFT) that can yield quantitatively accurate energy level alignment information for physisorbed metal–molecule interfaces. The method builds on the “DFT+Σ” approach, grounded in many-body perturbation theory, which introduces an approximate electron self-energy that corrects the level alignment obtained from conventional DFT for missing exchange and correlation effects associated with the gas-phase molecule and substrate polarization. Here, we extend the DFT+Σ approach in two important ways:more » first, we employ optimally tuned range-separated hybrid functionals to compute the gas-phase term, rather than rely on GW or total energy differences as in prior work; second, we use a nonclassical DFT-determined image-charge plane of the metallic surface to compute the substrate polarization term, rather than the classical DFT-derived image plane used previously. We validate this new approach by a detailed comparison with experimental and theoretical reference data for several prototypical molecule–metal interfaces, where excellent agreement with experiment is achieved: benzene on graphite (0001), and 1,4-benzenediamine, Cu-phthalocyanine, and 3,4,9,10-perylene-tetracarboxylic-dianhydride on Au(111). In particular, we show that the method correctly captures level alignment trends across chemical systems and that it retains its accuracy even for molecules for which conventional DFT suffers from severe self-interaction errors.« less

Efficient and Stable Ternary Organic Solar Cells Based on Two Planar Nonfullerene Acceptors with Tunable Crystallinity and Phase Miscibility.

PubMed

Wang, Jialin; Peng, Jiajun; Liu, Xiaoyu; Liang, Ziqi

2017-06-21

Planar perylene diimides (PDIs), when used as nonfullerene acceptors for organic photovoltaics, are constrained by their large π-aggregation in solid state. To tackle this issue, another planar nonfullerene acceptor 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone)-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']dithiophene (ITIC) with weak crystallinity and near-infrared light absorption is introduced into the PTB7-Th:PDI binary blend to fabricate efficient and stable ternary solar cells. We have finely tuned the PDI/ITIC weight ratio to investigate the influences of individual ITIC and PDI on the optical, electronic, and morphological properties of the PTB7-Th:ITIC:PDI ternary blend. Compared to the binary blend, complementary optical absorption is achieved in all ternary blends. More importantly, it is found that ITIC plays a critical role on largely suppressing the PDI aggregates in the PTB7-Th:PDI blend, while PDI aids to form an interpenetrating network morphology to facilitate charge transport in the PTB7-Th:ITIC blend. Consequently, when the PDI/ITIC ratio is 3:7 (w/w), the PTB7-Th:ITIC:PDI based inverted solar cells exhibit the highest power conversion efficiency of 8.64% due to their favorable out-of-plane π-π stacking, finest phase-separation morphology, and highest charge mobility. Remarkably, the optimal cells that are solution-processed in air show the promising efficiency of 7.09%, suggesting good ambient stability of such ternary solar cells.

J-V and C-V investigation of the effect of small molecular fullerene and non-fullerene acceptors for CH3NH3PbI3 perovskite solar cell

NASA Astrophysics Data System (ADS)

Zheng, Yanqiong; Wang, Chao; Yu, Junle; Yang, Fang; Zhang, Jing; Wei, Bin; Li, Weishi

2017-11-01

To find the ideal acceptors for perovskite solar cells (PSCs) and get insight into the dielectric property at the interface between perovskite and acceptor, series of small molecular fullerene and non-fullerene acceptors were comparatively investigated. Fullerene acceptors based PSCs show higher performance than non-fullerene acceptors based PSCs. However, the perylene tetracarboxylic diimide based PSC has achieved a η PCE of 4.70%, implying that it is a promising acceptor candidate for PSCs because of its suitable energy level, high electron mobility, and smooth surface. By employing double acceptors of (6,6)-phenyl-C61-butyric acid methyl ester (PCBM)/C60 or PCBM/3,4,9,10-perylenetetracarboxylic bisbenzimidazole, the PSC stability is greatly improved even without performance enhancement. The perovskite (Pero)/PCBM film shows smooth surface, suggesting that PCBM penetrates into the Pero layer. The hydrophobicity trend of Pero/acceptor composite films is same as the device performance by judging from the water contact angle, and Pero/PCBM as well as Pero/C60 show higher hydrophobicity than other Pero/small-molecular-acceptor composite films. Capacitance-voltage characteristics of the series of single and double acceptor based PSCs were measured. The double acceptor based PSCs show larger depletion layer width (W d) than single acceptor based PSCs. Meanwhile, the defect density (N A) in Pero layer for single acceptor based PSCs is larger than that for double acceptor based PSCs, implying better n-doping of Pero layer by using a single acceptor.

The presence and distribution of polycyclic aromatic hydrocarbons and inorganic elements in water and lakebed materials and the potential for bioconcentration in biota at established sampling sites on Lake Powell, Utah and Arizona

USGS Publications Warehouse

Schonauer, Kurt T.; Hart, Robert J.; Antweiler, Ronald C.

2014-01-01

The National Park Service is responsible for monitoring the effects of visitor use on the quality of water, lakebed material (bottom sediments), and biota, in Lake Powell, Utah and Arizona. A sampling program was begun in 2010 to assess the presence, distribution, and concentrations of organic and inorganic compounds in the water column and bottom sediment. In response to an Environmental Impact Statement regarding personal watercraft and as a continuation from previous studies by the U.S. Geological Survey and the National Park Service, Glen Canyon National Recreation Area, water samples were collected and analyzed for polycyclic aromatic hydrocarbons (PAHs) using semipermeable membrane devices and inorganic elements using a fixed-bottle sampler deployed at established monitoring sites during 2010 and 2011. Lakebed material samples were also analyzed for polycyclic aromatic hydrocarbons and inorganic elements, some of which could be harmful to aquatic biota if present at concentrations above established aquatic life criteria. Of the 44 PAH compounds analyzed, 26 individual compounds were detected above the censoring limit in the water column by semipermeable membrane devices. The highest number of compounds detected were at Lone Rock Beach, Wahweap Marina, Rainbow Bridge National Monument, and Antelope Marina which are all located in the southern part of Lake Powell where visitation and boat use is high. Because PAHs can remain near their source, the potential for bioconcentration is highest near these sites. The PAH compound found in the highest concentration was phenol (5,902 nanograms per liter), which is included in the U.S. Environmental Protection Agency’s priority pollutants list. The dissolved inorganic chemistry of water samples measured at the sampling sites in Lake Powell defined three different patterns of elements: (1) concentrations were similar between sites in the upper part of the lake near Farley Canyon downstream to Halls Crossing Marina, a distance of about 36 lake miles, (2) concentrations varied depending on the element between Halls Crossing Marina downstream to the mouth of the Escalante River, a distance of about 33 lake miles, and (3) concentrations were similar between sites from below the mouth of the Escalante River to Glen Canyon Dam, a distance of about 68 lake miles. Analysis of lakebed bottom sediment material samples detected PAH compounds at all sampling sites except at Halls Crossing Marina, Stanton Creek, and Forgotten Canyon. Twenty-four of 44 PAHs analyzed in lakebed material were detected above the reporting limit. Perylene was the most prevalent compound detected above the reporting limit in lakebed material and was detected at three sampling sites. Concentrations of perylene ranged from an estimate of 24.0 to 47.9 micrograms per kilogram (μg/kg). Fluoranthene had the highest concentration of any PAH and was detected at the Wahweap Marina with a concentration of 565 μg/kg. The highest sum of concentrations for all compounds found in lakebed material samples at one site was at the Wahweap Marina, which had concentrations five times higher than the next highest site. The three major tributaries to Lake Powell—the Colorado, Escalante, and San Juan Rivers—all showed elevated concentrations of inorganic elements in their delta sediments for most elements relative to the majority of the sediment samples taken from the lake itself. However, there were four lake sites that had concentrations for most inorganic elements that equaled or exceeded those of the tributaries. Two of these sites were at the northeast part of the lake, nearest to the Colorado River as it enters Lake Powell (Farley Canyon and Blue Notch Canyon), one was at the Escalante River below 50-Mile Canyon, and other was at Antelope Marina.

The influence of smoking in traditional conditions on content of polycyclic aromatic hydrocarbons in Petrovská klobása

NASA Astrophysics Data System (ADS)

Škaljac, S.; Petrović, Lj; Jokanović, M.; Tomović, V.; Tasić, T.; Ivić, M.; Šojić, B.; Ikonić, P.; Džinić, N.

2017-09-01

The aim of this study was to determine the content of 13 polycyclic aromatic hydrocarbons (acenaphthylene, fluorene, phenanthrene, anthracene, pyrene, benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene, dibenz[a,h]anthracene and benzo[ghi]perylene) the from Environmental Protection Agency list (US-EPA PAH) in traditional dry fermented sausage Petrovská klobása. Sausages were smoked in traditional conditions and samples for analyses were taken on day 0 of production (0), at the end of drying (T1) and at the end of the storage period (T2). The highest total content of 13 US-EPA PAHs was determined in sausages at the end of the storage period (73.5 μg/kg). Phenanthrene was the most abundant of the PAHs in all examined sausage samples (0-4.90 μg/kg T1-18.0 μg/kg and T2-26.3 μg/kg). Benzo[a]pyrene, with a maximum allowed content in smoked meat products of 2 µg/kg (EC No. 835/2011), was below the limit of detection in all examined samples. Also, PAH4 (the total content of benz[a]anthracene, chrysene, benzo[b]fluoranthene and benzo[a]pyrene) with a maximum allowed content in smoked meat products of 12 µg/kg (EC No. 835/2011), was below the limit of detection in all examined sausage samples. According to the results obtained in this study, and in regard to the European regulation on PAHs content, the dry fermented sausage Petrovská klobása, smoked in traditional conditions, was safe for consumers.

Photoinduced Electron Transfer and Hole Migration in Nanosized Helical Aromatic Oligoamide Foldamers.

PubMed

Li, Xuesong; Markandeya, Nagula; Jonusauskas, Gediminas; McClenaghan, Nathan D; Maurizot, Victor; Denisov, Sergey A; Huc, Ivan

2016-10-07

A series of photoactive triads have been synthesized and investigated in order to elucidate photoinduced electron transfer and hole migration mechanism across nanosized, rigid helical foldamers. The triads are comprised of a central helical oligoamide foldamer bridge with 9, 14, 18, 19, or 34 8-amino-2-quinolinecarboxylic acid repeat units, and of two chromophores, an N-terminal oligo(para-phenylenevinylene) electron donor and a C-terminal perylene bis-imide electron acceptor. Time-resolved fluorescence and transient absorption spectroscopic studies showed that, following photoexcitation of the electron acceptor, fast electron transfer occurs initially from the oligoquinoline bridge to the acceptor chromophore on the picosecond time scale. The oligo(para-phenylenevinylene) electron donor is oxidized after a time delay during which the hole migrates across the foldamer from the acceptor to the donor. The charge separated state that is finally generated was found to be remarkably long-lived (>80 μs). While the initial charge injection rate is largely invariant for all foldamer lengths (ca. 60 ps), the subsequent hole transfer to the donor varies from 1 × 10 9 s -1 for the longest sequence to 17 × 10 9 s -1 for the shortest. In all cases, charge transfer is very fast considering the foldamer length. Detailed analysis of the process in different media and at varying temperatures is consistent with a hopping mechanism of hole transport through the foldamer helix, with individual hops occurring on the subpicosecond time scale (k ET = 2.5 × 10 12 s -1 in CH 2 Cl 2 ). This work demonstrates the possibility of fast long-range hole transfer over 300 Å (through bonds) across a synthetic modular bridge, an achievement that had been previously observed principally with DNA structures.

Polycyclic aromatic hydrocarbons in soil of the Canadian River floodplain in Oklahoma

USGS Publications Warehouse

Sartori, F.; Wade, T.L.; Sericano, J.L.; Mohanty, B.P.; Smith, K.A.

2010-01-01

The accumulation of polycyclic aromatic hydrocarbons (PAH) in soil, plants, and water may impart negative eff ects on ecosystem and human health. We quantified the concentration and distribution of 41 PAH (n = 32), organic C, total N, and S (n = 140) and investigated PAH sources using a chronosequence of floodplain soils under a natural vegetation succession. Soil samples were collected between 0- and 260-cm depth in bare land (the control), wetland, forest, and grassland areas near a closed municipal landfill and an active asphalt plant (the contaminant sources) in the north bank of the Canadian River near Norman, OK. Principal component, cluster, and correlation analyses were used to investigate the spatial distribution of PAH, in combination with diagnostic ratios to distinguish pyrogenic vs. petrogenic PAH suites. Total PAH concentration (??PAH) had a mean of 1300 ng g-1, minimum of 16 ng g-1, and maximum of 12,000 ng g-1. At 0- to 20-cm depth, ??PAH was 3500 ?? 1600 ng g-1 (mean ?? 1 SE) near the contaminant sources. The most common compounds were nonalkylated, high molecular weight PAH of pyrogenic origin, i.e., fluoranthene (17%), pyrene (14%), phenanthrene (9%), benzo(b)fluoranthene (7%), chrysene (6%), and benzo(a)anthracene (5%). ??PAH in the control (130 ?? 23 ng g -1) was comparable to reported concentrations for the rural Great Plains. Perylene had a unique distribution pattern suggesting biological inputs. The main PAH contamination mechanisms were likely atmospheric deposition due to asphalt production at the 0- to 20-cm depth and past landfill operations at deeper depths. Copyright ?? 2010 by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America. All rights reserved.

Quantity and quality of stormwater collected from selected stormwater outfalls at industrial sites, Fort Gordon, Georgia, 2011

USGS Publications Warehouse

Nagle, Doug D.; Guimaraes, Wladmir B.

2012-01-01

An assessment of the quantity and quality of stormwater runoff associated with industrial activities at Fort Gordon was conducted from January through December 2011. The assessment was provided to satisfy the requirements from a general permit that authorizes the discharge of stormwater under the National Pollutant Discharge Elimination System from a site associated with industrial activities. The stormwater quantity refers to the runoff discharge at the point and time of the runoff sampling. The study was conducted by the U.S. Geological Survey, in cooperation with the U.S. Department of the Army Environmental and Natural Resources Management Office of the U.S. Army Signal Center and Fort Gordon. The initial scope of this study was to sample stormwater runoff from five stations at four industrial sites (two landfills and two heating and cooling sites). As a consequence of inadequate hydrologic conditions during 2011, no samples were collected at the two landfills; however, three samples were collected from the heating and cooling sites. The assessment included the collection of physical properties, such as water temperature, specific conductance, dissolved oxygen, and pH; the detection of suspended materials (total suspended solids, total fixed solids, total volatile solids), nutrients and organic compounds, and major and trace inorganic compounds (metals); and the detection of volatile and semivolatile organic compounds. Nutrients and organic compounds, major and trace inorganic compounds, and volatile and semivolatile organic compounds were detected above the laboratory reporting levels in all samples collected from the three stations. The detection of volatile and semivolatile organic compounds included anthracene, benzo[a]anthracene, benzo[a]pyrene, benzo[ghi]perylene, cis,1, 2-dichloroethene, dimethyl phthalate, fluoranthene, naphthalene, pyrene, acenaphthylene (station SWR11-3), and di-n-butyl phthalate (station SWR11-4).

EMICORON: A multi-targeting G4 ligand with a promising preclinical profile.

PubMed

Porru, Manuela; Zizza, Pasquale; Franceschin, Marco; Leonetti, Carlo; Biroccio, Annamaria

2017-05-01

During the last decade, guanine G-rich sequences folding into G-quadruplex (G4) structures have received a lot of attention and their biological role is now a matter of large debate. Rising amounts of experimental evidence have validated several G-rich motifs as molecular targets in cancer treatment. Despite that an increasing number of small molecules has been reported to possess excellent G4 stabilizing properties, none of them has progressed through the drug-development pipeline due to their poor drug-like properties. In this context, the identification of G4 ligands with more favorable pharmacological properties and with a well-defined target activity could be fruitful for anticancer therapy application. This manuscript outlines the current state of knowledge regarding EMICORON, a G4-interactive molecule structurally and biologically similar, on the one side, to coronene and, on the other side, to a bay-monosubstituted perylene. Overall this work evidences that EMICORON, a new promising G4 ligand, possesses a marked antitumoral activity both standing alone and in combination with chemotherapeutics. Moreover, EMICORON represents a good example of multimodal class of antitumoral drug, able to simultaneously affect multiple targets participating in several distinct signaling pathways, thus simplifying the treatment modalities and improving the selectivity against cancer cells. Due to the importance of G4 forming sequences in crucial biological processes participating in tumor progression, their successful targeting with small molecules could represent a very important innovation in the development of effective therapeutic strategies against cancer. This article is part of a Special Issue entitled "G-quadruplex" Guest Editor: Dr. Concetta Giancola and Dr. Daniela Montesarchio. Copyright © 2016 Elsevier B.V. All rights reserved.

Thermal analysis studies of doping effects on the conformational motions of polymer chains in solid solutions with lasing molecules

NASA Astrophysics Data System (ADS)

Kalogeras, Ioannis M.; Pallikari, Fotini; Vassilikou-Dova, Aglaia; Neagu, Eugen R.

2007-05-01

The advancement of the solid-state dye laser performance largely depends on the systematic study of the dye-matrix interactions at the nanoscopic scale. The current work deals with blends of a comparatively inert dye host, poly(methyl methacrylate) (PMMA), with nonionic/apolar (substituted perylenes) and ionic/polar (rhodamine 6G, pyrromethene 567) dyes at ≈10-4 mol L-1 loading. Differential scanning calorimetry (DSC) and thermally stimulated currents (TSC) were used to explore the relative strength of inter- and intramolecular guest-host interactions by monitoring blending-induced modifications of the high-temperature signals: the segmental relaxation, the space-charge relaxation, and the liquid-liquid transition. Both techniques revealed the antiplasticizing role of the oligomeric organics on the relaxation dynamics of polymer segments, evidenced by clear glass-transition temperature upshifts. It becomes apparent that this effect is independent of the size, polarity, and ionicity of the dopant, signifying a common mechanism underway. It is suggested that, at least for the dyes under investigation, the chromophores simply fill the voids within the matrix, imposing strong steric hindrances on the rearrangement of the long-range structure. A comparison between the present results and earlier low-temperature dielectric data reveals that the large-scale relaxation dynamics show stronger perturbations due to blending, in comparison to the localized rotational motion of the pendant groups. DSC provided estimates for the unconverted monomer percentages in the solid blends. These were also determined more accurately by nuclear magnetic resonance (NMR), which additionally confirmed that the tacticity of the chains is not affected by the presence of the dye.

Characteristics of PAHs in farmland soil and rainfall runoff in Tianjin, China.

PubMed

Shi, Rongguang; Xu, Mengmeng; Liu, Aifeng; Tian, Yong; Zhao, Zongshan

2017-10-14

Rainfall runoff can remove certain amounts of pollutants from contaminated farmland soil and result in a decline in water quality. However, the leaching behaviors of polycyclic aromatic hydrocarbons (PAHs) with rainfall have been rarely reported due to wide variations in the soil compositions, rainfall conditions, and sources of soil PAHs in complex farmland ecosystems. In this paper, the levels, spatial distributions, and composition profiles of PAHs in 30 farmland soil samples and 49 rainfall-runoff samples from the Tianjin region in 2012 were studied to investigate their leaching behaviors caused by rainfall runoff. The contents of the Σ 16 PAHs ranged from 58.53 to 3137.90 μg/kg in the soil and 146.58 to 3636.59 μg/L in the runoff. In total, most of the soil sampling sites (23 of 30) were contaminated, and biomass and petroleum combustion were proposed as the main sources of the soil PAHs. Both the spatial distributions of the soil and the runoff PAHs show a decreasing trend moving away from the downtown, which suggested that the leaching behaviors of PAHs in a larger region during rainfall may be mainly affected by the compounds themselves. In addition, 4- and 5-ring PAHs are the dominant components in farmland soil and 3- and 4-ring PAHs dominate the runoff. Comparisons of the PAH pairs and enrichment ratios showed that acenaphthylene, acenaphthene, benzo[a]anthracene, chrysene, and fluoranthene were more easily transferred into water systems from soil than benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[ghi]perylene, and indeno[123-cd]pyrene, which indicated that PAHs with low molecular weight are preferentially dissolved due to their higher solubility compared to those with high molecular weight.

3D-hierarchical MoSe2 nanoarchitecture as a highly efficient electrocatalyst for hydrogen evolution

NASA Astrophysics Data System (ADS)

Zheng, Binjie; Chen, Yuanfu; Qi, Fei; Wang, Xinqiang; Zhang, Wanli; Li, Yanrong; Li, Xuesong

2017-06-01

Clean hydrogen split from water by hydrogen evolution reaction (HER) is significant for sustainability, environmental emissions, and energy security. So far, it is still a big challenge to develop highly efficient noble metal-free electrocatalysts with comparable HER efficiency to platinum-based catalysts, which are mainly hindered by the intrinsic electrocatalytic property and particularly the reasonable nanostructure design of the electrocatalyst. Here we report a newly-designed three-dimensional hierarchical MoSe2 nanoarchitecture (3D-MoSe2) with outstanding HER performance. The 3D-MoSe2 is grown by chemical vapor deposition method with using perylene-3, 4, 9, 10-tetracarboxylic acid tetrapotassium salt as a seeding promoter. The as-grown 3D-MoSe2 nanoarchitecture is highly crystalline and constructed with curly few-layered vertical nanosheets onto the horizontal layer, which has much larger (~12 times) electrochemically active area and much smaller (only 2%) charge transfer resistance compared to conventional horizontal MoSe2 layer. With these advantages, the Tafel slope of 3D-MoSe2 can be as small as 47.3 mV/dev, which is the smallest record ever reported for pure MoSe2, even for pure two-dimensional transition metal dichalcogenides (2D-TMDs) catalysts. Furthermore, when 3D-MoSe2 is grown on the multiwall carbon nanotube film, its Tafel slope can be further reduced down to 32.5 mV/dec, which is close to the theoretical limit (29 mV/dec) of HER, and comparable to platinum-based electrocatalysts, making it promising as a highly efficient electrocatalyst for hydrogen evolution.

Three-dimensional graphene networks as a new substrate for immobilization of laccase and dopamine and its application in glucose/O2 biofuel cell.

PubMed

Zhang, Yijia; Chu, Mi; Yang, Lu; Tan, Yueming; Deng, Wenfang; Ma, Ming; Su, Xiaoli; Xie, Qingji

2014-08-13

We report here three-dimensional graphene networks (3D-GNs) as a novel substrate for the immobilization of laccase (Lac) and dopamine (DA) and its application in glucose/O2 biofuel cell. 3D-GNs were synthesized with an Ni(2+)-exchange/KOH activation combination method using a 732-type sulfonic acid ion-exchange resin as the carbon precursor. The 3D-GNs exhibited an interconnected network structure and a high specific surface area. DA was noncovalently functionalized on the surface of 3D-GNs with 3,4,9,10-perylene tetracarboxylic acid (PTCA) as a bridge and used as a novel immobilized mediating system for Lac-based bioelectrocatalytic reduction of oxygen. The 3D-GNs-PTCA-DA nanocomposite modified glassy carbon electrode (GCE) showed stable and well-defined redox current peaks for the catechol/o-quinone redox couple. Due to the mediated electron transfer by the 3D-GNs-PTCA-DA nanocomposite, the Nafion/Lac/3D-GNs-PTCA-DA/GCE exhibited high catalytic activity for oxygen reduction. The 3D-GNs are proven to be a better substrate for Lac and its mediator immobilization than 2D graphene nanosheets (2D-GNs) due to the interconnected network structure and high specific surface area of 3D-GNs. A glucose/O2 fuel cell using Nafion/Lac/3D-GNs-PTCA-DA/GCE as the cathode and Nafion/glucose oxidase/ferrocence/3D-GNs/GCE as the anode can output a maximum power density of 112 μW cm(-2) and a short-circuit current density of 0.96 mA cm(-2). This work may be helpful for exploiting the popular 3D-GNs as an efficient electrode material for many other biotechnology applications.

Change of PAHs with evolution of paddy soils from prehistoric to present over the last six millennia in the Yangtze River Delta region, China.

PubMed

Zhang, Jin; Cornelia, Mueller-Niggemann; Wang, Minyan; Cao, Zhihong; Luo, Xiping; Wong, Minghung; Chen, Wei

2013-04-01

To evaluate the influence of hydroponics management on soil organic components with evolution of paddy soil over the last six millennia, PAHs, as a biomarker, as well as total organic carbon content were used to explore changes of paddy soil organic carbon in two entirely buried ancient paddy soil profiles. The results showed that hydroponics management can cause organic carbon deposition in rice paddy. The changing of total PAH concentrations was not always in accordance with the changing of total organic carbon contents in layers of the buried ancient paddy soils. The PAHs in 6280 BP prehistoric paddy soil layer was 3-ring>5-ring>4-ring>6-ring, while in layers of the present paddy soil and the prehistoric upland were 3-ring>4-ring>5-ring>6-ring. The contribution of phenanthrene to total PAHs in two profiles and the increasing ratio of phenanthrene to alkylated PAHs from parent material/6280 BP prehistoric upland to 6280 BP paddy suggested substantial increase of the anthropogenic influence of hydroponics management on rice paddy soil. And in view of the (14)C age and bioremains in the two profiles, it was only possible for PAHs to be derived from hydroponics management with evolution of the paddy soils form the Neolithic age. Cadalene could be used as an indicator for biological sources of PAHs released by rice plant residues, and benzo[g,h,i]fluoranthene and benzo[g,h,i]perylene for pyrogenic sources released by field vegetation fires. Crown Copyright © 2013. Published by Elsevier B.V. All rights reserved.

π-Extended Star-Shaped Polycyclic Aromatic Hydrocarbons based on Fused Truxenes: Synthesis, Self-Assembly, and Facilely Tunable Emission Properties.

PubMed

Cheng, Cheng; Jiang, Yi; Liu, Cheng-Fang; Zhang, Jian-Dong; Lai, Wen-Yong; Huang, Wei

2016-12-19

A new set of star-shaped polycyclic aromatic hydrocarbons (PAHs) based on naphthalene-fused truxenes, TrNaCn (n=1-4), were synthesized and characterized. The synthesis involved a microwave-assisted six-fold Suzuki coupling reaction, followed by oxidative cyclodehydrogenation. Multiple dehydrocyclization products could be effectively isolated in a single reaction, thus suggesting that the oxidative cyclodehydrogenation reaction involved a stepwise ring-closing process. The thermal, optical, and electrochemical properties and the self-assembly behavior of the resulting oxidized samples were investigated to understand the impact of the ring-fusing process on the properties of the star-shaped PAHs. Distinct bathochromic shift of the absorption maxima (λ max ) revealed that the molecular conjugation extended with the stepwise ring-closing reactions. The optical band-gap energy of these PAHs varied significantly on increasing the number of fused rings, thereby resulting in readily tunable emissive properties of the resultant star-shaped PAHs. Interestingly, the generation of rigid "arms" by using perylene analogues caused TrNaC2 and TrNaC3 to show significantly enhanced photoluminescence quantum yields (PLQYs) in solution (η=0.65 and 0.66, respectively) in comparison with those of TrNa and TrNaC1 (η=0.08 and 0.16, respectively). Owing to strong intermolecular interactions, the TrNa precursor was able to self-assemble into rod-like microcrystals, which could be facilely identified by the naked eye, whilst TrNaC1 self-assembled into nanosheets once the naphthalene rings had fused. This study offers a unique platform to gain further insight into-and a better understanding of-the photophysical and self-assembly properties of π-extended star-shaped PAHs. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A comparative study to evaluate natural attenuation, mycoaugmentation, phytoremediation, and microbial-assisted phytoremediation strategies for the bioremediation of an aged PAH-polluted soil.

PubMed

García-Sánchez, Mercedes; Košnář, Zdeněk; Mercl, Filip; Aranda, Elisabet; Tlustoš, Pavel

2018-01-01

Biological treatments are considered an environmentally option to clean-up polluted soil with polycyclic aromatic hydrocarbons (PAHs). A pot experiment was conducted to comparatively evaluate four different strategies, including natural attenuation (NA), mycoaugmentation (M) by using Crucibulum leave, phytoremediation (P) using maize plants, and microbial-assisted phytoremediation (MAP) for the bioremediation of an aged PAH-polluted soil at 180 days. The P treatment had higher affinity degrading 2-3 and 4 ring compounds than NA and M treatments, respectively. However, M and P treatments were more efficient in regards to naphthalene, indeno[l,2,3-c,d]pyrene and benzo[g,h,i]perylene degradation respect to NA. However, 4, 5-6 rings undergo a strong decline during the microbe-assisted phytoremediation, being the treatment which determined the highest rates of PAHs degradation. Sixteen PAH compounds, except fluorene and dibenzo[a,h]anthracene, were found in maize roots, whereas the naphthalene, phenanthrene, anthracene, fluoranthene, and pyrene were accumulated in the shoots, in both P and MAP treatments. However, higher PAH content in maize biomass was achieved during the MAP treatment respect to P treatment. The bioconversion and translocation factors were less than 1, indicating that phystabilization/phytodegradation processes occurred rather than phytoextraction. The microbial biomass, activity and ergosterol content were significantly boosted in the MAP treatment respect to the other treatments at 180 days. Ours results demonstrated that maize-C. laeve association was the most profitable technique for the treatment of an aged PAH-polluted soil when compared to other bioremediation approaches. Copyright © 2017 Elsevier Inc. All rights reserved.

Site specific risk assessment of an energy-from-waste/thermal treatment facility in Durham Region, Ontario, Canada. Part B: Ecological risk assessment.

PubMed

Ollson, Christopher A; Whitfield Aslund, Melissa L; Knopper, Loren D; Dan, Tereza

2014-01-01

The regions of Durham and York in Ontario, Canada have partnered to construct an energy-from-waste (EFW) thermal treatment facility as part of a long term strategy for the management of their municipal solid waste. In this paper we present the results of a comprehensive ecological risk assessment (ERA) for this planned facility, based on baseline sampling and site specific modeling to predict facility-related emissions, which was subsequently accepted by regulatory authorities. Emissions were estimated for both the approved initial operating design capacity of the facility (140,000 tonnes per year) and the maximum design capacity (400,000 tonnes per year). In general, calculated ecological hazard quotients (EHQs) and screening ratios (SRs) for receptors did not exceed the benchmark value (1.0). The only exceedances noted were generally due to existing baseline media concentrations, which did not differ from those expected for similar unimpacted sites in Ontario. This suggests that these exceedances reflect conservative assumptions applied in the risk assessment rather than actual potential risk. However, under predicted upset conditions at 400,000 tonnes per year (i.e., facility start-up, shutdown, and loss of air pollution control), a potential unacceptable risk was estimated for freshwater receptors with respect to benzo(g,h,i)perylene (SR=1.1), which could not be attributed to baseline conditions. Although this slight exceedance reflects a conservative worst-case scenario (upset conditions coinciding with worst-case meteorological conditions), further investigation of potential ecological risk should be performed if this facility is expanded to the maximum operating capacity in the future. © 2013.

Pressurized liquid extraction of diesel and air particulate standard reference materials: effect of extraction temperature and pressure.

PubMed

Schantz, Michele M; McGaw, Elizabeth; Wise, Stephen A

2012-10-02

Four particulate matter Standard Reference Materials (SRMs) available from the National Institute of Standards and Technology (NIST) were used to evaluate the effect of solvent, number of static cycles and static times, pressure, and temperature when using pressurized liquid extraction (PLE) for the extraction of polycyclic aromatic hydrocarbons (PAHs) and nitrated-PAHs. The four materials used in the study were SRM 1648a Urban Particulate Matter, SRM 1649b Urban Dust, SRM 1650b Diesel Particulate Matter, and SRM 2975 Diesel Particulate Matter (Industrial Forklift). The results from the study indicate that the choice of solvent, dichloromethane compared to toluene and toluene/methanol mixtures, had little effect on the extraction efficiency. With three to five extraction cycles, increasing the extraction time for each cycle from 5 to 30 min had no significant effect on the extraction efficiency. The differences in extraction efficiency were not significant (with over 95% of the differences being <10%) when the pressure was increased from 13.8 to 20.7 MPa. The largest increase in extraction efficiency occurred for selected PAHs when the temperature of extraction was increased from 100 to 200 °C. At 200 °C naphthalene, biphenyl, fluorene, dibenzothiophene, and anthracene show substantially higher mass fractions (>30%) than when extracted at 100 °C in all the SRMs studied. For SRM 2975, large increases (>100%) are also observed for some other PAHs including benz[a]anthracene, benzo[k]fluoranthene, benzo[e]pyrene, benzo[a]pyrene, benzo[ghi]perylene, and benzo[b]chrysene when extracted at the higher temperatures; however, similar trends were not observed for the other diesel particulate sample, SRM 1650b. The results are discussed in relation to the use of the SRMs for evaluating analytical methods.

Concentration-Driven Assembly and Sol–Gel Transition of π-Conjugated Oligopeptides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Yuecheng; Li, Bo; Li, Songsong

Advances in supramolecular assembly have enabled the design and synthesis of functional materials with well-defined structures across multiple length scales. Biopolymer-synthetic hybrid materials can assemble into supramolecular structures with a broad range of structural and functional diversity through precisely controlled noncovalent interactions between subunits. Despite recent progress, there is a need to understand the mechanisms underlying the assembly of biohybrid/synthetic molecular building blocks, which ultimately control the emergent properties of hierarchical assemblies. Here in this work, we study the concentration-driven self-assembly and gelation of π-conjugated synthetic oligopeptides containing different π-conjugated cores (quaterthiophene and perylene diimide) using a combination of particlemore » tracking microrheology, confocal fluorescence microscopy, optical spectroscopy, and electron microscopy. Our results show that π-conjugated oligopeptides self-assemble into β-sheet-rich fiber-like structures at neutral pH, even in the absence of electrostatic screening of charged residues. A critical fiber formation concentration c fiber and a critical gel concentration c gel are determined for fiber-forming π-conjugated oligopeptides, and the linear viscoelastic moduli (storage modulus G' and loss modulus G") are determined across a wide range of peptide concentrations. These results suggest that the underlying chemical structure of the synthetic π-conjugated cores greatly influences the self-assembly process, such that oligopeptides appended to π-conjugated cores with greater torsional flexibility tend to form more robust fibers upon increasing peptide concentration compared to oligopeptides with sterically constrained cores. Overall, our work focuses on the molecular assembly of π-conjugated oligopeptides driven by concentration, which is controlled by a combination of enthalpic and entropic interactions between oligopeptide subunits.« less

Polycyclic aromatic hydrocarbons (PAHs) concentration levels, pattern, source identification and soil toxicity assessment in urban traffic soil of Dhanbad, India.

PubMed

Suman, Swapnil; Sinha, Alok; Tarafdar, Abhrajyoti

2016-03-01

Present study was carried out to assess and understand potential health risk and to examine the impact of vehicular traffic on the contamination status of urban traffic soils in Dhanbad City with respect to polycyclic aromatic hydrocarbons (PAHs). Eight urban traffic sites and two control/rural site surface soils were analyzed and the contents of 13 priority PAHs was determined. Total PAH concentration at traffic sites ranged from 1.019 μg g(-1) to 10.856 μg g(-1) with an average value of 3.488 μg g(-1). At control/rural site, average concentration of total PAHs was found to be 0.640 μg g(-1). PAH pattern was dominated by four- and five-ring PAHs (contributing >50% to the total PAHs) at all the eight traffic sites. On the other hand, rural soil showed a predominance of low molecular weight three-ring PAHs (contributing >30% to the total PAHs). Indeno[123-cd]pyrene/benz[ghi]perylene (IP/BgP) ratio indicated that PAH load at the traffic sites is predominated by the gasoline-driven vehicles. The ratio of Ant/(Ant+Phe) varied from 0.03 to 0.44, averaging 0.10; Fla/(Fla+Pyr) from 0.39 to 0.954, averaging 0.52; BaA/(BaA+Chry) from 0.156 to 0.60, averaging 0.44; and IP/(IP+BgP) from 0.176 to 0.811, averaging 0.286. The results indicated that vehicular emission was the major source for PAHs contamination with moderate effect of coal combustion and biomass combustion. Carcinogenic potency of PAH load in traffic soil was nearly 6.15 times higher as compared to the control/rural soil. Copyright © 2015 Elsevier B.V. All rights reserved.

Field measurements of the atmospheric dry deposition fluxes and velocities of polycyclic aromatic hydrocarbons to the global oceans.

PubMed

González-Gaya, Belén; Zúñiga-Rival, Javier; Ojeda, María-José; Jiménez, Begoña; Dachs, Jordi

2014-05-20

The atmospheric dry deposition fluxes of 16 polycyclic aromatic hydrocarbons (PAHs) have been measured, for the first time, in the tropical and subtropical Atlantic, Pacific, and Indian Oceans. Depositional fluxes for fine (0.7-2.7 μm) and coarse (>2.7 μm) aerosol fractions were simultaneously determined with the suspended aerosol phase concentrations, allowing the determination of PAH deposition velocities (vD). PAH dry deposition fluxes (FDD) bound to coarse aerosols were higher than those of fine aerosols for 83% of the measurements. Average FDD for total (fine + coarse) Σ16PAHs (sum of 16 individual PAHs) ranged from 8.33 ng m(-2)d(-1) to 52.38 ng m(-2)d(-1). Mean FDD for coarse aerosol's individual PAHs ranged between 0.13 ng m(-2)d(-1) (Perylene) and 1.96 ng m(-2)d(-1) (Methyl Pyrene), and for the fine aerosol fraction these ranged between 0.06 ng m(-2)d(-1) (Dimethyl Pyrene) and 1.25 ng m(-2)d(-1) (Methyl Chrysene). The estimated deposition velocities went from the highest mean vD for Methyl Chrysene (0.17-13.30 cm s(-1)), followed by Dibenzo(ah)Anthracene (0.29-1.38 cm s(-1)), and other high MW PAHs to minimum values of vD for Dimethyl Pyrene (<0.04 cm s(-1)) and Pyrene (<0.06 cm s(-1)). Dry depositional processes depend on the concentration of PAHs in the suspended aerosol, but also on physicochemical properties and environmental variables (vapor pressure, wind speed, and on the affinity of aerosols for depositing to the sea surface). Empirical parametrizations are proposed to predict the dry depositional velocities of semivolatile organic compounds to the global oceans.

Concentration-Driven Assembly and Sol–Gel Transition of π-Conjugated Oligopeptides

DOE PAGES

Zhou, Yuecheng; Li, Bo; Li, Songsong; ...

2017-08-17

Advances in supramolecular assembly have enabled the design and synthesis of functional materials with well-defined structures across multiple length scales. Biopolymer-synthetic hybrid materials can assemble into supramolecular structures with a broad range of structural and functional diversity through precisely controlled noncovalent interactions between subunits. Despite recent progress, there is a need to understand the mechanisms underlying the assembly of biohybrid/synthetic molecular building blocks, which ultimately control the emergent properties of hierarchical assemblies. Here in this work, we study the concentration-driven self-assembly and gelation of π-conjugated synthetic oligopeptides containing different π-conjugated cores (quaterthiophene and perylene diimide) using a combination of particlemore » tracking microrheology, confocal fluorescence microscopy, optical spectroscopy, and electron microscopy. Our results show that π-conjugated oligopeptides self-assemble into β-sheet-rich fiber-like structures at neutral pH, even in the absence of electrostatic screening of charged residues. A critical fiber formation concentration c fiber and a critical gel concentration c gel are determined for fiber-forming π-conjugated oligopeptides, and the linear viscoelastic moduli (storage modulus G' and loss modulus G") are determined across a wide range of peptide concentrations. These results suggest that the underlying chemical structure of the synthetic π-conjugated cores greatly influences the self-assembly process, such that oligopeptides appended to π-conjugated cores with greater torsional flexibility tend to form more robust fibers upon increasing peptide concentration compared to oligopeptides with sterically constrained cores. Overall, our work focuses on the molecular assembly of π-conjugated oligopeptides driven by concentration, which is controlled by a combination of enthalpic and entropic interactions between oligopeptide subunits.« less

[Polycyclic aromatic hydrocarbons and soluble organic fraction in fine particles from solid fraction of biodiesel exhaust fumes].

PubMed

Szewczyńska, Małgorzata; Pośniak, Małgorzata

2012-01-01

This paper presents the results of investigations into the distribution of fine particles in the biodiesel exhaust fumes (bio-DEP), as well as into the content of polycyclic aromatic hydrocarbons (PAHs) and soluble organic fraction (SOF) in the study fractions. Samples of biodiesel B20 and B40 exhaust combustion fumes were generated at the model station composed of a diesel engine from Diesel TDI 2007 Volkswagen. Sioutas personal cascade impactor (SPCI) with Teflon filters and low-pressure impactor ELIPI (Dekati Low Pressure Impactor) were used for sampling diesel exhaust fine particles. The analysis of PAHs adsorbed on particulate fractions was performed by high performance liquid chromatography with fluorescence detection (HPLC/FL). For the determination of dry residue soluble organic fraction of biodiesel exhaust particles the gravimetric method was used. The combustion exhaust fumes of 100% ON contained mainly naphthalene, acenaphthalene, fluorene, phenanthrene, fluoranthene, pyrene, benzo(a)anthracene and chrysene, whilst the exhaust of B40-single PAHs of 4 and 5 rings, such as chrysene, benzo(k)fluoranthene, dibenzo (ah)anthracene and benzo(ghi)perylene. The total content of PAHs in diesel exhaust particles averaged 910 ng/m3 for 100% ON and 340 ng/m3 for B40. The concentrations of benzo(a)antarcene were at the levels of 310 ng/m3 (100% ON) and 90 ng/m3 (B40). The investigations indicated that a fraction < 025 microm represents the main component of diesel exhaust particles, regardless of the used fuel. Bioester B 100 commonly added to diesel fuel (ON) causes a reduction of the total particulates emission and thus reduces the amount of toxic substances adsorbed on their surface.

Polycyclic aromatic hydrocarbons in mountain soils of the subtropical Atlantic.

PubMed

Ribes, A; Grimalt, J O; Torres García, C J; Cuevas, E

2003-01-01

Surface soil samples from various altitudes on Tenerife Island, ranging from sea level up to 3400 m above mean sea level, were analyzed to study the distribution of 26 polycyclic aromatic hydrocarbons (PAHs) in a remote subtropical area. The stable atmospheric conditions in this island define three vertically stratified layers: marine boundary, trade-wind inversion, and free troposphere. Total PAH concentrations, 1.9 to 6000 microg/kg dry wt., were high when compared with those in tropical areas and in a similar range to those in temperate areas. In the marine boundary layer, fluoranthene (Fla), pyrene (Pyr), benz [a]anthracene (BaA), and chrysene (C + T) were largely dominant. The predominance of Fla over Pyr may reflect photo-oxidative processes during atmospheric transport, although coal combustion inputs cannot be excluded. The PAHs found in higher concentration in the soils from the inversion layer were benzo[b + j]fluoranthene (BbjF) + benzo[k]fluoranthene (BkF) > benzo[e]pyrene (BeP) approximately indeno[1,2, 3-cd]pyrene (Ind) > benzo[a]pyrene (BaP) approximately benzo[ghi]perylene (Bghi) > coronene (Cor) approximately dibenz[a,h]anthracene (Dib), reflecting that high temperatures and insolation prevent the accumulation of PAHs more volatile than BbjF in significant amounts. These climatic conditions involve a process of standardization that prevents the identification of specific PAH sources such as traffic, forest fires, or industrial inputs. Only soils with high total organic carbon (TOC) (e.g., 10-30%) preserve the more volatile compounds such as phenanthrene (Phe), methylphenanthrenes (MPhe), dimethylphenanthrenes (DMPhe), and retene (Ret). However, no relation between PAHs and soil TOC and black carbon (BC) was found. The specific PAH distributions of the free tropospheric region suggest a direct input from pyrolytic processes related to the volcanic emission of gases in Teide.

A nanoscale study of charge extraction in organic solar cells: the impact of interfacial molecular configurations.

PubMed

Tang, Fu-Ching; Wu, Fu-Chiao; Yen, Chia-Te; Chang, Jay; Chou, Wei-Yang; Gilbert Chang, Shih-Hui; Cheng, Horng-Long

2015-01-07

In the optimization of organic solar cells (OSCs), a key problem lies in the maximization of charge carriers from the active layer to the electrodes. Hence, this study focused on the interfacial molecular configurations in efficient OSC charge extraction by theoretical investigations and experiments, including small molecule-based bilayer-heterojunction (sm-BLHJ) and polymer-based bulk-heterojunction (p-BHJ) OSCs. We first examined a well-defined sm-BLHJ model system of OSC composed of p-type pentacene, an n-type perylene derivative, and a nanogroove-structured poly(3,4-ethylenedioxythiophene) (NS-PEDOT) hole extraction layer. The OSC with NS-PEDOT shows a 230% increment in the short circuit current density compared with that of the conventional planar PEDOT layer. Our theoretical calculations indicated that small variations in the microscopic intermolecular interaction among these interfacial configurations could induce significant differences in charge extraction efficiency. Experimentally, different interfacial configurations were generated between the photo-active layer and the nanostructured charge extraction layer with periodic nanogroove structures. In addition to pentacene, poly(3-hexylthiophene), the most commonly used electron-donor material system in p-BHJ OSCs was also explored in terms of its possible use as a photo-active layer. Local conductive atomic force microscopy was used to measure the nanoscale charge extraction efficiency at different locations within the nanogroove, thus highlighting the importance of interfacial molecular configurations in efficient charge extraction. This study enriches understanding regarding the optimization of the photovoltaic properties of several types of OSCs by conducting appropriate interfacial engineering based on organic/polymer molecular orientations. The ultimate power conversion efficiency beyond at least 15% is highly expected when the best state-of-the-art p-BHJ OSCs are combined with present arguments.

Personal inhalation exposure to polycyclic aromatic hydrocarbons and their nitro-derivatives in rural residents in northern Thailand.

PubMed

Orakij, Walaiporn; Chetiyanukornkul, Thaneeya; Chuesaard, Thanyarat; Kaganoi, Yuichi; Uozaki, Waka; Homma, Chiharu; Boongla, Yaowatat; Tang, Ning; Hayakawa, Kazuichi; Toriba, Akira

2017-09-18

A personal inhalation exposure and cancer risk assessment of rural residents in Lampang, Thailand, was conducted for the first time. This highlighted important factors that may be associated with the highest areal incidence of lung cancer. Personal exposure of rural residents to polycyclic aromatic hydrocarbons (PAHs) and their nitro-derivatives (NPAHs) through inhalation of fine particulate matter (PM 2.5 ) was investigated in addition to stationary air sampling in an urban area. The personal exposure of the subjects to PM 2.5 ranged from 44.4 to 316 μg/m 3 , and the concentrations of PAHs (4.2-224 ng/m 3 ) and NPAHs (120-1449 pg/m 3 ) were higher than those at the urban site, indicating that personal exposure was affected by microenvironments through individual activities. The smoking behaviors of the rural residents barely affected their exposure to PAHs and NPAHs compared to other sources. The most important factor concerning the exposure of rural populations to PAHs was cooking activity, especially the use of charcoal open fires. The emission sources for rural residents and urban air were evaluated using diagnostic ratios, 1-nitropyrene/pyrene, and benzo[a]pyrene/benzo[ghi]perylene. Their analyses showed a significant contribution to emission from residents' personal activities in addition to the atmospheric environment. Furthermore, the personal inhalation cancer risks for all rural subjects exceeded the USEPA guideline value, suggesting that the residents have a potentially increased cancer risk. The use of open fires showed the highest cancer risk. A reduction in exposure to air pollutants for the residents could potentially be achieved by using clean fuel such as liquid petroleum gas or electricity for daily cooking.

Coexisting sea-based and land-based sources of contamination by PAHs in the continental shelf sediments of Coatzacoalcos River discharge area (Gulf of Mexico).

PubMed

Ruiz-Fernández, Ana Carolina; Portela, Julián Mauricio Betancourt; Sericano, José Luis; Sanchez-Cabeza, Joan-Albert; Espinosa, Luisa Fernanda; Cardoso-Mohedano, José Gilberto; Pérez-Bernal, Libia Hascibe; Tinoco, Jesús Antonio Garay

2016-02-01

The oldest refinery and the major petrochemical complexes of Mexico are located in the lower reach of the Coatzacoalcos River, considered the most polluted coastal area of Mexico. A (210)Pb-dated sediment core, from the continental shelf of the Coatzacoalcos River, was studied to assess the contamination impact by the oil industry in the southern Gulf of Mexico. The sedimentary record showed the prevalence of petrogenic PAHs between 1950s and 1970s, a period during which waste discharges from the oil industry were not regulated. Later on, sediments exhibited higher contents of pyrogenic PAHs, attributed to the incineration of petrochemical industry wastes and recurrent wildfires in open dumpsites at the nearby swamps. The total concentration of the 16 EPA-priority PAHs indicated low levels of contamination (<100 ng g(-1)), except a peak value (>1000 ng g(-1)) during the late 1970s, most likely due to the major oil spill produced by the blowout of the Ixtoc-I offshore oil rig in deep waters of the southwestern Gulf of Mexico. Most of the PAH congeners did not show defined temporal trends but, according to a Factor Analysis, apparently have a common origin, probably waste released from the nearby oil industry. The only exceptions were the pyrogenic benzo(b)fluoranthene and benzo(a)pyrene, and the biogenic perylene, that showed increasing concentration trends with time, which we attributed to erosional input of contaminated soil from the catchment area. Our study confirmed chronic oil contamination in the Coatzacoalcos River coastal area from land based sources for more than 60 years (since 1950s). Copyright © 2015 Elsevier Ltd. All rights reserved.

Chemistry and palynology of carbon seams and associated rocks from the Witwatersrand goldfields, South Africa

USGS Publications Warehouse

Ebert, L.B.; Robbins, E.I.; Rose, K.D.; Kastrup, R.V.; Scanlon, J.C.; Gebhard, L.A.; Garcia, A.R.

1990-01-01

Carbon seams in the Witwatersrand System of South Africa host some of the richest gold concentrations in the world. A study of the microscopic characteristics in thin sections and acid residues, and of the chemical and physical nature of the carbon-bearing phases, was undertaken to gain some understanding of the biological precursors and thermal changes that have occurred since the seams were buried. The HClHF acid-resistant organic tissues in this Early Proterozoic coal are filamentous and spherical, which are typical morphologies for microorganisms. The tissues are carbonized black as would be expected for metamorphic rocks, so usual palynological techniques were of limited use. Therefore, the chemical and physical nature of the organic remains was studied by H C ratios, X-ray diffraction (XRD), 13C nuclear magnetic resonance (NMR), reductive chemistry, crosspolarization/magic angle spinning NMR (CP/MAS), and electron spin resonance (ESR). The H C ratios of the samples examined are similar to those of semi-anthracite and petroleum cokes from delayed cokers. XRD shows graphite is not present and that the gold is in elemental form, not chemically bound or intercalated between carbon planes. NMR shows that both aromatic and paraffinic carbons are present. Integration of the carbon NMR spectra suggests that 80% of the carbon is sp2-hybridized and 20% is sp3-hybridized. Reductive chemistry shows that the benzenoid entities are larger than common polynuclear aromatic hydrocarbons such as perylene and decacyclene. Dipolar dephasing CP/MAS NMR suggests the presence of two types of paraffinic carbons, a rigid methylene group and a rotating methyl group. The narrowing of the ESR linewidth between room temperature and 300??C shows that the materials examined have not previously been subjected to temperatures as high as 300??C. ?? 1990.

[Size distribution of particle and polycyclic aromatic hydrocarbons in particle emissions from simulated emission sources].

PubMed

Fu, Hai-Huan; Tian, Na; Shang, Hui-Bin; Zhang, Bin; Ye, Su-Fen; Chen, Xiao-Qiu; Wu, Shui-Ping

2014-01-01

Particles from cooking lampblack, biomass and plastics burning smoke, gasoline vehicular exhausts and gasoline generator exhausts were prepared in a resuspension test chamber and collected using a cascade MOUDI impactor. A total of 18 polycyclic aromatic hydrocarbons (PAHs) associated with particles were analyzed by GC-MS. The results showed that there were two peaks in the range of 0.44-1.0 microm and 2.5-10 microm for cooking lampblack, and only one peak in the range of 0.44-1.0 microm for straw and wood burning smoke. But there were no clear peak for plastics burning smoke. The peak for gasoline vehicular exhausts was found in the range of 2.5-10 microm due to the influence of water vapor associated with particles, while the particles from gasoline generator exhausts were mainly in the range of < or = 2.5 microm (accounting for 93% of the total mass). The peak in 2.5-10 microm was clear for cooking lampblack and gasoline vehicular exhausts. The peak in the range of 0.44-1.0 microm became more and more apparent with the increase of PAHs molecular weight. The fraction of PAH on particles less than 1.0 microm to that on the total particles increased along with PAH's molecular weight. Phenanthrene was the dominant compound for cooking lampblack and combustion smoke, while gasoline vehicular exhausts and generator exhausts were characterized with significantly high levels of naphthalene and benzo[g, h, i] perylene, respectively. The distribution of source characteristic ratios indicated that PAHs from cooking lampblack and biomass burning were close and they were different from those of vehicular exhausts and generator exhausts.

Infrared Spectroscopy of Polycyclic Aromatic Hydrocarbon Cations. 3; The Members

NASA Technical Reports Server (NTRS)

Hudgins, D. M.; Allamandola, L. J.; Wittebon, Fred C. (Technical Monitor)

1994-01-01

In spite of the fact that the infrared spectroscopic properties of only a few isolated ionized polycyclic aromatic hydrocarbons (PAHs) are known, gaseous, ionized PAHs are thought to be responsible for a very common family of infrared interstellar emission bands. In order to provide a data base to test this hypothesis and, if borne out, to use this emission band family as a probe of many different interstellar environments, we are carrying out a thorough study of the infrared spectroscopic properties of neutral and ionized PAHs in argon matrices. Here we present the near and mid-infrared spectra of the cations of the five most thermodynamically favored PAHs up to coronene: phenanthrene, pyrene, benzo[e]pyrene, benzo[ghilperylene, and coronene. The properties of naphthalene, the first member of the series, are given elsewhere. The spectra of perdeuterated phenanthrene and pyrene are also reported. For those molecules which have been previously studied (pyrene, d(10)-pyrene, and coronene), band positions and relative intensities are in agreement. In all cases we report additional features. Absolute integrated absorbance values are given for the phenanthrene, perdeutero-phenanthrene, pyrene, benzo[ghi]perylene, and coronene cations. With the exception of coronene,the cation bands corresponding to the CC modes are typically 2-5 times more intense than those of the CH out-of-plane bending vibrations. For the cations the CC stretching and CH in-plane bending modes give rise to bands which are an order of magnitude stronger than for the neutral species, and the CH out-of-plane bends produce bands which are 5-20 times weaker than in the neutral species. This behavior is similar to that found in most other PAH cations studied to date. The astronomical implications of these PAH cation spectra are also discussed.

Polycyclic Aromatic Hydrocarbons In Edible Mushrooms from Niger Delta, Nigeria: Carcinogenic and Non-Carcinogenic Health Risk Assessment

PubMed

Igbiri, Sorbari; Udowelle, Nnaemeka Arinze; Ekhator, Osazuwa Clinton; Asomugha, Rose Ngozi; Igweze, Zelinjo Nkeiruka; Orisakwe, Orish Ebere

2017-02-01

In the oil-rich Niger Delta, hydrocarbon pollution and oil spillages, gas flaring and sundry anthropogenic activities constitute sources of polycyclic aromatic hydrocarbons (PAHs), with food contamination playing a major role in human exposure. In this study we assessed PAH levels in wild and cultivated edible mushroom species consumed by the general population from the oil producing Niger Delta, Nigeria. The concentrations of USEPA-16 PAHs were determined by gas chromatography and carcinogenic and non-carcinogenic health risks were calculated. The concentrations of USEPA-16 PAHs ranged from 0.02 mg/kg – 3.37 mg/kg. The dietary intake of carcinogenic and non-carcinogenic USEPA-16 PAHs (Naphthalene, Acenaphthylene, Acenaphthene, Anthracene, Phenanthrene, Flourene, Flouranthene, Pyrene, Benzo[a]Anthracene, Chrysene, Benzo[a]Pyrene, Benzo[b]Flouranthene, Benzo[K]Flouranthene, Benzo[g,h,i] Perylene, Dibenz[a,h]Anthracene and Ideno[1,2,3-cd]Pyrene) for adults, adolescents and seniors ranged from 0.00 – 0.05 mg/kg/day, 0.00 – 0.06 mg/kg/day and 0.00 – 0.07 mg/kg/day. The BaPeq ranged from 0.02 – 2.76 with margin of exposure MOE values of BaP ranging from 3,500,000 to 700,000, 3,500,000 and 3,500,000 to 7,000,000 for adults, adolescents and seniors indicating very insignificant health risk. The incremental lifetime cancer risk was within the safe range of 1.56x10-8 – 1.73x10-6 with the highest calculated risk found for wild Pleurotus ostreatus mushroom species from the study area. Creative Commons Attribution License

Polycyclic aromatic hydrocarbons associated with particles in ambient air from urban and industrial areas.

PubMed

Rehwagen, Martina; Müller, Andrea; Massolo, Laura; Herbarth, Olf; Ronco, Alicia

2005-09-15

This study takes into consideration an analysis of the chemical polycyclic aromatic hydrocarbon (PAH) profile and its distribution in inhalable and respirable particulate matter in urban and industrial areas in La Plata, Argentina, and Leipzig, Germany. Representative samples from three locations in La Plata (industrial, traffic influenced and control area) and two locations in Leipzig (traffic influenced and control area) were obtained in summer and winter. The sampling of particulate matter was carried out with high volume collectors using cascade impactors to separate six size fractions. PAHs were extracted with hexane through a solid-liquid equilibrium extraction and analysed by HPLC/UV/fluorescence detection. The results showed a PAH seasonal behaviour in both regions, with lower contents in summer and higher ones in winter. Highest concentrations of total PAHs were found in the industrial area in La Plata. The size distribution of particles demonstrates the greater relevance of smaller particles. More than 50% of PAHs were associated with particles of less than 0.49 microm. Moreover, this particle size fraction was associated with traffic, whereas other sources of combustion were related also to particles between 0.49 and 0.95 microm. Considering the ratio of benzo(ghi)perylene (BgP)/benzo(a)pyrene (BaP) as an indicator for traffic influence, it was observed that La Plata City was more affected than Leipzig by the same proportion in summer and in winter. The BgP/InP (indeno(123-cd)pyrene) ratio was lower in winter than in summer in both places and indicates the presence of domestic combustion sources. It is important to point out the significance of using fingerprint compound ratios to identify possible sources of pollution with PAHs bound to particles.

Comparing PAH availability from manufactured gas plant soils and sediments with chemical and biological tests. 1. PAH release during water desorption and supercritical carbon dioxide extraction.

PubMed

Hawthorne, Steven B; Poppendieck, Dustin G; Grabanski, Carol B; Loehr, Raymond C

2002-11-15

Soil and sediment samples from oil gas (OG) and coal gas (CG) manufactured gas plant (MGP) sites were selected to represent a range of PAH concentrations (150-40,000 mg/kg) and sample matrix compositions. Samples varied from vegetated soils to lampblack soot and had carbon contents from 3 to 87 wt %. SFE desorption (120 min) and water/XAD2 desorption (120 days) curves were determined and fit with a simple two-site model to determine the rapid-released fraction (F) for PAHs ranging from naphthalene to benzo[ghi]perylene. F values varied greatly among the samples, from ca. 10% to >90% for the two- and three-ring PAHs and from <1% to ca. 50% for the five- and six-ring PAHs. Release rates did not correlate with sample matrix characteristics including PAH concentrations, elemental composition (C, H, N, S), or "hard" and "softs" organic carbon, indicating that PAH release cannot easily be estimated on the basis of sample matrix composition. Fvalues for CG site samples obtained with SFE and water desorption agreed well (linear correlation coefficient, r2 = 0.87, slope = 0.93), but SFE yielded higher F values for the OG samples. These behaviors were attributed to the stronger ability of carbon dioxide than water to desorb PAHs from the highly aromatic (hard) carbon of the OG matrixes, while carbon dioxide and water showed similar abilities to desorb PAHs from the more polar (soft) carbon of the CG samples. The combined SFE and water desorption approaches should improve the understanding of PAH sequestration and release from contaminated soils and sediments and provide the basis for subsequent studies using the same samples to compare PAH release with PAH availability to earthworms.

Photochemistry of Polycyclic Aromatic Hydrocarbons in Cosmic Water Ice: The Role of PAH Ionization and Concentration

NASA Astrophysics Data System (ADS)

Cook, Amanda M.; Ricca, Alessandra; Mattioda, Andrew L.; Bouwman, Jordy; Roser, Joseph; Linnartz, Harold; Bregman, Jonathan; Allamandola, Louis J.

2015-01-01

Infrared spectroscopic studies of ultraviolet (UV) irradiated, water-rich, cosmic ice analogs containing small polycyclic aromatic hydrocarbons (PAHs) are described. The irradiation studies of anthracene:H2O, pyrene:H2O, and benzo[ghi]perylene:H2O ices (14 K) at various concentrations reported by Bouwman et al. are extended. While aromatic alcohols and ketones have been reported in residues after irradiated PAH:H2O ices were warmed to 270 K, it was not known if they formed during ice irradiation or during warm-up when reactants interact as H2O sublimes. Recent work has shown that they form in low temperature ice. Using DFT computed IR spectra to identify photoproducts and PAH cations, we tentatively identify the production of specific alcohols [PAH(OH) n ] and quinones [PAH(O) n ] for all PAH:H2O ices considered here. Little evidence is found for hydrogenation at 14 K, consistent with the findings of Gudipati & Yang. Addition of O and OH to the parent PAH is the dominant photochemical reaction, but PAH erosion to smaller PAHs (producing CO2 and H2CO) is also important. DFT spectra are used to assess the contribution of PAH-related species to interstellar absorption features from 5 to 9 μm. The case is made that PAH cations are important contributors to the C2 component and PAH(OH) n and PAH(O) n to the C5 component described by Boogert et al. Thus, interstellar ices should contain neutral and ionized PAHs, alcohols, ketones and quinones at the ~2%-4% level relative to H2O. PAHs, their photoproducts, and ion-mediated processes should therefore be considered when modeling interstellar ice processes.

Biodegradation in seawater of PAH and alkylphenols from produced water of a North Sea platform.

PubMed

Lofthus, Synnøve; Almås, Inger K; Evans, Peter; Pelz, Oliver; Brakstad, Odd Gunnar

2018-09-01

Operational planned discharges of produced water (PW) to the marine environment from offshore oil production installations, contain low concentrations of dispersed oil compounds, like polycyclic aromatic hydrocarbons (PAHs) and alkylated phenols (APs). Biotransformation in natural seawater (SW) of naphthalenes/PAHs and phenol/APs in field-collected PW from a North Sea platform was investigated in this biodegradation study. The PW was diluted in SW from a Norwegian fjord, and the biodegradation study was performed in slowly rotating carousels at 13 °C over a period of 62 days. Naphthalenes/PAHs and phenol/APs biotransformation was determined by first-order rate kinetics, after normalization against the recalcitrant biomarker 17α(H),21β(H)-Hopane. The results from this study showed total biotransformation half-lives ranging from 10 to 19 days for groups of naphthalenes and PAHs, while half-lives for APs (C0- to C9-alkylated) were 10-14 days. Biotransformation half-lives of single compounds ranged from 8 to >100 days for naphthalenes and PAHs (median 16 days), and from 5 to 70 days (median 15 days) for phenols and APs. Four of the tested PAHs (chrysene, benzo(b)fluoranthene, benzo(e)pyrene, benzo(g,h,i)perylene) and one AP (4-tert-butylphenol) showed biotransformation half-lives >50 days. This is one of a few studies that has investigated the potential for biodegradation of PW in natural SW. Methods and data from this study may be used as a part of Risk Based Approaches (RBA) for assessments of environmental fate of PW released to the marine environment and as part of the persistence related to risk. Crown Copyright © 2018. Published by Elsevier Ltd. All rights reserved.

Monitoring of atmospheric gaseous and particulate polycyclic aromatic hydrocarbons in South African platinum mines utilising portable denuder sampling with analysis by thermal desorption-comprehensive gas chromatography-mass spectrometry.

PubMed

Geldenhuys, G; Rohwer, E R; Naudé, Y; Forbes, P B C

2015-02-06

Concentrations of diesel particulate matter and polycyclic aromatic hydrocarbons (PAHs) in platinum mine environments are likely to be higher than in ambient air due to the use of diesel machinery in confined environments. Airborne PAHs may be present in gaseous or particle phases each of which has different human health impacts due to their ultimate fate in the body. Here we report on the simultaneous sampling of both phases of airborne PAHs for the first time in underground platinum mines in South Africa, which was made possible by employing small, portable denuder sampling devices consisting of two polydimethylsiloxane (PDMS) multi-channel traps connected in series separated by a quartz fibre filter, which only require small, battery operated portable personal sampling pumps for air sampling. Thermal desorption coupled with comprehensive gas chromatography-mass spectrometry (TD-GC×GC-TofMS) was used to analyse denuder samples taken in three different platinum mines. The samples from a range of underground environments revealed that PAHs were predominantly found in the gas phase with naphthalene and mono-methylated naphthalene derivatives being detected at the highest concentrations ranging from 0.01 to 18 μg m(-3). The particle bound PAHs were found in the highest concentrations at the idling load haul dump vehicle exhausts with a dominance of fluoranthene and pyrene. Particle associated PAH concentrations ranged from 0.47 to 260 ng m(-3) and included benzo[k]fluoranthene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene and benzo[ghi]perylene. This work highlights the need to characterise both phases in order to assess occupational exposure to PAHs in this challenging sampling environment. Copyright © 2015 Elsevier B.V. All rights reserved.

Organic anodes and sulfur/selenium cathodes for advanced Li and Na batteries

NASA Astrophysics Data System (ADS)

Luo, Chao

To address energy crisis and environmental pollution induced by fossil fuels, there is an urgent demand to develop sustainable, renewable, environmental benign, low cost and high capacity energy storage devices to power electric vehicles and enhance clean energy approaches such as solar energy, wind energy and hydroenergy. However, the commercial Li-ion batteries cannot satisfy the critical requirements for next generation rechargeable batteries. The commercial electrode materials (graphite anode and LiCoO 2 cathode) are unsustainable, unrenewable and environmental harmful. Organic materials derived from biomasses are promising candidates for next generation rechargeable battery anodes due to their sustainability, renewability, environmental benignity and low cost. Driven by the high potential of organic materials for next generation batteries, I initiated a new research direction on exploring advanced organic compounds for Li-ion and Na-ion battery anodes. In my work, I employed croconic acid disodium salt and 2,5-Dihydroxy-1,4-benzoquinone disodium salt as models to investigate the effects of size and carbon coating on electrochemical performance for Li-ion and Na-ion batteries. The results demonstrate that the minimization of organic particle size into nano-scale and wrapping organic materials with graphene oxide can remarkably enhance the rate capability and cycling stability of organic anodes in both Li-ion and Na-ion batteries. To match with organic anodes, high capacity sulfur and selenium cathodes were also investigated. However, sulfur and selenium cathodes suffer from low electrical conductivity and shuttle reaction, which result in capacity fading and poor lifetime. To circumvent the drawbacks of sulfur and selenium, carbon matrixes such as mesoporous carbon, carbonized polyacrylonitrile and carbonized perylene-3, 4, 9, 10-tetracarboxylic dianhydride are employed to encapsulate sulfur, selenium and selenium sulfide. The resulting composites exhibit exceptional electrochemical performance owing to the high conductivity of carbon and effective restriction of polysulfides and polyselenides in carbon matrix, which avoids shuttle reaction.

Polyfluorophore Excimers and Exciplexes as FRET Donors in DNA

PubMed Central

Teo, Yin Nah; Kool, Eric T.

2009-01-01

We describe studies aimed at testing whether oligomeric exciplex- and excimer fluorophores conjugated to DNA have the potential to act as donors for energy transfer by the Förster mechanism. Oligodeoxyfluorosides (ODFs) are composed of stacked, electronically interacting fluorophores replacing the bases on a DNA scaffold. The monomer chromophores in the twenty tetramer-length ODFs studied here include pyrene (Y), benzopyrene (B), perylene (E), dimethylaminostilbene (D), and a nonfluorescent spacer (S); these are conjugated in varied combinations at the 3’ end of a 14mer DNA probe sequence. In the absence of an acceptor chromophore, many of the ODF-DNAs show broad, unstructured long-wavelength emission peaks characteristic of excimer and exciplex excited states, similar to what has been observed for unconjugated ODFs. Although such delocalized excited states have been widely studied, we know of no prior report of their use in FRET. We tested the ability of the twenty ODFs to donate energy to Cy5 and TAMRA dyes conjugated to a complementary strand of DNA, with these acceptors oriented either at the near or far end of the ODF-conjugated probes. Results showed that a number of the ODF fluorophores exhibited relatively efficient energy transfer characteristic of the Förster mechanism, as judged by drops in donor emission quantum yield and fluorescence lifetime, accompanied by increases in intensity of acceptor emission bands. Excimer/exciplex bands in the donors were selectively quenched while shorter-wavelength monomer emission stayed relatively constant, consistent with the notion that the delocalized excited states, rather than individual fluorophores, are the donors. Interestingly, only specific sequences of ODFs were able to act as donors, while others did not, even though their emission wavelengths were similar. The new FRET donors possess large Stokes shifts, which can be beneficial for multiple applications. In addition, all ODFs can be excited at a single wavelength; thus, ODFs may be candidates as “universal FRET donors”, thus allowing multicolor FRET of multiple species to be carried out with one excitation. PMID:19916519

Intra-molecular Charge Transfer and Electron Delocalization in Non-fullerene Organic Solar Cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Qinghe; Zhao, Donglin; Goldey, Matthew B.

Two types of electron acceptors were synthesized by coupling two kinds of electron-rich cores with four equivalent perylene diimides (PDIs) at the a position. With fully aromatic cores, TPB and TPSe have pi-orbitals spread continuously over the whole aromatic conjugated backbone, unlike TPC and TPSi, which contain isolated PDI units due to the use of a tetrahedron carbon or silicon linker. Density functional theory calculations of the projected density of states showed that the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) for TPB are localized in separate regions of space. Further, the LUMO of TPB showsmore » a greater contribution from the orbitals belonging to the connective core of the molecules than that of TPC. Overall, the properties of the HOMO and LUMO point at increased intra-molecular delocalization of negative charge carriers for TPB and TPSe than for TPC and TPSi and hence at a more facile intra-molecular charge transfer for the former. The film absorption and emission spectra showed evidences for the inter -molecular electron delocalization in TPB and TPSe, which is consistent with the network structure revealed by X-ray diffraction studies on single crystals of TPB. These features benefit the formation of charge transfer states and/or facilitate charge transport. Thus, higher electron mobility and higher charge dissociation probabilities under J(sc) condition were observed in blend films of TPB:PTB7-Th and TPSe:PTB7-Th than those in TPC:PTB7Th and TPSi:PTB7-Th blend films. As a result, the J(sc) and fill factor values of 15.02 mA/cm(2), 0.58 and 14.36 mA/cm(2), 0.55 for TPB- and TPSe-based solar cell are observed, whereas those for TPC and TPSi are 11.55 mA/cm2, 0.47 and 10.35 mA/cm(2), 0.42, respectively.« less

Syn-anti conformational switching in an ethane-bridged Co(II)bisporphyrin induced by external stimuli: effects of inter-macrocyclic interactions, axial ligation and chemical and electrochemical oxidations.

PubMed

Dey, Soumyajit; Rath, Sankar Prasad

2014-02-07

The syn-anti conformational switching has been demonstrated in the ethane-bridged dicobalt(II)bisporphyrin which is present in the syn-form only. The addition of either perylene or axial ligands to Co(II)(bisporphyrin) completely transforms the syn form into the anti because of strong π-π interaction and axial coordination, respectively. The complex undergoes four 1e-oxidations in CH2Cl2 which are indicative of strong through space interactions between the two cofacial Co-porphyrins at 295 K. The first oxidation is a metal centered one and occurs at a potential much lower than that of the monomeric analog. However, the second oxidation, which is again metal centered, was at a significantly higher potential. The large difference between the first two oxidations, as observed here, is due to much stronger inter-porphyrin interactions. The step-wise oxidations have been performed both chemically and electro-chemically while the progress of the reactions was monitored by UV-visible and (1)H NMR spectroscopy. After 1e-oxidation, a very broad (1)H NMR signal results with increased difference between two meso resonances, which indicates that the two macrocycles are in the syn-form with lesser interplanar separation as also observed by DFT. However, 2e-oxidation results in the stabilization of the anti form. The addition of axial ligands to Co(II)(bisporphyrin) also completely transforms the syn form into the anti form. While additions of THF and I2/I(-) both result in the formation of five-coordinate complexes, Co(II) is oxidized to Co(III) in the case of the latter. However, additions of 1-methylimidazole, pyridine and pyrazine as axial ligands result in the formation of a six-coordinate complex in which Co(II) is spontaneously oxidized to Co(III) in air.

Human exposure to polycyclic aromatic hydrocarbons (PAHs) using data from a duplicate diet study in Catalonia, Spain.

PubMed

Martorell, Isabel; Nieto, Antonio; Nadal, Martí; Perelló, Gemma; Marcé, Rosa M; Domingo, José L

2012-11-01

In this study, the dietary intake of 16 polycyclic aromatic hydrocarbons (PAHs) by the population of Tarragona County (Catalonia, Spain) was assessed using the duplicate diet approach. Duplicate diet samples, prepared as per consumption, were collected during September 2010 in various restaurants offering a variety of daily menus (breakfast, lunch, and dinner). For analysis of PAHs, a total of 90 composite samples were prepared. Analytical procedure of PAHs was performed by means of gas chromatography/mass spectrometry. Intake calculations were made for the standard male adult population. The highest intakes corresponded to acenaphthylene (12.7 μg/day), acenaphthene (12.4 μg/day), and fluorene (11.9 μg/day), while the lowest intake corresponded to dibenz[a,h]anthracene (0.12 μg/day), being also comparatively low those of pyrene, benzo[b]fluoranthene+benzo[j]fluoranthene, benzo[a]pyrene and benzo[ghi]perylene (0.13 μg/day in all cases). The results were compared with data from previous total diet studies (TDS) recently performed in the same geographical area. In the present study, the estimated mean dietary intake for a standard male adult living in Catalonia was 59.2 μg/day, a value notably higher than that found in our recent TDS (6.72 μg/day). However, it is essential to remark that important methodological differences exist between both surveys, reflecting that calculation methods should be similar when the purpose is to compare results from different surveys. In general terms, we conclude that for PAHs, duplicate diet studies may be a good alternative to total diet studies, especially when there are important economical limitations to perform a suitable TDS. The costs associated to the former may be notably lower, as they do not require such an extensive number of samples for chemical analysis. Moreover, a duplicate diet approach may even be more realistic, as cooked foodstuffs are used for dietary exposure assessment. Copyright © 2012 Elsevier Ltd. All rights reserved.

Degradation of polycyclic aromatic hydrocarbons (PAHs) present in used motor oil and implications for urban runoff quality

NASA Astrophysics Data System (ADS)

Ferreira, M.; Stenstrom, M. K.; Lau, S.

2013-12-01

Polycyclic aromatic hydrocarbons (PAHs) are common organic pollutants of urban stormwater runoff due to atmospheric deposition, vehicle-related discharges, and coal tar pavement sealants. The US EPA lists sixteen PAHs as priority pollutants and seven of those are potential carcinogenic compounds. Due to their molecular structure, PAHs tend to attach to particles that will subsequently be deposited as sediments in waterways. This study focuses on the degradation of PAHs present in used motor oil. Four experimental setups were used to simulate volatilization and photooxidation in the degradation of sixteen PAHs as observed for up to 54 days. The volatilization-only experiment showed substantial reduction only in the concentration of Napthalene (Nap). However, photooxidation-only was more efficient in degrading PAHs. In this process, substantial reduction in the concentrations of Nap, Acenapthene (Anthe), Anthracene (ANT), Fluoranthene (FLT), Pyrene (PYR), Benz[a]anthracene (BaA), Benzo[a]pyrene (BaP), Indeno[1,2,3,cd]pyrene (INP), and Benz[g,h,i]perylene (BghiP) were observed as early as five days. The two volatilization-photooxidation experiments exhibited substantial reduction in the concentrations of Fluorene (FLU), Chrysene (CHR) and Benzo[b]fluoranthene (BbF), in addition to the PAHs reduced by photooxidation-only. Phenanthrene (PHE), Fluoranthene (FLT), and Benzo[b]fluoranthene (BbF) only exhibited substantial decreased concentrations after 20 days in the volatilization-photooxidation experiment. One PAH, acenapthylene (Anthy), was not detected in the original sample of used motor oil. The highest degradations were observed in the combined volatilization-photooxidation experiment. In regions with infrequent rainfall, such as Southern California, molecules of PAHs attached to highway particles will have time to undergo degradation prior to transport. Therefore, PAHs may be present in lower concentrations in highway runoff in dry climates than in rainy climates. To support this hypothesis, a review of highway-related PAHs concentrations is presented.

Wholly Aromatic Ether-Imides as n-Type Semiconductors

NASA Technical Reports Server (NTRS)

Weiser, Erik; St. Clair, Terry L.; Dingemans, Theo J.; Samulski, Edward T.; Irene, Gene

2006-01-01

Some wholly aromatic ether-imides consisting of rod-shaped, relatively-low-mass molecules that can form liquid crystals have been investigated for potential utility as electron-donor-type (ntype) organic semiconductors. It is envisioned that after further research to improve understanding of their physical and chemical properties, compounds of this type would be used to make thin film semiconductor devices (e.g., photovoltaic cells and field-effect transistors) on flexible electronic-circuit substrates. This investigation was inspired by several prior developments: Poly(ether-imides) [PEIs] are a class of engineering plastics that have been used extensively in the form of films in a variety of electronic applications, including insulating layers, circuit boards, and low-permittivity coatings. Wholly aromatic PEIs containing naphthalene and perylene moieties have been shown to be useful as electrochromic polymers. More recently, low-molecular-weight imides comprising naphthalene-based molecules with terminal fluorinated tails were shown to be useful as n-type organic semiconductors in such devices as field-effect transistors and Schottky diodes. Poly(etherimide)s as structural resins have been extensively investigated at NASA Langley Research Center for over 30 years. More recently, the need for multi-functional materials has become increasingly important. This n-type semiconductor illustrates the scope of current work towards new families of PEIs that not only can be used as structural resins for carbon-fiber reinforced composites, but also can function as sensors. Such a multi-functional material would permit so-called in-situ health monitoring of composite structures during service. The work presented here demonstrates that parts of the PEI backbone can be used as an n-type semiconductor with such materials being sensitive to damage, temperature, stress, and pressure. In the near future, multi-functional or "smart" composite structures are envisioned to be able to communicate such important parameters to the flight crew and provide vital information with respect to the operational status of their aircraft.

Molecules for Fluorescence Detection of Specific Chemicals

NASA Technical Reports Server (NTRS)

Fedor, Steve

2008-01-01

A family of fluorescent dye molecules has been developed for use in on-off fluorescence detection of specific chemicals. By themselves, these molecules do not fluoresce. However, when exposed to certain chemical analytes in liquid or vapor forms, they do fluoresce (see figure). These compounds are amenable to fixation on or in a variety of substrates for use in fluorescence-based detection devices: they can be chemically modified to anchor them to porous or non-porous solid supports or can be incorporated into polymer films. Potential applications for these compounds include detection of chemical warfare agents, sensing of acidity or alkalinity, and fluorescent tagging of proteins in pharmaceutical research and development. These molecules could also be exploited for use as two-photon materials for photodynamic therapy in the treatment of certain cancers and other diseases. A molecule in this family consists of a fluorescent core (such as an anthracene or pyrene) attached to two end groups that, when the dye is excited by absorption of light, transfer an electron to the core, thereby quenching the fluorescence. The end groups can be engineered so that they react chemically with certain analytes. Upon reaction, electrons on the end groups are no longer available for transfer to the core and, consequently, the fluorescence from the core is no longer quenched. The chemoselectivity of these molecules can be changed by changing the end groups. For example, aniline end groups afford a capability for sensing acids or acid halides (including those contained in chemical warfare agents). Pyridine or bipyridyl end groups would enable sensing of metal ions. Other chemicals that can be selectively detected through suitable choice of end groups include glucose and proteins. Moreover, the fluorescent cores can be changed to alter light-absorption and -emission characteristics: anthracene cores fluoresce at wavelengths around 500 nm, whereas perylene cores absorb and emit at wavelengths of about 600 nm.

In Vivo Lighted Fluorescence via Fenton Reaction: Approach for Imaging of Hydrogen Peroxide in Living Systems.

PubMed

Liu, Changhui; Chen, Weiju; Qing, Zhihe; Zheng, Jing; Xiao, Yue; Yang, Sheng; Wang, Lili; Li, Yinhui; Yang, Ronghua

2016-04-05

By virtue of its high sensitivity and rapidity, Fenton reaction has been demonstrated as a powerful tool for in vitro biochemical analysis; however, in vivo applications of Fenton reaction still remain to be exploited. Herein, we report, for the first time, the design, formation and testing of Fenton reaction for in vivo fluorescence imaging of hydrogen peroxide (H2O2). To realize in vivo fluorescence imaging of H2O2 via Fenton reaction, a functional nanosphere, Fc@MSN-FDNA/PTAD, is fabricated from mesoporous silica nanoparticle (MSN), a Fenton reagent of ferrocene (Fc), ROX-labeled DNA (FDNA), and a cationic perylene derivative (PTAD). The ferrocene molecules are locked in the pore entrances of MSN, and exterior of MSN is covalently immobilized with FDNA. As a key part, PTAD acts as not only the gatekeeper of MSN but also the efficient quencher of ROX. H2O2 can permeate into the nanosphere and react with ferrocene to product hydroxyl radical (·OH) via Fenton reaction, which cleaves FDNA to detach ROX from PTAD, thus in turn, lights the ROX fluorescence. Under physiological condition, H2O2 can be determined from 5.0 nM to 1.0 μM with a detection limit of 2.4 nM. Because of the rapid kinetics of Fenton reaction and high specificity for H2O2, the proposed method meets the requirement for real applications. The feasibility of Fc@MSN-FDNA/PTAD for in vivo applications is demonstrated for fluorescence imaging of exogenous and endogenous H2O2 in cells and mice. We expect that this work will not only contribute to the H2O2-releated studies but also open up a new way to exploit in vivo Fenton reaction for biochemical research.

Source-oriented risk assessment of inhalation exposure to ambient polycyclic aromatic hydrocarbons and contributions of non-priority isomers in urban Nanjing, a megacity located in Yangtze River Delta, China.

PubMed

Zhuo, Shaojie; Shen, Guofeng; Zhu, Ying; Du, Wei; Pan, Xuelian; Li, Tongchao; Han, Yang; Li, Bengang; Liu, Junfeng; Cheng, Hefa; Xing, Baoshan; Tao, Shu

2017-05-01

Sixteen U.S. EPA priority polycyclic aromatic hydrocarbons (PAHs) and eleven non-priority isomers including some dibenzopyrenes were analyzed to evaluate health risk attributable to inhalation exposure to ambient PAHs and contributions of the non-priority PAHs in a megacity Nanjing, east China. The annual average mass concentration of the total 16 EPA priority PAHs in air was 51.1 ± 29.8 ng/m 3 , comprising up to 93% of the mass concentration of all 27 PAHs, however, the estimated Incremental Lifetime Cancer Risk (ILCR) due to inhalation exposure would be underestimated by 63% on average if only accounting the 16 EPA priority PAHs. The risk would be underestimated by 13% if only particulate PAHs were considered, though gaseous PAHs made up to about 70% of the total mass concentration. During the last fifteen years, ambient Benzo[a]pyrene decreased significantly in the city which was consistent with the declining trend of PAHs emissions. Source contributions to the estimated ILCR were much different from the contributions for the total mass concentration, calling for the introduce of important source-oriented risk assessments. Emissions from gasoline vehicles contributed to 12% of the total mass concentration of 27 PAHs analyzed, but regarding relative contributions to the overall health risk, gasoline vehicle emissions contributed 45% of the calculated ILCR. Dibenzopyrenes were a group of non-priority isomers largely contributing to the calculated ILCR, and vehicle emissions were probably important sources of these high molecular weight isomers. Ambient dibenzo[a,l]pyrene positively correlated with the priority PAH Benzo[g,h,i]perylene. The study indicates that inclusion of non-priority PAHs could be valuable for both PAH source apportionment and health risk assessment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Evaluation of 8-hydroxy-2'-deoxyguanosine (8-OHdG) adduct levels and DNA strand breaks in human peripheral blood lymphocytes exposed in vitro to polycyclic aromatic hydrocarbons with or without animal metabolic activation.

PubMed

Isabel, Rodríguez-Romero María; Sandra, Gómez-Arroyo; Rafael, Villalobos-Pietrini; Carmen, Martínez-Valenzuela; Josefina, Cortés-Eslava; del Carmen, Calderón-Ezquerro María; Rocío, García-Martínez; Francisco, Arenas-Huertero; Elena, Calderón-Segura María

2012-04-01

The polycyclic aromatic hydrocarbons (PAHs) dibenzo(a,h)anthracene, benzo(ghi)perylene, benzo(b)fluoranthene and benzo(a)pyrene have been identified in urban air from Mexico City and some of them are classified as human carcinogens. In the present study, human peripheral blood lymphocytes were exposed in vitro to different concentrations of PAHs with (+S9) or without (-S9) metabolic activation. The genotoxic and cytotoxic effects of each PAH were examined with an alkaline comet assay and trypan blue dye exclusion, and oxidative DNA damage was determined via the detection of 8-hydroxy-2'-deoxyguanosine (8-OhdG) adduct levels by enzyme-linked immunosorbent assay (ELISA). The DNA damage was evaluated with two genotoxicity parameters: the frequency of comets and the comet tail length. Concentrations of 20, 40, 80, 160 and 320 µM DB(a,h)A-S9; 20, 40, 80, 160 and 240 µM B(ghi)P-S9; 20, 30, 40, 60 and 80 µM B(b)F-S9; and 80 µM B(a)P-S9 for 24 h induced a small but significant increase in the means of comet frequency, in the tail length and in the 8-oHDg levels in relation to the control (0.5% DMSO-S9). However, all PAHs+S9 produced a more significant increase in DNA strand breaks and the level of 8-OHdG compared with the control (0.5% DMSO+S9), with a concentration-effect relationship. The viability of lymphocytes exposed to all PAHs-S9 and PAHs+S9 was not modified compared with the control. The results of this study demonstrate that the comet and ELISA are rapid, suitable and sensitive methods to detect in vitro PAH-induced DNA damage in human peripheral lymphocytes.

Occurrence, characteristics and sources of polycyclic aromatic hydrocarbons in arable soils of Beijing, China.

PubMed

Liu, Hang; Yu, Xiaolu; Liu, Zirui; Sun, Ying

2018-05-04

This study investigated the occurrence and sources of polycyclic aromatic hydrocarbons (PAHs) from arable soils in Beijing and compared them with 4 other types of soils: soil from uncultivated land, an incineration plant, a suburb and a woodland. The total concentrations of PAHs ranged from 189.3 to 888.7 μg/kg (mean: 518.2 μg/kg for greenhouses and 455.2 μg/kg for fields). The seven carcinogenic PAHs accounted for 11.2-81.3% of Σ15PAHs in arable soils. Benzo[a]pyrene toxic equivalent (BaP eq ) concentrations were 82.8 μg/kg and 85.4 μg/kg in greenhouses and fields, respectively. Greenhouses and fields were both dominated by PAHs with 3 and 4 rings. Acenaphthene (ACE), indeno[1,2,3-cd] pyrene (IcdP) and benzo[ghi]perylene (BghiP) were the major compounds. These results showed that there was insignificant difference between the soil from greenhouses and fields and both had low carcinogenic potential risk. The diagnostic ratios suggested that the arable soils were mainly contaminated by coal/biomass combustion. Based on a positive matrix factorization (PMF) model, six sources were identified including coal combustion, waste incineration, tar, diesel combustion, biomass burning and gasoline combustion. Coal and gasoline combustion contributed over 40% of the measured PAHs in arable soils. Diesel combustion, tar and waste incineration were the main sources of pollution for soil from the uncultivated land, woodland and incineration plant/suburban. It was concluded that PMF was effective in determining the source apportionment. Urbanization and the evolution of human activities have caused PAH sources to become more complicated in industrial areas compared to regions with little human disturbance. Because of this, various factors need to be considered to control the PAH contamination in arable soils. Copyright © 2018 Elsevier Inc. All rights reserved.

Developing chemical signatures of particulate air pollution in the Pearl River Delta region, China.

PubMed

Zheng, Mei; Cheng, Yuan; Zeng, Limin; Zhang, Yuanhang

2011-01-01

PM2.5 samples were collected in a regional sampling network with three sites in Hong Kong and four sites in the adjacent inland Pearl River Delta (PRD) or Guangdong Province during four months/seasons from 2002-2003. Trans-boundary transport between Hong Kong and the inland PRD is inevitable under the influence of Asian monsoon. In summer, Hong Kong serves as the upwind site of the inland PRD while during other seasons it is under the influence of continental emissions. Previous studies have recognized the importance of using chemical signatures to differentiate local vs. regional contributions to air pollutants in Hong Kong such as the CO/NOx ratio, ratios of different VOC species. In this study, detailed chemical speciation by gas chromatography-mass spectrometry was performed with PM2.5 samples to identify new chemical signatures to distinguish aerosols in Hong Kong from those from the inland PRD. Since Hong Kong is not influenced by the continental emissions from the inland PRD during summer, comparison focused on chemical data obtained from this season for chemical signatures. The new ratios developed from the current study include LCPI/HCPI ratio of alkanes (0.39 +/- 0.02 in Hong Kong vs. 0.78 +/- 0.08 in the inland PRD), pyrene to benzo[ghi]perylene ratio (0.97 +/- 0.21 in Hong Kong compared to 0.20 +/- 0.06 in the inland PRD), and the ratio of 1,2-benzenedioic acid to 1,4-benzenedioic acid (1.8 +/- 0.1 in Hong Kong vs. 0.6 +/- 0.05 in the inland PRD). Results from this study also revealed that Hong Kong was impacted by ship emissions as reflected by substantially high V/Ni ratio (9 +/- 2) while this ratio was about 1-2 at all sites in the inland PRD, which is very close to typical ratios from residual oil combustion.

Single molecule studies of solvent-dependent diffusion and entrapment in poly(dimethylsiloxane) thin films.

PubMed

Lange, Jeffrey J; Culbertson, Christopher T; Higgins, Daniel A

2008-12-15

Single molecule microscopic and spectroscopic methods are employed to probe the mobility and physical entrapment of dye molecules in dry and solvent-loaded poly(dimethylsiloxane) (PDMS) films. PDMS films of approximately 220 nm thickness are prepared by spin casting dilute solutions of Sylgard 184 onto glass coverslips, followed by low temperature curing. A perylene diimide dye (BPPDI) is used to probe diffusion and molecule-matrix interactions. Two classes of dye-loaded samples are investigated: (i) those incorporating dye dispersed throughout the films ("in film" samples) and (ii) those in which the dye is restricted primarily to the PDMS surface ("on film" samples). Experiments are performed under dry nitrogen and at various levels of isopropyl alcohol (IPA) loading from the vapor phase. A PDMS-coated quartz-crystal microbalance is employed to monitor solvent loading and drying of the PDMS and to ensure equilibrium conditions are achieved. Single molecules are shown to be predominantly immobile under dry conditions and mostly mobile under IPA-saturated conditions. Quantitative methods for counting the fluorescent spots produced by immobile single molecules in optical images of the samples demonstrate that the population of mobile molecules increases nonlinearly with IPA loading. Even under IPA saturated conditions, the population of fixed molecules is found to be greater than zero and is greatest for "in film" samples. Fluorescence correlation spectroscopy is used to measure the apparent diffusion coefficient for the mobile molecules, yielding a mean value of D = 1.4(+/-0.4) x 10(-8) cm(2)/s that is virtually independent of IPA loading and sample class. It is concluded that a nonzero population of dye molecules is physically entrapped within the PDMS matrix under all conditions. The increase in the population of mobile molecules under high IPA conditions is attributed to the filling of film micropores with solvent, rather than by incorporation of molecularly dispersed solvent into the PDMS.

PHOTOCHEMISTRY OF POLYCYCLIC AROMATIC HYDROCARBONS IN COSMIC WATER ICE: THE ROLE OF PAH IONIZATION AND CONCENTRATION

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cook, Amanda M.; Mattioda, Andrew L.; Roser, Joseph

2015-01-20

Infrared spectroscopic studies of ultraviolet (UV) irradiated, water-rich, cosmic ice analogs containing small polycyclic aromatic hydrocarbons (PAHs) are described. The irradiation studies of anthracene:H{sub 2}O, pyrene:H{sub 2}O, and benzo[ghi]perylene:H{sub 2}O ices (14 K) at various concentrations reported by Bouwman et al. are extended. While aromatic alcohols and ketones have been reported in residues after irradiated PAH:H{sub 2}O ices were warmed to 270 K, it was not known if they formed during ice irradiation or during warm-up when reactants interact as H{sub 2}O sublimes. Recent work has shown that they form in low temperature ice. Using DFT computed IR spectra to identify photoproducts andmore » PAH cations, we tentatively identify the production of specific alcohols [PAH(OH) {sub n} ] and quinones [PAH(O) {sub n} ] for all PAH:H{sub 2}O ices considered here. Little evidence is found for hydrogenation at 14 K, consistent with the findings of Gudipati and Yang. Addition of O and OH to the parent PAH is the dominant photochemical reaction, but PAH erosion to smaller PAHs (producing CO{sub 2} and H{sub 2}CO) is also important. DFT spectra are used to assess the contribution of PAH-related species to interstellar absorption features from 5 to 9 μm. The case is made that PAH cations are important contributors to the C2 component and PAH(OH) {sub n} and PAH(O) {sub n} to the C5 component described by Boogert et al. Thus, interstellar ices should contain neutral and ionized PAHs, alcohols, ketones and quinones at the ∼2%-4% level relative to H{sub 2}O. PAHs, their photoproducts, and ion-mediated processes should therefore be considered when modeling interstellar ice processes.« less

Quantification of PAHs and oxy-PAHs on airborne particulate matter in Chiang Mai, Thailand, using gas chromatography high resolution mass spectrometry

NASA Astrophysics Data System (ADS)

Walgraeve, Christophe; Chantara, Somporn; Sopajaree, Khajornsak; De Wispelaere, Patrick; Demeestere, Kristof; Van Langenhove, Herman

2015-04-01

An analytical method using gas chromatography high resolution mass spectrometry was developed for the determination of 16 polycyclic aromatic hydrocarbons (PAHs) and 12 oxygenated PAHs (of which 4 diketones, 3 ketones, 4 aldehydes and one anhydride) on atmospheric particulate matter with an aerodynamic diameter less than 10 μm (PM10). The magnetic sector mass spectrometer was run in multiple ion detection mode (MID) with a mass resolution above 10 000 (10% valley definition) and allows for a selective accurate mass detection of the characteristic ions of the target analytes. Instrumental detection limits between 0.04 pg and 1.34 pg were obtained for the PAHs, whereas for the oxy-PAHs they ranged between 0.08 pg and 2.13 pg. Pressurized liquid extraction using dichloromethane was evaluated and excellent recoveries ranging between 87% and 98% for the PAHs and between 74% and 110% for 10 oxy-PAHs were obtained, when the optimum extraction temperature of 150 °C was applied. The developed method was finally used to determine PAHs and oxy-PAHs concentration levels from particulate matter samples collected in the wet season at 4 different locations in Chiang Mai, Thailand (n = 72). This study brings forward the first concentration levels of oxy-PAHs in Thailand. The median of the sum of the PAHs and oxy-PAHs concentrations was 3.4 ng/m3 and 1.1 ng/m3 respectively, which shows the importance of the group of the oxy-PAHs as PM10 constituents. High molecular weight PAHs contributed the most to the ∑PAHs. For example, benzo[ghi]perylene was responsible for 30-44% of the ∑PAHs. The highest contribution to ∑oxy-PAHs came from 1,8-napthalic anhydride (26-78%), followed by anthracene-9,10-dione (4-27%) and 7H-benzo[de]anthracene-7-one (6-26%). Indications of the degradation of PAHs and/or formation of oxy-PAHs were observed.

Photochemistry of polycyclic aromatic hydrocarbons in cosmic water ice. II. Near UV/VIS spectroscopy and ionization rates

NASA Astrophysics Data System (ADS)

Bouwman, J.; Cuppen, H. M.; Steglich, M.; Allamandola, L. J.; Linnartz, H.

2011-05-01

Context. Mid-infrared emission features originating from polycyclic aromatic hydrocarbons (PAHs) are observed towards photon dominated regions in space. Towards dense clouds, however, these emission features are quenched. Observations of dense clouds show that many simple volatile molecules are frozen out on interstellar grains, forming thin layers of ice. Recently, observations have shown that more complex non-volatile species, presumably including PAHs, also freeze out and contribute to the ongoing solid-state chemistry. Aims: The study presented here aims at obtaining reaction rate data that characterize PAH photochemistry upon vacuum ultraviolet (VUV) irradiation in an interstellar H2O ice analogue to explore the potential impact of PAH:H2O ice reactions on overall interstellar ice chemistry. To this end, the experimental results are implemented in a chemical model under simple interstellar cloud conditions. Methods: Time-dependent near-UV/VIS spectroscopy on the VUV photochemistry of anthracene, pyrene, benzo[ghi]perylene and coronene containing interstellar H2O ice analogs is performed at 25 and 125 K, using an optical absorption setup. Results: Near-UV/VIS absorption spectra are presented for these four PAHs and their photoproducts including cationic species trapped in H2O ice. Oscillator strengths of the cation absorption bands are derived relative to the oscillator strength of the neutral parent PAH. The loss of the parent and growth of PAH photoproducts are measured as a function of VUV dose, yielding solid state reaction constants. The rate constants are used in an exploratory astrochemical model, to assess the importance of PAH:H2O ice photoprocessing in UV exposed interstellar environments, compared with the timescales in which PAH molecules are incorporated in interstellar ices. Conclusions: All four PAHs studied here are found to be readily ionized upon VUV photolysis when trapped in H2O ice and exhibit similar rates for ionization at astronomically relevant temperatures. Depending on the relative efficiency of H2O photodesorption and PAH photoionization in H2O ice, the latter may trigger a charge induced aromatic solid state chemistry, in which PAH cations play a central role.

PCDD/F, PAH and heavy metals in the sewage sludge from six wastewater treatment plants in Beijing, China.

PubMed

Dai, Jiayin; Xu, Muqi; Chen, Jiping; Yang, Xiangping; Ke, Zhenshan

2007-01-01

In order to better understand land application of sewage sludge, the characterization of heavy metals, PCDD/F and PAHs in sewage sludge was investigated from six different wastewater treatment plants (WWTP) in Beijing City, China. It was found that the total concentrations of Zn in Wujiacun (WJC) sewage sludge, and Cd and Hg in sewage sludge generated from all of the six different places are higher than Chinese regulation limit of pollutants for sludge to be used for agriculture (GB18918-2002). The levels of 16 PAHs that have been categorized as priority pollutants by US EPA in the sewage sludge samples varied from 2467 to 25923 microg/kg (dry weight), the highest values of 25923 microg/kg being found in WJC WWTP. The concentrations of Benzo[a]pyrene were as high as 6.1mg/kg dry weight in WJC sewage sludge, exceeding the maximum permitted content by GB18918-2002. Individual PAH content varies considerably with sewage samples. The ratios of anthracene to anthracene plus phenanthrene (An/178), benz[a]anthracene to benz[a]anthracene plus chrysene (BaA/228), indene[1,2,3-cd]pyrene to indene[1,2,3-cd]pyrene plus benzo[g,h,i]perylene (In/In+BP), and fluoranthene to fluoranthene plus pyrene (Fl/Fl+Py) suggest that petroleum and combustion of fossil fuel were the dominant contributions for the PAHs in sewage sludge. The concentrations of total PCDD/F in the sewage sludge ranged from 330 to 4245 pg/g d.w. The toxicity equivalent concentrations is between 3.47-88.24 pg I-TEQ according to NATO/CCMS, which is below Chinese legislation limit value proposed for land application. The PCDD/F congener/homologue profiles found in the Beijing samples indicated that the high chlorinated PCDD/F contamination might originate mainly from PCP-related source and depositional sources while the low chlorinated PCDD/F homologues could be originating from incineration or coal combustion. The major source of PCDD/Fs in Beijing sludge is still unclear.

Evaluation of exposure to polycyclic aromatic hydrocarbons in a coke production and a graphite electrode manufacturing plant: assessment of urinary excretion of 1-hydroxypyrene as a biological indicator of exposure.

PubMed Central

Buchet, J P; Gennart, J P; Mercado-Calderon, F; Delavignette, J P; Cupers, L; Lauwerys, R

1992-01-01

OBJECTIVES--Characterisation of the airborne concentration of 13 polycyclic aromatic hydrocarbons (PAHs) at various workplaces in a graphite electrode and a coke production plant. Validation of the urinary excretion of 1-hydroxypyrene (hydroxypyrene) as a biological marker of exposure to PAH. DESIGN--Cross sectional study of workers exposed to PAHs (106 in the graphite electrode producing plant and 16 in the coke works). METHODS--Personal air sampling during at least six hours per workshift using a glass fibre filter and a Chromosorb 102 solid sorbent tube and analysis of PAHs by high performance liquid chromatography (HPLC) and spectrofluorometric detection (SFD). Collection of spot urine samples before and after the shift and analysis of 1-hydroxypyrene by HPLC and SFD. RESULTS--The workers most exposed to PAHs were those occupied at the topside area of the coke oven plant and those working in the blending and impregnation areas of the graphite electrode producing plant (mean airborne concentration of total PAHs: 199 and 223 micrograms/m3 respectively). Except for naphthalene and perylene, the relative proportion of the different PAHs did not differ between the plants. Pyrene concentration in air was highly correlated with the total airborne PAH concentration (r = 0.83, p < 0.0001) and the correlation coefficients between hydroxypyrene concentration in postshift urine samples and pyrene or total PAHs in air were 0.67 (p < 0.0001) and 0.72 (p < 0.0001) respectively. Excretion of hydroxypyrene doubled when the exposure to pyrene in air increased 10-fold. The half life for the urinary excretion of hydroxypyrene was around 18 hours (95% confidence interval 16.1-19.8). Smoking habits only explained 2.3% of the variance in hydroxypyrene excretion compared with 45% for the pyrene concentration in air. CONCLUSION--The determination of the urinary excretion of hydroxypyrene in postshift urine samples can be used as a suitable biomarker to assess individual exposure to PAHs in coke ovens and in graphite electrode manufacturing plants. PMID:1463676

Organic compounds of PM2.5 in Mexico Valley: spatial and temporal patterns, behavior and sources.

PubMed

Amador-Muñoz, O; Villalobos-Pietrini, R; Miranda, J; Vera-Avila, L E

2011-03-15

A longitudinal study on spatial and temporal behavior of particles less than 2.5 μm (PM(2.5)), solvent extracted organic matter (SEOM), polycyclic aromatic hydrocarbons (PAH), n-alkanes and nitro-PAH was carried out for a full year in 2006, at five sites simultaneously around the Metropolitan Zone of Mexico Valley (MZMV). There is rather uniform distribution of PM(2.5) and SEOM in the MZMV regarding gravimetric mass concentration, while some specific organic chemical components showed mass heterogeneity. The highest mass concentrations of target compounds occurred in the dry seasons with respect to the rainy season. Bonfires and fireworks are probably responsible for extreme values of PM(2.5), SEOM and PAH (≥ 228 gmol(-1)). Benzo[ghi]perylene was the most abundant PAH, with C(24)-C(26) the most abundant n-alkanes and 2-nitrofluoranthene and 9-nitroanthracene the most abundant nitro-PAH. The northeast zone was the area with the greatest presence of sources of incomplete diesel combustion, while the central for gasoline combustion. In the southwest, the biogenic sources were more abundant over the anthropogenic sources. This was opposite to the other sites. Factor analysis allowed us to relate different compounds to emitting sources. Three main factors were associated with combustion, pyrolysis and biogenic primary sources while the other factors were associated with secondary organic aerosol formation and industry. Correlation analyses indicated that SEOM originates from different primary emission sources or is formed by different processes than the other variables, except in southwest. Associations among variables suggest that PM(2.5) in the northwest and in the southeast originated mainly from primary emissions or consisted of primary organic compounds. PM(2.5) in the northeast, central and southwest contains a greater proportion of secondary organic compounds, with the less oxidized organic aerosols in the northeast and the most aged organic aerosol in the southwest. This follows the trends in the prevailing wind directions in MZMV during 2006. Copyright © 2010 Elsevier B.V. All rights reserved.

Raman correlation spectroscopy: A feasibility study of a new optical correlation technique and development of multi-component nanoparticles using the reprecipitation method

NASA Astrophysics Data System (ADS)

Nishida, Maki

The feasibility of Raman correlation spectroscopy (RCS) is investigated as a new temporal optical fluctuation spectroscopy in this dissertation. RCS analyzes the correlations of the intensity fluctuations of Raman scattering from particles in a suspension that undergo Brownian motion. Because each Raman emission line arises from a specific molecular bond, the RCS method could yield diffusion behavior of specific chemical species within a dispersion. Due to the nature of Raman scattering as a coherent process, RCS could provide similar information as acquired in dynamic light scattering (DLS) and be practical for various applications that requires the chemical specificity in dynamical information. The theoretical development is discussed, and four experimental implementations of this technique are explained. The autocorrelation of the intensity fluctuations from a beta-carotene solution is obtained using the some configurations; however, the difficulty in precise alignment and weak nature of Raman scattering prevented the achievement of high sensitivity and resolution. Possible fluctuations of the phase of Raman scattering could also be affecting the results. A possible explanation of the observed autocorrelation in terms of number fluctuations of particles is also examined to test the feasibility of RCS as a new optical characterization method. In order to investigate the complex systems for which RCS would be useful, strategies for the creation of a multicomponent nanoparticle system are also explored. Using regular solution theory along with the concept of Hansen solubility parameters, an analytical model is developed to predict whether two or more components will form single nanoparticles, and what effect various processing conditions would have. The reprecipitation method was used to demonstrate the formation of the multi-component system of the charge transfer complex perylene:TCNQ (tetracyanoquinodimethane) and the active pharmaceutical ingredient cocrystal of CBZ:NCT (carbamazepine:nicotinamide). The experimental results with various characterization methods including DLS, absorption spectroscopy, powder x-ray diffraction, and SEM imaging, verify formation of the multicomponent cocrystals. The observation of the self-assembly of TCNQ crystals is also discussed.

Distribution and sources of bioaccumulative air pollutants at Mezquital Valley, Mexico, as reflected by the atmospheric plant Tillandsia recurvata L.

NASA Astrophysics Data System (ADS)

Zambrano García, A.; Medina Coyotzin, C.; Rojas Amaro, A.; López Veneroni, D.; Martínez, L. Chang; Sosa Iglesias, G.

2009-09-01

Mezquital Valley (MV), a Mexican wastewater-based agricultural and industrial region, is a "hot spot" of regulated air pollutants emissions, but the concurrent unregulated ones, like hazardous metals and polycyclic aromatic hydrocarbons (PAH), remain undocumented. A biomonitoring survey with the epiphytic Tillandsia recurvata was conducted there to detect spatial patterns and potential sources of 20 airborne elements and 15 PAH. The natural δ13C and δ15N ratios of this plant helped in source identification. The regional mean concentration of most elements was two (Cr) to over 40 times (Ni, Pb, V) higher than reported for Tillandsia in other countries. Eleven elements, pyrene and chrysene had 18-214% higher mean concentration at the industrial south than at the agricultural north of MV. The total quantified PAH (mean, 572 ng g-1; range, 143-2568) were composed by medium (65%, phenanthrene to chrysene), low (28%, naphthalene to fluorene) and high molecular weight compounds (7%, Benzo(b)fluoranthene to indeno(1,2,3-cd)pyrene). The δ13C (mean, -14.6‰; range, -15.7‰ to -13.7‰) was consistently lower than -15‰ near the major petroleum combustion sources. The δ15N (mean, -3.0‰; range, -9.9‰ to 3.3‰) varied from positive at agriculture/industrial areas to negative at rural sites. Factor analysis provided a five-factor solution for 74% of the data variance: 1) crustal rocks, 39.5% (Al, Ba, Cu, Fe, Sr, Ti); 2) soils, 11.3%, contrasting contributions from natural (Mg, Mn, Zn) and saline agriculture soils (Na); 3) cement production and fossil fuel combustion, 9.8% (Ca, Ni, V, chrysene, pyrene); 4) probable agricultural biomass burning, 8.1% (K and benzo(g,h,i)perylene), and 5) agriculture with wastewater, 5.2% (δ15N and P). These results indicated high deposition of bioaccumulative air pollutants at MV, especially at the industrial area. Since T. recurvata reflected the regional differences in exposition, it is recommended as a biomonitor for comparisons within and among countries where it is distributed: southern USA to Argentina.

Distribution and sources of bioaccumulative air pollutants at Mezquital Valley, Mexico, as reflected by the atmospheric plant Tillandsia recurvata L.

NASA Astrophysics Data System (ADS)

Zambrano García, A.; Medina Coyotzin, C.; Rojas Amaro, A.; López Veneroni, D.; Martínez, L. Chang; Sosa Iglesias, G.

2009-03-01

Mezquital Valley (MV), a Mexican wastewater-based agricultural and industrial region, is a ''hot spot'' of regulated air pollutants emissions, but the concurrent unregulated ones, like hazardous metals and polycyclic aromatic hydrocarbons (PAH), remain undocumented. A biomonitoring survey with the epiphytic Tillandsia recurvata was conducted there to detect spatial patterns and potential sources of 20 airborne elements and 15 PAH. The natural δ13C and δ15N ratios of this plant helped in source identification. The regional mean concentrations of most elements was two (Cr) to over 40 times (Ni, Pb, V) higher than reported for Tillandsia in other countries. Eleven elements, pyrene and chrysene had 18-214% higher mean concentration at the industrial south than at the agricultural north of MV. The total quantified PAH (mean, 572 ng g-1; range, 142.6-2568) were composed by medium (65%, phenanthrene to chrysene), low (28%, naphthalene to fluorene) and high molecular weight compounds (7%, Benzo(b)fluoranthene to indeno(1,2,3-cd)pyrene). The δ13C (mean, -14.6‰; range, -5.7 to -13.7‰) was lower (<-15‰) near the major petroleum combustion sources. The δ15N (mean, -3.0‰; range, -9.9 to 3.3‰) varied from positive at agriculture/industrial areas to negative at rural sites. Factor analysis provided a five-factor solution for 74% of the data variance: (1) crustal rocks, 39.5% (Al, Ba, Cu, Fe, Sr, Ti); (2) soils, 11.3%, contrasting contributions from natural (Mg, Mn, Zn) and saline agriculture soils (Na); (3) cement production and fossil fuel combustion, 9.8% (Ca, Ni, V, chrysene, pyrene); (4) probable agricultural biomass burning, 8.1% (K and benzo(g,h,i)perylene), and (5) agriculture with wastewater, 5.2% (δ15N and P). These results indicated high deposition of bioaccumulative air pollutants at MV, especially at the industrial area. Since T. recurvata reflected the regional differences in exposition, it is recommended as a biomonitor for comparisons within and among countries where it is distributed: southern USA to Argentina.

CYP63A2, a catalytically versatile fungal P450 monooxygenase capable of oxidizing higher-molecular-weight polycyclic aromatic hydrocarbons, alkylphenols, and alkanes.

PubMed

Syed, Khajamohiddin; Porollo, Aleksey; Lam, Ying Wai; Grimmett, Paul E; Yadav, Jagjit S

2013-04-01

Cytochrome P450 monooxygenases (P450s) are known to oxidize hydrocarbons, albeit with limited substrate specificity across classes of these compounds. Here we report a P450 monooxygenase (CYP63A2) from the model ligninolytic white rot fungus Phanerochaete chrysosporium that was found to possess a broad oxidizing capability toward structurally diverse hydrocarbons belonging to mutagenic/carcinogenic fused-ring higher-molecular-weight polycyclic aromatic hydrocarbons (HMW-PAHs), endocrine-disrupting long-chain alkylphenols (APs), and crude oil aliphatic hydrocarbon n-alkanes. A homology-based three-dimensional (3D) model revealed the presence of an extraordinarily large active-site cavity in CYP63A2 compared to the mammalian PAH-oxidizing (CYP3A4, CYP1A2, and CYP1B1) and bacterial aliphatic-hydrocarbon-oxidizing (CYP101D and CYP102A1) P450s. This structural feature in conjunction with ligand docking simulations suggested potential versatility of the enzyme. Experimental characterization using recombinantly expressed CYP63A2 revealed its ability to oxidize HMW-PAHs of various ring sizes, including 4 rings (pyrene and fluoranthene), 5 rings [benzo(a)pyrene], and 6 rings [benzo(ghi)perylene], with the highest enzymatic activity being toward the 5-ring PAH followed by the 4-ring and 6-ring PAHs, in that order. Recombinant CYP63A2 activity yielded monohydroxylated PAH metabolites. The enzyme was found to also act as an alkane ω-hydroxylase that oxidized n-alkanes with various chain lengths (C9 to C12 and C15 to C19), as well as alkyl side chains (C3 to C9) in alkylphenols (APs). CYP63A2 showed preferential oxidation of long-chain APs and alkanes. To our knowledge, this is the first P450 identified from any of the biological kingdoms that possesses such broad substrate specificity toward structurally diverse xenobiotics (PAHs, APs, and alkanes), making it a potent enzyme biocatalyst candidate to handle mixed pollution (e.g., crude oil spills).

Remobilization of polycyclic aromatic hydrocarbons and organic matter in seawater during sediment resuspension experiments from a polluted coastal environment: Insights from Toulon Bay (France).

PubMed

Guigue, Catherine; Tedetti, Marc; Dang, Duc Huy; Mullot, Jean-Ulrich; Garnier, Cédric; Goutx, Madeleine

2017-10-01

Polycyclic aromatic hydrocarbons (PAHs) and organic matter contents were measured in seawater during resuspension experiments using sediments collected from Toulon Bay (Northwestern Mediterranean Sea, France). The studied sediments were very highly contaminated in PAHs, especially in 4-ring compounds emitted from combustion processes. The sediments used for resuspension experiments were collected at 0-2 cm (diagenetically new organic matter, OM) and 30-32 cm depths (diagenetically transformed OM). They were both mostly composed of fine particles (<63 μm), enriched in organic carbon (8.2 and 6.3%, respectively) and in PAHs (concentration of Σ34 PAHs: 38.2 and 35.7 × 10 3  ng g -1 , respectively). The resuspension of these sediments led to an increase in concentrations of dissolved Σ34 PAHs, dissolved organic carbon (DOC) and dissolved humic- and tryptophan-like fluorophores in seawater up to 10-, 1.3-, 4.4- and 5.7-fold, respectively. The remobilization in seawater was higher for 4-6 ring PAHs, especially benzo(g,h,i)perylene, whose concentration exceeded the threshold values of the European Water Framework Directive. This noted the potential harmful effects of sediment resuspension on marine biota. From these sediment resuspension experiments, we determined OC-normalized partition coefficients of PAHs between sediment and water (K oc ) and found that during such events, the transfer of PAHs from sediment particles to seawater was lower than that predicted from octanol-water partition coefficients (K ow ) (i.e., measured K oc  > K oc predicted from K ow ). The results confirmed the sequestration role of sedimentary OC quality and grain size on PAHs; the OM diagenetic state seemed to impact the partition process but in a relatively minor way. Furthermore, differences were observed between 2-4 ring and 5-6 ring PAHs, with the latter displaying a relatively higher mobility towards seawater. These differences may be explained by the distribution of these two PAH pools within different OM moieties, such as humic substances and black carbon. Copyright © 2017 Elsevier Ltd. All rights reserved.

Source apportionment of indoor, outdoor and personal PM2.5 exposure of pregnant women in Barcelona, Spain

NASA Astrophysics Data System (ADS)

Minguillón, M. C.; Schembari, A.; Triguero-Mas, M.; de Nazelle, A.; Dadvand, P.; Figueras, F.; Salvado, J. A.; Grimalt, J. O.; Nieuwenhuijsen, M.; Querol, X.

2012-11-01

Exposure to air pollution has been shown to adversely affect foetal development in the case of pregnant women. The present study aims to investigate the PM composition and sources influencing personal exposure of pregnant women in Barcelona. To this end, indoor, outdoor and personal exposure measurements were carried out for a selection of 54 pregnant women between November 2008 and November 2009. PM2.5 samples were collected during two consecutive days and then analysed for black smoke (BS), major and trace elements, and polycyclic aromatic hydrocarbons (PAHs) concentrations. Personal information such as commuting patterns and cosmetics use was also collected. PM2.5 concentrations were higher for personal samples than for indoor and outdoor environments. Indoor, outdoor and personal BS and sulphate concentrations were strongly correlated, although some specific indoor and outdoor sulphate sources may exist. Average trace elements concentrations were similar indoor, outdoor and for personal exposure, but the correlations were moderate for most of them. Most of the PAHs concentrations showed strong correlations indoor-outdoor. A source apportionment analysis of the PM composition data by means of a Positive Matrix Factorization (PMF) resulted in the identification of six sources for the outdoor and indoor environments: secondary sulphate, fueloil + sea salt (characterized by V, Ni, Na and Mg), mineral, cigarette (characterized by K, Ce, Cd, benzo(k)fluoranthene and benzo(ghi)perylene), road traffic (characterized by BS and low weight PAHs), and industrial (characterized by Pb, Sn, Cu, Mn and Fe). For personal exposure two specific sources were found: cosmetics (characterized by abundance of Ca, Li, Ti and Sr and the absence of Al) and train/subway (characterized by Fe, Mn, Cu and Ba). The contribution of the sources varied widely among women, especially for cigarette (from zero to up to 4 μg m-3), train/subway (up to more than 6 μg m-3) and cosmetics (up to more than 5 μg m-3). The source contributions showed generally strong correlations indoor-outdoor although the infiltration efficiencies varied among homes. This study emphasizes the importance of relying on personal exposure in epidemiological studies assessing the impact of air pollution on human health.

Opposing seasonal trends for polycyclic aromatic hydrocarbons and PM10: Health risk and sources in southwest Mexico City

NASA Astrophysics Data System (ADS)

Amador-Muñoz, Omar; Bazán-Torija, S.; Villa-Ferreira, S. A.; Villalobos-Pietrini, Rafael; Bravo-Cabrera, José Luis; Munive-Colín, Zenaida; Hernández-Mena, Leonel; Saldarriaga-Noreña, H.; Murillo-Tovar, M. A.

2013-03-01

This study reports the measurement of polycyclic aromatic hydrocarbons (PAHs) in airborne particles ≤ 10 μm (PM10) during four years. Seasonal variation was observed for PM10 and PAH in southwest Mexico City, with major mass concentrations during the dry season (November-April). A non linear decreasing trend of PM10 was observed during this period, while a linear increase (in the four years) was obtained for benzo[a]pyrene (88 pg m- 3), phenanthrene (29 pg m- 3), fluoranthene (88 pg m- 3), and benzo[ghi]perylene (438 pg m- 3). Coronene also showed an increasing trend but it was nonlinear. This suggests that air control strategies implemented by the government contributed to maintaining PM10 under the 24 h maximum limit and resulted in a decreasing trend during this period. However, these strategies did not result in controlling some organic constituents with mutagenic and/or carcinogenic properties as it is the case of benzo[a]pyrene. The annual average of this PAH exceeded the UK recommendation. It was estimated a median (10th-90th) lifetime health risk of 7.6 (3.4-17.2) additional cases of cancer per 10 million people in this zone exists and the health risk of PAH is almost three times greater in dry seasons than it is in rainy seasons. Specific humidity, temperature and wind speed acted as cleaners for PM10 and PAH from the atmosphere. PAH diagnostic ratios and correlation and principal component analyses suggest incomplete combustion from gasoline and diesel engines as the main contributor to PAH found in southwest Mexico City, where factor 1 grouped all PAH emitted from gasoline engines during first three years. During last year, factor 1 only grouped PAH markers of diesel engines. This suggests a change of emission amounts between gasoline and diesel combustion sources or a contribution of other source(s) which changed the PAH profiles. During four years retene was always separated from factors which grouped the rest of PAH, due to its wood combustion origin.

Biomonitoring, status and source risk assessment of polycyclic aromatic hydrocarbons (PAHs) using honeybees, pine tree leaves, and propolis.

PubMed

Kargar, Navid; Matin, Golnar; Matin, Amir Abbas; Buyukisik, Hasan Baha

2017-11-01

In this study, to identify and quantify the sources of airborne polycyclic aromatic hydrocarbons (PAHs), we gathered honeybee, pine tree leaf, and propolis samples to serve as bioindicators from five stations in the village of "Bozkoy" in the Aliaga industrial district of Izmir (Turkey) during April-May 2014. The PAH concentrations which measured by gas chromatography (GC) varied from 261.18 to 553.33 μg kg -1 dry weight (dw) in honeybee samples, 138.57-853.67 μg kg -1 dw in pine leaf samples, and 798.61-2905.53 μg kg -1 dw in propolis samples. The total PAH concentrations can be ranked as follows: propolis > pine leaves > honeybees. The ring sequence pattern was 5 > 3 > 6 > 4 > 2 for honeybees, 5 > 3 > 4 > 6 > 2 for pine leaves, and 5 > 4 > 6 > 3 > 2 for propolis. The diagnostic ratios [fluoranthene/fluoranthene + pyrene], [indeno(1,2,3-c,d)pyrene/indeno(1,2,3-c,d)pyrene + benzo(g,h,i)perylene], and [benzo(a)anthracene/benzo(a)anthracene + chrysene] indicate coal and biomass combustion to be the dominant PAH source in the study area. In biomonitoring studies of airborne PAHs based on honeybees, fluoranthene is considered to be a characteristic PAH compound. Distribution maps with different numbers of PAH rings among the sampling sites show the advantages of honeybee samples as indicators due to the honeybee's provision of a broader range of information with respect to heavier pollutants that are typically not in the gas or suspended phase for long periods of time. Our correlation, factor analysis, and principal components analysis (PCA) results indicate potential sources of PAH pollution in pine leaves and honeybees from airborne emissions, but we found propolis to be contaminated by PAHs due to the replacement of herbal sources of resins with synthetic gummy substances from paving materials (e.g., asphalt and tar leaks). Copyright © 2017 Elsevier Ltd. All rights reserved.

Investigating the use of oil platform marine fouling invertebrates as monitors of oil exposure in the Northern Gulf of Mexico.

PubMed

Pie, Hannah V; Heyes, Andrew; Mitchelmore, Carys L

2015-03-01

The concentration of 51 parent and alkylated PAHs was examined in oysters, Ostrea equestris, and corals, Tubastrea coccinea, collected from oil-rig structures off the coast of Louisiana during April and May 2011 to investigate their potential use as monitors for offshore contamination events. Corals and oysters collected from both sampling trips had lower PAH accumulation than most bivalves collected in previous studies near the shoreline of Louisiana and elsewhere in the Gulf of Mexico. In April, total PAH (TPAH) concentrations ranged from 8.73 to 15.17 ng g(-1) in corals and 2.52 to 22.04 ng g(-1) in oysters. In May, corals and oysters had elevated concentrations of TPAH ranging from 24.28 to 79.23 ng g(-1) and 7.18 to 95.55 ng g(-1), respectively. This increase could be a result of Mississippi River flooding that occurred during that time, as evidenced by the high perylene concentrations (3.92-41.49 ng g(-1)) measured in May oysters. Oysters and corals collected in May from MC21B, the closest rig to the Mississippi River Delta, had the highest TPAH concentrations observed among all locations and the only rig to have predominantly petrogenic source inputs. Overall, given the low baseline of PAHs demonstrated in this study and the rapid accumulation of diagnostic chemicals in response to a possible contamination event (i.e. sediment plume from May flooding), oil-rig invertebrates could make excellent monitoring tools to examine the exposure to and recovery from oil (and oil-spill response options) in the offshore Northern Gulf of Mexico. Pre-spill baseline data of chemical and biological biomarkers of contamination is key to better estimating the impacts and recovery of oil exposure. Therefore, this screen of PAH accumulation represents a crucial first step in determining baseline contaminant levels in order to utilize these unique resources as monitors for offshore oil exposure in the Northern Gulf of Mexico. Copyright © 2014 Elsevier B.V. All rights reserved.

Charge Generation and Recombination in Organic Materials for Photovoltaics

NASA Astrophysics Data System (ADS)

Ramirez, Jessica Jacklyn

Understanding the nature of molecular exciton states is critical for the design of organic photovoltaic materials that push current device efficiencies into the next realm. This thesis describes several research projects that have sought to further our understanding of the generation and recombination of charge carriers, facilitated by such excitonic states, in organic systems. We begin with fundamental studies on the excited-state dynamics of several fullerene derivatives. We also venture away from the traditional fullerene-based electron acceptors and consider several derivatized perylene diimides as alternate electron acceptors. We then report on the observation of a broad, structureless, emission emanating from charge-generating films comprised of perfluoroalkyl fullerene derivatives dilutely dispersed in polyfluorene hosts. We have determined that this red-shifted PL signature is the result of radiative recombination from a charge-transfer state that is populated initially as a precursor to charge generation, and may be repopulated upon charge recombination. Our data offers an observable link between charge-generation and charge-transfer emission that is kinetically associated with carrier recombination, and we utilize this link to probe the influence of driving force and polymer microstructure in the fundamental processes of charge generation and decay in small molecule/polymer heterojunctions. Thereafter, we sought to develop our understanding of a novel photophysical mechanism (known as energy pooling) which would allow for the energy of multiple excitons to be 'pooled' towards a central molecular moiety, where the individual exciton energies may add together to create a single highly excited excitonic state. This upconversion-like process would facilitate more efficient photocurrent generation in devices utilizing this mode of charge separation. The primary modes of inquiry utilized in this work come from the spectroscopic techniques of absorbance, steady-state and time-resolved photoluminescence, transient absorption and time-resolved microwave conductivity. Some secondary methods employed include cyclic voltammetry, X-ray diffraction and computational tools from density functional theory. This utilization of both experimental and theoretical methodologies provides a powerful approach to furthering our understanding of both the fundamental photophysics of the systems studied, as well as the charge generation and recombination pathways occurring at organic donor-acceptor interfaces, helping to guide the design of more efficient organic photovoltaics.

Sources of polycyclic hydrocarbons and pesticides in soluble fraction of deposition samples in Kocaeli, Turkey.

PubMed

Binici, Burcu; Yenisoy-Karakaş, Serpil; Bilsel, Mine; Durmaz-Hilmioğlu, Nilüfer

2014-02-01

A wet-dry deposition sampler was located at The Scientific and Technological Research Council of Turkey-National Metrology Institute (TUBITAK-UME) station, and a bulk deposition sampler was placed at the Kadıllı village to determine the atmospheric deposition flux of polycyclic aromatic hydrocarbons (PAHs) and pesticides (organochlorine and organophosphorus) in soluble fraction of samples in Kocaeli, Turkey. The 28 samples for each wet, dry, and total deposition were collected weekly from March 2006 to March 2007. Gas chromatography-tandem mass spectrometry was used to analyze the samples which were prepared by using solid-phase extraction (SPE) method. The sum of volume weighted mean of deposition fluxes was obtained as 7.43 μg m(-2) day(-1) for wet deposition, 0.28 μg m(-2) day(-1) for dry deposition and 0.54 μg m(-2) day(-1) for bulk deposition samples for PAHs and 9.88 μg m(-2) day(-1) for wet deposition, 4.49 μg m(-2) day(-1) for dry deposition, and 3.29 μg m(-2) day(-1) for bulk deposition samples for pesticides. While benzo(a)anthracene had the highest fluxes among PAH compounds for all types of depositions, guthion and phosphamidon had the highest deposition flux compared with the other pesticides. Benzo(ghi)perylene, dibenz(a,h)anthracene, indeno(1,2,3-c,d)pyrene, benzo(a)pyrene, and acenaphthene were not detected in any of the samples. Beta-HCH, gamma-HCH, and endrin aldehyde were the only compounds among 18 organochlorine pesticides to be detected in all deposition samples. The main sources of pesticides were the high number of greenhouses around the sampling stations. However, all of the organophosphorus pesticides were detected in all deposition samples. The pollution sources were identified as coal and natural gas combustion, petrogenic sources, and traffic for TUBITAK-UME station whereas coal and natural gas combustion and traffic were the main sources for Kadıllı station by considering the results of factor analysis, ratios, and wind sector analysis.

Polycyclic aromatic hydrocarbons associated with total suspended particles and surface soils in Kunming, China: distribution, possible sources, and cancer risks.

PubMed

Yang, Xiaoxia; Ren, Dong; Sun, Wenwen; Li, Xiaoman; Huang, Bin; Chen, Rong; Lin, Chan; Pan, Xuejun

2015-05-01

The concentrations, distribution, possible sources, and cancer risks of polycyclic aromatic hydrocarbons (PAHs) in total suspended particles (TSPs) and surface soils collected from the same sampling spots were compared in Kunming, China. The total PAH concentrations were 9.35-75.01 ng/m(3) and 101.64-693.30 ng/g dry weight (d.w.), respectively, in TSPs and surface soils. Fluoranthene (FLA), pyrene (PYR), chrysene (CHR), and phenanthrene (PHE) were the abundant compounds in TSP samples, and phenanthrene (PHE), fluorene (FLO), fluoranthene (FLA), benzo[b]fluoranthene (BbF), and benzo[g,h,i]perylene (BghiP) were the abundant compounds in surface soil samples. The spatial distribution of PAHs in TSPs is closely related to the surrounding environment, which varied significantly as a result of variations in source emission and changes in meteorology. However, the spatial distribution of PAHs in surface soils is supposed to correlate with a city's urbanization history, and high levels of PAHs were always observed in industry district, or central or old district of city. Based on the diagnostic ratios and principal component analysis (PCA), vehicle emissions (especially diesel-powered vehicles) and coal and wood combustion were the main sources of PAHs in TSPs, and the combustion of wood and coal, and spills of unburnt petroleum were the main sources of PAHs in the surface soils. The benzo[a]pyrene equivalent concentration (BaPeq) for the TSPs and surface soil samples were 0.16-2.57 ng/m(3) and 11.44-116.03 ng/g d.w., respectively. The incremental lifetime cancer risk (ILCR) exposed to particulate PAHs ranged from 10(-4) to 10(-3) indicating high potential of carcinogenic risk, and the ILCR exposed to soil PAHs was from 10(-7) to 10(-6) indicating virtual safety. These presented results showed that particle-bound PAHs had higher potential carcinogenic ability for human than soil PAHs. And, the values of cancer risk for children were always higher than for adults, which demonstrated that children were sensitive to carcinogenic effects of PAHs.

Update of on-line coupled liquid chromatography - gas chromatography for the analysis of mineral oil hydrocarbons in foods and cosmetics.

PubMed

Biedermann, Maurus; Munoz, Celine; Grob, Koni

2017-10-27

On-line coupled high performance liquid chromatography-gas chromatography-flame ionization detection (HPLC-GC-FID) is the most widely used method for the analysis of mineral oil hydrocarbons in food, food contact materials, tissues and cosmetics. With comprehensive two-dimensional gas chromatography (GCxGC), a tool became available for better establishing the elution sequence of the various types of hydrocarbons from the HPLC column used for isolating the mineral oil saturated hydrocarbons (MOSH) and mineral oil aromatic hydrocarbons (MOAH). The performance of a heavily used HPLC column with reduced retention for MOAH was investigated to improve the robustness of the method. Updates are recommended that render the MOSH/MOAH separation less dependent of the state of the HPLC column and more correct in cases of highly refined mineral oil products of high molecular mass. Cyclohexyl cyclohexane (Cycy), used as internal standard, turned out to be eluted slightly after cholestane (Cho); apparently the size exclusion effect predominates the extra retention by ring number on the 60Å pore size silica gel. Hence, Cycy can be used to determine the end of the MOSH fraction. Long chain alkyl benzenes were eluted earlier than tri-tert. butyl benzene (Tbb). It is proposed to start the MOAH transfer immediately after the MOSH fraction and use a gradient causing breakthrough of dichloromethane (visible in the UV chromatogram) at a time suitable to elute perylene (Per) at the end of the fraction. In this way, a decrease in retention power of the HPLC column can be tolerated without adjustment of the MOAH fraction until some MOAH start being eluted into the MOSH fraction. This critical point can be checked either with di(2-ethylhexyl) benzene (DEHB) as a marker or the HPLC-UV chromatogram. Finally, based on new findings in rats and human tissues, it is recommended to integrate the MOSH and MOAH up to the retention time of the n-alkane C40. Copyright © 2017 Elsevier B.V. All rights reserved.

CYP63A2, a Catalytically Versatile Fungal P450 Monooxygenase Capable of Oxidizing Higher-Molecular-Weight Polycyclic Aromatic Hydrocarbons, Alkylphenols, and Alkanes

PubMed Central

Syed, Khajamohiddin; Porollo, Aleksey; Lam, Ying Wai; Grimmett, Paul E.

2013-01-01

Cytochrome P450 monooxygenases (P450s) are known to oxidize hydrocarbons, albeit with limited substrate specificity across classes of these compounds. Here we report a P450 monooxygenase (CYP63A2) from the model ligninolytic white rot fungus Phanerochaete chrysosporium that was found to possess a broad oxidizing capability toward structurally diverse hydrocarbons belonging to mutagenic/carcinogenic fused-ring higher-molecular-weight polycyclic aromatic hydrocarbons (HMW-PAHs), endocrine-disrupting long-chain alkylphenols (APs), and crude oil aliphatic hydrocarbon n-alkanes. A homology-based three-dimensional (3D) model revealed the presence of an extraordinarily large active-site cavity in CYP63A2 compared to the mammalian PAH-oxidizing (CYP3A4, CYP1A2, and CYP1B1) and bacterial aliphatic-hydrocarbon-oxidizing (CYP101D and CYP102A1) P450s. This structural feature in conjunction with ligand docking simulations suggested potential versatility of the enzyme. Experimental characterization using recombinantly expressed CYP63A2 revealed its ability to oxidize HMW-PAHs of various ring sizes, including 4 rings (pyrene and fluoranthene), 5 rings [benzo(a)pyrene], and 6 rings [benzo(ghi)perylene], with the highest enzymatic activity being toward the 5-ring PAH followed by the 4-ring and 6-ring PAHs, in that order. Recombinant CYP63A2 activity yielded monohydroxylated PAH metabolites. The enzyme was found to also act as an alkane ω-hydroxylase that oxidized n-alkanes with various chain lengths (C9 to C12 and C15 to C19), as well as alkyl side chains (C3 to C9) in alkylphenols (APs). CYP63A2 showed preferential oxidation of long-chain APs and alkanes. To our knowledge, this is the first P450 identified from any of the biological kingdoms that possesses such broad substrate specificity toward structurally diverse xenobiotics (PAHs, APs, and alkanes), making it a potent enzyme biocatalyst candidate to handle mixed pollution (e.g., crude oil spills). PMID:23416995

Impact of electrochemical treatment of soil washing solution on PAH degradation efficiency and soil respirometry.

PubMed

Mousset, Emmanuel; Huguenot, David; van Hullebusch, Eric D; Oturan, Nihal; Guibaud, Gilles; Esposito, Giovanni; Oturan, Mehmet A

2016-04-01

The remediation of a genuinely PAH-contaminated soil was performed, for the first time, through a new and complete investigation, including PAH extraction followed by advanced oxidation treatment of the washing solution and its recirculation, and an analysis of the impact of the PAH extraction on soil respirometry. The study has been performed on the remediation of genuine PAH-contaminated soil, in the following three steps: (i) PAH extraction with soil washing (SW) techniques, (ii) PAH degradation with an electro-Fenton (EF) process, and (iii) recirculation of the partially oxidized effluent for another SW cycle. The following criteria were monitored during the successive washing cycles: PAH extraction efficiency, PAH oxidation rates and yields, extracting agent recovery, soil microbial activity, and pH of soil. Two representative extracting agents were compared: hydroxypropyl-beta-cyclodextrin (HPCD) and a non-ionic surfactant, Tween(®) 80. Six PAH with different numbers of rings were monitored: acenaphthene (ACE), phenanthrene (PHE), fluoranthene (FLA), pyrene (PYR), benzo(a)pyrene (BaP), and benzo(g,h,i)perylene (BghiP). Tween(®) 80 showed much better PAH extraction efficiency (after several SW cycles) than HPCD, regardless of the number of washing cycles. Based on successive SW experiments, a new mathematical relation taking into account the soil/water partition coefficient (Kd*) was established, and could predict the amount of each PAH extracted by the surfactant with a good correlation with experimental results (R(2) > 0.975). More HPCD was recovered (89%) than Tween(®) 80 (79%), while the monitored pollutants were completely degraded (>99%) after 4 h and 8 h, respectively. Even after being washed with partially oxidized solutions, the Tween(®) 80 solutions extracted significantly more PAH than HPCD and promoted better soil microbial activity, with higher oxygen consumption rates. Moreover, neither the oxidation by-products nor the acidic media (pH approximately 3) of the partially oxidized solution inhibited the general soil microbial activity during the washing cycle. Copyright © 2016 Elsevier Ltd. All rights reserved.

Survey on the micro-pollutants presence in surface water system of northern Serbia and environmental and health risk assessment.

PubMed

Škrbić, Biljana D; Kadokami, Kiwao; Antić, Igor

2018-06-07

This study demonstrates the occurrence of 940 organic micro-pollutants in surface water of four rivers, one irrigation canal system, and two lakes in Vojvodina Province, the northern part of Serbia, summing in total eighteen samples. The number of detected chemicals ranged from 22 to 84, with 127 micro-pollutants detected at least once, representing 13% of the studied substances. The targeted compounds include n-alkanes, sterols, polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides polychlorinated biphenyls, pesticides, pharmaceutical active compounds, industrial chemicals, plasticizers, etc. Among the analysed compounds, sterols were the most dominant with maximum quantified concentrations. The substances which were quantified with frequency over 50% were two PAHs (2-methylnaphthalene, benzo(ghi)perylene), five sterols (cholesterol, cholestanol, stigmasterol, fucosterol, beta-sitosterol), three pharmaceuticals and personal care products (L-menthol, diethyltoluamide, caffeine), and ten household chemicals (4-tert-octylphenol, dimethyl phthalate, methyl palmitate, phenylethyl alcohol, 1-nonanol, alpha-terpineol, 2-phenoxy-ethanol, methyl myristate, acetophenone, and 2-ethyl-1-hexanol). The list of priority substances under the European Union Directive 2013/39/EU includes 49 priority substances (PSs) out of which 34 were analysed. Among these, eleven PSs were quantified, and only two compounds (fluoranthene and benzo (a) pyrene) exceeded EU Environmental Quality Standards targeted values. The obtained results were compared with the previously published data that dealt with the same targeted number of micro-pollutants in sediment samples. This revealed connections between the same sampling locations. Environmental risk assessment showed the existence of potential ecological risk as 72% of the obtained values for the ecological hazard index (HI) at investigated locations were higher that the targeted value (HI > 1). Estimated values for hazard quotient (HQ) and hazard index (HI) for non-carcinogenic risk were lower than the targeted value, indicating no non-carcinogenic risk through dermal contact and non-intentional ingestion of water. Estimated values for cancer risk were all below 1 × 10 -6 , which is not considered to pose significant human health risk. Copyright © 2018. Published by Elsevier Inc.

Unimolecular reaction energies for polycyclic aromatic hydrocarbon ions.

PubMed

West, Brandi; Rodriguez Castillo, Sarah; Sit, Alicia; Mohamad, Sabria; Lowe, Bethany; Joblin, Christine; Bodi, Andras; Mayer, Paul M

2018-03-07

Imaging photoelectron photoion coincidence spectroscopy was employed to explore the unimolecular dissociation of the ionized polycyclic aromatic hydrocarbons (PAHs) acenaphthylene, fluorene, cyclopenta[d,e,f]phenanthrene, pyrene, perylene, fluoranthene, dibenzo[a,e]pyrene, dibenzo[a,l]pyrene, coronene and corannulene. The primary reaction is always hydrogen atom loss, with the smaller species also exhibiting loss of C 2 H 2 to varying extents. Combined with previous work on smaller PAH ions, trends in the reaction energies (E 0 ) for loss of H from sp 2 -C and sp 3 -C centres, along with hydrocarbon molecule loss were found as a function of the number of carbon atoms in the ionized PAHs ranging in size from naphthalene to coronene. In the case of molecules which possessed at least one sp 3 -C centre, the activation energy for the loss of an H atom from this site was 2.34 eV, with the exception of cyclopenta[d,e,f]phenanthrene (CPP) ions, for which the E 0 was 3.44 ± 0.86 eV due to steric constraints. The hydrogen loss from PAH cations and from their H-loss fragments exhibits two trends, depending on the number of unpaired electrons. For the loss of the first hydrogen atom, the energy is consistently ca. 4.40 eV, while the threshold to lose the second hydrogen atom is much lower at ca. 3.16 eV. The only exception was for the dibenzo[a,l]pyrene cation, which has a unique structure due to steric constraints, resulting in a low H loss reaction energy of 2.85 eV. If C 2 H 2 is lost directly from the precursor cation, the energy required for this dissociation is 4.16 eV. No other fragmentation channels were observed over a large enough sample set for trends to be extrapolated, though data on CH 3 and C 4 H 2 loss obtained in previous studies is included for completeness. The dissociation reactions were also studied by collision induced dissociation after ionization by atmospheric pressure chemical ionization. When modeled with a simple temperature-based theory for the post-collision internal energy distribution, there was reasonable agreement between the two sets of data.

Variations in speciated emissions from spark-ignition and compression-ignition motor vehicles in California's south coast air basin.

PubMed

Fujita, Eric M; Zielinska, Barbara; Campbell, David E; Arnott, W Patrick; Sagebiel, John C; Mazzoleni, Lynn; Chow, Judith C; Gabele, Peter A; Crews, William; Snow, Richard; Clark, Nigel N; Wayne, W Scott; Lawson, Douglas R

2007-06-01

The U.S. Department of Energy Gasoline/Diesel PM Split Study examined the sources of uncertainties in using an organic compound-based chemical mass balance receptor model to quantify the contributions of spark-ignition (SI) and compression-ignition (CI) engine exhaust to ambient fine particulate matter (PM2.5). This paper presents the chemical composition profiles of SI and CI engine exhaust from the vehicle-testing portion of the study. Chemical analysis of source samples consisted of gravimetric mass, elements, ions, organic carbon (OC), and elemental carbon (EC) by the Interagency Monitoring of Protected Visual Environments (IMPROVE) and Speciation Trends Network (STN) thermal/optical methods, polycyclic aromatic hydrocarbons (PAHs), hopanes, steranes, alkanes, and polar organic compounds. More than half of the mass of carbonaceous particles emitted by heavy-duty diesel trucks was EC (IMPROVE) and emissions from SI vehicles contained predominantly OC. Although total carbon (TC) by the IMPROVE and STN protocols agreed well for all of the samples, the STN/IMPROVE ratios for EC from SI exhaust decreased with decreasing sample loading. SI vehicles, whether low or high emitters, emitted greater amounts of high-molecular-weight particulate PAHs (benzo[ghi]perylene, indeno[1,2,3-cd]pyrene, and coronene) than did CI vehicles. Diesel emissions contained higher abundances of two- to four-ring semivolatile PAHs. Diacids were emitted by CI vehicles but are also prevalent in secondary organic aerosols, so they cannot be considered unique tracers. Hopanes and steranes were present in lubricating oil with similar composition for both gasoline and diesel vehicles and were negligible in gasoline or diesel fuels. CI vehicles emitted greater total amounts of hopanes and steranes on a mass per mile basis, but abundances were comparable to SI exhaust normalized to TC emissions within measurement uncertainty. The combustion-produced high-molecular-weight PAHs were found in used gasoline motor oil but not in fresh oil and are negligible in used diesel engine oil. The contributions of lubrication oils to abundances of these PAHs in the exhaust were large in some cases and were variable with the age and consumption rate of the oil. These factors contributed to the observed variations in their abundances to total carbon or PM2.5 among the SI composition profiles.

Monitoring of environmental exposure to polycyclic aromatic hydrocarbons: a review.

PubMed

Srogi, K

2007-01-01

Polycyclic aromatic hydrocarbons (PAHs) are a large group of organic compounds with two or more fused aromatic rings. They have a relatively low solubility in water, but are highly lipophilic. Most of the PAHs with low vapour pressure in the air are adsorbed on particles. When dissolved in water or adsorbed on particulate matter, PAHs can undergo photodecomposition when exposed to ultraviolet light from solar radiation. In the atmosphere, PAHs can react with pollutants such as ozone, nitrogen oxides and sulfur dioxide, yielding diones, nitro- and dinitro-PAHs, and sulfonic acids, respectively. PAHs may also be degraded by some microorganisms in the soil. PAHs are widespread environmental contaminants resulting from incomplete combustion of organic materials. The occurrence is largely a result of anthropogenic emissions such as fossil fuel-burning, motor vehicle, waste incinerator, oil refining, coke and asphalt production, and aluminum production, etc. PAHs have received increased attention in recent years in air pollution studies because some of these compounds are highly carcinogenic or mutagenic. Eight PAHs (Car-PAHs) typically considered as possible carcinogens are: benzo(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene (B(a)P), dibenzo(a,h)anthracene, indeno(1,2,3-cd)pyrene and benzo(g,h,i)perylene. In particular, benzo(a)pyrene has been identified as being highly carcinogenic. The US Environmental Protection Agency (EPA) has promulgated 16 unsubstituted PAHs (EPA-PAH) as priority pollutants. Thus, exposure assessments of PAHs in the developing world are important. The scope of this review will be to give an overview of PAH concentrations in various environmental samples and to discuss the advantages and limitations of applying these parameters in the assessment of environmental risks in ecosystems and human health. As it well known, there is an increasing trend to use the behavior of pollutants (i.e. bioaccumulation) as well as pollution-induced biological and biochemical effects on human organisms to evaluate or predict the impact of chemicals on ecosystems. Emphasis in this review will, therefore, be placed on the use of bioaccumulation and biomarker responses in air, soil, water and food, as monitoring tools for the assessment of the risks and hazards of PAH concentrations for the ecosystem, as well as on its limitations.

Cancer risk assessment, indicators, and guidelines for polycyclic aromatic hydrocarbons in the ambient air.

PubMed Central

Boström, Carl-Elis; Gerde, Per; Hanberg, Annika; Jernström, Bengt; Johansson, Christer; Kyrklund, Titus; Rannug, Agneta; Törnqvist, Margareta; Victorin, Katarina; Westerholm, Roger

2002-01-01

Polycyclic aromatic hydrocarbons (PAHs) are formed during incomplete combustion. Domestic wood burning and road traffic are the major sources of PAHs in Sweden. In Stockholm, the sum of 14 different PAHs is 100-200 ng/m(3) at the street-level site, the most abundant being phenanthrene. Benzo[a]pyrene (B[a]P) varies between 1 and 2 ng/m(3). Exposure to PAH-containing substances increases the risk of cancer in humans. The carcinogenicity of PAHs is associated with the complexity of the molecule, i.e., increasing number of benzenoid rings, and with metabolic activation to reactive diol epoxide intermediates and their subsequent covalent binding to critical targets in DNA. B[a]P is the main indicator of carcinogenic PAHs. Fluoranthene is an important volatile PAH because it occurs at high concentrations in ambient air and because it is an experimental carcinogen in certain test systems. Thus, fluoranthene is suggested as a complementary indicator to B[a]P. The most carcinogenic PAH identified, dibenzo[a,l]pyrene, is also suggested as an indicator, although it occurs at very low concentrations. Quantitative cancer risk estimates of PAHs as air pollutants are very uncertain because of the lack of useful, good-quality data. According to the World Health Organization Air Quality Guidelines for Europe, the unit risk is 9 X 10(-5) per ng/m(3) of B[a]P as indicator of the total PAH content, namely, lifetime exposure to 0.1 ng/m(3) would theoretically lead to one extra cancer case in 100,000 exposed individuals. This concentration of 0.1 ng/m(3) of B[a]P is suggested as a health-based guideline. Because the carcinogenic potency of fluoranthene has been estimated to be approximately 20 times less than that of B[a]P, a tentative guideline value of 2 ng/m(3) is suggested for fluoranthene. Other significant PAHs are phenanthrene, methylated phenanthrenes/anthracenes and pyrene (high air concentrations), and large-molecule PAHs such as dibenz[a,h]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene, and indeno[1,2,3-cd]pyrene (high carcinogenicity). Additional source-specific indicators are benzo[ghi]perylene for gasoline vehicles, retene for wood combustion, and dibenzothiophene and benzonaphthothiophene for sulfur-containing fuels. PMID:12060843